CA2264766A1 - Personal care compositions - Google Patents

Abstract

The present invention relates to personal care compositions comprising a copolymer complex and a volatile, hydrophobic solvent component for solubilizing or dispersing the copolymer complex. The copolymer complex is formed by complexing a fatty acid with a copolymer, wherein the copolymer comprises a hydrophobic monomer, a hydrophilic monomer such that at least 1 %, by weight of the total copolymer, comprises hydrophilic monomers bearing nitrogen functional groups, and optionally a hydrophobic macromonomer.

Description

W O 98/09608 PCTrUS97/15561 I

PERSONAL CARE COMPOSITIONS

TECHNICAL FIELD
This is a co~ ;o"-in-part of application Serial No. 08/736,316, filed on Oct. 23, 1996.
The present invention relates to personal care compositions co,."" ;si..g a copolymer complex and a volatile, hydlu~hobic solvent component for solubilizing or dispersing the copolymer complex. The copolymer complex is formed by complexing a fatty acid with a copolymer, wherein the copolymer colll~liae~ a hydrophobic monom~r, a hydrophiiic monomer such that at least 1%, by weight of the total copolymer, cc",.~" ises hydrophilic .. o,.~ bearing nitrogen filnrtion~l groups, and optionally a hyd,o~hobic l.,a."u..onomPn These culllpGailions provide improved delivery, deposition and retention to the hair and skin.
BACKGROUND OF THE INVENTION
In the hair care area, for example, style retention is generally accomplished by application of either permanent chemical alteration products or te.llpGI~uy styling products. A permanent chemical alteration product, which is commonly referred to as a "hair perm," typically involves treating the hair with various sulfur-c.~ g c ~puunds in order to break the disulfide bonds in the hair fibers, thereby enabling one to alter the shape and c,.i of the hair fibers. However, hair perm products have the disadvantage of being harsh and ~ ..a~,;ng to the hair, and of being long l~ting and difficult to reverse. Conversely, t~ lpGIal y styling products generally do not break the chemical bonds in the hair fibers. These te.llp~lal y styling products typically are in the form of gels, lotions, mousses, or sprays c~-nt~;..;.~p polymeric resins or gums for coating the hair fibers and bonding them together. Many t~!llpol~y styling products are inconvenient to use.and have the disadvantage of not allowing one to readily restyle the hair after the initial application and styling is cc F' ~ without further application of ~Arii~ion~l product. It would be ,~,.ef.,~dl.le to deliver styling and hold benefits using rinse-off products such as condition~rs and ch~rnpooC These types of rinse-off products, however, require styling agents that are substantive to the hair and not readily removed during the rinsing process. Fcpeci~lly useful styling and hold agents for rinse-off cc/"")G~ilions are hydrophobic polymeric materials. Such hydrophobic materials, however, may cause a buildup of an unsightly visible residue on the hair with repeated usage. This residue can eventually completely surround the hair shaft and can be difficult to remove with normal shampooing. Therefore, the need exists for improved compositions for providing temporary styling and hold of human hair without the residue and negatives often associated with such compositions. Similarly, a need remains for film-forming skin compositions which are readily washed off by soap and water.
It has surprisingly been found that hair care products, comprising a copolymer complex comprising a copolymer having at least one acid functional monomer and at least one nitrogen cont~ining functional monomer and at least one fatty acid complexed with the nitrogen cont~ining functional group, provide excellent t~ lpulaly styling and hold benefits in addition to improved "wash off' ~LaJact~,~iaIics. The copolymer complex of the present invention is soluble or dispersible in and readily deposited by hydrophobic solvent colllponcllla~ yet easily washed away by aqueous a~llG~ hllt solutions. These compûsitions can be made into any of a number of conve: -' forms i..cln~ , but not limited to, ahalllpoos, conrlition~s, mousses, gels, lotions, sprays and the like.
In addition to the afore-rn~ntione~ hair care benefits, it has been found that the copolymer complex and volatile, hydrophobic solvent col,.pol.~.,t of the present invention are also useful for inCCIl~JvlatiOIl into a wide variety of cosmetic and phal~ l collli)oailions for topical application to the skin. These materials provide topical CO".pO,i~;Ol-c which are more easily and uniformly spread upon the skin, which feel good upon the skin, and yet are highly sul.a~.Ii~e. Furthermore, these culllpoailiùns are useful for providing occlusion to enhance the penetration of a wide variety of cosmetic and pharrn~ceutic~l actives into the skin, or alternatively, through the skin for systemic delivery.
The co~ uailions of the present invention comprise a copolymer complex and a volatile, hydlupl~obic solvent co",pon~.,I suitable for application to the hair or skin. The copolymer complex cc""~";ses a copolymer having at least one nitrogen cont~ining filnctiorl~l group and at least one fatty acid complexed with the nitrogen cont~ining functional group.
It is IL.,.efvl~ an object of the present invention to provide copolymer co...p' es having ;"~nu~d solubility or J;ap~,laib;lity cLalacI.,~;aIics.
It is another object of the present invention to provide copolymer complexes that are soluble or di~ laible in h~Lùphcbi~ solvent cul.l~Jorl~l.La, and yet are readily washed away by aqueous a~llra-,LulI solutions.
It is another object of the present invention to provide personal care culll~oailions in the form of hair care co - pv~ u-\C having improved styling and/or hold ~.rùp~.Iics and having improved a~ ,l h~ t,~ c It is another object of the present invention to provide personal care c~.. po~ nc in the form of topical cosmetic and phal~ alic~l compositions useful for delivering and retaining a wide variety of cosmetic materials and pharrn~nen~ir~l actives to and/or through the skin.
It is another object of the present invention to provide rinse off co---pc,~ili.,ns useful for styling and holding hair.

CA 02264766 I ggg - o3 - o3 It is another object of the present invention to provide methods for styling and holding the hair.
It is another object of the present invention to provide methods for delivering and retaining to the skin cosmetic materials and pharm~eutic~l actives.
These and other objects will become readily apparent from the detailed description which follows.
SUMMARY OF THE INVENTION
The co...~,u~ilions of the present invention relate to personal care co~ osilions, co.,.~";~i,.~;.
A.) a copolymer complex CUIIIIJI ;~illg.
a.) a copolymer having a bacl~bonP formed from the copoly,...,. i~aliOn of repeating A monomPr and B ~.lonu,.,.,. units wherein the b~ckbonP has optionally grafted to it hydrophobic C macromonomer units wherein the copolymer is prepared by the poly"n,. on combination of the following relative weight pe~.lLbes of the A, B, and C units:
i) from about 10%.to about 99% by weight of the copolymer of one or more hydrophobic A ~ . units, wherein the A monomPr units are copoly ' 1~ with the B monc and C ma~,v ..o.\~ . units;
ii) from about 1% to about 40% by weight of the copolymer of one or more hydrophilic B ...ono...~ . units, wherein the B monomer units are copoly".c,iLab'- with the A monomer and C macrornonomPr units and wherein at least about 1% by weight of the copolymer, of the B monomer units, are selected from B l~O"u",.,. units having at least one nitrogen cont~inin~ fun~tion~l group; and iii)from 0 to about 50% by weight of the copolymer of one or more C
macror-on- mer units wherein the C units are hydrophobic n~a~ l"ûllomer units, copol~,..,c.iLable with the A monomer units and the B monomer units, the C macromonomer units having a number average molecular weight of from about 1,500 to about 50,000; and b.) a complexing fatty acid wherein the fatty acid forms a complex with the nitrogen con~ininE fi~nrtion~l group of the B monomPr units;
wherein the weight ratio of the copolymer to the fatty acid is from about 50 1 to about l: l;
and B.) a volatile, hy~ophobic solvent cu~lpùnent for the copolymer complex having a boiling point at l atmosphere of about 260~C or less and a solubility parameter of about 8.5 (caUcm3)1/2 or less wherein the copolymer complex is soluble or dispersible in the volatile, hydrophobic solvent c~ ol~..t.
In further embodiments, the present invention relates to a method of making a personal care comrositiQn, comprising the steps of:
a.) preparing a copolymer having a backbone formed from the copoly...c, i~aIiOIl of repeating A monomer and B monomer units wherein the b~bone has optionally grafted to it hy-llo~.hob:c C macromonomer units wherein the copolymer is prepared by the polymerization combination of the following relative weight p~ u~,~.. of the A, B, and C units:
i) from about l O% to about 99% by weight of the copolymer of one or more hyd~ophob:c A monomer units, wherein the A l~onu~c. units are copoly",c. ;~ble with the B mollornPr and C l"a~,~ u",o,lomer units;
ii) from about 1% to about 40% by weight of the copolymer of one or more hydrophilic B monomer units, wherein the B monomer units are copolymerizable with the A rnonom~r and C l"a."~ - units and wherein at least about 1% by weight of the copol,vmer, of the B monomer units, are selected from B units having at least one nitrogen cont~ining filn~tion~l group; and iii)from 0 to about 50% by weight of the copolymer of one or more C
macromonomer units wherein the C units are hyd.upllob:c ~"a~,u - onu ..
units, copolymerizable with the A monomer units and the B nlv.lû~
units, the C macromonomer units having a number average molecular weight of from about 1,500 to about 50,000; and b.) cu,.,?' g the copolymer with a fatty acid wherein the weight ratio of the copolymer to the fatty acid is from about 50:1 to about 1:1; and c.) dissolving or dispersing the copolymer complex in a volatile, hyd.u~,llobic solvent co.."~u"c.,I having a boiling point at I atmosphere of about 260~C or less and a solubility parameter of about 8.5 (caVcm3)1/2 or less.
In further emho~lim~n~c~ the present invention relates to a personal care culllpo~ ion which prior to mixing, cu...~ .,s.
A.) a copolymer complex COIII~JI; .i"g.
a.) a copolymer having a backbone formed from the copolymerization of r~pedli lgA monomer and B monomer units wherein the backbone has optionally grafted to it hydrophobic C macromonomer units wherein the copolymer is prepared by the polyl"~l;GaIion combination of the following relative weight p-,lce~llu~3,e~ of the A, B, and C units:

i) from about 10% to about 99% by weight of the copolymer of one or more hydrophobic A monomer units, wherein the A monomer units are copolymerizable with the B monomer and C macromonomer units;
ii) from about 1% to about 40% by weight of the copolymer of one or more hydrophilic B monomer units, wherein the B .-~vn~ units are - copoly.. c,i~ble with the A monomer and C macromonomer units and wherein at least about 1% by weight of the copolymer, of the B monomer units, are selected from B monomer units having at least one nitrogen contAinin~ group; and iii)from 0 to about 50% by weight of the copolymer of one or more C
macromonomer units wherein the C units are hydrophobic ..,a~
units, copolyl..~.iLab!e with the A Ill~ Ol..~,. units and the B mono~Pr units, the C macromonomer units having a number average molecular weight of from about 1,500 to about 50,000; and b.)a cu...~ ing fatty acid wherein the fatty acid forns a complex with the nitrogen cont~ining f ~ livon~l group of the B Iron~ ~ uniS
wherein the weight ratio of the copolymer to the fatty acid is from about 50:1 to about 1:1;
and B.) a volatile, hydrophobic solvent co...~,onent for the copolymer complex having a boiling point at I _n. o~l,k. .~: of about 260~C or less and a solubility p~ u,t~ of about 8.5 (cal/cm3)1/2 or less wherein the copolymer complex is soluble or di~ ible in the volatile, hydrophobic solvent c~...pùi.~..t.
Unless otherwise i~ ' all p~ gf,S and ratios used herein are by weight of the total cv~l~po~ n All weight p~ nl ~gf 5, unless otherwise in~l: ' i, are on an actives weight basis. All ,..e~.,~i...c..t~ made are at 25~C, unless otherwise dFclgl~AI ~1 The invention hereof can comprise, consist of, or ~ s 1" Pcc~nti~lly of, the essential as well as optional i..~ d;~ and co~ n~
de~ d herein.
DETAILED DESCRIPTION OF THE INVENTION
Essential Cu~ un~
The c~....pos;l;~.--c of the present invention comprise a copolymer complex and a volatile, hydrophobic solvent colll~Jo..f ,ll suitable for application to the hair and skin, wherein the copolymer complex co",~ ,.,s a copolymer complexed with a fatty acid.
The copolymers of the present invention can include graft copolymers. The term "graft copolymers" is familiar to one of ordinary skill in polymer science and is used herein to describe the copolymers which result by adding or "grafting" a polymeric chemical moiety (i.e. "grafts") onto CA 02264766 l999-03-03 another polymeric moiety commonly referred to as the "backbone" The backbone typically has a higher molecular weight than the grafts. Thus, graft copolymers can be described as polymers having pendant polymeric side chains, and as being formed from the "grafting" or incorporation of polymeric side chains onto or into a polymer. The polymer to which the grafis are i~co.l~o~ d can be homopolymers or copolymers. The graft copolymers are derived from a variety of monomer units.
The copolymers of the present invention can be prepared from the copol~ i of onoll-c- units and ~a~u~onG~ units such that the ~..a~ UlllOnUIIIC. units are "grafted" or inco",o. ~ into the resulting copoly.. The terrn ",.,a~,u.. ,o.. o.. ~,." is a term familiar to one of ordinary skill in polymer science, and is used to de~.;bcd a polymeric material cu~ ;..;..E a poly....,. ~'e moiety. In other words, a ...a~,.o...o,.u~ is a macromolecular ~ , which is PccPnti~lly a high molecular weight type of monomer building block unit which can be used in a poly....,.;L~liùn reaction to form polymers with itself, with other monomP s, or with other ma~ u~ono~ a.
The term "hydrophilic" is used herein .. ~ with its standard meaning of having affinity for water, whereas "hy~Lvphob " is used herein cou~ t with its standard meaning of lacking affinity for water. As used herein in relation to monomer units and polymeric materials, ;- ~1 1;. g the ...ac.u o~u -~ .a, copolymers, and solvents for the copolymers, "hydrophilic" means ,.II.s~ ly water soluble. "Sut.,li .t;~lly water soluble" shall refer to a material that is soluble in distilled (or equivalent) water, at 25~C, at a rCC_ ~ aliOn of 0.2% by weight, and are preferably soluble at 1.0%
by weight. In contrast, "hydrophobic" means 51.b~ y water insoluble. In this regard, "subsn~nti~lly water insoluble" shall refer to a material that is not soluble in distilled (or equivalent) water, at 25~C, at a cu..c~ iu.. of 0.2% by weight, and preferably not soluble at 0.1% by weight.
The term "soluble" or "solubility" as used herein, means the capability of a sv~ -.re to form a solution, i.e., either a true solution or a colloidal solution. A true solution being a uniformly di",~ d mixture at the molecular or ionic level, of one or more 5nh5~nrPc (the solute) in one or more c ~h,~ 5 (the solvent). These two parts of a solution are called phases. A colloidal d~ ,;oll is often called a solution. Since colloidal particles are larger than molecules it is strictly incorrect to call such d.~t,e. :- ~ solutions; however this terrn is widely used in the literature. The term "dia~ ibl~" or "d;~ a;b;lity" as used herein, means the capability of a sul. ~ e to form a dia~ aiOn, i.e., a two-phase system where one phase consists of finely divided particles (often in the colloidal size range) distributed Ill.ul.gl.oul a bulk s..b~ c~ the particles being the disperse or internal phase and the bulk substance the co..~ lous or external phase The term "rinse-off or wash off" is used herein to mean that the co,..~o~ilions of the present invention are used in a context whereby the co...pr";lirJn is ultimately rinsed or washed from the hair and/or skin either after or during the application of the product. Nonlimiting exarnples of rinse-off products of the present invention include hair conditioners, shampoos and soaps rhe term "sul/ala~-live" or "substantivity" as used herein, means the binding or retention of a chemical or pharrn~eutif ~1 active to the surface layer of the stratum corneum or to hair.
The term "suitable for application to human hair and skin" as used herein, means that the compositions or components thereof so described are suitable for use in contact with human hair and the scalp and skin without undue toxiCitY, incomratihility, instability, allergic response, and the like.
The ar~el.lclllioned definitions shall also apply to other materials so described herein, to the extent any other definitions regarding such materials are concictent with those stated above.
The c~ Oa;~ ions of the present invention comprise the following essential c- ..p Copolyrner complex The hair and skin care c~ o~;';ol~c of the present invention comprise from about 0.25% to about 30%, ~ f~.ably from about 2% to about 15%, and more in~r ~ably from about 2% to about 10%, by weight, based on the weight of the hair and skin care cf....pO.;~ ;f!-l, of a copolymer complex.
The copolymer complex c , iaes a copolymer having at least one nitrogen con~inir~g fu".
monomer ~ , ' f d with a fatty acid.
CoPolYmer The copolymer complex of the present invention co".~,. iaes from about 35% to about 99%, preferably from about 40% to about 90%, and more ~"~fc.~.bly from about 50% to about 70%, by weight, based on the weight of copolymer complex, of a copolymer. Based on the weight of the overall hair and skin care co---;~osiliol~ the copolymer COIlllJliaCS 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%, by weight.
~ rhe copolymers of the present invention have a weight average molecular weight, in grams/mole, of at least about 10,000. There is no upper limit for molecular weight except that which limits applicability of the invention for practical reasons, such as viscosity, pluce;~aillg~ aesthetic ch~a~h~ialics~ formulation COI .~ ;I.ility, etc. The weight average molecular weight is generally less than about 5,000,000, more generally less than about 2,500,000, and typically less than about 1,500,000. Preferably, the weight average rr~o'e 1~ weight is from about 10,000 to about 5,000,000, more ~I~;r~.ably from about 50,000 to about 2,000,000, even more preferably from about 75,000 to about l,000,000, and most preferably from about 75,000 to about 500,000.
The copolymers of the present invention are formed from the copolymerization of randomly repeating A ...OI.O units and B monomer units, I.fef~.dl)ly wherein the A ll~o~ llc.~ are polylll~,l i7dblc, ethylenically unsalul ~ monomers selected to meet the requirements of the copolymer. By "polymerizable", as used herein, is meant monomers that can be polymerized using any conventional synthetic te~hniq~Pc Monomers that are polymerizable using conventional free radical initiated tP~hniquec are p~ef~ d. The term "ethylenically unsaturated" is used herein to mean monomers that contain at least one polymerizable carbon-carbon double bond (which can be mono-, di-, tri-, or tetra-sub ~ ). The B monomer units are hydrophilic monomers which are CA 02264766 I ggg - o3 - o3 copoiymerizable with A and selected from polar monomers, preferably having a Tg or a Tm above about -20~C, and wherein at least 1%, by weight of the copolymer, of the hydrophilic B monomer is selected from hydrophilic B monomers having at least one nitrogen cont~ining funrtion~l group. The A monomer and B monomer units form what is termed the backbone of the polymer and can be selected from a wide variety of ~ U~,IUI~.S as long as the copolymer has the required properties and meets the molecular weight and other requil~..lc.ll~ described herein. The copolymers of the present invention may optionally hlCOIIJvl C Illâwv~lvnulll~,r units. The C ,..a~lulllono~ units are selected from at least one hydrophobic macromonomer unit which contains a polymeric portion and a moiety copolyllle- i~able with the A monom~r and the B Illol.oln~- . The C macrnmonomer units form hy~Lvphob r side chains on the copolymer.
The copolymers are prepared by the pO~ aliOn combination of A and B Ull a andcan be cllala~ ,d by the weight percent of the monomers charged to the reaction vessel in which the poly i~aliOn reaction is run. C ~I~acfolllvnol.~ may be optionally i..col~,G,.lted into the poly.llc,iLdlion reaction.
As will be clear to one skilled in the art and especially from the Examples, the copolymer may have one or more hydrophobic side chains grafted to the b~ hon~ As known in the art, synthetic graft cOpoly.ll~ alivll ~locesses may produce a mixture of polymer -le~ules co.,li.;..i..g no, one, or more than one hyd,uphol)ic side chains covalently bonded to and pendant from the polymeric ba~i~l,vne. From kn~..ledge of the amount and number average mal~ l~r weight of hydlupl~ side chains in a polymer sample, and the number average molecular weight of the polymer sample, it is possible to calculate the average number of hy.Lvphobic side chains per polymer b L l ~ù~e .
The copolymer complex of the present invention, when dried to a film having 0.5% or less of the volatile h~d~u?hob~ solvent coll.l)ore..l, have a Tg or Tm of at least about -20~C, more ~l~f lably at least about 20~C, so that the copolymers are not unduly sticky, or "tacky" to the touch.
As used herein, the abbreviation "Tg" refers to the glass ll all~iliun lLal~ UI ~; of the backbone of the polymer, and the abbreviation "Tm" refers to the crystalline melting point of the backbone, if such a tlall~ iull 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 grafted copolymers should satisfy the following criteria:
(I) the polymeric side chain portion is covalently bonded to the bacl~l,one portion; and

