CA2106060A1 - Cosmetic compositions containing hydrophobically modified nonionic polymer and unsaturated quaternary ammonium surfactant - Google Patents

Abstract

Disclosed is a vehicle system having a thickening system which comprises a nonionic long-chain alkylated water-soluble polymer and a specific cationic quaternary ammonium surfactant component dispersed in a compatible solvent. The quaternary surfactant component has an iodine value of at least about 15. The quaternary surfactant component is characterized by having a sufficient level of unsaturated C14-C22 alkyl or C14-C22 alkyl amido C2-C6 alkylene radicals such that the average iodine value is at least about 15. These vehicle systems are useful in cosmetic compositions which are used to deliver an active component to the hair or skin. The vehicle systems are particularly useful in hair care compositions, especially rinse-off hair conditioning and styling compositions. In a particular rinse-off hair styling and conditioning composition hereof, the composition contains a vehicle system, as described above, and additionally contains a hair setting agent, a distributing aid, and a mono-long chain, tri-short chain quaternary ammonium surfactant.

Description

w o 92/16187 2 1 ~ ~ ~ 6 0 PCT/US92/008~5 COSME~IC COMPOSITIONS CONTAINIHG HYDROPNOBICALLY
MODIFIED NONIONIC POLYMER AND UNSATURATED
QUATERNARY AMMONIUH SURFACTANT

IE~L~
The present invention relates to no~el Yehicle iy~'e"s. nd cosmet~c compos~tions formulated therewith~ ~ased en nenlonl: M~n~
chain al'~la~ed wat2r-solubl~ ~ol~m r der~at iue ~ an~ un ^l~n~n~n~.
quaternary ammonium surfactants in ~ ccmp~tible di`ue, particularly use;ul applicat~on of h~ pr sar.t inu~n~! n~ ~ N~
hair care compositions, especially rinse-off hair conditioning and/or styling compositions.
BACKGROUND OF THE INV~NTION
Typical hair conditioning products have a particular thlck rheology that is desirable for such products. These products are based on the combination of a surfactant, which is generally a quaternary ammonium compound, and a fatty alcohol. This combination results iff a gel-network structure which provides the composition with a thick rheology. However, while such compositions deliver conditioning benefits to the hair, such compositions also deposit on hair making hair look and feel dirty.
Alternat~ve thickening systems have been used in hair care compositions, but none have been found to date ~hich provide thi~
same desirabl~ rheology. Though hair care products thickened ~ith polymer thickeners can be made to have a thick rheology, these products generally are characterized by an undesirable ~slimy~
feel and do not hold their poured shape.
Nonionic water-soluble cellulose ethers are employed in a variety of applications, including hair care compositions. ~idely used, commercially-available nonionic cellulose ethers include methyl cellulose, hydroxy propyl methyl cellulose, hydroxyethyl w o 92/16~87 ~ PCTIUS92/00805

2 -cellulose, hydroxypropyl cellulose and ethyl hydroxyethyl cellulose.
Better 'h k kening eFF'ci?ilc~/ ~a rea7i~ed ~lth h gher molec-ular ~eight collulos~ ~2t.1~?`fS. .~O`i?`~ . OdUCb f on or such in~t~-rials is dif~icult an~ 'en~`l`,/?. Thou1;1 cr~s,1in'~ing OT thes~poly~ers ii ~n a~ -f~ ? ;.~ . ;;? ~ f~ f;U-tions, good crosslinkin9 teChn',t~ll?s lr? aot ~nown. O' eQ!Irse, high conct?lltfafioi)i o, po,,i,~ :i i ii àO ~;`O'liO? ;) if3~ viscosi~
but such ~ ~fpO ~ 1, ;J~
due to ~ ? ~ J.~ `?, ~ J
crosslinke~ ~fo1ym~rs ~ iu" ~3~ 3 ` ~ C ;fl1C;CellerS may result i~ l ? ;J`;~ vi` .;~ S~?il~
uses.
A l t i~? r n ~ t i Y i~ 'Y ~ ? r - S ~ . ? .^; ~ ? ^ ? `' '`~ ` ^ `'` ? `' ` ? S "i ^i ? l 15 to thicken hair c re c^ p^s t e . a-~ na"~ a' .a; ~,a~ s as guar gum, xanthan gum and locust bean gum.
A number of references toach th2 use of nonionic cellulose ethers and water^soluble gums for thickening hair care composi-tions. See for example, U.S. Patent 4,55J,928, Glover, issued December 10, 1985, teaching a hair conditioner comprising a suspension system which consists of one of glucan gum, guar gum, and hydroxyethylcellulose; and U~S. Patent 4,581,230, 6rollier et al., issued Apr;l 8, 1986, which teaches cosmetic compositions ~or treating hair which compri;e as thi;~-ning a~ents hyJroxye.hyl-cellulose, or water-soluble vegetable thickening agents, such as guar gum.- Japanese Patent Publication 61-053211, publ;shed March J, 1986, discloses a hair colorant containing an aromatic alcohol, xanthan gum, and hydroxyethylcellulosé.
Certain cellulose ethers have been disclosed in U.S. Patent 4,228,2J7, La~doll, issued October 14, ~980, ~h~ch are relat;vely low molecular weight but which are capable of producing highly viscous aqueous solutions ;n oractical concentrations. These materials are nonionic collulosa ethers having a suFFicient degr~oe of nonionic substitution selected from the group consisting of methyl, hydroxyethyl, and hydrox~ro~yl to cause thom to be w o 92/16187 ~ PCT/US92/00805

- 3 -water-soluble and which re further substltuted wlth a hydrocarbon radlcal having from about 10 to 2~ carbon atoms in an a~ount between about 0.2 weight percent and the amount wh kh renders said cellulose ether less than lX, by weight, soluble ~n ~a~er. ~he S cellulose ether to be modified ts prPferably one of low to ~ediuin molecular weight; i.e., less than about 800,000 ana ~re~r3Di~
between about 20,000 and 700,000 (about 7S to 2500 D.P.~.
These modif~ed cellulose ethers have been d,,closad .`or u;a ;n a variety of composition types. Landoll ('2J7) te~ches the use of these materials in shampoo formulations. Hersules `.~de literature teaches the use of these materiaîs in s;lampoos, lig~id soaps, and lotions. U.S~ Patent 4,6Q3,0~4, Goddard, ~ssueu dui~
28, 1987, discloses the use of these materials in mousse col~posl-tions for the hair. U.S. Patent ~,485,089~ Leipold. issued November 27, 1984, teaches dentifrice compositions con~aini^~
these materials.
These materials have now been found to provide a rheology very much like the desirable gel-network structure of typical hair contitioners (without the slimy feel associated with most poly-meric thickeners), when they are combined with surfactants at certain critical levels. Such compositions are disclosed in U.S.
Serial Nos. 07/551,118, 07/551,119, and 0~/5il,120, all filed July 16, 1990, by 8Olich, Norton, and Russell.
Still, it remains desirable to provide further improv2d vehicle systems for use for cosmetic compositions. In particular, it is desirable to improve perceived spreadability of the composi-tions upon application by the user to the hair or skin. It is also desirable to provide improved wet feel of the hatr on skin treated with such cosmetic compositions.
Hence, it is an object of the present invention to provide a vehicle system for a hair care and other cosmet k composition which provides a gel-network-like structure to the composition not based on a typical quaternary ammonium compound/fatty alcohol gel-network thickening system, which provides improved perceived WO 92/16187 ~ G !3 6 ~ Pcrtus92/oo8o5 . ~, spreadabtl1ty upon appltcatlon to th2 s~n or halr and bhlch provtdes tmproYed ~et feel of the hatr or s~ln to ~h~ t~uch.
It is also an ob~ect of the present tnYentton to proYtd~
vehtcl~ syst~m, as desc.~i~e?d ~ho~?! o; ~ c.~
cosmettc composittons which allC'f.i .`lr d.`~ On 0~ i .lil da variety of i?iCt i Y ~? h~i, i3i~
provtdtng tmproved wet feel and jsercaiYed spreadab~llty ~ilati~Je to such composittons 'iYith ~. io. ~ ,c~ d ```~`i " ? `_~ m~
In a particular aspect or ~his ~a~an~ i, an rb~ject ~o provide hatr styling~conditioniu~ n~ ~i'n~?` ' ~n' ~et hair ~? ? ~ ! ch ^o ~hich ~pic~'7~ aulu `~
facilitate spreadir,g o, ~he hain S~ eu~: `n"`n ~`j`'.i'~"`n ~C
hair. M~e ui~ o, diSLi`ibUl.in~ aidj, .i;3;n as ~ial''Z(.~ n 9Ui`;l, un~`or-tunately can negatively impac- ~e~ hair reei. Inus jt is anot~2r object of this invention to proYide a hair s-.~ling and condition-ing composition containing a distributing aid for the hair setting agent that has excellent wet hair feel characterist ks.
These tnd other objects will become readily apparent from the detailed description which follows.
SUMMARY OF THE INV~y~lQ~
The present invention relates to vehicle systems for use in cosmetic compositions which are polymer-based but which proYide a rheology to the cosmetic compositions which mimics gel-net~ork systems. These vehicle systems comprise a two component thickening system in a compatible diluent, wherein the primary thickener component is hydrophobica77y modified, nonionic, long chain alkoxylated polymer that is soluble in the diluent and the second thickener component is selected from quaternary ammonium surfactants having the formula, in salt form:
_ _ +

R3 - I - R~ ,~- a R2 a W O 92/16187 ~ I ~ 6 ~ ~ O PCT/US92/00805 wherein X ts a salt-form~ng anlon, ~s the ~onlc charge of X, the quaternary ammonium radicals R1, R2, R3, and R~ lndependently ara C~ - C22 alkyl, C14 - C22 alkyl amido C2 - C~ alkylene, or ben2yl, and from t~o to three of sald quaternary ammonlum rad~cals, preferably two, are C~-C22 alkyl or C~,-C22 alkyl amido C2^C5 alkyl2ne (pr~ferably C2-C~ alkylene), preferably C1~-C22 aiXyi, more preferably C~-C1~ alkyl, or mixtures thereof, no more than t~o of said rad~cals are either C~-C22 alkyl amido C2-C5 ~lkylen?
or a combination of C~,-C22 alkyl and C1, - C2~ alkyl amido C~-C
alkylene, from one to two of said quaternary ammonium radical3~
prerera~ly ~ d, are C1-C6 alk~l, p.~f~o,a~7y C1-C3 alkyl, mo.^o pre~erably ,~ethyl, and no mora tilan one of said ,^adicat.i i;
benzyl; or r (II) N --- CH2 Rl--C~ x-a ~ - CH2 a wherein X and d are as defined above, the radicals R1, R2, and R3 independently are C1-C22 alkyl or ben2yl, preferably C1-C22 alkyl, and two or three of said radicals are C1~-C22 alkyls, preferably C15-C22 alkyl, or C1,-C22 alkyl amido C2-C~ alkylene (preferably C2-C3 alkylene), or a mixture thereof, zero or one of said radl-cals are C1-C6 alkyl, preferably C~ -C3 alkyl, more preferably methyl, zero or one of said rad k als is ben2yl; or a mixture of Formula I and II surfactants; wherein the quaternary ammonium surfactant component of the above description has a sufficient level unsaturation in the C1,-C22 alkyl or C1,-C22 alkyl amido C2-C6 alkylene radicals, or mixtures thereof, such that average iodine value of said component is at least about 15.
More specific embodiments of the cosmetic compositions of the present invention comprise:
(a) from about 807. to about 100~., preferably from about 80X
to about 99.9%, of a vehicle system which comprises:

W0 92/16~87 '~ 1 5 ~. v n PCr/US92/00805 w (A) from about O.lX to about 10~ by weight of the cosmetlc compositilon of a hydroph~b1 a'l~ moJ~f~ied nonionic water-soluble pol~mer wh~ch comprises a ~at~r-so1 uble pol~ .
groups sel ectPd l``~^Om Lh'~ 9.'0U~ C`I~Si;; j "~3 o~.` C~-C~
alkyl, ~l ai'~
thereof; wherein the rat~o of h~droph,lic p~n~ti~,.n to hydrophob~c pQi'``, i ~ t ~
lO:l to about lOC0:1; a~?,.~ .h? ~ 1,o~ c-ally mod;f~ ni~ t~ t~ ?.' C^l~p`'isois ~i ~iO ii.,;',C S . ~`;,.,;? `i`;,~`,` ,iUJ."., su~r;ci;~in~ 3~ ? ~
~rom the group ool)~is~ y o; mo~h; " "yd.~,~;;;";', and hydroxypropy7 to causa i~ ;o oe W1Ler-;OjUbII~
and being further substitutad ~ .h l lonn ehll.R
alkyl radical having lO to 2~ carbon atoms in an amount between about 0.2 weight ~erc~nt and the amount wh;ch renders said cellulose ether less than 0.2, preferably less than 1%, by weight soluble in water;
(B) from about 0.02% to about 5.C% by weight of the cosmetic composition of unsaturated quaternary ammonium surfactant as descr~bed above; and (C) from about 6~% to about 99g by wetsht of thA
cosmetic composition of a compatible diluent, said nonionic water-soluble polymer being soluble in said diluent; and (b) from 0 to about 2cr~, preferably from about O.l~ to abcut 20X, of an additional active cosmetlc component;
wherein compositions comprising said vehicle system comprise no more than about 1.0%, preferably no more than about 0.5%, of water-soluble surfactant materials (at 25-C).
~he unsaturated cationic quaternary am~onium surfac+ant 3s set forth above, can provide improved perceived spreading and improved wet feel of the hair or s~in upon application by the WO 92/161B7 PCJ~/US92/00805 2~ ~o~o, user. These vehicle systems are particularly useful ln halr care composltions especially rlnse-off hair conditioners and styl1ng/
conditioners.
In another aspect of this invention, hair styling and condl-tioning compositions suitable for rinse-off appl~cation are provided ~ith yet further lmproved wet hair feel. These compo-sitions cont~in a two component thickening system ln a compatible solvent as described above and a hair setting agent dtspersed in the composit~on, a distributing aid for ~he ha~r sett~ng agent, and additionally comprise as an essential ingr~dient ~ mono-long chain, tri-short chain cationic ammonium quaternary surfactant wherein the long chain is selected from C" -C22 alkyl or Cl,-C22 alkyl ~mido C~-Cs alkylene and the short chains independently are s~l~c+ad from the group consisting of C~-C6 ~l~yl and ben~yl, ~.~i'h lS the number of ben~yl radicals per molecule being 2ero or l.
More specific embodiments of these hair styling and condi-tioning compositions comprise:
(a) from about 80% to about 99.5% of a vehicle system comprising:
(A) from about 0.1% to about lO.OX by weight of the cosmetic composition of a hydrophobically modified nonionic water-soluble polymer which comprises a water-soluble polymer backbone and hydrophobic groups selected from the group consisting of C~-C22 alkyl, aryl alkyl, alkyl aryl groups and mixtures thereof; wherein the ratio of the hydrophilic portion to the hydrophobic portion of the polymer is from about lO:l to about lOOO:l; and (B) from about 0.02% to about lO.0~ by weight of the cosmetic composition of unsaturated quaternary ammonium surfactant component of the formula:

(I) ~R3 - I -R, l X
L R2 ~

W o 92/~6~87 PCT/US92/00805 Gb ~ ~ Q - 8 -where1n X ls a salt-form1ng anlon, ~ ls the lontc charge of X, the quaternary l~onium r~dic~
R2, R3, and R~ independent1~ 3r;~ C~ - C~, al'~
Cl, C22 alkyl amido C - C~ al~7alle, or ~enxyl, and from two to three of said ~uaternar,~ am~onium radicals, are C~,-C22 a; ~tl ol C~ C~ ai ~3 amido C2-C6 alkylene or mixturos theroor! no ~or? th~n two of sa~d radicala ~eiil~ C~-C~. a, o~i amldo C2 CS alkylene or a combi~ tl' t`!
I0 and C~-C22 al~ mi~ C~
to two or said qua~ernanY ~i"i,ao,li~im naiiioais lia C~-C6 al~yls, and no mor~ '.,^n m~ P ~.a.~i s~`im^~.
is benzyl; or _ ( I I ) R I--C; I i X - a ~N\ CH~

wherein X is a salt-forming anion, a is the ionic charge of X, radicals Rl, R2, and R3 independently are CI_C22 alkyl or ben2yl, and two or three of said radicals are Cl~-C22 al~yl, or Cl~-C22 alkyl amido C2 C6 alkylene or a .mixture thereof, zero or one of said radicals are C~-C, alkyl, zero or one of said rad kals is benzyl, or a mixture of Formula I and II surfactants; wherein said the quaternary ammonium surfactant component has a sufficient level of unsaturation in the Cl~-C22 alkyl or C~-C22 alkyl amido C2^C~ alkylene radicals, or mixture thereof, such that average iodine value of said component is at least I5; and (C) from about 65% to about 99X by weight of the cosmetic composition of a compatible diluent; and (b) from 0.057. to about I0~, by wPight of the composition, of a hair setting agent;

WO 92/]6187 2 1 0 ~ 0 6 ~ PCI/US92/0080~
9 " .
(c) from about 0.01X to about 5X of ~ distr~but1ng ald; ~nd (d) from about 0.05X to about l.0%, by welght of the co~po-sltlon, of a mono-long chain, trl^short chain quaternary a~monium surfactant of the formula:
R~

( IV) R, - N - R, X'd erein X is a salt forming anion, d is the ionic charge of X~ the quaternary ammonium radical R~ is C~-022 :1~Y1 or C~-C~2 al~yl amido C~-C6 alkylene, and quaternary ammonium radicals R2, R3, and R, independently are C~-C6 alkyl or benzyl, wherein zero or one of said R2, R3, and R, radicals is ben~yl;
wherein said composition comprises no more than about 1.0% of water-soluble surfact~nts.
The compositions hereof comprise or, alternately, can consist essentially of or consist of the essential ingredients, as well as the optional ingredients, described herein.
DETAILED DESCR~PTlON OF T~ lEYE~IIn~
The essential as well as ~arious optional components of the present compositions are described below. All solubilities are determined at 25'C, unless otherwise indicated. All percentages and ratios are by weight unless otherwise lndlcated. All percentages are by weight of the total compos~tion, unless otherwise indicated.
HYdr~ 3~ fi~cL~LLter Soluble PolYme~
The vehicle systems of the present inYention contain, as an essential thickener component, a water soluble polymer. This thickening material is a hydrophobically modified nonionic water-soluble polymer. ~y ~hydrophobicatly modifled nonionlc water-soluble polymer~ is meant a nonionic water-soluble polymer which 2~Q~ Q - ~O- ' has been mod~fied by the substitution with ~ suf~icient amount of hydrophoblc groups to make the polymer~less soluble in ~at~r.
Hence, the polymer bac~bonP can bio oss~ntlally 3ily `,`j~ Uj~
polymer. For the compositions hereof, the unmodiri?d ~ol~er backbone should be sufflciently so7ub7a su;h ~h~' o~
substantially clear solution ~hen dissolvod in ~ater a~ a levo~
1%, by welght of the solutloR, at ~5'C. ~h~ hy~ ù~;
can be C~ to C22 al~yl, aryl al~l, al~yl a.~l grvups a"d m,;`ures thereof. 7he degree of hydrophobic subs`l`u` on o, ~,"~
backbone should be t.om about ~ o a-~o of the polymer, prafPrably from about .-.~. 'o a`co;;~. . ,. 1;~
generally, the ratio of hydrophilic ~ortion ~o i~ roo~r~ ~n of the polymer is from about 1~:! to abcut !QQ~
A nu~r ~f ~ p~ n , ~ ;ù",~
materials which meet the above requirements and whicn are userul in the present invention. U.S. Patent 4,496,708, Dehm et 1., issued January 29, 1985, teaches water-soluble polyurethanes having hydrophilic polyether backbones and pendant monovalent hydrophobic groups to result in a hydrophilic/lipophil k balance of between about 14 and about 19.5. U.S. Patent 4,426,485, Hoy et al., issued January 17, 1984, discloses a water-soluble thermo-plastic organic polymer having segments of bunched monovalent hydrophobic groups. U.S. Patent 4,415,701, Bauer, issued ,`~ovember 15, 1983, discloses copolymers containing a monoepoxide and a dioxolane.
The most preferred hydrophobically modified water soluble polymeric thickener materials for use in the present invention are disctosed in U.S. Patent 4,228,277, Landoll, lssued October 14, 1980, which is incorporated herein by reference. The materials disclosed therein are thickeners comprising a nonionic long chain alkylated cellulose ether.
The cellulose ethers have a sufficient degree or nonionic substitution selected from the group consisting of methyl, hy-droxyethyl and hydroxypropyl to cause them to be water-soluble.
The cellulose ethers are further substituted with a hydrocarbon WO 92~16187 2 ~ ~ 6 ~ 6 0 ~ US92/00805 - 11 - ` .
rad1cal having about 10 to 2~ carbon atoms 1n an umount between about 0.2 wPight percent and the amount ~hich renders sa1d cellu-los~ e'hor loss than 0.2%, preferably less than IX, by weight, soluble in water. The cellulose ether to be mod1f1ed 1s oreferably one of low to medium molecular weight, i.e., less than about ~00,~00 and preferably between about 20,000 and 700,000 (about ~ 'o ~500 D.P.).
ThP Landoll patent teaches that any nonionic water-soluble c~llul~;e ether c~n be employed as the cellulose ether substrate.
I~ Thus, e.~3., h~Jdroxyethyl cellulose, hydroxypropyl cellulos~, meth,~l :ellu~ose, hydroxypropyl methyl cellulose, ethyl hydroxy-etnyl oeilui~se~ and methyl hydroxyethyl cellulose can all be modifled. The amount of nonionic substituent such as methyl, ~y~;-o~ ~"y' ~ hydroxypropyl is taught not to b~ critical so lona as there is an amount sufficient to assure that the ether ls water-soluble.
The preferred cellulose ether substrate is hydroxyethyl cellulose (HEC) of about 50,000 to ~00,000 molecular welght.
Hydroxyethyl cellulose of this molecular weight level is the most hydrophilic of the materials contemplated. It can thus be modi-fied to a greater extent than can other water-soluble cellulose ether substrates before insolubility is achieved. Accordingly, control of the modification process and control of the properties of the modified product can be more precise with this substrate.
2S Hydrophilicity of the most commonly used nonionic cellulose ethers varies in the general direction: hydroxyethyl ~ hydroxypropyl hydroxypropyl methyl ~ methyl.
The long chain alkyl modifier can be attached to the cellu-lose ether substrate via an ether, ester or urethane linkage. The ether linkage is preferred.
Although the materials taught in Landoll are referred to as being ~long chain alkyl group modified~, it will be recognized that except in the case where modification is effected with an alkyl halide, the modifier is not a simple long chain alkyl group.
The group is actually an alphahydroxyalkyl radical in the case of w o 92/16~87 PCT/US92/00805 ~ v&~ 12 -an epoxide, a urethane radlcal in the case of an lsocyanate, or an acyl radlcal in the case of an acid or acyl chlor~de. ~Nonethe-less, the terminology ~long chain alkyl group~ ls u.ed ainCe ~h~
size and effect of the hydrocarbon portion of the modi~yil~g molecule completely obscure any noticeable effoct from 'h? .o~-necting group. Properties are not significantly diffarent f-^m those of the product modified ~ith th~ si~pl long c:lain s,k group.
Methods for making these modi~ied cellulo,e e~h-~?~i are :a~.;~;."
in Landoll ('277) at column 2, lines 3S-Si.
These materials haYe been found to be part~cula l~ des,;a'l~
for use in the vehicle systems of the cosmetic comoosittons o~ he present invention The materi~ls are able to st~b~l~aq suspee~,o^~
of dispersed phases, ~nd when used wi~h the add,:~ ni ;omron ~
in the vehicle systems of the present invention, they pro~uce rheologically thick products ~hich lack the slimy feel character-istic of most polymeric thickeners.
One commercially available material which meets these re-quirements is NATROSOL PLUS Grade 330, a hydrophobically modified hydroxyethylcellulose available from Aqualon Company, ~ilmington, Delaware. This material has a Cl6 alkyl substitution of from about 0.4% to about 0.8% by weight. The hydroxyethyl molar substitution for this material is from about 3.0 to about 3.7.
The average molecular weight for the water-soluble cellulose prior to modification is approximately 300,000. Another material of this type has a Cl6 alkyl substitution of from about 0.40% to about 0.95X, by weight. The hydroxyethyl molar substitution ~or this material is from about 2.3 to about 3.3, and may be as high as about 3.~. The average molecular weight for the water soluble cellulose prior to modification is approximately 700,000.
~he hydrophobically modified water soluble polymer thickener component is present in the cosmetic compositions o~ the present invention at from about O.lZ to about 10.0%, preferably from about 0.2Z to about 5.0%.
3i w o 92/16187 2 ~ o PCT/US92/00805 ~ 13 -Unsaturated OuaternarY Ammontum Surfac~ant The pras~nt Y~h~cle systems further comptlse, as a second essent~al com~onent, a second thickener which ls an unsaturated ~ater-tnsoluble, Cl4-C22 alkyl-substituted quaternary ammonlum S surfactant. 3y ~water-insoluble surfactant~ is meant surfactant materials wnici~ do not form clear isotropic solutlons when dissolY~d in ~at r at greater than 0.2 weight percent at 25-C. By ^unsaturate~' as applied to the C~-C22 alkyl substltuted ~uat3r~a,~y ~m~on~um iurfactant is meant quaternary ammonium sur,ac~ln~; "a~Jing a surricient amount of unsaturation such that it has an lodine Yalue of at least about 15. Generally, the iodtne iaiu~ i be ,rom about 20 to about 200. It should be understood that the iodine value is meant to describe the average le~al ^ n~ t~on of th~ ass~ti2l C1,-C2, ~lkyl substitut~d quaternary ~;r~oniym surfactant. ~Alkyl~ a5 used herein, includes unsaturated radicals as well as saturated.
The essential C1~-C22 alkyl-substituted quaternary ammonium surfactant component hereof constitutes materials of the formula, in salt form: _ (1) R~ ~
R3 - I - R~ X a _ R2 , a wherein X is a salt-forming anion, a is the ionic charge of X, the quaternary ammonium radicals R~, R2, R3, and R, independently are Cl - C22 alkyl, C1, - C22 alkyl amido C2 - C6 alkylene, or benzyl, and from two to three of said quaternary ammonium radicals, preferably two, are Cl,-C22 alkyl or C1~-C22 alkyl amido C2-C6 alkylene (preferably C2-C, alkylene), preferably C~,-C22 alkyl, more preferably C16_C1J alkyl, or mixtures thereof, no more than two of said radicals are either C1,-C22 alkyl amido C2-C6 alkylene or a combin~tion of Cl,-C22 alkyl and Cl~-C22 alkyl amido C2-C6 alkylene, from one to two of said quaternary ammonium radicals, preferably two, are Cl-C6 alkyls, preferably Cl-C3 alkyl, more WO 92/16187 PCI`/US92/00805 210~06~ - 14-preferably methyl, and no ~ore than one of sald radlcals ls benzyl; or S (II) Fll-- C~ a R2 R, wherein X and a are as defined above, the radicals R~, R~, and ;ndepend~ontty are C~-Ct2 alkyl or benzyl, sreferably C,-C2, ~ yl!
and two or three of said radicals, ~rPfor3bly t~o, a;^~ ~IJ-~2 alkyl, proforably C~ C22 71Xyl, ~ C22 ~7~Y7 ~ o ~ 2-~
alkylene (~referably C2-~3 alkyl2ne), or a mi~ture th~reo.`, L~rO
or one of ~aid radicals a,~ 6 alky1, preterao7y ~I-C3 alkyl, more preferably methyl, zero or one of said radicals is benzyl, or a mixture of Formula I and II surfactants; wherain the quaternary ammonium surfactant component of the above description has a sufficient level unsaturation in the CI,-C22 alkyl or Cl~-C22 alkyl amido C2-C6 alkylene radicals, or mixtures thereof, such that average iodine value of said component is at least about 15.
The anion X can be any salt-forming anion suitable for use in cosmetic compositions. Suitable anions include halogens (espe-cially chloride and bromide), acetate, phosphate, nitrate, sul-fate, and alkyl sulfate. Preferred anions ~enerally are chloride, acetate, sulfate, and methyl sulfate.
Examples of unsaturated quaternary ammonium surfactants hereof include the salts of dimethyl di(unsaturated) tallow ammonium, dimethyl distearyl ammonium, dimethyl di(unsaturated)-arachidyl ammonium, dioleyl dimethylammonium, di-rapeseed alkyl dimethyl ammonium, diricinoleyl dimethyl ammonium, and disoyadi-monium, olealkonium.
Other examples include the salts of methyl-l-oleyl amido ethyl-2-oleyl imidazolinium, dierucyl dimethyl ammonium, and methyl-l-soya amido ethyl-2-soya imidazolinium.
It will be recognized by those skilled in the art that unsaturated quaternary ammonium surfactants, when purchased w o 92tl6~87 ~ I O ~ ~ 6 0 PCT/US92/00805 commercially, wlll nor~ally also conta1n saturated quatern~ry ammon~um surfactants of other~tse simllar structure. An exa~ple of thls ~s ~OQG~ ~70, commerclally availabl~ from Sherex Chemic~l Compan~ (Du~lin, Ohio, USA), whkh contains a mtxture of saturated and uns~tur~ed ditallow dimethyl ammonium chloride. Compositlons containinc sucn materials are included within the scope of thls 'n~!en` .n ;s lon~ as thev contaln the minimum level of surfactant defined ~er~in having a level of unsaturatlon of surfact~nt ,~al1,ng 1 `h~,n .~c..,.ula ~I) and (~I) is suffictent such that the averaca i~u "e value is at least about lS.
r~ u~^ n~ry ammonium surfactant hereof is used at a level ot` IroiR a~ùu- ù.ù~ ,o abûut lO.~, preferably from about O.O5X to about ~ more preferably from about 0.05% to about 2.0X? by . ~ . . . _ _ _ ., . _ _ ., ~ ~ ~ .
l~ !in~r~oai .nP water insoluble unsaturated quaternary ammonium surfactant component hereof is referred to as a thickener material, it should also be recognized that it can also act as a conditioner for the hair and/or skin.
Dilue~
A third essential component in the vehlcle systems of the present invention is a diluent which is a solvent for the hydro-phobically modified water-soluble polymer and is compatible with the othsr components in the present compositions. Generally the diluent will comprise water or a water-lower alkanol (e.g., C2-C, alcohols) mixture; preferably it will include at least about 25%, more preferably at least about 50%, even more preferably at least abcut 75%, by total weisht of the diluent, of water. Rinse-off compositions, such as hair rinses, preferably utili2e water as the diluent. The diluent is present in the compositions of the present invention at a level of from about 65% to about g9% by weight of the cosmetic composition.
The other ~lehicle components are dispersed or mixed in the diluent to provide an optimum thick rheology to cosmetic compo-sitions formulated therewith which mimics the gel-n-twork rheology of typical hair conditioning compositions. This rheology is Wo 92/16187 PCI`/US92/00805 charactert~et by a shear stress of from O to about 50 pasul, over a shear rate range of 0.04 sec~l to 25 sec l. The rheology ls measured using a Bohlin Rheometer YOR ~ith the follo~.~lng con~ lnd plate set-up: cone has a 2.5 degree angle, plate ~s 3~mm in S diameter, the gap between the truncated cone and plate ~s set ~
70~m, and the torque bar used is 20.1~8 g-cm. The sample amount is 0.35ml and the sample is syringed onto the cent~r of the pli.
The system used ls as follows: there ls no initial d lay time, the strain delay time is 25 sec, the int~gration tim~ is ~ 52C, ~ha sensitiYity is set at IX, the shear s~.~eep is u~, th9 shear nang~
is from about 0.0~05 sec-l to 25.53 sec~l (shear ~o~ ~ 11 to 39~, and the ~emperatura is maintained constant bet~een series It ambient temperaturP (20-C to 25'C).
~ddition~l Thic~ener The present vehicle systems can also comprise an additional thickening component, such as water-soluble polymeric materials other than the hydrophobically modified water soluble polymers described above. Examples of ~ater-501uble polymers which may desirably be used as an additional thickening component in the present vehicle systems, are hydroxyethylcellulose, hydroxypropyl cellulose, hydroxypropyl methylcellulose, polyethylene glycol, polyacrylamide, polyacrylic acid, polyvinyl alcohol, polyvinyl `pyrrolidone ~-120, dextrans, for example Dextran purified crude Grade 2P, available from D~O Chemicals, carboxymethyl cellulose, plant exudates such as acacia, ghatti, and tragacanth, seaweed extracts such as sodium alginate, propylene glycol alginate and sodium carrageenan, and UCARE JR-polymer (a cationic modi~fied hydroxyethyl cellulose available from Union Carbide). Preferred as the optional additional thickener for the present vehicle systems are natural polysaccharide materials. Examples of such materials are guar gum, locust bean gum, and xanthan gum. Also preferred as the additional thickener in the present compositions is hydroxyethyl cellulose having a molecular weight of about 700,000. It is preferred that these polymer materials not contain 3~