(2) the number average molecular weight of the polymeric side chain portion is from about 1,500 to about 50,000.
The copolymers of the present invention are prepared by the poly.lleli~aliull combination of A monomers and B monomers. C macromonomers may optionally be incGI~,olaled into the polylllcl;~dlioll process. The copolymers can be synthPsi~d by free radical polymerization of the luonolllcl~ and macromonomers. The general plhl~i~,lcs of free radical polymerization methods are well understood. See, for example, Odiam "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 sl~fficient amount of a mutual solvent so that when the reaction is cv,..plet, the viscosity of the reaction is reasonable. Undesired tenninators, especially oxygen, are removed as needed.
This is done by e~la~uatiol. or by purging with an inert gas, such as argon or nitrogen. The initiator is u troduced and the reaction brought to the temperature needed for initiation to occur, ~ccllm jn~
thermal initiators are used. Alternatively, redox or radiation initiation can be used. The pol~ .iLalivn is allowed to proceed as long as needed for â 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 by ~JIcci~ til.g the copolymer by addition of a nonsolvent. The copoly,...,. can be further purified, as desired.
As an alternative to a batch reaction, the copolymer can be made by a semi-continllouc or cont~--nouC process. In the semi-co~ Jo~C process, two or more ~ iriitinnc of onr~mprs or ~.. a~.. o.. J.. - ,~ are made during the poly.. l~ ation reaction. This is adv~ E,eouc when the copolymer is made of several Il.onon.~ which react during the poly~ Lalion at different rates.
The prvl)ol livns of l..onv..~ added to the reaction at the separate points of addition can be adjusted by one of ordinary skill in the art such that the polymers of the final product have a more uniform structure. In other words, the polymers of the final product will have a more con~ monomer content distribution for each of the monomer types charged to the reaction.
Examples of related copolymers and how they are made are dc~c~ivcd in detail in U.S.
Patent 4,693,935, Mazurek, issued SeptP~nhpr 15, 1987, U.S. Patent 4,728,571, Clemens et al., issued March 1, 1988, both of which are i..cu.~,o.~lcd herein by reference. A i~iition~i grafted polymers are also iicrl-~ctd in U.S. Patents 5,166,276 and 5,480,634, Hayama, et al., issued November 24, 1992 and January 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., issued March 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 incvl~Jul ' by lcfclcnce herein in their entirety.
The copolymer ~ is chal a~,tc~ d by the amount of each monomPr charged to the polymerization reaction vessel, or alternatively used in a COI)tin~louc or semi-cont;..no.:~ process.
By a~"J.vlv.iate selection and combination of the particular n nrl~Pr units and macromonomer units, and by the choice of specific relative ratios of the units well within the ability of one of ordinary skill in the art, the copolymers can be optimi,Pd for various physical properties and for cvll~pdtib;lity with other i..~c1;~.lt~ commonly used in hair care applications.

A Monomer Units The copolymers of the present invention comprise from about 10% to about 99%, preferably from about 40% to about 80%, and more preferably from about 50% to about 70%, by weight of the hydrophobic copolymer, of A monomer units.
The A monomer unit is selected from copolymerizable hydrophobic monomers or mixtures thereof, IJI~f.,.ably ethylenically unsaturated ,..onG..,c,~. Either a single type of A monomer unit or combinations of two or more A monomer units can be utilized. The A monomPrs are selected to meet the r~i~luiu~,.u.,.lb of the copolymer. F'l~f~ably, the A units are soluble or dispersible in the volatile, hydrophobic solvent Co~ Jo..~.lt. By "copolymerizable", as used herein, is meant that the A
monomer can be reacted with or poly...c.ized with the B monomers or C macromonomPrs in a polymerization reaction using one or more conv~..'; ~~l synthetic 1~ h ~i ~u~C~ such as ionic, emulsion, dispersion, Ziegler-Natta, free radical, group transfer or step growth polymerization. In the present invention, monomers and macromonomers that are copol~ d~'e using conventional free radical initiated tP~hni~luPc are preferred. The terrn "ethylenically ullaalulat~l" is used herein to mean a material that contains at least one poly..,e.;~able carbon-carbon double bond, which can be mono-, di-, tri- or tetra-svb,l ;I..t. A
NonlimitinE classes of A hy~hopl-ot;c monomers useful herein include mgnclmprs selected from the group co.~i;~li..~ of ull~alulaI~,d carboxylic acid esters of Cl-C18 alcohols, unsatu,dt~d alcohols (preferably having about 12 to about 30 carbons), unsaturated hy~hul,allJol)s, aromatic hy~l-uc-ub~ ~ Cont~ininE unsalul-l~ d alkyl groups, vinyl esters of carboxylic acids, vinyl ethers, allyl esters of carboyxlic acids, allyl ethers, and mixtures thereof.
Re~"~s~..td~ e~.~..y~ec of hyd~ophobic monomers include acrylic or methacrylic acid esters of Cl-CIg alcohols such as methanol, ethanol, methoxy ethanol, I-propanol, I-butanol, 2-methyl- I -propanol, I -pentanol, I -decanol, 2-ethylhexanol, cyclohexanol, and the like;
dicyclo~ .yl acrylate; 4-biphenyl acrylate, pentachlorophenyl acrylate; 3,5-dimethylai~.,dntyl acrylate; 4-methoxycarbonylphenyl methacrylate, trimethylsilyl methacrylate; styrenes such as methyl styrene; t-butyl styrene, isopropyl sytrene; vinyl esters, such as vinyl acetate, vinyl r~c~-- - vinyl pivalate; and vinyl ~,.up on~~P; vinyl chloride; vinyl toluene; alkyl vinyl ethers, ;,,rl~ isobutyl.vinyl ether and s-butyl vinyl ether; allyl chloride, allyl acetate, 1,2-b~ , 1,3-J;~,.,e, 1,3-h~PY~ ~iPnP~ 1~3-cyclohpy~lipn~p; bicycloh~ l; .r; 2,3-d;~bu~ylmethyl-1,6-hP~ liPnl; ethylene; propylene; isoprene; I-butene, 2-butene, isobutylene, indene; norbornylene; ~-pinene; a-pinene; and mixtures thereof.
Preferred hyd, ophobic monomers suitable for use as the A monomer units include monomers selected from the group conc;cl;l~E of n-butyl methacrylate, isobutyl methacrylate, t-butyl acrylate, t-butyl methacrylate, 2-ethylhexyl methacrylate, methyl methacrylate, t-butyl styrene and mixtures thereof. More ~ f~ d are monomer units selected from the group concictin~ of t-butyl styrene, t-butyl acrylate, t-butyl methacrylate, 2-ethylhexyl methacrylate and mixtures thereof.

W O 98/09608 PCTrUS97/15561 ll B Monomer Units The copolymers of the present invention comprise from about 1% to about 40%, preferably from about 5% to about 30%, and more preferably from about 10% to about 20%, by weight of the copolymer, of B monomer units.
The B monomer unit is selected from hydrophilic, copolymerizable monomers, l~l~f~,.ably ethylenically una&lulalcd monomers, comprising at least one monomer copol~ able with the A
monomer unit. Either a single type of B ...om, ~-~ unit or combinations of two or more B rl.oll~
units can be utilized. The B rnonnmPrs are selected to meet the ~ ui.. of the copolymer. By "copoly...e. ;~ble", as used herein, is meant that the B monomer can be reacted with or poiy~ J
with the A monomers or C ma.,.o...ol,~,...c.a in a polymerization reaction using one or more conventional synthetic techniflllPc such as ionic, ~mulcjon dispersion, Ziegler-Natta, free radical, group transfer or step growth pol~.l.c.iLalion. In the present invention, .. o..~S....a and macromonomers that are cOpol~...c-i~ablc using conventional free radical initiated t,~ 5 are preferred. The term "ethylenically u..âdlu.a~cd" is used herein to mean a material that contains at least one poly...~. b!~ carbon-carbon double bond, which can be mono-, di-, tri- or tetra-a..~ in.~. rl The B ~"ono..,e, units are selected from hydrophilic . s wherein at least 1%, by weight based on the weight of the copolymer, of the copolymer, co...".i~,s hydrophilic monomers having at least one nitrogen cont~inine funrtion~l group. The hydrophilic monomers p.cf..ably are selected such that a polymer of these monomers has a Tg or a Tm above about -20~C
The hydrophilic, B monomer is preferably water soluble. The term "nitrogen con~ e funr~ --' group," as used herein means any nitrogen cnnt~ining functional group selected from the group .ùnC;~ e of amino fimction~l groups, acid a 1dition~1 salts thereof, q~ ~ .lised amino fu..,t; -l groups and nitrogen cont~inin~ heterocyclic rings. i'referably the nitrogen cont~ining functional group has a pKa such that it is cationic at a pH of below about 5. Preferred amino funrtion~l groups are ethylenically unalalu~àlod tertiary alkylamines. Monomers i~CO"~u~ g such amino fl ' groups include the dialkylamino-alkyl-acrylates and -methacrylates, especially preferred from within this group are mO..ulllC.a having amino alkyl groups of about 2 to 8 carbon atoms such as dialkyl~rninoethyL~ lhâ~lylate and the like. Also suitable for use herein are dialkyl~minn~lbylacrylamides or methacrylamides having amino alkyl groups of I to 8, ~ ;fc.ably 2 to S carbon atoms such as methacrylamidopropyl dimethyl amine and the like. The alkyl quaternised derivatives of the above tertiary amines having alkyl groups of generally I to 4 carbon atoms may also be used in the co~ o~ nc of the present invention. It remains critical, however, that at least about 1%, based on the weight of the copolymer, are B monomer units having at least one nitrogen cc-nt~inin~ fimrtion~l group.

C Macromonomer Units The 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%~ by weight of the copolymer of C macromonomer units.
The C macromonomer units are hydrophobic l..a.,.u.l.onomers copolymerizable with the A
and B monomers, said C ~la~ulllùnvlll~a preferably having an ethylenically ul.sd~ al~d moiety.
Either a single type of C macromonomer unit or combinations or two or more C macromonomer units can be utilized herein. The C ma~.ulnonulll-~ are selected to meet the requirements of the copolymer. By "copolyll,~,,iLdble", as used herein, is meant that the C macromonomers can be reacted with or poly",~ ,d with the A and B monornPrs in a polyl.leliLdtivn reaction using one or more cull~,ulivl~al synthetic t~f hni-luec, as de~. ;bed above.
C macromonomers that are useful herein contain a polymeric portion and a copolyermizable moiety which is pl~f. lably an ethylenically unsàlul~t~d moiety. Typically, the }..cr~ d C
macromonomers are those that are endc~pped with the ethylenically u~ alulaled moiety. By "Pn~ ,cd" as used herein is meant that the ethylenically UIlSdlul d moiety is at or near a terminal position of the ma.,.vl .on.,...- .
The C macromon- m~rs can be 5ynth~si7~d utilizing a variety of standard synthetic p.ocedu.~ familiar to the polymer chemist of ordinary skill in the art. Furthermore, these macromonomers can be synth~ci7~d starting from culll~ ;ally available polymers. The C
l.,a." . has a number average molecular weight from about l ,500 to about 50,000, p,ef~,ably from about 5,000 to about 50,000, more p,ere.ably rrom about 5,000 to about 30,000, and most ~ ,r~,ably from about 8,000 to about 25,000.
F'~.,f~,dbly, the C l..a.,.u-.,onol--cl units are selected from the group cQrlcictinE of polysiloxane ...a~ a- ~, polyalkylene macromonomers, and mixtures thereof.
Polysiloxane C ."a."~ ono,l,~"~ are exemplified by the general formula:
X(Y)nSi(R)3 mZm wherein X is an ethylenically ull:,alul_ ~ group copoly..,.,l;Lable with the A monomers, such as a vinyl group; Y is a divalent linking group; R is a hydrogen, hydroxyl, lower alkyl (e.g. Cl-C4), phenyl, Cl-C4 alkyl-sul~l;n~t~d aryl, Cl-C4 alkoxy, or Cl-C4 alkyl or dialkylamino; Z is a monovalent siloxane polymeric moiety having a number average molecular weight of at least about 1500, is ~cc~ntiolly unreactive under cûpol~lll.,l;~alion con~itionc, and is pendant from the vinyl polymeric ba~hone des~,l;bed above; n is 0 or 1; and m is an integer from I to 3.
Preferably, the C ,,,a~,ulllonulllcl has a formula selected from the following formulas:

W O 98/09608 PCTrUS97/15561 X~(CH2)s--Si(R1)3~, z~, (R2)~, or X--CH2--(CH2)s~Si(Rl)3-m--Zm or o Il X-C~0~(CH2)q~(0)p~si(R I ~3-mZm In these ~l~u~lule~ s is an integer from 0 to 6, preferably 0, 1, or 2, more pl~f~ably O or l; m is an integer from I to 3, preferably 1; p is 0 or 1; q is an integer from 2 to 6; R2 js selected from the group c.~ m.g of C1-CI0 alkyl or Cl-C4 alkyl-s~lb~ d aryl, ~ r~lably Cl-C6 alkyl or Cl-C4 alkyl-d aryl, more preferably Cl-C2 alkyl; n is an integer selected from 0 to 4, preferably 0 or 1, more preferably 0; Rl is hydrogen, hydroxyl, Cl-C4 alkyl, Cl-C4 alkoxy, Cl-C4 alkyl amino or dialkylamino, phenyl, Cl-C4 alkyl subs~ituted aryl, preferably Rl is Cl-C4 alkyl; X is CH=C-R3 is hydrogen or -COOH, preferably R3 is hydrogen; R4 is hydrogen, methyl or -CH2COOH, pler~,.abiy R4 is methyl; Z is R5-(-Si-O-)r;
I

R5, R6, and R7, i-~-F ~ 'y are Cl-C4 alkyl, Cl-C4 alkoxy, Cl-C4 alkyl or dialkylamino, phenyl, C I -C4 alkyl-sub,l ;n .t~ d aryl, hydrogen or hydroxyl, preferably R5, R6, and R7 are C I -C4 alkyl; and r is an integer of from about 20 to about 900, preferably âbOut 20 to about 675, more preferably r is frorn about 100 to about 325. Most preferably, R5, R6, and R7 are methyl, p=0, and q=3.
Polyalkylene macromonomers are exemplified by the general formula:
[I]n-[wlm-E
wherein I is an optionally present initiator (i.e. n = 0 or 1), W is a hydrophobic monomer unit, E is an endcapping 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 be derived from a chemical initiator or solvent used in the synthesis of the C macromonomer.

WO 98J~S~0~ PCT/US97/lSS61 NonlimitinE examples of such initiators from which I can be derived include hydrogen ion, hydrogen radical, hydride ion, hydroxide ion, hydroxyl radical, peroxide radical, peroxide anion, Cl-C20 carbocations, Cl-C20 carbanions, Cl-C20 carbon radicals, Cl-C20 aliphatic and aromatic alkoxy anions, ammonium ion, and substituted ammonium ions (e.g., Cl-C20 alkyl and Cl-C20 alkoxy substituted), and mixtures thereof. I can be derived from any useful solvent, nonlimitinE examples of which inelude water, methanol, ethanol, propanol, isopropanol, acetone, hexane, dichlo.v~ h- ,r, chloroform, benzene, toluene, and mixtures thereof.
W is selected from one or more hydrophobic monom~r units. Nonlimitin~ classes of sueh monomers inelude C I -C 18 acrylate esters, C I -C 18 (alk)acrylate esters, C2-C30 straight and branched chain alkenes, styrenes, Cl-C30 vinyl ethers, C4-C30 straight and branched chain dienes, and mixtures thereof.
Nor-limitinE eY: , lcs of W groups include those selected from the group c.~-~c;~;..e of n-butyl aerylate, dodecyl acrylate, ethyl acrylate, 2-ethybutyl acrylate, n-heptyl aerylate, n-hexylacrylate, iso-butyl acrylate, is~decyl acrylate, iso-propyl acrylate, 3-methylbutyl acrylate, 2-methylpentyl acrylate, nonyl acrylate, octyl acrylate, I-propyl acrylate, 2-ethylhexyl methacrylate, octyl methacrylate, n-dodecyl methacrylate, n-octadecyl methaerylate, n-deeyl methacrylate, n-pentyl methacrylate, isobutylene, isoprene, 1,2-bul--l;- .c, 1,3-1,~ , 5-methyl-1-hexene, 6-methyl-1-heptene, 4,4-dimethyl-1-pentene, iso-butyl vinyl ether, styrene, 2-methyl styrene, 3-methylstyrene, 4-methyl styrene, 2-t-butyl styrene, 3-t-butyl styrene, 4-t-butyl styrene, and mixtures thereof.
E is a copoly...~ ab'o moiety or "endcdp~,i..g" group. Preferably E is an ethylenically ull~alul.~tcd moiety. More preferred is when E is selected from the group concictinE of vinyl, allyl, acryloyl, methacryloyl, ethacryloyl, 2-vinylbenzyl, 3-vinylbenzyl, 4-vinylbenzyl, 2-vinylbenzoyl, 3-vinylbenzoyl, 4-vinylbenzoyl, I-butenyl, I-propenyl, isobutenyl, cyclohexenyl, cyclop~.,t~nyl, and mixtures thereo~ Even more ~-cf~,.-cd is when E is selected from the group collc;~ E of vinyl, allyl, acryloyl, methacryloyl, ethaeryloyl, 3-vinylbenzyl, 4-vinylbenzyl, 3-vinylbenzoyl, 4-vinylbenzoyl, I-butenyl, I-propenyl, isobutenyl, and mixtures thereof. Most preferred is when E is selected from the group CO~ ;..E of vinyl, allyl, acryloyl, methacryloyl, ethacryloyl, 3-vinylbenzyl, 4-vinylbenzyl, and mixtures thereof.
Nonl itj~E , ' of polysiloxane and polyalkylene C macromonomer units useful herein inelude those seleeted from the group concictinE of acryloyl, methaeryloyl, or 3-, or 4-vinylbenzyl endeapped polymers of polydimethylciloYPn.o, polydiethylciloY~n., polyphenylmethylcilox~nl~. polyphenylethylcilox~ne 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 (hexyl methacrylate), poly(decyl methacrylate), poly(octyl methacrylate), poly(octadecyl methacrylate). poly(dodecyl methacrylate), poly(n-pentyl methacrylate), poly(isobutylene), poly(isoprene), hyd.oge..aI~d poly(1,2-butadiene), hydrogenated poly(l,4-butadiene), hydrogenated poly(isoprene), poly( I ,2-butadiene), poly( I -butene), poly(5-methyl- 1 -hexene), poly(6-methyl- 1-heptene), poly(4,4-dimethyl-1-pentene), poly(iso-butyl vinyl ether), poly[4- -butyl vinyl benzene-co-2-ethylhexyl acrylatel, poly[2-ethylhexyl acrylate-co-octyl acrylamide), poly[2-ethyl vinyl benzene-co-octyl methacrylate)], and mixtures thereof.
"Copolymer" type C macromonomers cont~inin~ two or more different randomly ~~"~ eali..g ~--vnv~ units are useful herein. Nonlimiting examples of these "copolymer" type of macromonomers include acryloyl endcapped poly[co(4-t-butyl vinyl benzene)(2,4-dimethyl vinyl benzene)], poly[co(4-t-butyl vinyl benzene)(2-ethylhexyl acrylate)], polyIco(2,4-dimethyl vinyl benzene)(2-ethylhexyl acrylate)], poly[co(2-ethyl vinyl benzene)(octy' ' - ylate)], and the like.
Nonlimitinp ExamPles Of Polymers Of The Present Invention Nonlimiting eJ~..p'~ ~ of polymers useful for making the cv...p' ~oc of the present invention include those selected from the group c~-nc;~l...g of poly[(t-butylacrylate-co-dimethylaminopropylacrylamide)-graft-poly(dimethybilo~.c)], polyl(4-t-butylstyrene-co-dimethylaminopropylacrylamide)-graft-poly(dimethylsiloxane)l, poly~t-butylacrylate-co-dirnethylaminopropylacrylamide)-graft-poly(isobutylene)], poly[(4-t-butylstyrene-co-dimethylaminopropylacrylamide)-graft-poly(isobutylene)], poly[(t-butylstyrene-co-dimethylaminopropylacrylamide)-graft-poly(2-ethylhexyl methacrylate)], poly[(4-t-butylacrylate-co-styrene-co-dimethylaminopropylacrylamide)-graft-poly(isobutylene)], poly[(t-butylacrylate-co-dimethyl-~ninoethy' '- ylate)-graft-poly(dimethylsiloxane)], poly[(4-t-butylstyrene-co-dimethyl~rninoeth~L...,ll.a... ylate)-graft-poly(dimethylsiloxane)],poly[t-butylacrylate-co-dimethyl~minoethyh..e~.a~.ylate)-graR-poly(isobutylene)], poly[(4-t-butylstyrene-co-dimethy' inoethyh..~ll.a..ylate)-graR-poly(isobutylene)], poly[(t-butylstyrene-co-dimethyl-~inoethyL.,~,Iha.,.ylate)-graft-poly(2-ethylhexyl methacrylate)], poly[(4-t-butylacrylate-co-styrene-co-dimethyl-~inoethyhllLllla~lylate)-graR-poly(isobutylene)~ and mixtures thereof.
Preferred PolYmers Of The Present Invention Particularly preferred polymers for use in the present invention include the following (the weight percents below refer to the amount of reactants added in the poly...~,.i~lion reaction, not necessarily the amount in the finished polymer):
(I) a copolymer prepared from the pol~n..,.i~ioll reaction of 10 weight percent N,N-dimethyl~nn eeth~ln,clha~,lylate, 70 weight percent isobutyl"..,Ll,ac,ylate and 20 weight percent polydimethylsiloxane macromonomer having a weight average molecular weight of about 20,000.
(Il) a copolymer prepared from the polymerization reaction of 20 weight percent N,N-dimethyl~nninoeth~L"~.ha~,ylate, 62 weight percent t-butyl methacrylate and 18 weight percent polydimethylsiloxane macromonomer having a weight average molecular weight of about 15,000 (111) a copolymer prepared from the polymerization reaction of 50 weight percent t-butylacrylate, 10 weight percent t-butyl methacrylate, l0 weight percent N,N-dimethylaminoprop~h..~l.a~.ylate, 10 weight percent ethylhexyl methacrylate and 20 weight percent polydimethylsiloxane macromonomer having a weight average molecular weightofabout 10,000.
(IV) a copolymer prepared from the pol~ on reaction of 60 weight percent t-butylacrylate, 15 weight percent N,N-dimethylaminoethylmethacrylate, 10 weight percent ethylhexyl methacrylate and 15 weight percent polydimethylsiloxane ~~a~"~n ~n~
having a weight average molecular weight of about l 0,000.
(V) a copolymer prepared from the polylllc.i~ation reaction of 70 weight percent t-butylacrylate, l0 weight percent N,N-dimethylaminopropy!n.~ll,ac"date, and 20 weight percent polyisobutylene macromonorner having a weight average molecular weight of about lO,OOO.
(Vl) a copolymer prepared from the poly...-,.i~tiu" reaction of 75 weight pereent t-butylacrylate, 5 weight percent N,N-dimethyl~ninoethyL,.clha.,.ylate, and 20 weight percent poly-2-ethylhex~L..cll.a.;lylate macromonomer having a weight average molecular weight of about 10,000.
(Vll) a copolyrner prepared from the poly...~,.i~tion reaction of 70 weight percent t-butylacrylate, 10 weight percent N,N-dimethylaminoethy' :'- ylate, and 20 weightpercent ethylhexyl methacrylate.
Fatty Acid The copolymer ~.. .pon .l of the present h.~ tion c , i5t5 from about 1% to about 50%, ~"~f~.dl,ly from about 10% to about 40%, and more ~,.cir~ bly from about 15% to about 30%, based on the weight of the co~)oly..._. complex, of a culllpl ~illg, fatty acid.
The fatty acid utilized in the co...posiliol-s of the present invention ~ r~.dbly is a long chain fatty acid. Re~,r~ e fatty acids include fatty acid sulfonates, fatty acid carboxylates, polyearboxylates and their derivatives. Illustrative carboxylie aeids inelude ~ or u~ alu~dted straight or blal~lled chained ~lirh ~tir cycloalirh tir and aromatic mono- and poly basic carboxylic acids such as 2-ethylhexanoic acid, palmitic acid, stearic acid, oleic acid, linoleic aeid and behenic aeid. Suitable polyearboxylates include polyacrylates, polyn~ tPc polyacetates, polyhydroxyacrylates and polymethacrylates Copolymers of polyearboxylates are also suitable for use herein.
It is critical to the present invention that the copolymer complex formed by the nitrogen con~ining functional monomer and the complexing fatty acid be soluble in the volatile, hyd,oi)hobic solvent co,..ponc..l flicelJcc~ Without being limited by theory, it is believed that the fatty acids associate with the nitrogen con. ~ining functional groups of the copolymer b~cl~hone so as to shield the nitrogen containing functional groups from the hydrophobic solvent component, improving the stability of the solubilized and/or diayc.acd copolymer complex The copolymers of the present invention can be complexed with the fatty acids either during the polymerization process or after the polymerization process as part of a fnal complexing step preferably at a weight ratio of copolymer to fatty acid of from about 50:1 to about 1 1, more preferably from about 3: I to about 10:7, more p~t,fHably from about 15:7 to about 10:7.
Volatile, Hy~ù~)hobic Solvent Com~,~onent The cu,..p,o,ilions of the present i..v~-llion further CGI~ ;acS from about 1% to about 99.75%, p.Gr~. ~ly from about 4% to about 50%, and more preferably from about 4% to about 2û%, based on the weight of the cu...posilion, of a volatile, hy-J~upho'Gic solvent for the copolymer complex.
The term "solvent", as used herein, means a liquid suitable for solubilizing or dia~J~,Iai Ig one or more of a variety of snhstrncf s The term "solvent component" as used herein means a liquid cu...~"ised of a single solvent or a mixture solvents. The terrn "volatile", as used herein, means tnat the solvent exhibits a cipnifir~ vapor pressure at ambient con~i~ionc (e.g., I atlllual~hc~c at 25~C), as unde.atùod by those skilled in the scientific arts. Specially, the solvent c-, .ro~f a~ has a boiling point at one ~u. O~l.hl .c of about 260~C or less, preferably about 230~C or less, more preferably about 215~C or less, and most preferably about 210~C or less and a solubility palal..ct~. of about 8.5 (cal/cm3)1/2 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 con.l-u~ .t should also be acccplable for topical application to the hair and the skin. The copolymers cn...rc,sed of the monomer and/or ~..a~.u~c~
units of the present invention must be soluble or d~ ai'L~le in the volatile, hylLu?hobic solvent cu...,..u.,~ once co...pl ed with the fatty acid complexing agent of the present invention.
Hyd.ul,hob;c solvents suitable for use in the volatile, hydrophobic solvent cu~ Jollc~ll are selected from the group c~ - g of branched chain hy~Lu~,albOIls, silironec and mixtures thereof.
Preferred hyd~ùphobi~ branched chain hydlu.,a.l,u..s useful as the solvent co. pu..~ a herein contain from about 7 to about 14, more preferably from about 10 to about 13, and most pl~ fclal)ly from about 11 to about 12 carbon atoms. Saturated hydlocaJl.uns are ~.ef~ d, although it is not intended to exclude ~JIlaa~ul_ ' hydlu~allJuns~ Examples of such p.~;f~ ;d branched chain hydlu~a,l.ons include isulJalalTil~s of the above chain sizes. Is~ a arr~5 are co..u..~,.,ially available form Exxon Chemic~l Co; ex~mrles include Isopar E (Cg-Cg iSûpcuarru~5), lsoparTM H and K (Cl l-C12 isopa arr~.~S), and IsoparTM L (Cll-C13 isopalarl~ls) or mixtures thereof. Other suitable branched chain hyd.ocalbons are icodo-lPc~ne and isonn~c~nP IcododPr~ne is preferred and is commercially available from ~c~ ae~ Inc. (South Plainfield, NJ, USA) as PerrnethylTM 99A.
Preferred silicones useful as the volatile hydrophobic solvent CU.upOI.C..l include volatile siloxanes such as phenyl pPn~ nPthyl disiloxane, phenylethylp~ "~I.yl ~licilox~n~ hexamethyl CA 02264766 l999-03-03 WO 98/~9608 PCT/US97/15561 IB

~licilo~nP, methoxy propylheptamethyl cyclotetrasiloxane, chloropropyl p~... yl ~1i5ik~Y~n~, hydroxypropyl pent~mPthyl disiloxane, octamethyl cyclotetrasiloxane, d~ "~
cyclopentasiloxane, and mixtures thereof. More preferred among the silicones are cyclome-hiconPc examples of which include heA~,-Lt11yl disiloxane, octamethyl cyclo tetr~cil--x ne and dc~ "~ll,yl cyclopPnt ~cilox~nP, which are commonly referred to D4 and D5 cyclomethicone, respectively.
Small amounts of hydrophilic solvents such as water, the Cl-C6 alcohols, or mixtures thereof may also be inco,l,v,al~d herein so long as the solubility palall~Lt~,~ of the volatile, hydrophobic solvent co".por.~ ,1 is about 8.5 (cal/cm3)112 or less.
The copolymer complP~Yes of the present invention are soluble or dia~JL~aiblc in the volatile, h~d.o~hob ~ solvent co...pom,..t at a conc~i~llralion by weight of about 0.2%, pref~.~bly of about 0.5%, and more preferably of about 1%.
In the case of the improved hair styling Pmhodimentc the copolymer complex and the volatile, hydrophobic solvent are p.~fe.~.bly mixed such that the copolymer complex/solvent mixture has a viscosity above about 5,000 cps, preferably from about 7,000 cps to about 250,000 cps and more ~-~f~,.ably from about 7,000 cps to aoout 15,000 cps. All Vi5COai1i~S are I - ~,d at 25~C and at a shear rate of 10 sec~l using a Bohlin cone and plate visc(,...~,t~,. Model VOR (cone ~' .
30mrn; cone angle: 2.5~) and are tA~I~;.sed in c-,l;po;~ Without being limited by theory, it is believed that these higher viscosity Pmho-li...L.,I~ improve polymer deposition efficiency and/or improve the weld morphology of polymer droplets leading to improved hair style and hold.
Carriers Hair Care and Topical Skin Care Comrlositi~.nc The copolymers of the present invention can be formulated into a wide variety of product types, ;.~ch l;..g -ucsPs gels, lotions, creams, ointments, tonics, sprays, aerosols, ~1, ,poo5 con-litionPrs~ rinses, bar soaps, hand and body lotions, facial mu~.~lu. i~ a, solid gel sticks, sunscreens, anti-acne ~ Jalalions, topical analgesics, mascaras, allti~JL~a~JiJ~ulla, deodorants and the like. Carriers optionally used to formulate such product types should be immiscible with the volatile I.y~ hDbic solvent co...~- The term "immiscible" as used herein means the volatile, hy~LLrk b:- solvent co- .p., ~ t has a solubility in the carrier of less than 2% by weight, p.~:r~.ably less than 1%, most preferably less than 0.1% such that at least two liquid phases are formed upon combining the volatile, hydrophobic solvent conlponL..1 with the carrier. The optional Carriers and ition~l c-... 1'0'~ t~ vary with the product type and can be routinely chosen by one skilled in the art. The following is a desc. i~,lion of some of these carriers and ~ ition~l COIll~ lL.lla.