W o 92/16187 2 1 0 6 ~ ~ O PCT/US92/00805 cellulose as th1s may lnterfere wlth obtalnlng opti~um iscosl~es.
The add~tlonal thlckening component, if present ln the cosmet~c ;~mv3sitions of the present invention, 1s preferably used at a le~f~`1 o,` ,rom about 0.3X to about 5.~X, preferably from about Distributing Aid ~ n .~ `ion~1 component in the vehicle systems of the present ;nvention is a material which acts as a distributing ald for the !O composi`i!n ~;uch a ,naterial helps to distribute the cosmetic composl.i~n . '^ 'ha l~ir or s~in Ivoidin~ local;7ed doposition of b ;~ )r à ~ O U ~ S uch a componeni in ~ composl.ion, iome a;tive components in the composi-tion wo~lid no~ ve deposited and spredd out as evenly, and hence, I5 would not be cuite as effective. In particular, a distributing aid is especially useful if ingredients that are tacky are included, such as hair setting polymers.
Distributing aid materials useful in the present invention are actually a subclass of the class of materials that can be used as the optional water-soluble polymer additional thickener in the present invention. This subclass is defined as follows: water-soluble polymer materials having high molecular weight, i.e., greater than 1,000,000; and/or strong ionic character. By strong ionic character is meant that the material conducts electricity at 2~ greater than 30 millivolts. This can be measured by evaluating conductance of a lX solution of polymer in DRO (double reverse osmosis) wator preserved with 0.03% Kathon CG (methylchloroiso-thiazolinone and methylisothiazolinone, a preservat;ve available from Rohm ~ Haas) using a calibrated Corning 130 pH meter. The probes used were as follows: the reference electrode is an Orion Model gOOI single junction. The pH electrode is an Orion Model 9161, silver-silver chloride. The probes are set 3~8 of an inch apart. The ~H meter is set to millivolt readings. The absolute measurement is recorded after 4 minutes immersion.

WO 92/16187 PCl`/US92/00805 Examples of water soluble polymer materlals wh1ch meet these requlrements and hence, can act as dlstrlbut1ng aids ln the present composltions lnclude xanthan gum; Dextran purlfled crude Grade 2P aYailable from D~O chemicals; carboxymethyl celluloses;
for e~ample, C~C's 4~1F, ~M6F, ~HF, 7M8SF, 7LF, 9H4F, 9~8, 12M8P, 1~3i, ~al1 aYailable from Aqualon); ~lant exudates iuch as acacia, ghatti and tragacanth; seaweed extracts such as sodium alginate, pro~ylene glycol alginate, and sodium carrageenan; high molecular weight hydroxyethyl celluloses such as Natrosol 250H and I0 ~at,o~ol 250~HR (available from Aqualon); and pectin.
3~cause the class of materials which may act as distributing ~,~s n ~ ?san~ invontion is a subset of the optional `~tor-solubl~ additional thiekener, the mat~rials in ~his subclass i~ay be usa~ 'o p,c~;ide both ben~fits to th~ cc~po~ition. ,~or ex~mple, IS xanthan gum is a water-so7uble natural po~ysaccharide material which additionally has a high molecular weight. Hence, this material could be used by itself to provide both additional thickening benefits and distributing benefits. However, it may be necessary to use such materials at slightly higher levels to provide both benefits.
It is also possible to use two separate materials as the optional water-soluble polymer additional thickener and the distributing aid of the present invention. ~his would be done when the water-soluble polymer additional thickener was not a high molecular weight material or of strong ionic character. Locust bean gum is such a material. A distributing aid such as xanthan gum could be used with locust bean gum to provide the additional distributing benefits.
If a distributing aid is present in the cosmetic compositions of the present invention, it should be present at a level of from about 0.02% to about 2.5%, preferably from about 0.05% to about 1.0%, of the cosmetic composition. If the distributing aid is bifunctional, i.e., acting as both the optional additional thick-ener and the distributing aid it should be present at a level of from about 0.2X to about 5% of the composition. ~hus, in general, WO 92/16187 2 1 ~! ~i O ~ ~) PCI/US92/00805 _ ~9 .
the distributing aid will be used at a level of about 0.02X to about 5X.
A distributing aid is partlcularly usaful ln halr care compositl~n3 o, tho ~rosont invention especlally rinse-off hair conditl~n~-,. The distribtlting aid helps to spread some halr conditie~,i ; ;:m~ ;n`:s, ?s~e:~all~ h .ir sett~9 agQnts, ev~nly over the hair.
Th~ ~ es~nt vehiclQ systems and cosmetic compositians formu-lated therPwith should b~ substantially free of water soluble 0 sUrfaCt~ ;. 1 `'5e matelills ar~ not c^mDatible ~ith the vehicle syst~ms ^~ ? ,r~sent com~osi~ion. 3v ~substantially free of `~d~ei^-`iO,.`,`' `~ e~ he eom~ositions comprise less ~,~n ~. moun~ ~; Suc,l surfactlln., .hat will d~Qstroy the presell~ u~ a ~es"^~31a r.~eol~ `h~. is he ob~ct of the prevent invention~ ~enerally, this ~,~ili mean that the present compositions comprise no more than about 1~, preferably no more than about O.j~, of such materials. Examples of specific water-soluble surfactant materials that can be particularly harmful to the present vehicle systems are alkyl sulfates and ethoxylated alkyl sulfates, such as ammonium lauryl sulfate; amphoteric surfactants which are derivatives of aliphatic secondary and tertiary amines; nonionic surfactants produced by the condensation of alkylene oxide groups with an organic hydrophilic compound, such as laureth-23 (sold under the trademark Brij 35 by ICI
Americas); and high alkyl betaines, sulfo betaines, amido betaines and amido sulfobetaines, such as cetyl betaine.
The present vehicle systems and cosmetic compositions formu-lated there~ith are also preferably substantially free of fatty alcohol materials, such as stearyl-, cetyl-, myristyl-, behenyl-, lauryl-, and oleyl alcohol. 8y "substantially free of fatty alcohol materials~ is meant that the compositions of the present invention comprise no more than about lZ of these materials.
These materials are commonly used in vehicle systems for hair conditioner products. However, these materials tend to deposit on the hair and leave the hair feeling dirty after use. These w o 92/l6l87 PCr/US92/00805 mater1als are not requ1red ln the present vehlcle systems, as they are thickened with alternative materials whlch do not deposlt on hair.
Ihe presQnt vehicle systems can be used ~n essentially any cosmetic products having a thick gel-networ~ type rheology and .~hi~h ~ d ~ r ~cm~ Ic~ive component onto the hair or s~in. Such compositions would include skin moisturizing lotions, sunscreDn comoositions, and skin cleansing compositions. However, cosmetic c~mpositions most desirably used with the present vehicle systqms a,~ hai,^ care ~roducts, aspecially rinse-off hair care pnodtlct~ e~e s^mq acti~q hair care component is to be deposited ~-t~ `~.`? ~ ,,jq `~q'~ q r~ jn~; t~ compQn~qnt ~S dqs1r~
rinsed ~f o .h~ hair `Yith little or no deposition of the Yehicle m~t~
~ eneraiî~, ~he presen~ venicle systems ~ill not be useful in typical shampoo compositions since these compositions contain high levels of water-soluble surfactants, which as discussed supra, are incompatible with the present vehicle systems. However, the present vehicle systems are useful in typical hair coloring compositions, hair tonic or gel compositions, hair mousse compo-sitions, and especially hair conditioning compositions.
Active Cosmetic ComDonen~
The cosmetic compositions of the present invention generally wilt comprise an additional active cosmetic component which provides some benefit to the hair or skin. The term ~additional active component" is used since the unsaturated quaternary ammoni-um surfactant component hereof generally operates as a conditioner to hair or skin. Such materials may include moisturizing agents, sunscreen agents, cleaning agents (that are compatible with the present vehicle systems), and especially hair conditioning agents, hair styling agents, antidandruff agents, hair growth promoters, hair dyes and pigments, or perfumes.
A wide Yariety of conventional sunscreening agents are suitable for use in the cosmetic compositions of the present invention. Segarin, et al., at Chapter YIII, pages I8S et seq., 0 92/16187 2 ~ ~ ~ n ~ o PCT/US92/00805 of Cosmetlcs Science and TechnoloqY, dtsclose numerous suitableagents. Specific suitable sunscreening agents ~nclude, for example: p-aminobenzo k acld, its salts and its derivatlves;
anthranilatos; sllic~lates; cinnamic .cid deriYattves; dihydroxy~
cinnamic acid dq vativqs; trihydroxycinn~mic ~cld derivat~ves;
hydrociraons, l~n~n`.a e~ nq .r~ ~n~llao~o~hqnone; na~hthol-sulfonates; dihydroxy-naphthollc acid and its salts; coumarin derivat;ves; d;~707es; quinlno sal~s; n~u~nol'ne derivatlYes;
hydroxy- or ~ethoxy-substituted ben20phenones; urlc and vilouric acids; ~allnio -~c,J ~nd i`., derm~ativ~;; hJ~dioqu~,~ono; and benzo-phenones metho~ydiDq~ J~ y~ t.~Q~ ,h~o~, oct~l-dimethyl ~-a,,,~,,.v,o;~ vi; a;.d, di~a~ a~ ..v.aa~a, ',~-tihyd~^oxy-

4-methoxyb2n~ophenone, ot,ny~ bis~hydroxypropyl)~-aminobenzoate~
2-ethylhexyl-2-cyano-3,3-diphenYlacrylate~ 2-ethylhexylsalicylate, glyceryl p-aminobenzoate, 3,3,5-trimethylcyclohexylsalicylate, methylanthranilate, p-dimethyl-aminobenzoic acid or aminobenzoate, 2-ethylhexyl p-dimethylaminobenzoate, 2-phenylbenzimida~ole-5-sulfonic acid 2-(p-dimethyl-aminophenyl)-5-sulfonicbenzoxazoic acid, and mixtures of these compounds are particularly useful.
Examples of antidandruff aids 5uitable for use with the vehicle systems of the present invention include zinc pyrithione, sulphur, and sPlenium sulfide. One example of a hair growth promoter suitaole ~or use with the vehicle systems of the present invention is Minoxidil, (6-amino-1, 2-dihydro -1-hydroxy-2-imino-4-piperidino pyrimide! available from Upjohn.
Hair oxidizing (bleaching) agents, such as hydrogen peroxide, perborate and persulfate salts, and hair reducing agents such as thioglycolates may also be used.
Additional Conditioner~
Examples of conditioning materials suitable for use in the vehicle syste~s of the present invention are volatile liquid hydrocarbons. These are particularly useful for use in hair 3s treatments.