Hair Care Compositions The hair care composilions of the present invention can comprise a carrier, or a mixture of such carriers, which are suitable for application to the hair. The carriers are preferably present at from about 0.5% to about 99.5%, preferably from about 5.0% to about 99.5%, more preferably from about 10.0% to about 98.0%, of the composition. As used herein, the phrase "suitable for application to hair" means that the carrier does not damage or negatively affect the s~sthetics of hair or cause irritation to the underlying skin.
Carriers suitable for use with hair care compocitionC of the present invention include, for example, those used in the formulation of hair sprays, mousses, tonics, gels, shampoos, conrliti9~r and rinses. The choice of appl u~, carrier will also depend on the particular copolymer to be used, and whether the product formulated is meant to be leR on the surface to which it is applied (e.g., hair spray, mousse, tonic, or gel) or rinsed off after use (e.g., ~h~ nroo. conditi- ner~ rinse).
The carriers used herein can include a wide range of cGr-p~n~ ~ts conventionally used in hair care cu~lpû~ilions. The carriers can contain a solvent to dissolve or disperse ~ itiorlsl copolymers being used, with water, the Cl-C6 alcohols, and mixtures thereof being plef~ d; and water, methanol, ethanol, iso~"~",~,ol, and mixtures thereof being more p,ef~ d. The carriers can also contain a wide variety of a~flitinnAl materials inrh~ g but not limited to acetone, hy~Loc l,ons (such as i50bl11~1C, hexane, decene), halogenated hyd,~Jcd,bu~,s (such as Freons), linalool, esters (such as ethyl acetate, dibutyl phthalate), and volatile silicon derivatives (especially siloxanes such as phenyl p~ licilsx~ methoxypropyl h~ IJt- llclllyl cyclotetracilnY~r ~, chloropropyl p~ ~ yl flic;l~-- -, hydroxypropyl p~ .clhyl disiloxane, octamethyl cy~.lotet,A~;lsn ~I~CA~ YI CY~ r~AciloxArle, cyclomethicone and ~limethicom having for example, a viscosity at 25~C of about 2.5 C~..li~,oise or less), and mixtures thereof. When the hair care co...l.o~ n is a hair spray, 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 each other. Mousses and aerosol hair sprays can also utilize any of the conventional propellants to deliver the material as a foam (in the case of a mousse) or as a fine, uniform spray (in the case of an aerosol hair spray). F - , ' of suitable propellants include materials such as trichloro-nuO.I ~- e, dichloro~linuol.,...~ll.A.r difluoroethane, dimethylether, propane, n-butane or ;COb~ -C A tonic or hair spray product having a low viscosity may also utilize an emulsifying agent. Examples of suitable emulsifying agents include nonionic, cationic, anionic sl,lL~Ils, or mixtures thereof. Fluolo~wrac~l~ are especially preferred, particularly if the product is a hair spray c-...lposilion and most especially if it is a spray composition having relatively low levels of volatile organic solvents, such as alcohols, and relatively high levels of water (e.g., in excess of about 10%, by weight water). If such an emulsifying agent is used, it is preferably present at a level of from about 0.01% to about 7.5% of the composition. The level of propellant can be adjusted as desired but WO 9~ PCT/US97/15561 is generally from about 3% to about 30% of mousse compositions and from about 15% to about 70%
of the aerosol hair spray co.ll~osilions.
Suitable spray containers are well known in the art and include conventional, non-aerosol pump sprays i.e., "atomizers," aerosol containers or cans having propellant, as described above, and also pump aerosol cJlllaillc.a utilizing compressed air as the propellant. Pump aerosol co~ iJle,a are disclosed, for exarnple, in U.S. Patents 4,077,441, March 7, 1978, Olofsson and 4,850,577, July 25, 1989, TerStege, both il.collJolal~d by ~er.,.c.lce herein, and also in U.S. Serial No. 07/839,648, Gosselin, Lund, Sojka, and Lefebvre, filed February 21, 1992, "Consumer Product Package Incb",uldli lg A Spray Device Utilizing Large Diameter Bubbles. Pump aerosols hair sprays using colll~ sed air are also currently marketed by The Procter & Gamble Company under their tradename VIDAL SASSOON AIRSPRAY~ hair sprays.
Where the hair care CO..IIU~C;I;UIIC are con~ ionPrs and rinses, the carrier can include a wide variety of ~ ioninE materials. Where the hair care co,ll?oailions are :.h~llpoos, the carrier can include aulr~ a, sllcppnAinE agents, thickeners etc. Various additional co...l..,n .l~ useful in hair care colllpGsitions are des.,.il.cd in U.S. Patent No. 5,106,609, to Bolich, Jr. et al., issued April 21, 1992; and U.S. Patent No. 4,387,090, to Bolich, Jr. issued June 7, 1983; which are iJ.col~Jul,lt~,d by ~cr~ lce herein. Some ofthese aA~I;l;o~ al co... p o~ are described below.
Topical Skin Care Compositions The topical cosmetic and phall -- _ ' co...l~G,;~;ù~.c of the present ill~ iu.l can cu~ liae a carrier. The carrier should be "co~... Ii ~lly and/or pharm~eu~ic~lly acc~ le", which means that the carrier is suitable for topical application to the skin, has good aesthetic properties, is co...r.~1;1.1e with the copolymers of the present invention and any other co,..rol,. .,l~ and will not cause any u~.lu..al~ safety or toxicity concerns.
The carrier can be in a wide variety of forms. For example, ~mulsion carriers, inrluflinE but not lirnited to, oil-in-water, water-in-oil, water-in-oil-in-water, and oil-in-water-in-silicone emulsions, are useful herein. These eml-lcionc can cover a broad range of vicco,iliPs e.g, from about 100 cps to about 200,000 cps. These emlllciA~nc can also be delivered in the form of sprays using either .- P~ ' pump cull~ai,,~la or ~ sul;~d aerosol containers using conventional propell- . These carriers can also be delivered in the fûrrn of a mousse. Other suitable topical carriers include an-hydrous liquid solvents such as oils, alcohols, and silicones (e.g., mineral oil, ethanol, iaoplu~ lol, dimethicone, CYCIO~ h;fOne~ and the like); aqueous-based single phase liquid solvents (e.g., hydro-alcoholic solvent systems); and ~hi.-lfPn~d versions of these anhydrous and aqueous-based single phase solvents (e.g., where the viscosity of the solvent has been increased to form a solid or semi-solid by the addition of a~JIOpl i,~le gums, resins, waxes, polymers, salts, and the like). Examples of topical carrier systems useful in the present invention are described in the following four references all of which are hlCul~Jul ~I herein by l~rt:~nce in their entirety. "Sun Products Formulary"
Cosmetics & Toiletries, voJ. 105, pp. 122-139 (December 1990); "Sun Products Formulary", Cosmetics & Toiletries, vol. 102, pp. 117-136 (March 1987); U.S. Patent No. 4,960,764 to Figueroa et al., issued October 2, 1990; and U.S. Patent No. 4,254,105 to Fukuda et al., issued March 3, 1981.
The carriers of the skin care c~ ro~jlionc preferably comprise from about 50% to about 99% by weight of the csmrositions of the present invention, more preferably from about 75% to about 99%, and most preferably from about 85% to about 95%.
Preferred cocmetic~lly and/or phar~nP~eutir~lly acc~table topical carriers include hydro-alcoholic systems and oil-in-water ernlllci~nC When the carrier is a hydro-alcoholic system, the carrier can comprise from about 1% to about 50% of ethanol, iaoplopanol, or mixtures thereof, and from about 40% to about 99% of water. More preferred is a carrier culllpl;aillg from about 5% to about 60% of ethanol, is(",~op~ol, or mixtures thereof, and from about 40% to about 95% of wster.
Especially preferred is a carrier cu...p. isi..g from about 20% to about 50% of ethanol, iaul)lu~Jdnol, or mixtures thereof, and from about 50% to about 80% of water. When the carrier is an oil in ..
emnlcion~ the carrier can include any of the common excipient i..g.~i;.,nb for ~ncpalulg these emlllcionc Ad~iti-ln~l c~ o~ useful in formulating these topical ccllllpGai~ions are further dcs~. ibcd below.
Additional Co...voll.,.lb A wide variety of ~ ;u ~l - , can be employed in the hair care and topical skin co...~.ûsilions herein. Non-limiting ex~,.pl~- include the following:
Pl~a~ eul i ~1 Actives The co.~ o~ilionC ofthe present invention, especially the topical skin care co...l-o~ ..c, can comprise a safe and effective amount of a phal~~~A~e~ltir~l active. The phrase "safe and effective amount", as used herein, means an amount of an active high enough to signifirS ltly or positively modify the con~lition to be treated, but low enough to avoid serious side effects (at a .e;.( ' !e benefit/risk ratio), within the scope of sound medical j 1~m~nt A safe and effective amount of the ph~...~ c llir~l active will vary with the specific active, the ability of the c-.~..ruail;on to penetrate the active through the skin, the amount of co...~,o~ilion to be applied, the particular con~ition being treated, the age and physical corllition of the patient being treated, the severity of the condition, the duration of the llcdL..C~, the nature of; - ,c.,t therapy, and like factûrs.
The p~ r~nl;~ ~l actives which can be used in the co~ a;l;onC of the present invention preferably comprise from about 0.1% to about 20% by weight of the comroc~ nc~ more p.cr~.ably from about 0.1% to about 10%, and most preferably from about 0.1% to about 5%. Mixtures of phaJ...~ ~ I;r~l actives may also be used.
Noniimiting examples of pharrn~eutic~l actives can include the following:
Useful pha.ll.a - -I actives in the cun~l~ociliullc of the present invention include anti-acne actives. Anti-acne actives pref~ d for use in the present invention include the keratolytics such as salicylic 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 antimicrobials ... . ... . ..

such as benzoyl peroxide, octopirox, erythromycin, zinc, tetracyclin, triclosan, a_elaic acid and its derivatives, phenoxy ethanol and phenoxy proponol, ethylacetate. clindamycin and meclocycline;
sebostats such as flavinoids; alpha and beta hydroxy acids; and bile salts such as scymnol sulfate and its derivatives, deoxycholate, and cholate. ~'referred for use herein is salicylic acid.
Useful pharrn Irelltic ~1 actives in the cG.,.po~ ions of the present invention include analgesic actives. Analgesic actives suitable for use in the present compositions include salicylic acid derivatives such as methyl-salicylate, species and derivatives of the genus rarsir~m such as capsaicin and non-steroidal anti-infl~mm~ory drugs (NSAIDS). The NSAIDS can be selected from the following g~ ie;,. p,u~,: ~ acid derivatives; acetic acid derivatives; fenamic acid derivatives;
biphenylcarboxylic acid derivatives; and oxicams. All of these NSAIDS are fully des.,ibcd in the U.S. Patent 4,985,459 to Sunshine et al., issued January 15, 199l, il~co"~v,aled by ~f~.~nce herein.
Most preferred are the ~"u~:onic NSAIDS including but not limited to aspirin, --~ inophPn ibuprofen, naproxen, benoxaprofen, llul 1,;". ufell, fenoprofen, fenbufen, kc.~.. ur~ , indoprofen, pirprofen, ca.~,rùf~ , oxd~,.uLill7 pranoprofen, miroprofen, tioxaprofen, suprofen, a minoprofen, tiaprofenic acid, fluprofen and bucloxic acid. Also useful are the steroidal anti-infl~mm~( ry drugs inc!llfling hydlùco.lisone and the like.
Useful F' ~ ;cq~ actives in the coll~po~;l;onc of the present i.,..: include allliplulllic drugs. Anli~u~ilic actives preferred for inclusion in compositions of the present invention include pharm~~eutic~lly-acceptable salts of methtlili7ine and 1~ .7laLhlc. Useful pha~ ;r~1 actives in the cull.~,oailions of the present invention include al,e;,ll.~,l,c actives.
~nPsth~tjc actives preferred for inrhlcion in c~""posilions of the present invention include pharrnaceutic~lly-âcc~lable salts of lidocaine, bupivacaine, chlOl~7lucaillc, ~lib~lc~ine, etidû; e, .cph/aLaillc, t~t~ e, dyclonine, hexylcaine, procaine, ***e, ket~ njn~ pramoxine and phenol.
Useful pna,. a _ ' actives in the ~"..pûsilions of the present invention include antimicrobial actives (~nti~'~ ;al" c~ V71~ anliproluzoal and antiviral drugs). Antimicrobial actives preferred for inclusion in .c l~ - . of the present invention include pl.~u l"~7r~ lly-acc~tal,le salts of b-lactam drugs, ~ e drugs, ciprofloxacin, norfloxacin, tetracycline, erythromycin, ~mik~ri7l triclosan, doxycycline, ca~"~u...ycin, chlorhrYi-lin~, chlo,t~l,acJ~line, oxytetracycline, clindamycin, eth~ nbu~ol~ tl~ pent~-nirlin~o gentamicin, kanamycin, lineomycin, methacycline, methen-amine, minocycline, neomycin, netilmicin, paromomycin, streptomycin, tobramycin, micnn~7nle and ~rn~nf~inl- Antimicrobial drugs "..f,,..~d for inclusion in compositions of the present invention include tetracycline hydrochloride, erythromycin estolate, erythromycin stearate (salt), amikacin sulfate, doxycycline hydrochloride, ca,~".io",ycin sulfate, chlorhexidine gluconate, chlorhexidine hydrochloride, chlortetracycline hydrochloride, oxytetracycline hydrochloride, clindamycin hydro-chloride, ethambutol hydrochloride, metronidazole hydrochloride, pent~rni<lin~ hydrochloride, gent~nnirirl sulfate, kanamycin sulfate, lineomycin hydrochloride, methacycline hydrochloride, methen~ nine hippurate",~.lh ., - ..ine m~n~e!ate minocycline hydrochloride, neomycin sulfate, WO 9EI'~,~CC- PCT/US97/15561 netilmirin sulfate, paromomycin sulfate, streptomycin sulfate, tobramycin sulfate, miconazole hydrochloride, ~ n~nf~ ine hydrochloride, :lm~nf~ine sulfate, triclosan, octopirox, parachlorometa xylenol, nystatin, tolnaftate and clotrimazole.
Also useful herein are sunscreening agents. A wide variety of suns~ "ing actives are described in U.S. Patent No. 5,087,445, to Haffey et al., issued February 11, 1992; U.S. Patent No.
5,073,372, to Tumer et al., issued December 17, 1991; U.S. Patent No. 5,073,371, to Turner et al.
issued De~,.,...bc. 17, 1991; and Segarin, et al., at Chapter Vlll, pages 189 et seq., of Cosmetics Science and Technolo~Y. all of which are i..co.~,o. ~ herein by rcf~.~.lce in their entirety.
Preferred among those ~u-.sc...,"s which are useful in the co...~,Gailions of the instant invention are those selected from the group con~ ,e of 2-ethylhexyl p-methoxye 2-ethylhexyl N,N-dimethyl-p-~minoben~ p ~mil-ob~.~7~Jic acid, 2-phenylhPn7inniA~7-.1e-5-sulfonic acid, octocrylene, oxybenzone, homomenthyl salicylate, octyl salicylate, 4,4'-methoxy-t-butyldib~,,,zoylmeth~ 4-isopropyl dibenzoylmethane, 3-benzylidene camphor, 3-(4-methylbenzylidene) camphor, titanium dioxide, zinc oxide, silica, iron oxide, and mixtures thereof.
Still other useful ~.I..s~,C.,,.s are those llicclnsf~d in U.S. Patent No. 4,937,370, to S~h~-e~
issued June 26, 1990; and U.S. Patent No. 4,999,186, to Sabatelli et al., issued March 12, 1991; these two r~f~,~,nces are inco.~,v.~ ,d by rer~ ,.lce herein in their entirety. The aLus~.~e..i..g actives ed therein have, in a single molecule, two distinct cl..u...ophole moieties which exhibit different ultra-violet radiation absù.~lion spectra. One of the chromophore moieties absorbs pre-dom Iy in the UVB radiation range and the other absorbs strongly in the UVA radiation range.
These 5u~law~ ng actives provide higher efficacy, broader UV absorption, lower skin p.,.l~llalion and longer lasting efficacy relative to conventional S~ aCI.~.l5. Especially preferred examples of these :~h...~ . include those selected from the group concic~ine of 4-N,N-(2-ethylhexyl)methyl-aminobenzoic acid ester of 2,4-dihydroxyb ~70pllf nOllC, 4-N,N-(2-ethylhexyl)methylaminobc..Lu:c acid ester with 4-hydroxydibenzoylmeth~n~, 4-N,N- (2-ethylhexyl)methylaminobenzoic acid ester of 2-hydroxy-4-(2-hydroxyethoxy)l,. ..7Oph~ ,-one 4-N,N-(2-ethylhexyl)-methylaminobenzoic acid ester of 4-(2-hydroxyethoxy)dibenzoyl~ r, and mixtures thereof.
Generally, the sunscreens can comprise from about 0.5% to about 20% of the co...pos:l;o!.c useful herein. Exact amounts will vary ~epen~line upon the au..sc.~n chosen and the desired Sun l~.t~ Factor (SPF). SPF is a cornmonly used measure of pholû~J~ut~ ion of a su..sc..~,.. against erythema. See Federal Re~ister, Vol. 43, No. 166, pp. 38206-38269, August 25, 1978, which is h.co.~,u...~,d 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 be used in combination with the suns~ .. agents.
Other useful actives include skin bl~- ' ine (or livh~nine) actives incllllline but not limited to hydroquinone, ascorbic acid, kojic acid and sodium metabisulfite.

Other useful actives which are especially useful for hair care compositions include anti-dandruffactives such as zinc pyrithione, octopirox, selenium ~iculfiAP sulfur, coal tar, and the like.
Other useful actives include antiperspirant actives. Suitable for use herein are those which comprise any compound, cornpocition or mixture thereof having a~ a~Jilalll activity. Astringent metallic salts are preferred al~ 7~.a~ alll materials for use herein, particularly the inorganic and organic salts of ~lllminl~m zirconium and zinc, as well as mixtures thereof. Particularly preferred are the ~Inmim~m and zirconium salts, such as ~lllminllm halides, ~lllminl~m hydroxy halides, zirconyl oxide halides, zirconyl hydroxy halides, and mixtures thereof.
AA~1itisn~lly~ deodorant actives in the form of ba~,t~.iosldla may be ...coliu~,l..t~,d into the present co...~,~,ailions. Suitable deodolaut bacteriostats include 2,2'-methyl.l.cb;s(3,4,6-trichlo,cpr -1), 2,4,4'-trichloro-2'-hydroxy(diphenyl ether), zinc phenolsulfonate, 2,2'-thiobis(4,6-dichlo.~ 1), p-chloro-m-xylenol, dichloro-m-xylenol and the like. Most preferred is 2,4,4'-trichloro-2'-hydroxy(diphenyl etner), which is generically known as triclosan and available from the Ciba-Geigy COl~JulaliOll under the trademark, Irgasan DP-300 Registered TM. Wl~en triclosan is utilized it will be present in a range from about 0.05 to about 0.9%, pl~r ~ably from about 0.1 to about 0.5% by weight of the c~r~ o~:~;n~ Other types of bact~.;osldta include sodium N-lauroyl Salu~~ - sodium N-palmitoyl aalCOaulC, lauroyl Sal~aillc, N-myristoyl glycine, pu~ N-lauroyl sa~,oail~e and ~Illminllm chlorhydroxy lactate (sold by Reheis Chemical Company under d~.ll~k of Chloracel).
ConAitioners Con~itinninE agents useful herein, and especially useful for hair care co,..pG~;l;onc include hyd~oca,'uons, silicone fluids, and cationic materials.
The h~hO~,al; - can be either straight or l,.ancl.ed chain and can contain from about 10 to about 16, p~e~.dbly from about 12 to about 16 carbon atoms. F , ' of suitable h~dlo~ ,olls are decane, dc ~e -, t~ de - tridecane, and mixtures thereof.
Silicone c~ .J:~;ol-il-E agents useful herein can include either cyclic or linear polydimethyicilnYr l~s phenyl and alkyl phenyl $ilirones, and silicone copolyols. The linear volatile silicones generally have vicro~;l;. s of less than about 5 '-es at 25 C, while the cyclic materials have vic~osi~iPs less than about 10 centi~ok.Ps Cationic co~u~ inE agents useful herein include q-- Ilaly ~mmonillm salts or the salts of fatty amines. These ~IAitinn~l cationic agents are used herein for the purpose of providing conAitiorinE and are separate and apart from the complexing agents of the present invention.
Preferred ~ llaly ~ nmonillm salts are dialkyl dimethyl ammonium chlorides, wherein the alkyl groups have from 12 to 22 carbon atoms and are derived from long-chain fatty acids. Rc~ a~ dti~e examples of ql llaly ammonium salts include ditallow dimethyl ammonium chloride, ditallow dimethyl .. ,OI.i.. methyl sulfate, Ai~lPY~dpcyl dimethyl ~mmonillm chloride, and di(h~LoL,e.. at~d tallow) ~mmnnillm chloride. Other quaternary ammonium salts useful herein are dicationics such as tallow propane diammonium dichloride. Quaternary imidazolinium salts are also useful herein.
Examples of such materials are those imidazolinium salts containing C12-22 alkyl groups such as 1-methyl-l-[(stearoylamide)ethyl]-2-heptadecyl-4, 5-dihydroimidazolinium chloride, I-methyl-l-[(palmitoylamide)ethyl]-2-octadecyl-4,5-dihydroimidazolinium chloride and l-methyl-l-[(tallowamide)-ethyl]-2-tallow-imidazolinium methyl sulfate. Also useful herein are salts of fatty amines. Examples of such componn~lc include stearylamine hydrochloride, soyamine hydrochloride, and stearylamine formate. Useful conditioning agents are disclosed in U.S. Patent No. 4,387,090, to Bolich, issued June 7, 1983, which is ~ulal~d by r~,f~ ce herein.
Hulllc~,~allla and Moisturizers The co...;.o~ c of the present invention can contain one or more 1~ - - or moisturizing materials. A variety of these materials can be employed and each can be present at a level of from about 0.1% to about 20%, more preferably from about 1% to about 10% and most preferably from about 2% to about 5%. These materials include urea; ~ inP: glycolic acid and glycol ate salts (e.g. oni - and ~u "~y alkyl ammonium); lactic acid and lactate salts (e.g.
.~ nmt-ni~Jm and ~ ,la,y alkyl ~mmOnilJm); aloe vera in any of its variety of forms (e.g., aloe vera gel); polyhydroxy alcohols such as sorbitol, glycerol, hc~allel~iol, propylene glycol, butylene glycol, hexylene glycol and the like; polyethylene glycols; sugars and starches; sugar and starch derivatives (e.g., alkoxylated glucose); hyaluronic acid; l~t.~ le monoethanolamine; ~re~irle monu~hd~lGlallline; and mixtures thereof. Preferred l.~u..e~L~t~ and moi,Lu~ are glycerol, butylene glycol, hexylene glycol, and mixtures thereof.