Wo 92/~6]87 PCr/US92/00805 These ~aterlals preferably h;ve a bolling po~nt ln the range of about 99'C to about 260'C and have a solub~llty ln water of less than about 0.1~. The hydrocarbons may be elther stra1ght or br~ncn.d ;hain and may oontain ;rom about 10 to about 16, prefer-j ably -From ~bol!t 12 to about. lS carbon atoms. Examples of suitable ,n~dr^ ~ n~ d?:ln~! do~-~eca,le, ~etradecan~, tridecane and mixtures ~i~ereor.
Yolat~,l? iilicon~s user`ul as an active conditioning component in the c~mposicions or the present invention include silicone flu,ds .,:~h ~ clic lr.d linear pol~dimethylsiloxan2s. The number of cilico~l atoms in the c~clic sillcones is Dreferably from 1;`''~ J'~ 01`mllla ~or t~ cyclic silicones is . .
~, 1 S ~ S i -0~ r~
I

~herein n ~ 3-~. The linear polydimethylsiloxanes have from about 3 to 9 silicon atoms and have the general formula:
(cH3)~si-o-[-si(cH~)2-o-]n-si(cH3)3 n - 1-7.
Silicones of the above type, both cyclic and linear, are available from Dow Corning Corporation, Dow Corning 3~4, 345 and 200 fluids;
Union Carbide, Silicone 7202 and Silicone 7158; and Stauffer Chemical, S~S-0331~.
Tne linear volatile silicones generally have viscosities of less than about 5 centipoise at 25-C while the cyclic materials have viscosities less than about 10 centipoise at 25'C. A
description of volatile silicones is found in Todd and Byers, ~Yolatile Silicone Fluids for Cosmetics~, Cosmetics and Toi1etr~es, Vol~ 91~ January 1976, pp. 27-32, incorporated herein by reference-The volatile agent may be present in the compositions of thisinvention at a level of from about 1~ to about 20%, preferably fro~ about 2~ to about !5Y~. The volatile silicones are the preferred volatile agents.

o 92/16187 2 ~ PCT/US92/00805 Nonvolat11e s111cone flu1ds are useful as the act1ve h~1rcondit1Oning compon~nt 1n th~ composltions of the pres~nt invention. They ~ill generall~ haY~ a viscostty ln axc2ss of lO
centipoise at 25-6. ~am,~1as o-,` ,u.h ~ater~a1s lnclud~
polydimethylsilo~anes (rluids lrld gums) aminosilicones and phenylsilico~a~s. ,he,e ii1Cî~id' ;ol~'a~ l Oi` polyanyi iiioxanes with the following structur~:
r 1 1 ~
lOA - Si ~ o I I ~ , wherein ~ is alX~/l or an~d Y ~ n int~r ,^nom about 7 to about 5, '~00 ,.my ''' '~ 'd ~` ` i S`'~ 'i '.h`~; ` b ' ~ca 'he ends lS of the si7icone chains.
The alkyl or`aryl groups substitut~d on the siloxane chain (R) or at the ends of the siloxane chains (A) may have any struc-ture as long as the resultin~ silicones remain fluid at room temperature, are hydrophobic, are neither irritating, toxic nor otherwise harmful when applied to the hair, are compatible with the other components of the composition, are chemically stable under normal use and storage conditions, and are capable of being deposited on and of conditioning hair.
Suitable A groups inctud~ methyl, methoxy, ethoxy, propoxy, and aryloxy. The two R groups on the silicone atcm may represent the same group or different groups. Preferably, the two R groups represent the same grou?. Suitable ~ groups include methyl, ethyl, propyl, phenyl, methylphenyl and phenvlmethyl. The pre-ferred silicones are polydimethyl siloxane, polydiethylsiloxane, and polymethylphenylsiloxane. Polydimethylsiloxane is especially preferred.
Suitable ~ethods for preparing these silicone materials are disclosed in U.S. Patents 2,826,551 and 3,964,500 and references cited therein. Silicones useful in the present invention are also commercially available. Suitable examples include Yiscasil, a trademark of the ~eneral Electric Company and silicones offered by Wo 92/16~87 PCr/US92/00805 Do~ Corning Corporatlon and by S~S Slltcones, ~ dlvlslon of Stauffer Chemlcal Company.
Other useful sll~cone materials lnclude materlals of the ~ormu~ 1:
r l~

L~ C~ ~' ¦ ~H
o I i~H, _ ; n ~ ' ' m~ ri :~il i C.1 de~nd on the mo~ecu1ar weigh~, ~he ~a~39~ rolecular ~eigilt o~ing approximately bet~een

5,~ ana i~ . Inis ~oiymer is a7so known as ~amodi~ethicone~
1~ Other silicone cationic oolymers which can be used in the present composition correspond to the formula:
(~l)aG3-a-Si-(-OsiG2)n-(osiGb(Rl)2-b)m-o-siG3-a(R~)a in which G is chosen from the group consisting of hydrogen, phenyl, OH, Cl-C~ alkyl and preferably methyl; a denotes O or an integer from 1 to 3, and preferably equals 0;
b denotes O or 1 and preferably equals 1; the sum n+m is a number from 1 to 2,000 and preferably from 50 to 150, n being able to denote a number from O to 1,999 and preferably from ~9 to l49 and m being ab7e to denote an integer from 1 to 2,000 and prefer-ably from 1 to 10;
Rl is a monovalent radical of formula CqH2qL in which q is an integer from 2 to 8 and L is chosèn from the groups -N(R2 ~H2 -C~2 -N(~2 ) 2 -N(R2)2 -N+(R2)3A
-N+tR2)2CH2 -CH2-N+(R2)3A
in which R2 is chosen from the group consisting of hydrogen, phenyl, benzyl, a saturated hydrocarbon radical, preferably an alkyl radical containing from 1 to 20 carbon atoms, and A- denotes a halide ion.

Wo 92/16187 ~ ~ Q ~ ~ ~ PCr/US92/00805 These compounds are descr1bed ln greatPr detlll 1n European Patent Appllcatlon EP 95,238. An es~ecially preferred polymer corresponding to th~s formula ts the polymer kno~n as ~tr~methyl-silylamodimethicon~ of formul~:

I CH~ I ~~ f~

~ C~; ~ n ~ (C'~
I !~ I

ComposiLions of the ~r~si~n~ InVenbtOI~ ~n~t~l~9 ~hii Inaterial typically will Jmprise up to about l.O~ of the trimethylsilyl amodimethicone silicone conditioning material.
Other silicone cationic polymers may also be used in the present compositions, such as those of the formula:

R,-CH2-CHOH-CH2-N(R3)3Q-(R,),-Si-O--¦~Si-O~ Si-O--¦--Si-(R,), 2S in which R~ denotes a monovalent hydrocarbon radical having from l to 18 carbon atoms, and more especially an alkyl or alkenyl radical such as methyl;
R, denotes a hydrocarbon radical such as, pr2ferably a C~-C;t alkylene radical or a C~-CI~, and preferably Cl-C~, alkyleneoxy radical;
Q~ is a halide ion, preferably chloride;
r denotes an average statistical value from 2 to 20, preferably from 2 t; ;
s denotes an average statistical value from 20 to 200, and prefer-ably from 20 to SO.

WO 92/16187 ,` PCI`/US92/00805 Thesic compourds ar~ descr~bed ln greater det~tl ln U.S.
Patent ~ S,~17.
A polymer of thls class which is especlally preferred is that sold by "~ P~3I2' und~r t~h~ n~lme 'UC.~ SILICONE ALE 56~.
Sil~,ca;,~ ~o,.d.t,ûn.-9 ~se~ts are used in thP prQsent compo-si~.c,~s ~ .cc ~ .o ~^u~ lS." ~retQrably from about O,5.v to about l~
?;^~.~rr ~' s~. i o.~e condi~icning ~e~its for use in the present composi~ions com~ris~ combi~atio~s o, ~olatile silicone ~luids 10 havina ,i;o.s;~c ~ s.; `hln Ibùu~ iv~ c~ntipoisei, and from V ~ J~ L~q`~ n 5~v to ~b~ut 1,CCO,~ id to gum of frûm^
a ~ o u ~ , ù . . ù . ù i ù v u ~ . v: , v, ~ l, i . u ,~ u li i, 3 ~ o ~ ~ u L
50:50.
AlternatiYe ,o.eferable nonvolatile silicone materials for use in the present invention comprise non-volatile silicone fluids having viscosities of less that about 100,000 cP (centipoise) at 25'C, and from about 0.015% to about 9.0%, preferably from about 0.5% to about 2.0Y., of silicone gums having viscosities greater than about 1,000,000 cP at 25'C, especially polydimethylsiloxane gums and polyphenylmethylsiloxane gums, at ratios of non-volatile fluid to gum of from about 70:.30 to about 30:70, preferably from about 60:40 to about ~:60.
The efficacy of nonvolatile sil kone hair conditioning agents can be enhanced through the use of silicone resin which is miscible with he silicone hair condiLioning agent. Silicone resins arP highly crosslinked polymeric siloxane systPms. The crosslinking is introduced throu~h the incorporation of trifunctional and tetrafunctional silanes with monofunctional or difunctional, or both, monomer units during manufacture of the silicone resin~ As is well understood in the art, the degree of crosslinking that is required in order to result in a silicone resin will vary according to the specific silane units incorporated intû the silicone rosin. In g~oneral, ~ilicone W 0 92/16187 2 ~3~ PCT/US92/00805 - 2~ -mater~als whlch have a sufffic~ent level of trifunctlonal and tetrafunctional siloxane monom~or units ~and h~nce, ~ su~f~clent level of crosslinklng) such that they dry down to a r'igld, or hard, film are considered to b2 S i1 icon~ resin~ ,na ra~o o;
oxygen atoms to silicon atoms is i"dicati~ ~r thP leY~l 07 crosslin~ing in a particular s;7icon~ m~ niii. ~i,icone ~sin~
will generally have at least about 1.1 oxy~en atoms per sillcon atom. Pr~ferably, the ratic o.~ ox,~en: - s~ 4'n ~
least about 1.2:1Ø Typical silanes used in 'he manu~acture of silicone resins are monomethyl-~ime~n/~ m.
methyl phPny7~ onoviilyl-~ qild "~ " l"~, ;"~
tetrachlorosilane. Preferreu r~slil. s^a silicone resins, such as thoSe o,`,~r~ y ~neral ~lec;,tc as SS4230 and SS426J. CommerciallY available siiic~ne rQsins ~111 generally be supplied in an unhardened form in a lo~ viscoSjtv volatile or nonvolatile silicone fluid. The si1icone resins for use herein should be supplied and incorporated into the present compositions in such non-hardened form rather than as a hardened resin, as will be readily apparent to those skilled in the art.
The weight ratio of the nonvolatile sil kone fluid conditioning component to the silicone resin component is preferably from about 4:1 to about 400:1. More preferably such ratio is from about 9:1 to about 200:1, most preferably from about 19:1 to about 100:1, particularly ~hen the silicone fluid component is a polydimethylsiloxane fluid or a mixture of polydimethylsiloxane fluid and polydimethylsiloxane gum, as described above.
Other active hair care materials for use with the vehicle systems of the present invention are silicone polymer materials which provide both style` retention and conditioning benefits to the hair. These include silicone polymers that are rigid silicone polymers. Such materials are described in U~S. Patent 4,902,499, Bolich et al., issued February 20, 1990, incorporated herein by reference.

W O 92/16187 PCT/US92/00805.

Addltlonal catlonlc condltloning ;aterlals may be used ln the present comjposlt~ons. In si?ner.~l, c~t~on~c surfactants useful as hatr cond~tioning agents includei both quaternary ammonlum and amine cat/;in^,; iU`~^f~Ctan~ mai~er~ iuch a material other 5 than thi? ;2C~n~idar`/ ~hiCi;eileir CQmaC~en~ i inc7ud2d in the present compo~ p i o 3bout 2.5%, prefera~l~ at f,om about C.jX to about ~.C~, by weight of th~i c~ si.~
Cation c ;uriac~nts ~.hat. et,n ~Q usad~ eneral, contain lmino ~ h~c~ ~tr~
"lpo~ n o~
the pr~ ?1 `.` :n ' U~. `` i;` n~. .; ~.'.~C `n ` ~..mc~o ~.hose uset`ul herein are i~ ei in ~ 3110`.:iny CvCùmeîltS~ all ,nc~rporated by reterence ~-rei,~ ubiis,lina ~o.. `-!cCutcheon' 5 ~ _ Qeter aents ~ Emulsifi~rs! ~No,th American 'd;~.ion l~9); Schwart~, et al., Surface Activ~ Acents, Their Chemistrv and Technoloqy, New York: Interscience Publishers, 1949; U.S. Patent ~ 5,591, Hilfer, issued November 3, 1964; U.S. Patent 3,929,678, Laughlin, et al., issued December 30, 19~5; U.S. Patent 3,959,461, Bailey, et al., issued May 25, 1976i and U.S. Patent 4,38~,090, Bolich, Jr., issued June ~, 1983.
Specific quaternary ammonium salts include dialkyldimethyl-ammonium chlorides, wherein the alkyl grou?s have from about 12 to about 22 carbon atoms and are deriYed from long-chain fatty acids, such as hydrogenated tallow fatty acid (tallow fatty acids yield quaternary compounds wherein R1 and R2 have predominately from 16 to 18 carbon atoms). Exampl~s of ~uaternary ammonium salts useful in the present invention include ditallowdimethyl ammonium chlo-ride, ditallowdimethyl ammonium methyl sulfate, dihexadecyl dimethyl ammonium chloride, di(hydro~enated tallow) dimethyl ammonium chloride, dioctadecyl dimethyl ammonium chloride, diei-cosyl dimethyl ammonium chloride, didocosyl dimethyl ammonium chloride, di(hydrosenated tallo~) di,ethyl ar,~monium ac~tat~, dihexadecyl dimethyl ammonium chloride, dihexadecy1 dimethyl ammonium acetate, ditallo~.~ diproD~l ammonium phosphate, ditallow W O 92/16187 2 .t Q ~ PCT/US92/00805 dimethyl ammontum nltrate, d~(coconutalkyl) dlmethyl ammon~u~
chloride, and stearyl dimethyl ben2yl a~mon1um chlorl~e. Dlt311 dimethyl ammonium chloride, dicetyl dimethyl amron~um chlorlde, and stearyl dimethyl benzyl ammonium chlo,id~o ~r~ oo,mcnl~ ~s d S quaternary ammonium salts.
Salts of primaryt secondary ana Lar`,a,y ,`a~y .;".".~. ai~
also preferred catlonic surfactant materials for usa here1n. The alkyl groups of such amines preferably hav2 Crom ~,~ou~
22 carbon atoms, and may be slJbstituted or unsubs~itutad. Second-I0 ary and tertiary amines are preferred, t~rtl~ry rl~? p~
ticularly preferr~d. Such amines, US21-Ul ' amido propyl àimethy1 amine, die~hy~ ~U,~ "~
dimethyl stoaramine, dimethyl soyamine, soy~ in~ decy7 amine, ethyl stearylamine, ethoxyîateà ~ oies ................. ~) IS stearylamine, dihydroxyethyl stearylamine, and ~rachidylbehenyl-amine~ Suitable amine sa1ts include the halogen, acetate, phos-phate, nitrate, citrate, lactate and alkyl sulfatP salts~ Such salts include stearylamine hydrochloride, soyamine chloride, stearylamine formate, N-tallowpropane diamine dichloride and stearamidopropyl dimethylamine citrate. Cationic amine surfac-tants included among those useful in the present invention are disclosed in U.S. Patent 4,275,055, Nachtigal, et al., issued June 23, 1981, incorporated by reference here;n.
A particular category of cationic quaternary ammonium sur-factants that can be advantageously incorporated into the presentcompositions in combination with the above-descrlbed essential unsaturated quaternary ammonium surfactants, are water insoluble materials having the formula, in salt form:

~ Rl 1 +

(III) L R3 - N - R~ X a R2 a W O 92/]6187 P ~ /US92/00805 2 ~ ereln X ls ~ salt-formlng an~ion as prevlously descr1bed, is the char~ of the ani^n v" t~;? radlcals ~ , .q~, and ~
independently are Cl-C. al~ 0-C~ al.~yl, or benzyl ~herain one of ;~ld ~ t~ 2~ t l~t.;~ t ~ t~ tC~^~ 0 to three of said radieali ~;^a ^~ re;e~^abl~ C~-03~ more prefera~ t~ ; " ~ i tt~ t ~
The long chain al~byl (1.?. t~ct u,~ C~ al~yl) can be e~ither saturat~td ~r ~..s~'t.~ t may also fall ~ithin the SCOa? ~`t; th ? ~s;en~.Jal unsaturatQd quatern~r~ oni~ t?~ t~

quatern~ "~"~ "~
compositicns ~reo;.
A quaternary air"io,l1u"i sur-lct.n; o,` '~ormluia ~!r OartiCUl.lrly contemplated her2in is: di~ethvl be~Qnvl ben-vl a~monium salt (alternately referred to as behenalkonium salt), available from ~itco Chemical Corp~ (Memphis, Tenn~ssee, USA) as a chloride salt under the trade name KEMAMIHE BQ-2802C. Another particularly contemplated Formula Ill material is dimethyl arachidyl benzyl ammonium salt.
The quaternary ammonium surfactant of Formula III is generally used at a level of from about 0.02% to about lO.OZ., preferably from about 0.05Z to about 3.0X., more prefPrably from about 0.05% to about 2~0X, by weight, or the comp~sition.
Preferred combinations are compositions containing the sùrfactant of Formula III, especially in saturated form, in combination with the surfact2nts of ror,.,ulas I or II, or a mixture thereof, wherein the Formula I isnd Il component comprises C1,-C~
unsaturated alkyls, preferably at a weight ratio of (Formulas I
and II):(Formula III) of a~out 1:1 to about 4:1.
A particularly useful combination of cationic surfactants that can be used comprises a mixture of di(unsaturated) C~6-C18 alkyl (preferably tallo~) dime'.h~l 3mmQniUm salt (e.g. the chloride salt as commercially available from Sherex Chemicals under the tradename AGOGEN ~70)~ and dimethyl (saturated or WO 92/16187 ~ n ~ ~ PCT/US92/00805 unsaturated behen~l and/or arachld~1, preferabl~ saturated) benzyl ammonium salt (e.g. the chloride salt, at a ~elght ratio of about 1:1 at about 4:1, more preferably about 1:1 to about 3:1.
These combinations of cationic surfactants can p, ovtde improved overall performance for hair styling/cond,t~Qning prsd~
ucts, especially for as hair rinse produc.s can;î`Hl`ng `~ s"~ltng conditioning copolymer. Whereas the unsaturated quaternary ammonium surfactant thickener component, ~speciall~ the ~re$e,r?d dimethyl, di(Cl6-Cl~) alkyl-substitut~d surfactants, can ~rovide products w;th excellent rheology, hair condit;on;ng, and s~y7 hold, style hold can bP improved through the us~ o~ `h? '~n5 cna~-~C20-C22 alkyl-substituted materials o, 'or-,u,, ;:; ih~
the excellent rheology and conditioning ~ene,^i.s o,` ~ha ~..;a' rated thic~ener component.
lS Hydrolyzed animal protein hair conditioning agents may also be included in the present compositions. Such materials are present in the compositions at levels of from about O.lX to about 1.5%. An example of a commercially available material is sold under the tradename Crotein Q~ from Croda, Inc.
Fatty alcohols are known hair conditioning agents and may be included in the present compositions. However, as described supra such materials tend to deposit on hair and leaYe hair feeling dirty after use. Hence, it may be described that any fatty alcohol-materials included in the compositions of the present invention be present at leYels no greater than about 1%.
Combinations of the aforementioned conditioning agents may also be used in the present compos`itions.
Hair SettinQ A~ent The compositions of the present invention also can contain an effective amount of a hair setting agent to impart styling bene-fits upon application to hair. The term ~hair setting agent~
means a hair setting polymer and any carrier or diluent, not including the diluent of the vehic.e system described above, that may be used in conjunction with the polymer. As used herein, ~hair styling polymer~ means any polymer, natural or synthet~c, WO 92/16187 ~ 32 - PCI`/US92/00805 that can prov1de halr sett1ng ben~f1ts. Poly~ers of tlhls type ~re well kno~n ln the art. Generally, t3he l~Yel ~f h~lr styl~ng polymer used ~ll be at least about 0.05~, by ~e~ght, of th~
compositlon. T~picall~, lt ~ ?r~s~i~ at a l~vql OT ;. ^~3 about O.l~ to abou~ lv,., p,~ ~?i'~ i O.~ ~OU~ .t ~.v itvOU~

polymers, terpolymers, etc. As usod herein, ~he ~rm ~pol~mer~
shall ~ncomp3ss all of~ .U ~`l `y~ ;' p,~1 }~
conven'3ence in describing the ~ol~mors inqrqo~ monomeric ulnits present in the ool~ s .~ ;. ? ` ? ` ?~ ?`~ i?C~, `?`'`; .^Oil which ~ y ;~
anionic, cationic, aim?no~
~xamples of anionic monum~r ~
(i) unsaturated carDox~iic Icl~ ",onomers SUCil as ~cryiic acid, methacrylic acid, maleic ~cid~ m~leic acid half ester~
itaconic acid, fumaric acid, and crotonic acid;
(ii) half esters of an unsaturated polybasic acid anhydride such as succinic anhydride, phthalic anhydride or the like ~ith a hydroxyl group-containing acrylate and/or methacrylate such as hydroxyethyl acrylate and, hydroxyethyl methacrylate, hydroxy-propyl acrylate and the like;
(iii) monomers having a sulfonic acid group such as styrene-sulfonic acid, sulfoethyl acrylate and methacrylate, and the like;
and (iv) monomers haYing a phosphoric acid group such as acid phosphooxyethyl acrylate and methacrylate, 3-chloro-2-acid phos-phooxypropyl acrylate and methacrylat~, and the like.
Examples of cationic monomers in;1ude:
(i) monomers deri~ed from acrylic acid or methacrylic acid, which is referred to hereinafter collectively as (meth)acrylic acid, and a quaternarized epihalohydrin product of a trialkylamine having 1 to 5 carbon atoms in the alkyl such as (meth)acryl-oxypropyltrimethylammonium ch10ride and (meth)acryloxypropyl-triethylammonium bromide;

w o 92/~6187 2 1~ ~ ~ n O PCT/US92/00805 (li) amlne derlvat1ves of (meth)acryllc acid or amlne derivatlves of (meth)acrylamide dertved from (meth)acryt k acid or (meth)acrylamtde and a dialkylalkanolamine havlng Cl-C, alkyl sroups such as dimethylaminoethyl (meth)acrylate, diethylami,lo-ethyl (meth)acrylate, dimethylaminopropyl (meth)acr~la.e, ordimethylaminopropyl (meth)acrylamide; and tiii) derivatives of the products of the group (it) above by (1) neutralization with an acid such as hydrochlorio acid, or lactic acid, (2) modification with a halogenated alkyl, such as methyl chloride, ethyl chloride, methyl bromide, or ~thyl icdide, (3) modirication with a ha10genated ,a.ty acid ~s.er ;uc~ hJ'l monochloroac~t~t~, or methyl monochloropropionate, ana ~`i modification with a dial~yl sulrate such as dimethyl sulfat~, or diethyl sulfat~.
Further cationic unsaturated monomers include amine deriva-tives of allyl compounds such as diallyldimethylammonium chloride and the like.
The cationic unsaturated monomers can be polymerized in cationic form. As an alternative, they can be polymeri~ed in the form of their nonionic precursors, which are optionally modified to be cationic, for example, by a quaternizing agent (e.g. ethyl monochloroacetate, dimethyl sulfate, etc.).
Examples of the amphoteric monomers include zwitterionized derivatives of the aforementioned amine derivatives of (meth)-acrylic acids or the amine derivatives of (meth)acrylamide such asdimethylaminoethyl (meth)acrylate, dimethylaminopropyl(meth)acryl-amide ~y a halogenated fatty acid salt such as potassium mono-chloroacetate, sodium monobromopropionate, aminomethylproptnol salt of monochloroacetic acid, triethanolamine salts of mono-chloroacetic acid and the like; and amine derivatives of (meth~-acrylic acid or (meth)acrylamide, as discussed above, modified with propanesultone.
These amphoteric monomers, like the aforementioned cationic monomers, can be polymerized in amphoteric form or, as an alterna-3~ tive, they can also be polymerized in the form of their W o 92/]6187 PY~rlUS92/00805 ~ 3~
precursors, ~hich are then optionally converted lnto the amphoteric state.
Preferred 10nic monomers lnclud~ ac.~lic iciJt methacr~licacid, dimethylaminoethyl meLnac;^yl~ u~tar.li ~d i~mq~hyl-aminoethyl methacrylat~ a7~iC `~Cid, `mli ~io anh`;di^iqe hal;esters, crotdnic a--~d, i'ac nlic i~ " ", chloride, polar vinyl heterocyclics slleh ~s Yinyl im~d~l207 ', vinVt pyridino, styreno sulfcnat~, an .~;ur~s ;hcr.o,`. :soe;,al1 preferred ionlc monom~rs include lc ~lic ~.o~d. ~ime~ a-l~no.~y methacryl.lte, quatorni-ed di '~?~hy;''``,'```," `, `~';``C ` ` ``
mixturei 'h ,~of.
Itle ilair je~in-3 ?~ym";`;i .1~ ```` ? ;` i1 0% to lOC~. ionic ~.onom~rs ~ f.o,., ~ o 1~.. ..o",o~,; ",onomers, preferably from about ~ to abo~ .. ioniC :~a.~nmer:; lnd ,`r^~
about 25% to about 98~ nonionic ~o,~ners~ ~ore ~rof?ra~?y f about 5X to about SG~. ionic monomers and from about 5CX to about 95% nonionic monomers.
Representative examples of low polarity nonionic monomers are acrylic or methacrylic acid esters of Cl-C2~ alcohols, such as methanol, ethanol, l-propanol, 2-propanol, l-butanol, 2-methyl-1-propanol, l-pentanol, 2-pentanol, 3-pentanol, 2-methyl-1-butanol, l-methyl-l-butanol, 3-methyl-1-butanol, l-methyl-l pentanol, 2-methyl-1-pentanol, 3-methyl-1-pentanol, t~butanol, cyclohexanol, 2-ethyl-1-butanol, 3-he~tanol, hen2vl alcohol, 2-o.tanol, S
methyl-l-heptanol~ 2-ethyl-1-hexanol, 3,5~dimethyl-1-hexanol, 3,5,5-trimethyl-1-hexanol, l-decanol, I-dodecanol, l-hexadecanol, l-octadecanol, and the lik~, the alc~hols ~aving from about 1-24 carbon atoms ~ith the average number of carboR atoms preferably being from about 4-18, more preferably from about 4-12; styrene;
chlorostyrene; vinyl esters such as vinyl acetate; vinyl chloride;
vinylidene chloride; acrylonitrile; alpha~methylstyrene; t-butyl-styrene; butadiene; cyclohexadiene; ethylene; propylene; vinyl toluene; alkoxyalkyl (meth)acrylate, such as methoxy ~thyl (meth)-acrylate, butoxyethyl (meth)acrylate; and mixtures thereof. Other 3s nonionic monomers include acrylate ~nu methacryl3t2 derivatives O 92/16~87 2 ~ o o PCI`/US92/00805 such as allyl acrylate and ~ethacrylate, cyclohexyl acrylate ndmethacrylate, and methacrylate, oleyl acrylate and methacrylate, benzyl acrylate and methacrylate, tetrahydrofurfuryl acrylate and methacrylate, ethylene glycol di-acrylate and -methacrytate, S 1,3-butyleneglycol di-acrylate and -methacrylate, diacetonacryl-amide, isobornyl (meth)acrylate, and the li~e.
Preferred nonionic monomers include n-butyl methacrylat2, isobutyl methacrylate, 2-ethylhexyl methacrylate, methyl m2.h-acrylate, t-butylacrylate, t-butylmethacrylato, and mi~tures thereof.
Representati~e polar nonionic monomers inc7ude acry1amide, N,N-dimethylacrylamide, methacrylamide, N-t-but~l acrylamide, methacrylonitrile, acrylate, and ~ethacrylate alcohols ~e.g. C2-C6 acrylate and methacrylate alcohols such as hydroxyethy! acrylato.
hydroxyproxyl acrylate, hydroxyethyl methacrylate, and hydroxypropyl methacrylate), vinyl pyrrolidone, vinyl ethers, such as methyl vinyl ether, acyl lactones, vinyl pyridlne, allyl alcohols, vinyl alcohols and vinyt caprolactam.
Examples of anionic hair styling polymers are copolymers of vinyl acetate and crotonic acid, terpolymers of v;nyl acetate, crotonic acid and a vinyl ester of an alpha-branched saturated aliphatic monocarboxylic acid such as vinyl neodecanoate; and copolymers of methyl vinyl ether and maleic anhydride (molar ratio about 1:1) wherein such copolymers are 50X esterified with a saturated aliphatic alcohol containing from 1 to 4 carbon atoms such as ethanol or butanol; and acrylic copolymers and terpolymers containing acrylic acid or methacrylic acid as the anionic radical containing moiety such as copolymers with methacrylic acid, butyl acrylate, ethyl methacrylate, etc. Another example of an acrylic polymer which can be employed in the compositions of the present invention is a polymer of tertiary-butyl acrylamide, acrylic acid, and ethyl acrylate.
An example of an amphoteric polymer which can be used in the present invention is Octylacrylamide/Acrylates/Butylaminoethyl Methacrylate Copolymer, described generally in U.S. Pat. No.

W 0 92/16187 ~ ~ ~ - 36 PCT/US92/00805 ~,l92,a61 as belng a polymer of N-tert-octyl acrylamlde, methyl methacrylate, hydroxypropyl methacrylat~, ac,-yl~c acid ~nd ~-but~' amlnoethyl methacrylate, of appropriate moliecul~r weight for purposes hereof.
Examples of cationic hair stylin~ ?ol~ers aî ~ CJ?oi~,~merS of amino-functional acrylate monomers s ;n ~s ~-c ~ m acrylate or methacrylate monomers such as dimethyl aminoe~h~
methacrylate w;th compatible moncme.s ;~ h a., ~ n~ rj~^~^ol;~
or alkyl methacrylates such as methvl m?thlc,-~?~ta ~uld methacrylate and al~yl acrylates such a.; ma~n,m `;~ .e acrylat~. Citionic poly,ners con'~a,n~ n~
commercialiy aYai1able rrom ~ orp.
Still oth~r organic, hatr styiil,y ?oi;",cr^, ln;;ù~e .a,~o~y-methyl cellulose, copolymers of PY~ and croton~c ~c ;i~ ;o~o7`~?r-of PVA and maleic anhydride, sodium polvstvrene s~ or~e~
ethylmethacrylate/methacrylic acid terpolymer, vinyl aceta~e/cro-tonic acid/viny1 neodecanoaté copolymer, octylacrylamide/acrylat~s copolymer, monoethyl ester of poly(methyl vinyl ether-maleic acid), and octylacrylamide/acrylate/butylaminoethyl methacrylate copolymers. Mixtures of polymers may àlso be used.
Highly preferred active hair care materials for use with the vehicle systems of the present invent~ion are hair holding/styling polymers. Any of the silicone-containing hair sty1ing polymers known in the art for this purpose can ~e used.
In its broadest sense, the silicone-containing polymers useful in the compositions of the present invention lnclude all copolymers of silicone with a non-silicone adhesiYe polymer which:
(a) when dried, the copolymer phase-separates into 3 discontinuous phase which includes the silicone portion and a continuous phase which includes the non-silicone portion; and (b) the silicone portion is co~alently attached to the non-silicone portion. ~he silicone-containing polymers hereof are such that when formulated into the finished hair care compositicn, when dried, the polyme, phase separates into a discontinuous phase which includes the polydimethylsiloxane macromer and a continuous phase which w o 92/16187 2 t ~ 6 ~ PcT/usg2/oo8n5 lncludes the backbone. The phase-separatlng nature of ~he compositlons of the present inventlon may be determined as follows:
The polymer ts cast as a solid film out of a good solvent 5 (i.e., a solvent which dissolves both the backbone and the slll-conP). Ihis film is then sectioned and examined by transmission electron micrography. Microphase separation is demonstrated by the observation of inclusions in the continuous phase. ~hese ;ncluslons should have the proper size to match the size of the si1icone chain (typically a few hundred nm or less) and the proper densi~y ~o mdkh the amount or silicone present. This behavior is well documented in the literature for polymers with this structure tsee, ~or example, S. D. Smith, Ph.D. Thesis, University of Virginia~ 1987, and references cited theréin).
A sec^nd method for determining phase-separating character-istics involves examining the enrichment of the concentration of silicone at the surface of a polymer film relative to the concen-tration in the bulk polymer. Since the silicone prefers the low energy air interface, it preferentially orients on the polymer surface. This produces a surface which is entirely covered by - silicone even when the concentration of the silicone by weight in the whole polymner is low (2% to 20%). This is demonstrated experimentally by ESCA (electron spectroscopy for chemical analy-sis) of the dried film surface. Such an analysis shows a high level of silicone and a greatly reduced level of backbone polymer when the film surface is analy~ed. (Surface here means the first few tens of Angstroms of film thickness.) By varying the angle of the interrogating beam the surface can be analy~ed to varying depths.
~he most preferred silicone-containing polymers comprise a vinyl polymeric backbone, preferably having a Tg or a Tm above about -20'C and, grafted to the backbone, a polydimethylsiloxane macromer having a weight average molecular weight of from about 1,000 to about 50,000, preferably from about 5,000 to about 40~000, most preferably about 10,000 to about 20,000. As used W o 92/16187 PCT/US92/00805 herein, the abbreviat10n ~9~ refers to the 91aS5 trans1t10n temperature of the non-sil~con~ bac~bono, and ~he abbre~JIa~3on ~Tm~ refers to the crystalllne melttng ?oint of the n^n-s~l~^ane backbone, lf such a trans;tion ~xists for a gt~en ~ol~m~,.
H;ghly preferred examples of such mater,~ ,e `h~
cone-containing copolymers as descriDed in ~ne ,oilowiila p~t?nt.
appl kations: Serial Number 07/758~3'9, TO-Oer^`O~l, 9?1'^` 'n~
Garbe, filed August 27, I99fl; and ~eriai ,~umoe~ J~jt3'0, Bolich and Torgerson, filed Augus' ^,~ o~h ~ncorporated by refereflca herein, and M~ ~ rs~e~
Application gO307528.I, Hayama et al. ~P~nb1iclti~qn `'o~ '?
January 16, I99l). Such polymers typicalli ;,~ ;.e,~l~ .u~ e molecular weight Ot at least about lO~000~ generallv '~rom ~llt 75,000 to about 3,000,000, l,ld ~lso pre~a~^a~
least about -20-C~
In addition to the graft copolymers described aboYe, usoful copolymers include block copolymers containing up to about 50%
(preferably from about lOX to about 20%) by weight of one or more polydimethyl siloxane blocks and one or more non-silicone blocks (preferably acrylates or vinyls) Preferred polymers comprise a vinyl polymeric backbone having a Tg or a Tm above about -20'C and, grafted to the backbone, a polydimethylsiloxane macromer having a wei~ht aYerasc molecular weight of from about l,000 to about jO,000, pre;erabiy rrom about 5,000 to about 40,000, most preferably about 20,000.
The silicone-containing polymers utilized as styling/condi-tioning agents generally comprise C monomers together ~ith mono-mers selected from the group consisting of A monomers, B monomers, and mixtures thereof, as described in more detail below. These copolymers contain at least A or B monomers together with C
monomers, and preferred copolymers contain A, B and C monomers.
Examples of useful copolymers and how the~ are made are described in detail in U.S. Patent 4,B93,9~ azurek, issued September 15, I987, and U.S. Patent 4,728,571, Clemens et al., issued March 1, 1988, both of ~hich are incor?orated herein by 2l~n~0 WO 92/~6187 PCI`/US92/00805 reference. These copolymers are comprised of ~onomers A, C and, optionally, B, ~hlch are deftned as follo~s. A, ~hen used, ls at least one free rad kally polymerizable ~onomer or monomers. B, ~.~hen us~d, comprises at least one monomer copolymerizable wlth A
and is s~lect2d from the group consisting of polar (relatlve to A) monom~n~ and nacromers having a Tg or a Tm above about -20-C.
~hen used, ~ may be up to about 98%, preferably up to about 80X, m,or~ pr~;ara~ up to about 2G%, of the total monomers ln the co-polymer. Polar monomers include ionic monomers as ~ell as polar ncnionic mcncmars. Monomer C comprises from about 0.01X to about io ~ o,10l~lP~s 1~ copoly~r.
~e!~r~a~ a~i~Je examples ot A monomers ar~ acrylic or meth-ac~yiic acid ~sters of Cl~C1~ alcohols, such as methanol, ethanol, I-Dropanol. ~-propanol, I-butanol, 2-methyl-1-propanol, l-penta-nol, 2-~entanol, 3-pentanol, 2-methyl-1-butanol, l-methyl-l-butanol, 3-methyl-1-butanol, l-methyl-l-pentanol, 2-methyl-1-pentanol, 3-methyl-1-pentanol, t-butanol, cyclohexanol, 2-ethyl-l-butanol, 3-heptanol, ben2yl alcohol, 2-octanol, 6-methyl-1-heptanol, 2-ethyl-1-hexanol, 3,5-dimethyl-1-hexanol, ~,5,5-tri-methyl-l-hexanOl, l-decanol, l-dodecanol, l-hexadecanol, l-octa-decanol, and the like, the alcohols having from about 1-18 carbon atoms ~ith the aYerage number of carbon atoms being from about 4-12; styrenei vinyl acetate; vinyl chloride; vinylidene chloride, acrylonitriTe; alpha-methylstyrene; t-butylstyrene; butadiene;
cyclohexadiene; ethylene; propylene; vinyl toluene; and mixtures thereof. Preferred A monomers include n-butyl methacrylate, isobutyl m.ethacrylate, 2-ethylhexyl methacrylate, methyl meth-acrylate, t-butytacrylate, t-butylmethacrylate, and mixtures thereof.
Representative examples of B monomers include acrylic acid, methacrylic acid, N,N-dimethylacrylamide, dimethylaminoethyl methacrylate, quaternized dimethylaminoethyl methacrylate, meth-acrylonitrile, polystyrene macromer, methacrylamide, maleic anhydride and its half esters, itaconic acid, acrylamide, acrylate alcohols, hydroxyethyl methacrylate, diallyld;methyl ammonium WO 92/16187 ~ PCr/US92/00805 chloride, vinyl pyrrolldone, vlnyl ethers (such as ~ethyl vinyl ether), malei~ides, acylactones, vinyl pyrid~ne, Y~nyl ~m1daz~
other polar ~inyl heterocycl~cs, styren2 sulfonat~, and ,~ixtur~s thereof. Preferred B monomers lnclude acryl~c acid, .`~ dime;,l,/7-S acrylamide, dimethylaminoethyl methacrylate, quat~rni2ed dim~`nr~i-aminoethyl methacrylate, Yinyl pyrrolidone, and mi~t~re, a.,an o,~`.
Additional suitable A and B monomers are described abo~/e ~n thq discussion of non-silicone-conta~nin~ polym~r;.
The C monomer has the general formula:
X(Y)nSi(R)3-mzn~
wher~in X is a Y.nyl g.oup copol~meri,able ;~i~n ~"a i ~r,~ i monomersi `l i~ a divaient lin~in~ group; R is ~ h~c 3~
alkyl, aryl or alko~y; 2 is a monovalent silo~ana ~olymeric ,~o1e~y ha~ing a number average molecular ~eight of at least about. ~"o ~,A, essentially unreactive under copolymeri~ation conditions a~ is pendant from the vinyl polymeric bac~bone, described above; n is 0 or l; and m is an integer from I to 3. C has a weight average molecular weight of from about l,000 to about 50,000, preferably from about 5,000 to about 40,000, most preferably from about 10,000 to about 20,000. Preferably, -the C monomer has the formula: 1l X-C-0-(CH2)q~(0)p~Si(R~)3-m Zm In those structures, m is 1, 2 or 3 (preferably m - ]); ? 15 0 or 1; R~ is alkyl or hydrogen; q is an integer from 2 to 6; s is an integer from 0 to 2; X i5 CH~C- ;
Rl R2 Rl is hydrogen or -COOH (preferably Rl is hydrogen); R2 is hydro-gen, methyl or -CH2COOH (preferably R2 is methyl); 2 is R4-(-Si--)r;

WO 92/16187 2 ~ O ~ O ~ o PCI`/US92/00805 R' ls alkyl, alkoxy, alkylamtno, aryl, or hydrox~l (preferabl~ R' ~s a1~yl); and r is ~n integer from about 5 to about 700 (prefer-ably r ls about 130 to about 250). Particularly preferred ls when p~0 and q~3.
Th~ ?ref~rred polymers useful in the present invent~on genera71y comprise rrom 0% to about 98X (preferably from about 5%
to abollt. 9~, more ~referably from about 50% to about 90X) of monomer ~, rrom 0~ to about 98X (preferably from about 7.5X to abcut ~.X) of monomer ~, and ,rom about O.IX to about SC% (prefer-~o ~bly ,~lm ~bou~ 0.~ to aboùt IGX, most preferably from about 2X
to abou~ ! Ot monomer C. The combination of the A and B
monoman~ ~re,~e,aoly comprises from about 50.0X to about 99.gX
(more Dreferably about 60~. to about 99X, most preferably from ~bel!t ?~ ~n ~bout 95X) of the polymer. ~he composition of any particular copolymer will help determine its formulational pro-perties. For example, polymers which are soluble in an aqueous formulation preferably have the composition: from OX to about 70%
(preferably from about 5% to about ~0%) monomer A, from about 30%
to about 98% (preferably from about 3% to about 807.) monomer B, and from about 1% to about 40X monomer C. Polymers which are dispersible have the preferred composition: from 0% to about 70%
(more preferably from about 5% to about 70%) monomer A, from about 20% to about 80% (more preferably from about 20% to about 60%) monomer 8, and from about IX to about 40Y. monomer C.
Polymers for use in the present invention include the fol-lowing (the weight percents below refer to the amount of reactants added in the polymerization reaction, not necessarily the amount in the finished polymer):
acrylic acid/n-butylmethacrylate/polydimethylsiloxane (PDMS) macromer-20,000 molecular weight (e.g., 10/70/20 w/w/w) (I) N,N-dimethylacrylamide/isobutyl methacrylate/PDMS macromer -20,000 molecular weight (e.g., 20/60/20 w/w/w) (II) r ~ - ~2 -

6~ dimethylaminoethyl ~ethacrylate/isobut~l ~ethacrylate/2-ethylhexyl-methacrylate/PDMS macromer-20,000 molecular ~eight (e.g., 25/40/15/20 w/w/w/w) (III) dimethylacrylamide/PDS~ macromer-20,0~0 ~olecular ~eig~t (e.g., Q0/20 w/w) (IV) t-butylacry1ate/t-butylmethacrylate/PDMS macromer-lO,~00 mol~cular ~.~eight (q.g., 5~/24/20 ~/w~.~) ('J) t-butylacrylate/PDMS macromer-10,000 mol~cular ~eight ~.9., 30f~u ~

t~butylacryiat~q/H,~I - dimethylacrylamid2~POMS macromer-lO,~G0 molecular weight (e.g., 70/lO/20 ~ ) (YII~
t-butylacrylate/acrylic acid/PDMS macromer-10,000 molecular weight (e.g., 75/5/20 ~/w/w) (VIII).