sll.r~
The c.. l~os:~ nc of the present invention, especially the shampoo and con~lition~Pr compositi~.nc, can contain one or more surfactants. These surfactants are useful adjuncts for the carriers of the present cc~ o~ nc and are not required for solubilizing, dis~ aing or cu~l~?~ ~
the copolymers of the present invention. For a shampoo, the level is preferably from about 10% to about 30%, ~"~fi,,al ly from 12% to about 25%, of the ~ ,-Gailion. For conditinn~rs, the preferred level of aulL~ is from about 0.2% to about 3%. Surfactants useful in c~...,l~os;l;ons of the present invention include anionic, nonil~nic cationic, zwitterionic and ~rhot.oric Sulra~ ts. A wide variety of aulL~,~Ib useful herein are disclosed in U.S. Patent No. 5,151,209, to Mc Call et al., issued S~t~ .b 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 inco",o.al~d by ~ ~fe. ~,nce herein.
Nonlimitin~ eY.~nrleS of these surfactants include anionic aulL such as alkyl and alkyl ether sulfates. These materials typically have the respective formulae ROSO M and RO(C H O) SO M, wherein R is alkyl or alkenyl of from about 10 to about 20 carbon atoms, x is I
2 4 x 3 to 10, and M is a water-soluble cation such as ammonium, sodium, pot~cc~ n and triethanolamine.

.. .. .. ..

Another suitable class of anionic surfactants are the water-soluble salts of the organic, sulfuric acid reaction products of the formula:
Rl--SO3--M
wherein Rl is chosen from the group COllai~ g of a straight or branched chain, saturated aliphatic hydrocarbon radical having from about 8 to about 24, preferably about 12 to about 18, carbon atoms;
and M is a cation. Additional exarnples of anionic synthetic Sulra~ ta which come within the terms of the present invention are the reaction products of fatty acids esterified with icethionic acid and neutralized 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 ~Y~p'e~ are derived from coconut oil. Still other anionic synthetic s~llra~ a include the class d~sign~~d as su~c ~ olefin sulfonates having about 12 to about 24 carbon atoms, and b-alkyl-oxy alkane sulfonates. Many ~ ition~l nonsoap synthetic anionic aulLLkulta are dc~ ;l.cd in McCutcheon's, Det~ lta and Emulsifiers. 1984 AnnuaL publiahed by Allured Publishing Corporation, which is incc,.~,o.dt~,d herein by ref~ nce. Also U.S. Patent 3,929,678, Laughlin et al., issued December 30, 1975, discloses many other anionic as well as other sulra.,lault types and is inco~,uldt~d herein by ~ .,ce.
Nonionic sulra.,~b useful herein are preferably used in c~mhin~tion with an anionic, a llphvt.,.;c or Gwili~.;onic su~ra~ ~u~. These nonionic sulra~ can be broadly defined as co...L)oullds produced by the c~ A~ ion of alkylene oxide groups (hydrophilic in nature) with an organic hydrophobic cc ,,llJuulld, which may be aliphatic or alkyl aromatic in nature.
Cationic sulr~ u1t~ useful in culllpoailions of the present invention are ~iiccl~sed in the following do~u..~ all hlco.~.o...t~d by reference herein: M.C. Publishing Co., McCutcheon's, D~t~ nta & Emulsifiers, (North American edition 1979); Schwartz, et al., Surface Active A~ents~
Their ChemistrY and Technolo~y~ New York~ L~au;~ e Publishers, 1949; U.S. Patent 3,155,591, Hilfer, issued November 3, 1964; U.S. Patent 3,929,678,1 ~ughlin 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, Ir., issued June 7, 1983. If included in the comrosi~ionc of the present invention, the cationic surfactant is present at from about 0.05% to about 5%.
Z~.ilt~.ionic Sulra~aulb are exemplified by those which can be broadly dc;.~,libcd as derivatives of aliphatic 4~1~t~11auy ammonium, phosphonium, and sulfonium co...rou .~k in which the aliphatic radicals can be straight or branched chain, and wherein one of the aliphatic s~ lim t~
contains from about 8 to about 18 carbon atoms and one contains an anionic water-solubilizing group, e.g., carboxy, sulfonate, sulfate, phosphate, or phocrho~~tP Other zwill~,.iol1ics such as betaines are also useful in the present invention. Examples of betaines include the high alkyl betaines, such as coco dimethyl carboxymethyl betaine, lauryl dimethyl carboxymethyl betaine, lauryl dimethyl alphacarboxyethyl betaine~ cetyl dimethyl carboxymethyl betaine, lauryl bis-(2-hydroxyethyl) carboxymethyl betaine, stearyl bis-(2-hydroxypropyl) carboxymethyl betaine, oleyl dimethyi gamma-carboxypropyl be~aine, lauryl bis-(2-hydroxypropyl)alpha-carboxyethyl betaine, coco dimethyl sulfopropyl betaine, stearyl dimethyl sulfopropyl betaine, lauryl dimethyl sulfoethyl betaine, lauryl bis-(2-hydroxyethyl) sulfopropyl betaine, and amidobetaines and ~nidos~lfobetaines (wherein the RCONH(CH2)3 radical is attached to the nitrogen atom of the betaine).
Examples of amphoteric sulra~ la which can be used in the compositions of the present invention are those which are broadly described as derivatives of aliphatic scconda,y and tertiary amines in which the aliphatic radical can be straight or branched chain and wherein one of the aliphatic substitupnts contains from about 8 to about 18 carbon atoms and one contains an anionic water solubilizing group, e.g., carboxy, sulfonate, sulfate, phosphate, or phocl)h~ e FY: r~ of compo~n~lC falling within this defini~ion are sodium 3-dodecyl-aminopropionate, sodium 3-dodecylaminol,lupaue sulfonate, N-alkyltaurines such as the one prepared by reacting dodecylamine with sodium icethion~~e accoldi..g to the teaching of U.S. Patent 2,658,072, N-higher alkyl aspartic acids such as those p.uJuced according to the teaching of U.S. Patent 2,438,091, and the products sold under the trade name "Miranol" and des~libed in U.S. Patent 2,528,378.
Carboxylic Acid Copolymer Thickeners Another cc .-pon~n~ useful in the co~rG~;~ionC herein is a carboxylic copolymer thickener.
These croccl '-Pd polymers contain one or more monomPrs derived from acrylic acid, c"~ ..r.~
acrylic acids, and salts and esters of these acrylic acids and the substit''ted acrylic acids, wherein the crocclink g agent contains two or more carbon-carbon double bonds and is derived from a polyhydric alcohol. These polymers are included in addition to the fatty acid cc--.l.~.. ,t of the present invention to provide a thirkPning action and are not required for solubilizing, d;s~JI,.aillg, or complexing the copolymers of the present invention. The preferred polymers for use herein are of two general types. The first type of polymer is a crocsl '-Pd homopolymer of an acrylic acid monomer or derivative t~hereof (e.g., wherein the acrylic acid has subctitllprltc on the two and three carbon positions in~kppendpntly selected from the group concicting of Cl 4 allcyl, -CN, -COOH, and mixtures thereof). The second type of polymer is a crosclinl~Pd copolymer having a first m~n~
selected from the group c~--.ci,li.,p of an acrylic acid monomer or derivative thereof (as just described in the previous sentence), a short chain alcohol (i.e. a Cl 4) acrylate ester monomer or derivative thereof (e.g., wherein the acrylic acid portion of the ester has subsliln .~ on the two and three carbon positions ir~ PpPnflpntly selected from the group concicting of Cl 4 alkyl, -CN, -COOH, and mixtures thereofl, and mixtures thereof; and a second monomer which is a long chain alcohol (i.e.
Cg 40) acrylate ester monomer or derivative thereof (e.g., wherein the acrylic acid portion of the ester has ,uh.~ on the two and three carbon positions in-lepen~Pntly selected from the group conC;c~ g of Cl 4 alkyl, -CN, -COOH, and mixtures thereof). Combinations of these two types of polymers are also useful herein.
In the first type of crocclin~ed homopolymers the monomers are preferably selected from the group col,c;~;..p of acrylic acid, methacrylic acid, ethacrylic acid, and mixtures thereof, with . , ~

acrylic acid being most preferred. In the second type of crosslinked copolymers the acrylic acid monomer or derivative thereof is preferably selected from the group col-ci~l;.,g of acrylic acid, methacrylic acid, ethacrylic acid, and mixtures thereof, with acrylic acid, methacrylic acid, and mixtures thereof being most preferred. The short chain alcohol acrylate ester monomer or derivative thereof is ",~rt,ably selected from the group concic~ing of C 1 4 alcohol acrylate esters, C 1 4 alcohol methacrylate esters, Cl 4 alcohol ethacrylate esters, and mixtures thereof, with the Cl 4 alcohol acrylate esters, Cl 4 alcohol methacrylate esters, and mixtures thereof, being most ~.efL.led. The long chain alcohol acrylate ester monomer is selected from Cg 40 alkyl acrylate esters, with C10 30 alkyl acrylate esters being ,..,~f. .,~,d.
The croCcl ' " agent in both of these types of polymers is a polya]kenyl polyether of a polyhydric alcohol c~nt~ining more than one alkenyl ether group per molecule, wheréin the parent polyhydric alcohol contains at least 3 carbon atoms and at least 3 hydroxyl groups. Preferred crosslinkers are those selected from the group concicting of allyl ethers of sucrose and allyl ethers of pentaerythritol, and mixtures thereof. These polymers useful in the present invention are more fully described in U.S. Patent No. S,087,445, to Haffey et al., issued February 11, 1992; U.S. Patent No 4,509,949, to Huang et al., issued April 5, 1985; U.S. Patent No. 2,798,053, to Brown, issued July 2, 1957; which are inco",u, ~ by rcf~.~,.,ce herein See also, CTFA International Cosmetic l"~id;~.~t Dictionary~ fourth edition, 1991, pp. 12 and 80; which are also L~cul~JulalLd herein by ,~f~ ..ce.
F ;' of cu",...~.~ially available homopolymers of the first type useful herein include the calL :., which are homopolymers of acrylic acid crocclin~ed with allyl ethers of sucrose or pentaerytritol. The bu~ are available as the Carbopol~9 900 series from B.F. Goodrich Examples of cu~lllllcl~ially available copolymers of the second type useful herein include copolymers of C10 30 alkyl acrylates with one or more m~nomPrS of acrylic acid, methacrylic acid, or one of their short chain (i.e. Cl 4 alcohol) esters, wherein the crosslinl ing agent is an allyl ether of sucrose or pentaerytritol. These copolymers are known as acrylates/C I û-30 alkyl acrylate crosspolymers and are - ~ially available as C~l,upo'~ 1342, Pemulen TR-I, and Pemulen TR-2, from B.F
Gûodrich. In other wûrds, eY , ' of carboxylic acid polymer thickeners useful herein are those selected frûm the group cu..~ ;..g of calbu"..,.~, acrylates/C10-C30 alkyl acrylate crosspolymers, and mixtures thereof.
The co-..posilionc of the present can co".~";se from about 0.025% to about 1%, more preferably from about 0.05% to about 0.75% and most preferably from about 0.10% tû about 0.50%
of the carboxylic acid polymer thickeners.
F.mulcifiPrs The co...poCil;onC herein can contain various emulsifiers. These ernlllcifiPrs are useful for emulsifying the various carrier col..~,(,l,.,l~t~ of the compositions herein, and are not required for solubilizing or di:",.,.:,illg the copolymers of the present invention. Suitable emulsifiers can include any of a wide variety of nonionic, cationic, anionic, and zwitterionic emulsifiers disclosed in the prior WO 98/09608 PCTtUS97/15561 patents and other l~r~l~nces. See McCutcheon's, Detereents and Emulsifiers, North American Edition (1986), published by Allured Publishing Corporation; U.S. Patent No. 5,011,681 to Ciotti et al., issued April 30, 1991; U.S. Patent No. 4,421,769 to Dixon et al., issued December 20, 1983; and U.S. Patent No. 3,755,560 to Dickert et al., issued August 28, 1973; these four tef~ ces are inCVG~ ~)UI t~ i herein by l~fe,~.,ce in their entirety.
Suitable emulsifier types include esters of glycerin, esters of propylene glycol, fatty acid esters of polyethylene glycol, fatty acid esters of polypropylene glycol, esters of sorbitol, esters of sorbitan anhydrides, carboxylic acid copolymers, esters and ethers of glucose, ethoxylated ethers, ethoxylated alcohols, alkyl i~hs ;~ Y--- s, polyoxyethylene fatty ether phl~sy I ~., fatty acid a nides, acyl lactylates, soaps and mixtures thereof.
Suitable e~nulcifiPrs can include, but are not limited to, polyethylene glycol 20 sorbitan monolaurate (Polysorbate 20), polyethylene glycol 5 soya sterol, Steareth-20, Ceteareth-20, PPG-2 methyl glucose ether ~ LcoJ~t~, Ceteth-10, Polysorbate 80, cetyl Y~ho~pl.- t-, pvt~,~.aiulll cetyl pho~lYh~f diethanolamine cetyl phosphate, Polysorbate 60, glyceryl stearate, PEG-100 stearate, and mixtures thereof. The emulsifiers can be used individually or as a mixture of two or more and can cG~n~.liac. from about 0.1% to about 10%, more preferably from about 1% to about 7%, and most preferably from about 1% to about 5% of the cvln,vGailivlls of the present invention.
Emollients The co~ uc;lionc useful in the methods of the present invention can also optionally co.npliae at least one emollient. FY~ s of suitable emollients include, but are not limited to, volatile and non-volatile silicone oils, highly branched hydiloca,i,ulls, and non-pol_r carboxylic acid and alcohol esters, 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 illCvl ~JOI 1~: Ci herein by r~re~ lce in its entirety.
The C...O" I can typically cG...~,.ise in total from about 1% to about 50%, preferably from about 1% to about 25%, and more preferably from about 1% to about 10% by weight of the cC~ c~ nnc useful in the present invention.
Additional Cv..." ~
A variety of A~lrlitionAI cullllJone~ tj can be i Icul~uldted into the c~ ~-po~ :~;ons herein. Non-lirniting , ' of these a~klitionAI co,nro~ include vitamins and derivatives thereof (e.g.
ascorbic acid, vitamin E, tocoph.,.yl acetate, retinoic acid, retinol, retinoids, and the like); low pH
thirl~ning agents (e.g. polyacrylanide and C13 14 isoparamn and laureth-7, available as Sepigel from Seppic Col~GI~liiun; polyquaternium and mineral oil, available as Salcare SC92, from Allied Colloids; crvccli~rd methyl quaternized dimethylaminomethacrylate and mineral oil, available as Salcare SC95 from Allied Colloids; resins; gums and thickeners such as xanthan gum, carboxymethyl cellulose, hydroxy~methyl cellulose, hydroxyethyl cellulose, alkyl-modified hydroxyalkyl celluloses (e.g. Iong chain aikyl modified hydroxyethyi celluloses such as cetyl hydroxyethylcellnlose), and .... . . . ... . . .. .. .

mç.pnPcj.lm z~lllnninlnn silicate; cationic polymers and thickeners (e.g., cationic guar gum derivatives such as guar hydroxypropyltrimonium chloride and hydroxypropyl guar hydroxypropyltrimonium chloride, available as the Jaguar C series from Rhone-Poulenc; polymers for aiding the film-forming properties and substantivity of the composition (such as a copolymer of eicosene and vinyl pyrrolidone, an example of which is available from GAF Chemical Corporation as Ganex~9 V-220);
sllcpPnAing agents such as ethylene glycol di~l~alaIe and the like; preservatives for mqints.ining the antimicrobial integrity of the co.l~l,oaiIions; skin penetration aids such as DMSO, 1-dodecylazacycloheptan-2-one (available as Azone from the Upjohn Co.) and the like; ~tioxid~ntc;
chelators and sequestrants; and aesthetic co...l)on ~ such as G~ atlces~ ~CCIJIiIIgS~ essential oils, skin sensates, a~llill C.l~, skin soothing agents, skin healing agents and the like, nonlimiting examples of these aesthetic c ., ~! include panthenol and derivatives (e.g. ethyl panthenol), rs~ntothPnic acid and its derivatives, clove oil, menthol, camphor, eucalyptus oil, eugenol, me~nthyl lactate, witch hazel distillate, slll~ntr: bisabalol, dipOIas~iulll glycyrrhizinate and the like.
Method of Usin~ Hair and Skin Care Compositions The hair care and skin care cu,..po,il ;o..~ of the present invention are used in conventional ways to provide the desired benefit appl u~,l iale to the product such as hai} styling, holding, cl~ Ig conAitir g and the like for hair care c r- onc and benefits such as moi,lu~ iull~ sun prote~liolI, anti-acne, anti-~l '-ling artificial tanning, analgesic, and other cosmetic and pha,.--~c-~l;r ' benefits for skin care co~ o~;lionc Such methods of use depend upon the type of c("llpGsilion employed but generally involve application of an effective amount of the product to the hair or skin, which may Lhen be rinsed from the hair or skin (as in the case of shampoos and some conAitiorlin~ products) or allowed to remain on the hair (as in the case of spray, mousse, or gel products), or allowed to remain on the skin (as in the case of the skin care comrocitionc) By "effective amount" is meant an amount sufficient to provide the benefit desired. Preferably, hair rinse, mousse, and gel products are applied to wet or damp hair prior to drying and styling of the hair.
After such cu...l.o. :~ are applied to the hair, the hair is dried and styled in the usual ways of the user. Hair sprays are typically applied to dry hair after it has already been dried and styled.
CosmPtic and ph~ul..~r~ l topical skin care col,lposilions are applied to and rubbed into the skin.
EXAMPLES
The following examples further illustrate preferred ennhoAi-- ~ within the scope of the present ill~e.l~iun. The examples are given solely for the purposes of illustration and are not to be col,slll.ed as limits~tinnc of the present invention as many variations of the invention are possible without d~yal~illg from its spirit and scope.
Ir.~eJ;~ are jA~ntified by chemical or CTFA name.
The following synthetic prùceJulc is exemplary of the methods useful for synthrci~ing the copolymers of the present invention.