The particle s ke of the hair setting agent of the present compositions may have some effect on performance in product.
This, of course, will vary from polymer to polymer and from product to product.
The hair setting polymers are preferably provided in a solvent for the polymer, generally prior to combination ~ith the vehicle systems of the present invention.
The solvent selected must be able to dissolve or disperse the particular hair styling polymer being used. Suitable solvents for use in the present invention, in general, ;nclude, but are not limited to, alkyl alcohols (such as linalool and decyl alcohol), hydrocarbons (such as isobutane, hexane, decane, dodecane, and tridecane), hydrocarbon esters (such as C~-C~2 alkanoates, e.g.
methyl decanoate, di (C2-C3) a1kyl adipates, e.g. diisopropyl adipate, C6-C10 alkyl acetates, e.g. octyl acetate, and benzoates, e.g. butyl benzoate,), volatile silicon derivatives, especially siloxanes (such as phenyl pentamethyl disiloxane, phenethyl

7 21~ } O PCI~/US92/00805 - ~3 -pentamethyl dls~loxane, methoxypropyl heptamethyl cyclotetr~-s~lox~ne, chloropropyl pentamethyl dls~loxane, hydroxypropyl pent~methyl disiloxane, octamethyl cyclotetrasiloxane, deca~#thyl cyclopentasilo~an ), eth~rs, such as dl (C~-C,) alkylethers, and i mixtur~s thoreo,. ~r-f~rr~d solvents include volatlle slllcone f1uids, and ,niAtures o, sl7ic3n~ ,luids `~ith ester, ether, and or hydroea,hnn sol~ nts. The choice of solvent ~)ll depend upon the particuia, hair s~t~in9 ~o7ymer ohosen and he ~iluent utilized for `h~? `''hi;~ S'S~, lS described above. In general, it is prere r~ ~h.~ ~nhe nl;;r se~ . ooly~.2r solve,lt be dispersible, but i~-mtsclbie, :titn ~he ve~licie system ài~uent. A7so, the hair set;i"~ .ù,~ e' Soi~J~s is ~re~eraol~ ~olatile and not soluble in water. ~or purposes hereo;, ~volatile~ means a boiling point, at atmcs~ - ^ ?r?SS!', e, ef ~?SS than about 300-C~ preferably from lS abou~ 1ûO'C .~ about 300-C, and ~not soluble in water~ means a water solubility in water at 2S-C of 0.2X or less, preferably about O.lX or less, on a water plus solvent weight basis~
The performance of the styling polymers can be improved through the incorporation of a nonvolatile plasticizer into the styling polymer-solvent solution. The preferred solvents in these systems are volatile silicone fluids in which the styling polymer is soluble or dispersible. The plasticizer will generally be present in the compositions it a plasticizer: styling polymer weight ratio of about 1:20: to about 1:1, preferably from about 1:15 to about 1:2, more preferably from about 1:12 to about 1:2.5.
- As used herein, ~nonvolatile~ in regard to plasticizers means that the pl2sticizer exhibits essentially no vapor pressure at atmos-pheric pressure and 2S'C. ~he polymer-volatile solvent solution should not suffer from substantial plasticizer weight loss ~hile the volatile solvent is evaporating, since this would reduce plasticization of the styling polymer during use. ~he plasti-cizers for use herein should generally have boiling points of about 250'C or higher. Such plasticizers are nonvolatile for purposes hereof.

WO g2/16187 r PCI/VS92/00805 ~he plastlcizer should also be compatlble ~lth the ha1r styl~ng polymer-volatlle solvent solut10n. By ~compatlble~ ~ith respect to the plasticizer and the polymer-volatlle solvent ,olut'on, lt ~s ~Pant that the plasticizer does not adversely int~rac. ~ the hair styling/conditioning copolymer, and must be misc~le h~ d solutl.on. in general, the nonvolatile plastl-cizers for U52 herein will be of relatively low water solubllity.
v SO1IIe;j1~'JI jaarar~eti?r ~f these plasticizers w~ll generally be hotween ~dUt 7 and about lO, preferably bet~een about 8 and about 0 9 (~ .5 ~ (Cll~CC~ , The solubility parameter is defined ~n ~.a ~ ",e,~ ,~a,ldboo`~ d ~d. (Jo~ '1i7ey and ~ons, New York), J ~:^,i`iSi``!.~ !na .h. h~,mergu~, C,~apti?r `JII, pp. 5l9-jj9, as the squlre r~ot o,` the ;ohesi~e energy density and describes the at~racti~o s~,engt~ bet~.Yeen molecules of the material. Solubility ~5 parameters ma~ be determined by direct measurement, correlations - with other physical properties, or indirect calculation as set forth by Immergut.
Plasticizers are well known in the art and are generally described in Kirk-Othmer EncYcloDedia of Chemtcal Technology, second edition, Volume lS, pp. 720-789 IJohn ~iley ~ Sons, Inc.
New York, 1968) under the topic heading ~Plastici2ers~, and by J.
Kern Sears and Joseph R. Darby in the text The TechnolocY of Plastici~eE (John ~iley ~ Sons, Inc., New York, 1982), both incorporated herein ~y referenca. See especially in the Appendix of Sears/Darby Table A.9 at pages 983 1063 where a wide variety of plasticizers are disclosed.
The plasticizers for use herein include both cyclic and acyclic nonvolatile materials. Suitable categories of nonvolatile plasticizers include adipates, phthalates, isophthalates, aze-lates, stearates, citrates, trimellitates, silicone copolyols iso Cl,-C22 alcohols, methyl alkyl silicones, carbonates, sebacates, isobutgrates, oleates, phosphates, myristates, ricinoleates, pelargonates, Yalerates, oleates, camphor, and castor oil, and silicone copolyols.

WO 92/16187 21 G v ~ 6 0 Pcr/us92/oo8os - ~5 -Examples of ad~pate plastlcl2ers lnclude adlplc ac1d derlvat~Yes such as dl~30butyl ad~pate, ~ls(2-ethy1hexyl) adlpate, diisodecyl adipate, bis(2-butoxyethyl) ad~pate, and dl-n^hexyl adipat~.
Exampl;as o,` ~ilthalato plastici7ers include phthallc acid dPrivat.Je. SUC~l as dibu~ ntilaia~ uty7 octyl phthalate, di-n-octyl phthalate, diisooctyl ohthalate, bis(2-ethylhexyl) phthalate, ll~oc',J1 n-~ec;, ~nLhalaLa~ d,-n-haxyl phtha7ate, isooct~l isodec~ h~hallte, diisodec,l ~hthalate, ditridecyl pht,~al~ 7 ;`~ hthalate, buty7 ben.;, ph~nalaLe~ dic;~c.ohi~a~i pi~ ala~e~ diphenyl pntha-late, ;500~C.~ tnZ`,'j ~n~n~ n.~ ~i S it`e`~ ~0,~2thyl) phthal ate.
Iiopht,~ala-e pla3.ici2i~rs include ~is(2-etnylhexyl) iso-phthallte~ ~nd di;sooct.Yl ben2vl l~hthalate.
lS Ev1m~l~s of azelate ~lasticizers inclu~e azPlaic acid deri-vatives such as di(2-ethylhexyl) a2elate, and bis(2-ethylhexyl) azelate.
Examples of stearate plasticizers include stearic acid deri~atives such as n-butyl stearate, butyl acetoxystearate, and butoxyethyl stearate.
Examples of citrate plasticizers include citric acid deriva-tives such as acetyl tri-n-butyl citrate, tri-n-butyl citrate, and acetal tri-2-ethyl hexyl citrate.
~xam?les of trimell~tat~ plastici~ers include tri-(2-ethyl-hexyl) trimellitate, and triisooctyl trimellitate.
Other examples of plasticizers include dibutyl carbonate, butyl oleate, n-butyl, butyrate, isobutyl butyrate, isopropyl butyrate, dtbutyl carbonat2, ethyl ?almitate~ isooctyl palmitate, methyl ricinoleate, butyl ricinoleate, diisooctyl sebacate, triisobutyl phosphate, isodecy pelar50nate, ethyl valerate, isocetyl alcohol, octododecanol, isopropyl myristate, isostearyl alcohol and methyl alkyl silicones having C2-C20 alkyl and from l to about 500 siloxane monomPr units.
Silicone copolyols, described supra, can also be used as plasticizers.

WO 92/16187 PCI`/US92/00805 If ~ plastlcl2~r ls used, the ~olecul~r ~elght, ~elght aYerage, cf ~he styltn9 polymer ls preferably at least about 200,000, more ~referably from about 300,000 to about 800,000, ~ost pre~rlbly frc;~ a~Oi'lt ~00,C00 to about SOO,OOC.
~ er.~d ~at.onic quatPrnary a~monium surfactants for inc!u r ~ `h~ : ;m~o..~ n. heiecf, as a supplemental catlonic condi~ioning ~gent, are mono-long chain, tri-short cha;n ammonium quat~?.i-u~ ,c`an~;. Suitlb1e surfactants of this category are those ha~ing ~h~ rormula, tn salt form:
lù _ ~I`ll , I
. ,~-`3 , wherein X is a salt-forming anion as previously described, a is the charge of ~he anion X, ~1 is a Cl,-C22 alkyl or Cl,-C22 alkyl amido C2-Cs alkylene, preferably Cls-C22, and R2, R3, and R, independently are Cl-C5 alkyl, or benzyl, preferably Cl-C~ or benzyl, more preferably methyl or benzyl, ~herein only one of the short chain radicals is benzyl. The ~ong chain radtcal can be either saturated or unsaturated. ~he Formula IY surfactant utilized preferably is more water-soluble than the quaternary surfactants of Formulas I and II that are present tn the composition.
These cationic surfactants are particular1y useful for improving ~et feel of the compositions in formulations also containing a distr;buting aid. In particular, they are adYantageQusly utili~Pd in ccmpositions containing hair styling agents, or other tac~y matertals, which require a dtstributing aid for adequate distributton of the hair setting agent or other tacky add;tive.
Preferred surfactants of Formula (IV) include Cl,-C22 alkyl (saturated or unsaturated~ dimethyl benzyl ammonium chlorides such as stearyl benzyl dimethyl ammonium chloride, and C~-C22 alkyl (saturated or unsaturated~ trimethyl ammonium chlorides.

W 0 92/16187 2 3 IJ ~ PCTIUS92/00805 - 4~ -Surfactants of For~ul~ (IY) ar~ generall~ used at levels of from about O.O5X to ~bout l.OX by ~eight of the compos1tlon, preferably from about 9.IX to about 0.75X, more preferably from about 0.1~ to about 0.1~ lso, ~referablv, the r~t~o of Formula I plus Ii surfactants ,o ro~"iula I`J su.,^actan,s is from about 1:20 to abou. 2~ o~ "^~ 15~ o~
preferably from about 2:1 to about 10 1.
"neso additional act~ eOSmetl;C ma.er~.a1S are generllly present at a total 1eYe1 Of from about G~X to about 20X, preferably from abollt 0.1, to ~.~ou~ J i~i~h~ o~ ? C~S;~?~.;C COmDOSj-t~on. ~ ?~ "?~ o;~ r compo~l~n~i s;~ Qi`~ l UI~
surfact~nts ~nich are enco~ aiied by oin~ a~ I a,ld ~I, even though sucn surfac~an~s ~ene:~aîi,~ ii; hdYe Caà~,le~iC ~I~l';oacy~ eg.
as hair or s~in conditioners. The 0~. level reflects the situation when one of the vehicle component provides the hair care activity to the present compositions. For example, if the vehicle system comprises a water-insoluble quaternary ammonium compound, this material will provide hair conditioning benefits as well. The level of the active cosmetic care material varies depending upon which active material is chosen, the particular cosmetic composi-tions to be formulated therewith, and the level of benefit desired.
Other optional components that can be added to the cosmetic compositions of the present invention do not provide any direct cosmetic care benefit but instead enhance the composition in some way. Examples of such materia7s are coloring agents, such as any of the FD~C or D~C dyes; oDac.fiers, pearlescsnt aids, such as ethylene glycol distearate or ~i02 coated mica; pH modifiers, such as citric acid, succinic acid, phosphoric acid, sodium hydroxide, and sodium carbonate; perservatives, such as benzyl alcohol, ethyl paraben, propyl paraben, and im;dazolidonyl urea; and antioxi-dants. Such agents generally are used individually at a level of from about 0.00lX to about lO~o, preferably from about 0.01% to about 5%, of the hair care composition.

W o 92/~6187 PCT/US92/00805

8 -~ he ~eh~cl~ systems and cosmetlc composltions of the present lnYent~Zon can be ~ade uslng conYention3l for~ulat~on and mlxin~
techniques. In one ~rocedure for manufacture " slllcone condl-tlon~ qua~na~ .,,mon'u;~ ;ur,^actant, and at least a portton of the som~ oai~lDoil~Zl~ ~re o~ ixeZd ?rior to the addition of the ~'2~ . V~ ;.i`3 i~ yp~Zs O,^ cosmet~c compositions ~re described more spQcifically ln the following ~.Y ~m,~ l ? ~ .
Ihe ,`ollo~.~ing ?xam~les illust.lte the Dresent invQntion. It 1O ~i71 )? ',0~ 0'`1'` ~d .;~lt ~`;``~n ~.~cdi ~ iCations of the present ,",~ posi~ion i;;;~u; ~3~rting trom ~h~

~ a,.i, ,~e~^cen~agei, ana ra~ios nerein are by ~eight unless other~ise soecified.
E~amDle I
The following is a hair styling rinse composition representative of the present invention.
Component ~eiqht %
Stvlinq Aqent Premix Silicone Copolymer 1 2.00 Phenylpentamethyl disiloxane 9.oo Xanthan Premix Xanthan gum 0.25 DR0 H20 25.00 Main MiX
Dioleyl-dimethylammonium ch7Oride (DODMAC) 0.50 EDTA, disodium salt 0.10 D.C. 929 2 2.00 Perfume 0.10 Natrosol Plus CS Grade D-67 ~ 0,7s Locust bean gum 0,75 Kathon CG ' 0,04 DR0 H~0 q.s. to IOOX