WO 98/09608 PCr/US97/15561 EXAMPLE I
Synthesis of Polyr(t-butyl acrylate)-(dimethvlaminopropvlacrvlamide)- raft-PolYdimethYIsilo%ane)l Place 70 parts of t-butyl acrylate, 10 parts dimethylaminopropylacrylaimde and 20 parts of polydimethylsiloxane macromonomer (13,000 MW) (co~ .c.cially available from 3M, St. Paul, MN) in a flask. Add sufficient acetone as the reaction solvent to produce a final monomer conc~ lalion of 20%. Purge the vessel with an inert a~mQsrhere, preferably nitrogen or argon. Add initiator, (2,2'-~obiai~obulyronitrile) to a level àppfOIJl idle 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 of monomer. Heat to 60~C and maintain this te,ll~,dlure for 6 hours while aeit~tine Terminate the reaction by cooling to room le~ ,.dl-~c. The polymer is purified by drying off the reaction solvent in an oven.

Synthesis of Poly~(t-butyl acrylate)-(dimethvlaminoelhv/methacrvlate)-~raft-DolYdimethvlsiloxane)l Place 60 parts of t-butyl acrylate, 20 parts dimethylaminoethylrnethacrylate and 20 parts of polydirnethylsiloxane ~,.ac,.,l.lon(,lll~,. (13,000 MW) (cullllll~,lcidlly available from 3M, St. Paul, MN) in a flask. Add surr~ t acetone as the reaction solvent to produce a final monom~r co.lc~i,lnalio" of 20%. Purge the vessel with an inert atmosphere, preferably nitrogen or argon. Add initiator, (2,2'-aLobi~isob.llyronitrile) to a level al~ln~l~JI iate 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 of monomer. Heat to 60~C and maintain this le~llp.,lalulc for 6 hours while ~gjt:~ing Terminate the reaction by cooling to room hlll~J.,lalulc. The polymer is purified by drying off the reaction solvent in an oven.

Synthesis of PolY~(t-butyl acrYlate~(dimethvlaminoethvlmethacrvlate )-(2-ethylhex~ ylate~l Place ~0 parts of t-butyl acrylate, 10 parts dimethyl~minoerhylmethacrylate and 20 parts of 2-ethylhexyL.,~tha~lylate in a flask. Add sufficiPnt acetone as the reaction solvent to produce a final l.-OI~---U, co..cc.ll-alion of 20%. Purge the vessel with an inert ~mosrhere~ preferably nitrogen or argon. Add initiator, (2,2'-a~obi~iaob,Jlyronitrile) to a level ap~,iop.;ate 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 of monomer. Heat to 60~C and maintain this t~llp~,~àtule for 6 hours while :~git~~ing Terminate the reaction by cooling to room t~ "dlure. The polymer is purified by drying offthe reaction solvent in an oven.

Synthesis of Poly~(t-butyl acrylate)-(dimethvlaminoProPvlacrvlamide)-~raft-PolYisobutylene)l Place 70 parts of t-butyl acrylate, 10 parts dimethylaminopropylacrylaimde and 20 parts of polyisobutylene macromonomer in a flask. Add sufficient acetone as the reaction solvent to produce a final Illon~,lllcl couc~ ldlion of 20%. Purge the vessel with an inert -~nosphere, preferably .. ..

WO 98/09608 PCT/US9711S~;61 nitrogen or argon. Add initiator, (2,2'-azobisisobutyronitrile) to a level alJplOplialc 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 of monomer. Heat to 60~C and maintain this temperature for 6 hours while agit~ltin~
Terrninate the reaction by cooling to room temperature. The polymer is purified by drying off the reaction solvent in an oven.

Synthesis of Polyr(t-butyl acrylate)-(dime~ laminoet~7Y' . hac, ~late ~-~raft-polvisobutylene)l Place 60 parts of t-butyl acrylate, 20 parts dimethyl~minoethylmethacrylate and 20 parts of polyisobutylene macromonom.or in a flask. Add sufficient acetone as the reaction solvent to produce a final monomer CO~ lra~iOn of 20%. Purge the vessel with an inert ~trns p~ c, preferably nitrogen or argon. Add initiator, (2,2'-azobisisobutyronitrile) to a level apl)ro~Jliale 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 of orlomPr. Heat to 60~C and maintain this te.l.p~,.al~t for 6 hours while ~git~tirlg Terminate the reaction by cooling to room temperature. The polymer is purified by drying off the reaction solvent in an oven.

Synthesis of Polyr(t-butYI acrYlate)-(c' . 5.~1am.,~o~h~ ~ 51a~"Jlate )-(2-ethvlhex~ll,..,lha." ylate)l Place 70 parts of t-butyl acrylâte, 10 parts dimethylaminoethyl,.,~,ll,al,lylate and 20 parts of 2-ethylhexylmethacrylate in a flask. Add sufficiont acetone as the reaction solvent to produce a final l,.unû...c. cu~ce~ alion of 20%. Purge the vessel with an inert atmosph~-re, plcrc.àbly nitrogen or argon. Add initiator, (2,2'-azobisisobutyronitrile) to a level a~ u~JIiale 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 of monomer. Heat to 60~C and maintain this le~llP~ IUIC for 6 hours while agit~iny Terminate the reaction by cooling to room l~ IUIC. The polymer is purified by drying off the reaction solvent in an oven.
By varying the rn. ~ m~rs and ,..a."u...unomers used, the general l,locedu~cs given above in FYI'~I - 1-6 are used to prepare other copolymers of the present invention.

The following is a hair con~ - - composirior ,c~)resc.l~li~e of the present inv~..lion.
Component Weight %
Water Q.S. to 100%
Hy~Lo?hobically Modified Hydroxyethylcellulose [1] 0.25 %
Stearalkonium Chloride 0.87 %
Cetyl Alcohol 1.85 %
Stearyl Alcohol 0.21 %
Stearamidopropyl Dimethylamine 0.50 %
CF1213~!s (Dimethicone Gum) [2] 2.33%

Methyichloroisothiazolinone Methylico-hi~7nlinone 0.03 %
Perfume 0-33 %
Copolymer # 1 2.00 %
myristoleic acid 0.27 %
CyclomPthicone D4 9.63 %
- [ I ] Polysurf 67~ supplied by Aqualon [2] Col.ll..~.~,ially available from GE

[3] CO~ ,.ciàlly available from Akzo This product is prepared by d;~ ulg the copolymer #1 in C;.,lo~ .icn~-e D4 (solvent) then adding the myristoleic acid. Heat the solution to 65 C and use an a~Jp~ulJ~idle homogenizer to facilitate ulcu~luldlion of the copolymer into the solvent. The other c~ por : (except Kathon and perfume) are mixed in a separate vessel at â h.lll,~.dllJre high enough (80 C) to melt the solids. The polymer/solvent mixture and the dim~hirone gum are added s~,cu - !y to the other cu...l.o~,~ al~ after those have been cooled to at least 45~C. Finally, Kathon and perfume are added, and the product cooled to ambient. This co- ~.o-:l;o.. is useful for application to the hair to provide cC!n~litinn -styling and hold benefits.

The following is a hair cQn~lition~r composition l~ples~ a~ e of the present invention.
Component Weight %
Water Q.S. to 100%
Hy-hu~ obically Modified Hydroxyethylcellulose [1] 0.50 %
StearAll~onillm Chloride 0.87 %
Cetyl Alcohol 1.85 %
Stearyl Alcohol 0.21 %
Sle~ idnpropyl Dimethylamine 0.50 %
CF1213~!s (Dim~-hi~nrle Gum) [2] 2.33%
Methylchloroico~hiq~olinone Methyiicothiq~olinone 0.03 %
Perfume 0 33 %
Cûpolyrner # 2 2.00 %
OleicAcid 0.71 %
Icnde~e -- 9.63 %
[ 11 Polysurf 67~!9 supplied by Aqualon [2] Commercially avàilable from GE
This product is prepared by dispersing the copolymer #2 in Isododecane (solvent) then adding the oleic acid. Heat the solution to 65~C and use an a~ lupl;ale homogenizer to facilitate u~coll,olàtion of the copolymer into the solvent. The other comronen~C (except Kathon and perfume) are mixed in a separate vessel at a temperature high enough (80~C) to melt the solids. The WO 98/09608 PCTrUS97/1~561 polymerlsolvent mixture and the dimethicone gum are added separately to the other components after those have been cooled to at least 45~C. Finally, Kathon and perfiJme are added, and the product cooled to ambient. This composition is useful for application to the hair to provide conditioning, styling and hold benefits.

The following is a hair shampoo composition ~ s~lali~e of the present invention.Component Weight %
Water Q.S. to 100 %
Ammonium Lauryl Sulfate 3.14 %
,~mmonhlm Laureth Sulfate 13.56 %
Cetyl Alcohol 0.45 %
Stearyl Alcohol 0.19 %
Coco Mono~ ol Amide 3.00 %
Ethylene Glycol Distearate 2.00 %
Tricetyl Methyl Ammonium Chloride 0.50 %
Methylchloroisothiazolinone Methylisothiazolinone 0.03 %
Perfume 0.20 %
Copolymer # 1 4.00 %
Palmitoleic acid 0.60 %
Icodo~ ~ 7.40 %
This product is prepared by dia~sing the copolymer #l in icodod~Pr~lP (solvent) then adding the palmitoleic acid. Heat the solution to 65~C and use an applu~lidte homogenizer to facilitate incu.~,v,~ion of the copolymer into the solvent.. The other components are mixed in a separate vessel at a te.ll~J~.a~ul~ high enough to melt the solids. The polymer/solvent mixture is added to the other CGIl~pOn ~1~ after those have been cooled. This cc,lllposilion is useful for applicadon to the hair to provide cleansing, styling and hold benefits.

The following is a hair shampoo co,..pû~ilion n,~JIc5~ dtive of the present invention.
Component Weight %
Water Q.S. to 100 %
Coco~ nidf~propyl Betaine 8.30 %
Ammonium Lauryl Sulfate 2.12 %
Ammonium Laureth Sulfate 6.35 %
Coco ~ noeth~nol Amide 1.50 %
Hydroxypropyl M~ ll.ocelh~lose (K15) 0.25 %
Ethylene Glycol Distearate 1.50 %
Tricetyl Methyl Ammonium Chloride 0.50 %

W O 98/09608 PCT~US97/lS561 Methylchloroisothiazolinone Methylisothiazolinone 0.03 %
Perfume 0.20 %
Copolymer # 1 3.00 %
oleic acid 0.50 %
ieodotlPC~ 10 00 %
[I] Ccs.,.~ .L;ally available from Akzo This product is prepared by ~Jia~ ahlg the copolymer #l in icodo-lerSne (solvent) then adding the oleic acid. Heat the solution to 65~C and use an aiJ~roplidl~ homogenizer to facilitate hlcOI~olaliù.. of the copolymer into the solvent. The other co",ponenla are mixed in a separate vessel at a t~.llpC.dt~.~ high enough to melt the solids. The polyrner/solvent solution is added to the other colllpo..e.lla after those have been cooled.
EXAMPLE I I
The following is a hair styling gel collll)osilion ~ s~llalive of the present invention.
Cc FOn~ t Weight ~/O
Polvrner-Solvent Mix Copolyrner # I 1.25 %
palmitoleic acid 0.19 %
Isopar H~ ~ I ] 3.75 %
Premix Water 43.00 %
Hy~Lug~ ~ Ditallowdimonium Chloride 1.00 %
(Qllqt~rni~n 18) Main Mix Water 48.47 %
Carbopol 940~ 0 75 %
Triethanol Amine 1.00 %
Panthenol 0 05 %
Pe~me 0.20 %
[I] Cll-C12lsop~an~l, available from Exxon Chemical Co.
This product is prepared by dispersing the copolymer #1 in Isopar Has (solvent) then adding the palmitoleic acid. Heat the solution to 65 C and use an a~lulJI;at~ homogenizer to facilitate inco,~,ûldtiun of the copolymer into the solvent. Quaternium 18 is mixed with water at 80~C. The polymer-solvent mixture is added to the Quaternium 18 cont~ining premix at either high or low te.lllJ~ t~ . The other ccsllll~oll. ma are mixed in a separate vessel at ambient temperature. The Quaternium 18 premix with the polymer/solvent mixture is cooled (if needed) and added to the other co~ n~ , This c~ -.pC~;~;OIl is useful for application to the hair to provide con~1itjoning styling and hold benefits.

CA 02264766 l99s-03-03 The following is a spray-on gel hair composition .~t"cscllldlive of the present invention.
Component Weight %
Water Q.S. to 100 %
Tallowtrimonium Chloride 0. I 0 %
Hy~llu~,~,naled Ditallowdimonium Chloride0.90 %
(Quaternium 18) Panthenol 0.05 %
Perfume 0.20 %
Copolymer # 3 1.00 %
Oleic Acid 0.18 %
Hexamethyl ~iciloY"nt. 3 0O %
This product is prepared by dissolving the copolymer #2 in h~xPmt~-hyl ~ Ys~n~ (solvent) then adding the oleic acid. Heat the solution to 65~C and use an a~ O~n iale homogenizer to facilitate i.,co~,o~dlion of the copolymer into the solvent.. The other C~""~O"C.~I;, are mixed in a separate vessel at a t~ .e.dnl~c high enough (70~C) to melt the solids. The polymer/solvent solution is added to the other c~.,.,pollt .l~ at either high or low ~ p~ldlUlC. This co""~oailion is useful for application to the hair to provide con~iitionin~, styling and hold benefits.

The following is a hair styling rinse composition, ~p,~c.lldli~/e of the present invention.
Component Weight %
Premix A
Water 8.14 %.
Ditallowdim. oni~m Chloride (Varisoft 470)1.43 %
CFI213~s (Dim~thicone Gum) [2] 2.33%
~.,.O.I;.. I~ .n~ 0.lO %
Premix B
Water 5 45 %
Stear~lbl)ni.~m Chloride 0.30 %
Panthenol DL 0.225 %
Pantyl Ethyl Ether 0.025 %
Main Mix Water 67.05 %
Hydrophobically Modified Hydroxyethylc~lh~lose ~1] 1.23 %
Xanthan Gum 0.25%
Citric Acid 0.02 %
Sodium Citrate 0.09 %

Cetyl Alcohol 0.12 %
Stearyl Alcohol 0.08 %
Polymer-Solvent Mixture Copolymer # 1 2.00 %
Cyclomethicone D4 10.00 %
myristoleic acid 0.30 %
Methylchloroisothiazolinone Methylisothiazolinone 0.03 %
Perfume o 33 %
Benzyl Alcohol 0.50 %
[ I ] Polysurf 67D supplied by Aqualon ~2] Cu~ llc.~;iàlly available from GE
This product is prepared by dispersing the copolymer #1 in the cyclomethicone D4(solvent) then adding the myristoleic acid. Heat the solution to 65~C and use an al"JIo~J. hon~ogeni7Pr to facilitate illCul~,ul_ on of the copolymer into the solvent. Premixes A and B are prepared by Culllt; ' g materials at 70~C. Premix A goes through a colloid mill and is cooled to 38~C. ~ ials in 'Main Mix', except benzyl alcohol, are mixed at 65~C. The polymer solution is then added to the 'Main Mix'. Main mix goes through a colloid mill and is cooled to 38~C. Premixes and 'Main Mix are cvlll~ cd at 38~C. Then the benzyl alcohol is added. This colnpo~iIion is useful for application to the hair to provide conditioning, styling and hold benefits.

The following is a hair styling mousse co. ~pos;lion Jl,pl~s~ ali~e of the present invention.
Component Weight ~/O
Water Q.S. to 100 %
Tallowtrimonium Chloride 0.10 %
Hyd.v~,~,.lal~d Ditalluwdill-onium Chloride 0.90 %
(Quaternium 18) Lauramine Oxide 0.20 %
P~ ol ~~~S %
Perfwne 0.20 %
Copolymer ~ 2 1.00 %
oleic acid 0.36 %
He.. :' yl disiloxane 3.00 %
Isobutane 7 00 %
This product is prepared by dissolving the copolymer #2 in h ~ i,yl flicilox:~ne (solvent) then adding the oleic acid. Heat the solution to 65~C and use an a~",.oplh.Ie homogenizer to facilitate illCOIpOIatiOII of the copolymer into the solvent. The other co,..rù.l~ except isobutane) are mixed in a separate vessel at a temperature high enough (70~C) to melt the solids. The .. .. . . . . .. ..

polymer/solvent solution is added to the other components after those have been cooled. Al~minnm aerosol cans are then filled with 93 parts of this batch affixed with a valve which is crimped into position and lastly pressure filled with 7 parts Isobutane. lllis c~ .po~ilion is useful for application to the hair to provide conditioning, styling and hold benefits.

The following is a hair styling spray composition l ~l esLI~ti~/e of the present in~c Cc pa-- t Weight%
Water Q.S. to 100 %
Panthenol 0 05 %
Perfume 0.20 %
Copolymer # 1 2.00 %
palmitoleic acid 0.30 %
Cyclc.methi~one D4 7.00 %
i~obnt~ ~- 25.00 %
This product is prepared by di",~,: g the copolymer #1 in Cyclomethicone D4 (solvent) then adding the p~imi~ol~ ~ acid. Heat the solution to 65 C and use an d~)plv~l ~ homogenizer to facilitate ~ - ~olalion of the copolymer into the solvent. The other ~ (except iiot -) are mixed in a separate vessel. The poly l~olv. ..t solution is added to the other co~ .v"~
,~h-minllm aerosol cans are then filled with 75 par~s of this batch affixed with a valve which is crimped into position, and lastly pressure filled with 25 parts Isobutane. This co"")o~ilion is useful for application to the hair to provide con~itinning styling and hold benefits When the co",posilions defined in Examples 4 - 12 are applied to hair in the conventional manner, they provide effective hair conditio~in~ and styling/hold benefits without leaving the hair with a sticky/stiff feel.

The following is a hair styling rinse co...?o~ilio., ~L~Ics~ ui~e of the present i l~ tion.
C~ r-rert Weight %
Premix A
Water 8.14 %.
Ditallowdimonium Chloride (Varisoft 470) 1.43 %
CF1213~!D (Dime~hi~on~ Gum) [2I 2.33%
,~mo~limethi~ on~ 0.10 %

CA 02264766 l999-03-03 Premix B
Water 5.45 %
Stearalkonium Chloride 0.30 %
Panthenol DL 0.225 %
Pantyl Ethyl Ether 0.025 %
Main Mix Water 70 47 %
Hy~Lu?hob;cally Modified Hydroxyethylcellulose [1] 1.23 %
Xanthan Gum 0.25%
Citric Acid 0.02 %
Sodium Citrate 0-09 %
Cetyl Alcohol 0.12 %
Stearyl Alcohol 0.08 %
Polymer-Solvent Mixture Copolymer # 1 2.00 %
Cyclomethi~one D4 6.58 %
myristoleic acid 0.30 %
Methylchloroisothiazolinone Methylicothi~- linone 0.03 %
Perfume 0.33 %
Benzyl Alcohol 0.50 %
[ I ] Polysurf 67~!P supplied by Aqualon [2~ Commercially available from GE
This product is prepared by di~ g the copolymer #1 in the cycl~methh~o~o D4(solvent) then adding the myristoleic acid. Heat the solution to 65 C and use an àp~lu~.liate hom~geni7~o~ to facilitate hlcol~Juldliou of the copolymer into the solvent. Premixes A and B are prepared by combining I --t~ ' at 70~C. Premix A goes through a colloid mill and is cooled to 38~C. Materials in 'Main Mix', except benzyl alcohol, are mixed at 65~C. The polymer solution is then added to the 'Main Mix'. Main mix goes through a colloid mill and is cooled to 38~C. Premixes and 'Main Mix are colllb ICd at 38~C. Then the benzyl alcohol is added. This co.~poa:~ion is useful for application to the hair to provide ~ - ing styling and hold benefits.

The following is a hair styling rinse composition ~ s~l~Ldli~e of the present invention.
Component Weight %
Premix A
Water 8.14 %.
Ditallowdimonium Chloride (Varisoft 470) 1.43 %
CF1213~s (Dimethicone Gum) [2] 2.33%
,~motlimethjrnnf. O 10%
Premix B
Water 5 45 %
Stear~ ni~lm Chloride 0.30 %
Panthenol DL 0.225 %
Pantyl Ethyl Ether 0.025 %
Main Mix Water 71.35 %
Hyd.u~,' o~.~ Ily Modified Hydroxyethylcell~ se [1] 1.23 %
Xanthan Gum 0.25%
Citric Acid 0.02 %
Sodium Citrate 0.09 %
Cetyl Alcohol 0.12 %
Stearyl Alcohol 0.08 %
Polymer-Solvent Mixture Copolymer # 1 2.00 %
Cy.ln . Il.ir~ D4 5.7 %
myristoleic acid 0.30 %
Methylchlorc-icothi~- linone Methylisothi~7O1inone 0.03 %
Perfume 0 33 %
Benzyl Alcohol 0.50 %
[ I ] Polysurf 67~!9 supplied by Aqualon [2~ G,...~ ially available from GE
This product is prepared by dispersing the copolymer #1 in the cyclomethicone D4(solvent) then adding the myristoleic acid. Heat the solution to 65 C and use an ay~JIu~Jlial~ homogenizer to facilitate i,.col~ tion of the copolyrner into the solvent. Premixes A and B are prepared by combining materials at 70~C. Premix A goes through a colloid mill and is cooled to 38~C. Materials in 'Main Mix', except benzyl alcohol, are mixed at 65~C. The polymer solution is then added to the 'Main Mix'. Main mix goes through a colloid mill and is cooled to 38~C. Premixes and 'Main Mix are combined at 38~C. Then the benzyl alcohol is added. This composition is useful for application to the hair to provide conditioning, styling and hold benefits.

The following is a hair styling rinse composition l~p~es~ltaLi~/e of the present i.,ve..tio.,.
Component Weight %
Premix A
Water 8.14 %.
Ditallow~limr ni~n Chloride (VarisoR 470)1.43 %
CFI213~9 (Dimpthicc~ne Gum) 121 2.33%
,~morl~ thi-~nnP 0,10%
Premix B
Water 5.45 %
Stear~ onil~n Chloride 0.30 %
Panthenol DL 0.225 %
Pantyl Ethyl Ether 0.025 %
Main Mix Water 72.08 %
Hy~llophobically Modified Hydroxyethylce~ ose ~1] 1.23 %
Xanthan Gum 0.25%
Citric Acid 0.02 %
Sodium Citrate 0.09 %
Cetyl Alcohol 0.12 %
Stearyl Alcohol 0.08 %
Polymer-Solvent Mixture Copolymer # 1 2.00 %
~codo~ 4 97 %
myristoleic acid 0.30 %
Methylchloroisothiazolinone Methylicothi~7-~1inone 0.03 %
Perfume 0 33 %
Benzyl Alcohol 0.50 %
[ I ] Polysurf 67~9 supplied by Aqualon [2] Commercially available from GE
This product is prepared by dispersing the copolymer #1 in the cyclomethicone D4(solvent) then adding the myristoleic acid. Heat the solution to 65 C and use an a~ U~JliaL~ homogenizer to facilitate hlcvl~JvlaLion of the copolymer into the solvent. Premixes A and B are prepared by combining materials at 70~C. Premix A goes through a colloid mill and is cooled to 38~C. Materials in 'Main Mix', except ben_yl alcohol, are mixed at 65~C. The polymer solution is then added to the WO 98/09608 PCT/US97/15~61 'Main Mix'. Main mix goes through a colloid mill and is cooled to 38~C. Premixes and 'Main Mix are combined at 38~C. Then the benzyl alcohol is added. This c~ s~iliQn is useful for application to the hair to provide con-liti-ning, styling and hold benefits.

Sunscreen Composition An oil-in-water emulsion is prepared by combining the following C~JII~POII~ utilizing conventional mixing techni~luPs In~redients Phase A Wei~ht %
Water QS 100 Carbomer 954[1 ] 0.24 Carbomer 1342[2] 0.16 Disodium EDTA 0.05 Phase B
Isoarachidyl Neo~ o [3] 2.00 PVP Eicosene Copolymer[4] 2.00 Octyl Methoxy~; .. ~ .. -e 7.50 Octocrylene 4.00 Oxybenzone 1.00 Titanium Dioxide 2.00 Cetyl Palmitate 0.75 Stearoxytrimethylsilane (and) Stearyl Alcohol[5] 0.50 Glyceryl T- ;I-f k~ e 0.7S
Dimethi.~on~P 1.00 Tocopheryl Acetate 0.10 DEA-Cetyl Pho~ dle 0.20 Phase C
Water 2.00 TrhPth~nol~rn inP 99% 0.60 Phase D
Water 2.00 Butylene Glycol 2.00 DMDM Hydantoin (and) lodopropynyl Butylc~L, [6] 0.25 dL Panthenol 1.00 Phase E

Cyclomethicone D4 4.00 Copolymer #2 1 00 oleic acid 0.36 [ I ] Available as Carbopol~9 954 from B.F. Goodrich.
[2] Available as Carbopol~ 1342 from B.F. Goodrich.
[3] Available as Ganex V-220 from GAF Corporation.

[4] Available as DC 580 Wax from Dow Coming.

[5] Available as Sy-.~,l.lu..d~ HRC from Croda.

[6] Available as Glydant Plus from Lonza.
In a suitable vessel the Phase A ingredients are ~ ed in the water and heated to 75-85~C. In a separate vessel the Phase B ingredients (except DEA-Cetyl rh-, ~ ) are combined and heated to 85-90~C until melted. Next, the DEA-Cetyl Phosphate is added to the liquid Phase B and stirred until di~aolved. This mixture is then added to Phase A to fomm the ennuicion The Phase C
i..~;.~d..,..~ are combined unti1 dissolved and then added to the emulsion. The emulsion is then cooled to 40-45~C with contin~d mixing. In another vessel, the Phase D h.gl~,die-.b are heated with mixing to 40-45~C until a clear solution is formed and this solution is then added to the .omlllcjr~n Finally, the emulsion is cooled to 35~C and the Phase E ingredients are combined at 65~C, use an a~JplO~ e homogenizer to facilitate incorporation of the copolymer into the solvent. Phase E is the cooled to 35~C, added and mixed.
This emulsion is useful for topical application to the skin to provide protection from the harmful effects of ultraviolet radiation.

Facial Moistu-i~L.,.
A leave-on facial emulsion cr~mpositiorl cont~ining a cationic hydrophobic surfactant is prepared by combining the following components utilizing conventional mixing t~chnirlues In~redient WeiRht %
Phase A
Water QS100 Glycerin 3.00 Cetyl Palmitate 3.00 Cetyl Alcohol 1.26 Quatemium-22 1.00 Glyceryl Monohydroxy Stearate 0.74 Dimethicone 0.60 Stearic Acid 0.55 Octyldodecyl Myristate 0.30 Potassium Hydroxide 0.20 ... ..

WO 98109608 rCT/US97/15561 Carbomer 1342 0.125 Tetrasodium EDTA 0 10 DMDM Hydantoin and lodopropynyl Butyl Carbamate 0.10 Carbomer 951 0.075 Phase B
Icoclo~- - 4.00 Copolymer from example 2 1.00 oleic acid 0.36 In a suitable vessel the Phase A ingredients are co~ ed to form an enn~ ion Phase B is prepared by dispersing the copolymer #2 in lcodot~er~-le (solvent) then adding the Shalalllil.C. Heat the solution to 65 C and use an a~J~JIo~lk.tc homogenizer to facilitate h~cvl~Jvlaliu~ of the copolymer into the solvent. Cool the Phase B and mix into Phase A using conventional mixing techni~ln~c This emulsion is useful for application to the skin as a moisturizer.

The following is an anti-p~ ,..anl cv~-pv~ilion Icplesc.-~live of the present in~ IlliU...
Component Weight ~/0 PPG 2 Myristyl ~opi - 34.00 %
Glyceryl Clg - C36 Wax Acid Ester 0.40 %
Cyclornethirone 32.75 %
Copolymer # 3 1.00 %
Oleic Acid 0.18 %
Ah~minnrn Chlorohydrate 19.00 %
PPG 5 Ceteth 20 7.50 ~/0 Water 1.50 %
Mix PPG 2 Myristyl Propionate and Glyceryl Clg - C36 Wax Acid Ester, heat to 75~C.
Disperse the Chlorohydrate. Disperse the copolymer #3 in Cyclomethicone (solvent) then add the dirnethylmyristarnine. Heat the solution to 65CC and use an a~J~Iv~/lidle hornogeni7~r to facilitate i-.co.~,u.diùn of the copolymer into the solvent. Add the cyclomethicone mixture to the Chlorohydrate dia~ ioll. Mix PPG 5 Ceteth 20 and the water, the add to oils, perfume and cool.

CA 02264766 l999-03-03 The following is an anti-acne composition .eplesentalive of the present invention Component Weight %
Cowlymer-Solvent Mix Copolymer # 3 I 00 %
Oleic Acid 0.18 %
Isopar H~ ] 3-75 %
Main Mix Water Q.S. to 100 %
Ethanol (SDA 40) 40.00 %
Carbopol 940~ 0 75 %
Triethanol Amine l .00 %
Salicylic Acid 2.00 %
[I] Cl l-Cl2 Isoparaffin. available from Exxon Chemical Co.
This product is prepared by di~ i..g the copolymer # l in Isopar H0 (solv~nl) then adding the dimethylpal~nit~-ninP Heat the solution to 65~C and use an a~plo~ homogPni7Pr to facilitate illcol~Juldlion of the copolymer into the solvent. The other cc r are mixed in a separate vessel at ambient t~ . The copolymer-solvent premix is cooled (if needed) and added to the other cu,-",on~.,t~. This co~nrosi~ion is useful for application to the skin to provide improve water .esi~ e and is useful in the IJ. at",c.-l of acne.

The following is an anti-acne CC~ pOSiliu" ~p,~;.c.,lalive of the present invention Component Weight %
Copolyrner-Solvent Mix Copolymer # 3 I .00 %
Oleic Acid 0 18 %
Isopar H~ Il] 3.75 %
Main Mix Water Q.S. to 100 %
Ethanol (SDA 40) 20.00 %
Carbopol 940~!9 0.75 %
Triethanol Amine 1 00 %
Ibuprofen 2.00 %
[I] Cl I -C~2 Isoparaffin, available from Exxon Chemir~l Co This product is prepared by dispersing the copolymer # I in Isopar H~9 (solvent) then adding the dimethylp~l nit~ine Heat the solution to 65~C and use an app-o~"iale homogenizer to facilitate i"cu",~"dlion of the copolymer into the solvent. The other components are mixed in a separate . , . .. . . , _ vessel at ambient temperature. The copolymer-solvent premix is cooled (if needed) and added to the other cul~po~ This composition is useful for application to the skin to provide improve water resistance and is useful for the anal~esic effects.

Claims (27)

WHAT IS CLAIMED IS:

1. A personal care composition, comprising:
A.) a copolymer complex comprising:
a.) a copolymer having a backbone formed from the copolymerization of repeating A monomer and B monomer units wherein the backbone has optionally grafted to it hydrophobic C macromonomer units wherein the copolymer is prepared by the polymerization combination of the following relative weight percentages of the A, B, and C units:
i) from 10% to 99% by weight of the copolymer of one or more hydrophobic A monomer units, wherein the A monomer units are copolymerizable with the B monomer and C macromonomer units;
ii) from 1% to 40% by weight of the copolymer of one or more hydrophilic B monomer units, wherein the B monomer units are copolymerizable with the A monomer and C macromonomer units and wherein at least 1% by weight of the copolymer, of the B monomer units, are selected from B
monomer units having at least one nitrogen containing functional group;
and iii)from 0 to 50%, preferably from 5% to 40%, by weight of the copolymer of one or more C macromonomer units wherein the C units are hydrophobic macromonomer units, copolymerizable with the A monomer units and the B monomer units, the C macromonomer units having a number average molecular weight of from 1,500 to 50,000; and b.) a complexing fatty acid wherein the fatty acid forms a complex with the nitrogen containing functional group of the B monomer units;
wherein the weight ratio of the copolymer to the fatty acid is from 50:1 to 1:1;and B.) a volatile, hydrophobic solvent component for the copolymer complex having aboiling point at 1 atmosphere of 260°C or less and a solubility parameter of 8.5 (cal/cm3)1/2 or less wherein the copolymer complex is soluble or dispersible in the volatile, hydrophobic solvent component.

2. A personal care composition according to Claim 1 wherein said A monomer and B
monomer units are ethylenically unsaturated and wherein the C macromonomer units have a polymeric portion and an ethylenically unsaturated moiety, preferably a polyalkylene.

3. A personal care composition according to any one of the preceding Claims wherein said polyalkylene macromonomers correspond to the formula [I]n-[W]m-E
wherein I is an initiator moiety, n is an integer of 0 or 1, W is a hydrophobic monomer unit, E is an endcapping group, and m is an integer from 10 to 2000.

4. A personal care composition according to any one of the preceding Claims wherein I is selected form the group consisting of initiators derived from hydrogen ion, hydrogen radical, hydride ion, hydroxide ion, hydroxyl radical, peroxide radical, peroxide anion, C1-C20 carbocations, C1-C20 carbanions, C1-C20 carbon radicals, C1-C20 aliphaticalkoxy anionis, C1-C20 aromatic alkoxy anions, ammonium ion, C1-C20 alkyl substituted ammonium ions, C1-C20 alkoxy substituted ammonium ions, and mixtures thereof; W is 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-methylpentyl acrylate, nonyl acrylate, octyl acrylate, 1-propyl acrylate, 2-ethylhexyl methacrylate, octyl methacrylate, n-dodecyl methacrylate, n-octadecyl methacrylate, n-decyl methacrylate, n-pentylmethacrylate, isobutylene, isoprene, 1,2-butadiene, 1,3-butadiene, 5-methyl-1-hexene, 6-methyl-1-heptene, 4,4-dimethyl-1-pentene, iso-butyl vinyl ether, styrene, 2-methyl styrene, 3-methylstyrene, 4-methyl styrene, 2-t-butyl styrene, and mixtures thereof; and E
is selected from the group consisting of vinyl, allyl, acryloyl, methacryloyl, ethacryloyl, 3-vinylbenzyl, 4-vinylbenzyl, 3-vinylbenzyl, 4-vinylbenzoyl, 1-butenyl, 1-propenyl, isobutenyl, and mixtures thereof.

5. A personal care composition according to any one of the preceding Claims, wherein said C
macromonomer units are selected from the group consisting of acryloyl, methacryloyl, or 2-, 3-, or 4-vinylbenzyl endcarped polymers of poly(n-butyl acrylate), poly(dodecyl acrylate), poly(2-ethylhexyl acrylate), poly(2-ethylbutyl acrylate), poly(n-ethyl acrylate), poly(n-heptyl acrylate), poly(n-hexyl acrylate), poly(iso-butyl acrylate), poly(iso-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 (hexyl methacrylate), poly(decyl methacrylate), poly(octyl methacrylate), poly(octadecyl methacrylate), poly(dodecyl methacrylate), poly(n-pentyl methacrylate), poly(isobutylene), poly(isoprene), hydrogenated poly(1,2-butadiene), hydrogenated poly(1,4-butadiene), hydrogenated poly(isoprene), poly(1,2-butadiene), poly(1-butene), poly(5-methyl-1-hexene), poly(6-methyl-1-heptene), poly(4,4-dimethyl-1-pentene), poly(iso-butyl vinyl ether), Poly[4-~-butyl vinyl benzene-co-2-ethylhexyl acrylate], poly[2-ethylhexyl acrylate-co-octyl acrylamide), poly~2-ethyl vinyl benzene-co-octyl methacrylate)], and mixtures thereof.

6. A personal care composition according to any one of the preceding Claims, wherein the copolymer of the copolymer complex is prepared by the polymerization combination of the following relative weight percentages of said A, B and C units:
a. from 40% to 80% of said hydrophobic A unit;
b. from 5 % to 30 % of said hydrophilic B unit; and c. from 5% to 40% of said hydrophobic C unit wherein said C unit has a weight average molecular weight of from 5,000 to 50,000.

7. A personal care composition, comprising:
A.) a copolymer complex comprising:
a.) a copolymer having a backbone formed from the copolymerization of repeating A monomer and B monomer units wherein the backbone has optionally grafted to it hydrophobic C macromonomer units wherein the copolymer is prepared by the polymerization combination of the following relative weight percentages of the A, B, and C units:
i) from 10% to 99% by weight of the copolymer of one or more hydrophobic A monomer units, wherein the A monomer units are copolymerizable with the B monomer and C macromonomer units;
ii) from 1% to 40% by weight of the copolymer of one or more hydrophilic B monomer units, wherein the B monomer units are copolymerizable with the A monomer and C macromonomer units and wherein at least 1% by weight of the copolymer, of the B monomer units, are selected from B
monomer units having at least one nitrogen containing functional group;
and iii)from 0 to 50%, preferably 5% to 40%, by weight of the copolymer of one or more C macromonomer units wherein the C units are hydrophobic macromonomer units, copolymerizable with the A monomer units and the B monomer units, the C macromonomer units having a number average molecular weight of from 1,500 to 50,000; and b.)a complexing fatty acid wherein the fatty acid forms a complex with the nitrogen containing functional group of the B monomer units wherein the weight ratio of the copolymer to the fatty acid is from 50:1 to 1:1;

and B.) a volatile, hydrophobic solvent component for the copolymer complex having aboiling point at 1 atmosphere of 260°C or less and a solubility parameter of 8.5 (cal/cm3)1/2 or less; and C.) a carrier immiscible with the volatile hydrophobic solvent component wherein the copolymer complex is soluble or dispersible in the volatile, hydrophobic solvent component.

8. A hair styling and conditioning composition, comprising;
A.) a copolymer complex comprising a.) a copolymer having a backbone formed from the copolymerization of repeating A monomer and B monomer units wherein the backbone has optionally grafted to it hydrophobic C macromonomer units wherein the copolymer is prepared by the polymerization combination of the following relative weight percentages of the A, B, and C units:
i) from 10% to 99% by weight of the copolymer of one or more hydrophobic A monomer units, wherein the A monomer units are copolymerizable with the B monomer and C macromonomer units;
ii) from 1 % to 40 % by weight of the copolymer of one or more hydrophilic B monomer units, wherein the B monomer units are copolymerizable with the A monomer and C macromonomer units and wherein at least 1% by weight of the copolymer, of the B monomer units, are selected from B
monomer units having at least one nitrogen containing functional group;
and iii) from 0 to 50 %, preferably 5 % to 40% by weight of the copolymer of one or more C macromonomer units wherein the C units are hydrophobic macromonomer units, copolymerizable with the A monomer units and the B monomer units, the C macromonomer units having a number average molecular weight of from 1,500 to 50,000;and b.) a complexing fatty acid wherein the fatty acid forms a complex with the nitrogen containing group of the B monomer units;
wherein the weight ratio of the copolymer to the fatty acid is from 50:1 to 1:1;and B.) a volatile, hydrophobic solvent component for the copolymer complex having aboiling point at 1 atmosphere of 260°C or less and a solubility parameter of 8.5 (cal/cm3) 1/2 or less wherein the copolymer complex is soluble or dispersible in the volatile, hydrophobic solvent component and wherein the copolymer complex and volatile, hydrophobic solvent component mixture has a viscosity of above 5,000 cps.

9. A hair care composition, comprising:
I.) a hair styling and conditioning component, comprising:
A.) a copolymer complex comprising:
a.) a copolymer having a backbone formed from the copolymerization of repeating A monomer and B monomer units wherein the backbone has optionally grafted to it hydrophobic C macromonomer units wherein the copolymer is prepared by the polymerization combination of the following relative weight percentages of the A, B, and C units:
i) from 10% to 99% by weight of the copolymer of one or more hydrophobic A monomer units, wherein the A monomer units are copolymerizable with the B monomer and C macromonomer units;
ii) from 1% to 40% by weight of the copolymer of one or more hydrophilic B monomer units, wherein the B monomer units are copolymerizable with the A monomer and C macromonomer units and wherein at least 1% by weight of the copolymer, of the B monomer units, are selected from B monomer units having at least one nitrogen containing functional group; and iii) from 0 to 50 %, preferably 5 % to 40 %, by weight of the copolymer of one or more C macromonomer units wherein the C
units are hydrophobic macromonomer units, copolymerizable with the A monomer units and the B monomer units, the C
macromonomer units having a number average molecular weight of from 1,500 to 50,000; and b.)a complexing fatty acid wherein the fatty acid forms a complex with the nitrogen containing functional group of the B monomer units wherein the weight ratio of the copolymer to the fatty acid is from 50:1 to 1:1;
and B.) a volatile, hydrophobic solvent component for the copolymer et complex having a boiling point at 1 atmosphere of 260°C or less and a solubility parameter of 8.5 (cal/cm3)1/2 or less and wherein the copolymer complex is soluble or dispersiblein the volatile, hydrophobic solvent component wherein the copolymer complex and volatile, hydrophobic solvent component mixture has a viscosity of above 5,000 cps;
and II.) a carrier immiscible with the volatile hydrophobic solvent component.

10. A personal care composition, comprising:
A.) a copolymer complex comprising:
a.) a copolymer having a backbone formed from the copolymerization of repeating A monomer and B monomer units wherein the backbone has optionally grafted to it siloxane based C macromonomer units wherein the copolymer is prepared by the polymerization combination of the following relative weight percentages of the A, B, and C units:
i) from 10% to 99% by weight of the copolymer of one or more hydrophobic A monomer units, wherein the A monomer units are copolymerizable with the B monomer and C macromonomer units;
ii) from 1% to 40% by weight of the copolymer of one or more hydrophilic B monomer units, wherein the B monomer units are copolymerizable with the A monomer units and C macromonomer units and wherein at least 1%, by weight of the copolymer, of the B monomer units are selected from B monomer units having at least one nitrogen containing functional group;
iii) from 0 to 50%, preferably 5% to 40%, by weight of the copolymer of one or more C units wherein the C macromonomer units are polysiloxane-containing macromonomer units, copolymerizable with the A monomer units and the B monomer units, the C macromonomer units having a number average molecular weight of from 1,500 to 50,000;
and b.) a complexing fatty acid wherein the fatty acid forms a complex with the nitrogen containing group of the B monomer units wherein the weight ratio of the copolymer to the fatty acid is from 50:1 to 1:1;and B.) a volatile, hydrophobic solvent component for the copolymer complex having aboiling point at I atmosphere of 260°C or less and a solubility parameter of 8.5 (cal/cm3)1/2 or less wherein the copolymer complex is soluble or dispersible in the volatile, hydrophobic solvent component.

11. A personal care composition according to any one of the preceding Claims, wherein the A
monomer and B monomer units are ethylenically unsaturated and wherein the C
macromonomer unit has the general formula:
X(Y) n Si(R)3-m (Z) m wherein:
X is a vinyl group copolymerizable with the A monomers and the B monomers;
Y is a divalent linking group;
R is a hydrogen, C1 -C4 alkyl, C1-C4 alkyl substituted aryl or C1 -C4 alkoxy;
Z is a monovalent siloxane polymeric moiety having a number average molecular weight of at least 1500, is essentially y unreactive under copolymerization conditions, and is pendant from the vinyl polymeric backbone after polymerization;
n is 0 or 1 ; and m is an integer from 1 to 3.

12. A personal care composition according to any one of the preceding Claims, wherein said hydrophobic A unit is selected from the group consisting of acrylic acid esters,methacrylic acid esters, vinyl compounds, vinylidene compounds, unsaturated hydrocarbons, C1-C18 alcohol esters of organic acids and organic acid anhydride, and mixtures thereof, preferably selected from the group consisting of t-butyl acrylate, t-butyl methacrylate, t-butyl styrene, 2-ethylhexyl methacrylate and mixtures thereof.

13. A personal care composition according to any one of the preceding Claims, wherein said hydrophilic B unit is selected from the group consisting of dialkylaminoacrylates, dialkylaminomethacrylates, dialkylaminoalkylacryamides, dialkylaminoalkylmethacrylamides, acid salts thereof, quaternary addition salts thereof and mixtures thereof, preferably selected from the group consisting of N,N-dialkylaminoethylacrylate, N,N-dialkylaminoethylmethacrylate, N,N-dialkylaminopropylacrylate, N,N-dialkylaminopropylmethacrylate, N,N-dialkylaminopropylacrylamide, N,N-dialkaminopropylmethacrylamide, acid salts thereof, quaternary addition salts thereof and mixtures thereof.

14. A personal care composition according to any one of the preceding Claims, wherein the polysiloxane-containing C unit has a formula selected from the following group consisting of or X~CH2~(CH2)s~ Si(R1)3 m~Zm or wherein s is 0, 1, 2, 3, 4, 5 or 6; m is 1,2 or 3; p is 0; q is 2, 3, 4, 5 or 6; R1 is hydrogen, hydroxyl, lower alkyl, alkoxy, alkylamino, aryl, or alkylaryl; R2 is C1-C6 alkyl or C7-C10 alkylaryl; n is 0, 1, 2, 3 or 4; X is wherein R3 is hydrogen or ; is hydrogen, methyl or -CH2COOH; Z is R5, R6, and R7 independently are lower alkyl, alkoxy, alkylamino, aryl, alkylaryl, hydrogen or hydroxyl; and r is an integer of from 20 to 675.

A personal care composition according to any one of the preceding Claims, wherein the polysiloxane-containing C unit has the formula:
wherein m is 1; p is 0; q is 3; R1 is methyl; X is wherein R3 is hydrogen; R4 is methyl; and Z is R5, R6, and R7 are all methyl; and r is an integer of from 100 to 325.

16. A personal care composition according to any one of the preceding Claims, wherein the complexing fatty acid is selected from the group consisting of fatty acid sulfonates, fatty acid carboxylates, polycarboxylates, derivatives thereof, salts thereof and mixtures thereof, preferably a fatty acid carboxylate.

17. A personal care composition according to any one of the preceding Claims, wherein the fatty acid carboxylate is selected from the group consisting of 2-ethylhexanoic acid, palmitic acid, stearic acid, oleic acid, linoleic acid, behenic acid, salts thereof and mixtures thereof.

18. A personal care composition according to Claim 43 wherein the copolymer of the copolymer complex is prepared by the polymerization combination of the following relative weight percentages of the A, B and C units:
a. from 40% to 80% of the hydrophobic A unit;
b. from 5 % to 30 % of the hydrophilic B unit; and c. from 5% to 40% of the polysiloxane-containing C unit wherein the C
unit has a number average molecular weight of from 5,000 to 30,000.

19. A personal care composition according to any one of the preceding Claims, wherein said volatile, hydrophobic solvent component is selected from the group consisting ofhydrophobic, volatile C7-C14 branched hydrocarbons, hydrophobic, volatile silicones and mixtures thereof, preferably selected from the group consisting of hexamethyl disiloxane, isododecane, cyclomethicone and mixtures thereof.

20. A personal care composition according to any one of the preceding Claims, further comprising a carrier selected from the group consisting of mousses, gels, lotions, creams, ointments, tonics, sprays, aerosols, shampoos, conditioners, rinses, bar soaps, hand and body lotions, facial moisturizers, solid gel sticks, preferably a shampoo.

21. A personal care composition according to any one of the preceding Claims, wherein said composition further comprising from 10% to 30% by weight of the composition of asynthetic surfactant, preferably selected from the group consisting of alkyl sulfates, ethoxylated alkyl sulfates, and mixtures thereof.

22. A personal care composition according to any one of the preceding Claims, wherein the composition further comprises a conditioning agent comprising:
A. from 0.1% to 10% of a lipid vehicle material; and B. from 0.05 % to 5 % of a cationic surfactant.

23. A personal care composition according to any one of the preceding Claims, wherein the composition is a conditioner.

24. A personal care composition according to any one of the preceding Claims, wherein said composition further comprises a pharmaceutical active selected from the group consisting of antiacne actives, analgesic actives, antipruritic actives, anesthetic actives, antimicrobial actives, sunscreen actives, sunless tanning actives, skin-bleaching actives, anti-dandruff actives, antiperspirant actives, deodorant actives and mixtures thereof.

25. A personal care composition, comprising:
A.) a copolymer complex comprising:
a.) a copolymer having a backbone formed from the copolymerization of repeating A monomer and B monomer units wherein the backbone has optionally grafted to it siloxane based C macromonomer units wherein the copolymer is prepared by the polymerization combination of the following relative weight percentages of the A, B, and C units:
i) from 10% to 99% by weight of the copolymer of one or more hydrophobic A monomer units, wherein the A monomer units are copolymerizable with the B monomer and C macromonomer units;
ii) from 1% to 40% by weight of the copolymer of one or more hydrophilic B monomer units, wherein the B monomer units are copolymerizable with the A monomer units and C macromonomer units and wherein at least 1 %, by weight of the copolymer, of the B monomer units are selected from B monomer units having at least one nitrogen containing functional group;
iii) from 0 to 50%, preferably 5% to 40%, by weight of the copolymer of one or more C units wherein the C macromonomer units are polysiloxane-containingmacromonomer units, copolymerizable with the A monomer units and the B monomer units, the C macromonomer units having a number average molecular weight of from 1,500 to 50,000;
and b.) a complexing fatty acid wherein the fatty acid forms a complex with the nitrogen containing group of the B monomer units wherein the weight ratio of the copolymer to the fatty acid is from 50:1 to 1:1;and B.) a volatile, hydrophobic solvent component for the copolymer complex having aboiling point at 1 atmosphere of 260°C or less and a solubility parameter of 8.5 (cal/cm3)1/2 or less; and C.) a carrier immiscible with the volatile hydrophobic solvent component wherein the copolymer complex is soluble or dispersible in the volatile, hydrophobic solvent component.

26. A hair styling and conditioning composition, comprising:
A.) a copolymer complex comprising:
a.) a copolymer having a backbone formed from the copolymerization of repeating A monomer and B monomer units wherein the backbone has optionally grafted to it siloxane based C macromonomer units wherein the copolymer is prepared by the polymerization combination of the following relative weight percentages of the A, B, and C units:
i) from 10 % to 99 % by weight of the copolymer of one or more hydrophobic A monomer units, wherein the A monomer units are copolymerizable with the B monomer and C macromonomer units;
ii) from 1 % to 40 % by weight of the copolymer of one or more hydrophilic B monomer units, wherein the B monomer units are copolymerizable with the A monomer units and C macromonomer units and wherein at least 1 %, by weight of the copolymer, of the B monomer units are selected from B monomer units having at least one nitrogen containing functional group;
iii) from 0 to 50% by weight of the copolymer of one or more C units wherein the C macromonomer units are polysiloxane-containing macromonomer units, copolymerizable with the A monomer units and the B monomer units, the C macromonomer units having a number average molecular weight of from 1,500 to 50,000;
and b.) a complexing fatty acid wherein the fatty acid forms a complex with the nitrogen containing group of the B monomer units wherein the weight ratio of the copolymer to the fatty acid is from 50:1 to 1:1;and B.) a volatile, hydrophobic solvent component for the copolymer complex having aboiling point at 1 atmosphere of 260°C or less and a solubility parameter of 8.5 (cal/cm3)1/2 or less wherein the copolymer complex is soluble or dispersible in the volatile, hydrophobic solvent component and wherein the copolymer complex and volatile, hydrophobic solvent component mixture has a viscosity of above 5,000 cps.

27. A hair care composition, comprising:
I.) a hair styling and conditioning component comprising:
A.) a copolymer complex comprising:
a.) a copolymer having a backbone formed from the copolymerization of repeating A monomer and B monomer units wherein the backbone has optionally grafted to it siloxane based C macromonomer units wherein the copolymer is prepared by the polymerization combination of the following relative weight percentages of the A, B, and C units:
i) from 10% to 99% by weight of the copolymer of one or more hydrophobic A monomer units, wherein the A monomer units are copolymerizable with the B monomer and C macromonomer units;
ii) from 1% to 40% by weight of the copolymer of one or more hydrophilic B monomer units, wherein the B monomer units are copolymerizable with the A monomer units and C macromonomer units and wherein at least 1%, by weight of the copolymer, of the B monomer units are selected from B monomer units having at least one nitrogen containing functional group;
iii) from 0 to 50% by weight of the copolymer of one or more C units wherein the C macromonomer units are polysiloxane-containing macromonomer units, copolymerizable with the A monomer units and the B monomer units, the C macromonomer units having a number average molecular weight of from 1,500 to 50,000;
and b.) a complexing fatty acid wherein the fatty acid forms a complex with the nitrogen containing group of the B monomer units wherein the weight ratio of the, copolymer to the fatty acid is from 50:1 to 1:1;
and B.) a volatile, hydrophobic solvent component for the copolymer complex having aboiling point at 1 atmosphere of 260°C or less and a solubility parameter of 8.5 (cal/cm3)1/2 or less and wherein the copolymer complex is soluble or dispersiblein the volatile, hydrophobic solvent component wherein the copolymer complex and volatile, hydrophobic solvent component mixture has a viscosity of above 5,000 cps;
II.) a carrier immiscible with the volatile hydrophobic solvent component.