WO 92/16~87 2 1 v ~ ~ ~) O PCI`/US92/00805 ~,9 .
20/60/20 N,H-dimethylacrylamide/isobutyl ~ethacrylate/PCMS
macromer (20,000 M~), polymer molecular ~e~ght ~bout 300,000.
2 Amodimethlcone, com~nercially available from Do~ Sorning 3 Hydrophob~cally modif~ad h,~droxoth~lcollules~ ha~1ng 3 Cl~
alkyl substitution of ifrom ~bou~ 0.5C~n ~3 abou~ 0.9~X~ by weight, and a hydrox~q~h~1 ^o ai~ subs` ~u'~n . .~ cu~
to about 3.3, and where the average molecular ~eight of tha hydro~yethyl cellulos~ pri3r to ~;;bsti ~"t`H3~ is a,~ro~ a~,aly 700,000, available from Aqualon Com~an~.
~ preservative commercially aYail~bi? ~ m ~ lild '~l the cu"position is prqr~ ~d ~s P^` n;~
revers~ osmo~is) wa~r is ,irs`~ ,J"~, and D.C. 929 are added to the ~a~el ~nd ni~ er ~bout 5 Ininu~es The Natrosol is aàded to the comDos,-ion ~ ing. Ihe locust Bean Gum is added to the composition ~ith mixin~ The comoosltlon is then homogen ked with a disperser, for example a Gifford-`~ood mill, for about 2 minutes. The batch is then cooled to 38-F. The xanthan gum premix, styling agent premix, perfume and Kathan CG
are added to the composition with mixing for about 10 minutes.
The batch is cooled to ambient temperature and stored.
ExamDle II
The following is à hair styling rinse composition representa-tive of the present invention.
ComDonent ~'eiaht %
Stvlinc Aqent Premix Silicone Copolymer 1 3 00 Phenylpentamethyl disiloxane g oo Hydroxypropylpentamethyl disiloxane 5.00 Silicone Gum Premix Silicone Gum 6.E. SE 76 2 0.50 Decamethyl cyclopentasiloxane 4 00 Main Mix Natrosol Plus CS Grade D-67 3 0.60 Locust bean gum 0 50 EDTA, disodium salt 0.15 q~ 50 PCI`/US92/0080S

AOOGEN 470~ 0.65 Glydant ~ g.~o Perfu~e 0.20 t)RO n~l) q.s. to lOCX
1 10/;~j2i3 ;~c~lic Icid~n-bu~ ?~nac,y~.L~si7icone? macromer, iil~i? :ll`C~ ?; i ~ ?~.: il li' .. 'i~,.`., `. ;~out ;70,~0~, preparod in a manner ilm31ar to xa~ola C-~c of U.S. Patent ~, 7^~ i ?:n ?.`_, ' .. _" ~? ' '~ O ~ olat:ulai~
weigh~ ~ollt 3~J~
lo 2 C~ ?~ ? ~
J llyd~ u,ù,~ -iilC?~Cia7 îy pri~s r~;u~t~ m~r~ia33; a`;3 `3ab~a ,r3m u~yc~, Inc.
~ Part;a;lY ;1~:a.3U~n~t~ `Lal~O`~ dir,eth~l m;!ionillm chloridet con!mer5l~11v ~ bl? î-nm .Sh~rox 9ho~ltc~l Co~tn~ny, ~ublirl, Ohio, USA.
The composition is prepared as follo~s. The DRO water is heated to 71'F. The ADOGEN 470, EDTA, and silicone gum premix are added to the water with mixing for about 5 minutes. The Natrosol is added with mixing. The Locust Bean 6um is added with mixing.
The composition is then homogenized with a disperser, for example a Gifford-~ood mill, for about 2 minutes. The batch is cooled to 38-F and the styling agent premix, thP per,u".e and the Glydant are added with miYin~ for about 10 minutes. The batch is cooled to ambient temperature and stored.
~xam~le lll ThP followi.,g is a hair styling rinsP composition representative of the present inYention.
Component ~eiqht X
Natrosol Plus CS Grade D-671 1.20 Xanthan Gum 0.25 Citric Acid 0 073 Sodium Citrate 0.175 Kathon C6 0.033 ADOG~N 470~ ; 0.75 W O 92/16187 21 D ~ ~ ~ O PCT/US92/0080~

Hydrogenated Tallow Bet~lne 0.~3 Stvlinq A~ent Pre~x T-Butyl Acrylate/PDMS Copolymer (10,000 ~W - 80/20 ~/~) 2.
Phenethyl Pentamethyl Disiloxane l.d7 D~ Cyclomethicone j j~j Sllicone Pr~m~i~
Polydimethyl Siloxane Gu~/
DS Cyclomethicone (15/8S)2 ~ 3 Perfume ; ;
DR0 Wa-er ~s. ;~ i~u;;
Hydrophobically modified hydrox~et,~yl c~imi o,a ;a,ilio e m~m:
Aqualon Corp.
2 G.E. SE~76 gum available from G E. Silicon?~
IS 3 Partially hydrogenated ditallow dimethyl ~m^ni~m chlo,,da, commercially available from Sherex Chemical Company, Dublin, Ohio, USA
The composition ts prepared as follows. The xanthan gum is first slurried in water at 4% xanthan gum, until fully hydrated.
In a separate vessel the copolymer is-mixed into the phenethyl pentamethyl distloxane and D4 cyclomethicone.
The remaining water is preheated to about Jl-C. The ADOGEN
~70, citric acid, sodium citrate, and hydrogenated tallow betatne are added to the water and mixed until melted. This mixture ts then cooled to about 65-C. The Natrosol Plus, silicone gum premix, Kathon and perfume are added and mixed unttl homogeneous.
This mixture is then cooled to about 38'C. The xanthan gum premix and copolymer premix are then added and the mtxture ts agttated until homogeneoUS. The resulting composition is cooled to ambient temperature.
Examp_e IV
The following is a hair conditioning rinse composition which is representative of the present invention.
Component Wt. X
Si!icone Gum Prem~

W O 92/16187 PCTtUS92/00805 Octamethyl Cyclotetraslloxane 3.00 6.E. S 7S ' a.5 M~in Mi~
Natrosol Plui CS Gr~ D-~7 ~ 5 Di rapes~oed a~ îleth,~ l ~.mmOil'i ~,',7 chloride ~ .t.'DM'~O,` ù.75 Stearamide D~A q.10 Kathon CG o,o~
DRO !t~ter ~nd " ~r~n~ 0 ~,v, d;~?.~ "~ bl~ ~r~m Aquai~n 2 Silic~n~ yU~ v~"~ 7~c~ic The com~osit~ ,s ~lr?~lr?~ T~ ~ n~
first heated to 71-C. Th~ nB~D~AC~ .toa ~",md~ B'.~, ,I;.r~sol, and the Silicone gum premix are added with mixing. The composition is then homogenized with a disperser, ~ S . a Gifford-Wood mill, for about 2 minutes. The composition is cooled to 38-C and the Kathon and perfume are added with mixing for about 10 minutes. The batch is cooled to ambient temperature and stored.
Example V
The following is a hair styling conditioner composition which is representative of the present invention.
Component ~t.
Disodium EDTA O 15 Monosodium Phosphate 0.04 Disodium Phosphate o.l~
ADOGEN 470' 0,75 locust Bean Gum 0,70 Natrosol Plus CS Grade D-67 ' ~ ~o Glydant 0 37 Xanthan Gum 0.25 Perfume 0.02 ~ater q.s.to 100%
Silicone Gum Premix WO 92/16187 ~ O PCI'/US92/00805 6. E. S E 76 2 o.5o Octamethyl Cyclotetraslloxane 3.30 Stvlinq Pol~mer Pr ml~
Styling Polymer 3 3 oo Phenyl Pentamethyl Disiloxane 9.0q Hydroxypropyl Pentamethyl Disiloxane 6m)d Hydrophobically modif~ed hydroxyethylcollulcse ~sv~ t~ 'r mm Aqualon 2 Silicone Gum available from Gen~ra7 lec~ric ~ Isobutylmethacrylate/2-ethylhexylm~hac ~ a'a,~3 ! n ~ m? ;"`~
acrylamide copolymer 80/5/15 Partially hydrogenated ditallow dime~yl ,~oni~ln clioride, commercially available from Sherex Chemical Companv Oublin~
Ohio, USA.
The composition is prepared as follows. The ~3 ~ater is heated to 71-C. The ADOGEN 470, disodium EDTA, monosodium phosphate, and disodium phosphate are added and the composition is mixed for about S minutes. The silicone gum premix, locust bean gum, and Natrosol are added with mixing. The composition is then homogenized using a disperser, e.g., a Gifford-~ood Mill, for about 2 minutes. The batch is cooled to 38-F and the Xanthan Gum premix, styling polymer premix, perfume and Glydant are added and mixed for about 10 minutes. The composition is then coolcd to ambient temperature and stored.
Example_~l The following is a styling rinse composition representative of the present invention.
ComDOnent ~t. X
Stvlinq Agent Silicone Copolymer~ 3.00 Octamethyl cyclotetrasiloxane g.oo Prem~
Silicone Gum GE SE762 o.50 Decamethyl cyclopentosiloxane 4.00 Main Mix WO 92/16187 . PCI`/US92/00805 5~
N~trosol Plus CS Grade D-67 ~ 1.25 ADOGEH ~70 ~ ~ . 30 KEMAMINE Q- 1 902C 3 0, .ao Kathon CG ~ I) . i~3 I~idazol e 1, . I j Perfume v DRO H20 g 5 t.n loo~
80/2~ u~a~l~y7.1~":.,ià ~ c.o~ "~ving a mol~cul~r ~.Y~
similar `o ~ ")1? ~ ns issued ,`~arcn 1, 2 Co~merc~ ù`~
3 hydrOpl`'lObiCal7y-1nOdiYied ;ly~irOXyQ~hyl OeliUiOsa commerica71y avai1able from .dcualnn ~
15 ' preser~ative com~erc.~ a~.alla~'~ f.~m, ~s,~m" ~ 'ta;i S Partially hydrogenated ditallow dimethyl a~monium chloride, co~mercially available from Sherex Chemical Company, Dublin, Ohio, USA.
6 Dimethyl dibehenyl/diarachidyl ammonium chloride, commerically available from ~itco Chemical Corporation, ` Memphis, Tennessee, USA.
The composition is prepared as follows. The Styling Agent and Premix are blended separateiy by conYentional means. The Main Mix is prepared by addin~ all ;he ing,edien.; and heating to 3~'C
for 1/2 hour with agitation. As the batch is cooled to about 60-C, the Premix and Styling Agent mixes are added to the Main Mix with agitation and the batch is cooled to amoient temperatur xa",Dle VL~
The following is a hair styling composition which is repre-sentatiYe of the present invention.
Ingredient ~t. X
Premix l:
G. . SE 7~ Gum 1 u.~û
Cab-O-Sil HS-5 2 û.2û
Decamethylcyclopentasilùxane ~.~o WO 92/16187 2 ~ PCI'/US92/00805 - 5~ -Premlx 2:
G. E. SE 76 Gum o.5o Decamethylcyclopentasiloxane 2.80 Natrosol Plus CS Grade D-67 3 1.39 Diricinoleyl dimethyl ammonium methylsulfate (DRDMAMS) O.~o Glydant 1 0.37 Disodium phosphate 0.l2 Monosodium phosphate 0.03 I0 Disodium EDTA 5 0.1~
Fragrance 0.02 DR0 H20 q.s. to lO~
1 Polydimethylsiloxane gum offered by General Electric 2 ,'umed silica offered by the Cabot Corp.
3 Hydrophobically modified hydroxyethyl cellulose available from Aqualon Co~
Preservative offered by Glyco, Inc.
5 Ethylene diamine tetraacetic acid The composition is prepared as follows. The DR0 water is heated to 65-F. The EDTA, phosphates, and DRDMAMS are added to the water with mixing for about I0 minutes. The Natrosol is then added with mixing for about 5 minutes. The silicone gum premixes are then added with mixing. The composit;on is then homogenized with a disperser, for example a Gifford-~ood Mill, for about 2 minutes. The batch is cooled to IOO'F. The 61ydant and perfume are added with mixing for about I0 minutes. The batch is cooled to ambient temperature and stored.
Example VIII
The following is a hair conditioner which is representative of the present invention.
Inqredient Wt. 7O
Premix:
G. E. SE 76 Gum 1 0.10 W O 92/16187 PCT/USg2/0080 6 ~ 6 ~ - 56 -Decameth~lcyclopentasltoxane 0.60 Natrosol Plus CS Grade D-67 2 1.50 Hydrogenated tallowamide DEA 0.?0 Adogen 4703 o.j~
Glydant ' ~ n7 Disodlum EDTA 3 Disodium phosphate Monosodium phosphate ,) ,~^
Fragranc~ o DRO H20 "
Pol yd i methyl s i l oxane gum o f f ered ov ~,~n sr ~ c ~
2 Mydrophobically modi,~i~d h~GrOX~'e~h`/ ~ ,`rom Aqualon 3 Di partically(hydrogenatqd` tl?l~ t 'mm..m offered by Sherex Chemical Co.
PreservatiYe offered by Glyco, Inc.
Ethylene diamine tetraacetic acid The composition is prepared as follows. The DRO water is heated to 65'F. The EDTA, phosphates, DEA, and Adogen are added to the water with mixing for about 10 minutes. The Natrosol is then added with mixing for about 5 minutes. The si1icone gum premix is then added with mixing. The composition is then homo-genized with a disperser, for examp1e a Gifford-~ood Mill, for about 2 minutes. The batch is cooled to 38'F. Th~ Glydant ~nd perfume are added with mixing for about 10 minutes. The batch is cooled to ambient temperature and stored.
Examole TX
The following is a hair styting rinse composition representa-tive of the present invention.
Componen~ Weiqht %
Natroso1 Plus CS Grade D-671 1.15 ADOGEH 4705 0.75 Citric Acid 0.07 Sodium Citrate 0.17 Styling Polymer Premix -WO 92/16187 2 1 ~ ~ ~ o O PCr/US92/00805 - 5~-Styl1ng Polymer2 2.5 Phenyl Ethyl Pentamethyl Disiloxane 1.875 Octamethyl Cyclotetrasiloxane 5.625 Butyl Stearate 0.20 Silicone Gum Premix -Polydimethyl Siloxane Gum3 0.35 ~camethyl Cyclopentasiloxane 1.98 ~atnon CG ~ 033 Perfume 0.2 ~an~han Guml 0 ~5 DRO '.~ater q.s. to 100%
: ,~yc ophobic311y modified hydroxyethyl cellulose available from Aqualon Corp.
2 ~0,~ t-qutylacrylate/PDMS macromer, the macromer haYing a mo1ecula. weight of about 10,000, prepared in a manner similar to Example C-2b of U.S. Patent 4,728,571, Clemens, issued March 1, 1988 3 S.E.-76 gum available from General Electric ' Readily dispersible xanthan gum Partially hydrogenated ditallow dimethyl ammonium chloride, commercially available from Sherex Chemical Company, Dublin, Ohio, USA.
The composition is prepared as follows.
The styling polymer premix is prepared by combining the styling polymer, phenyl ethyl pentamethyl disiloxane, butyl stearate, and the octamethyl cyclotetrasiloxane.
The silicone gum premix is prepared by combining, in a separate vessel and mixing the silicone gum and the decamethyl cyclopenta siloxane until homogeneous.
About one-half of the DRO water is first heated to about 66-C. The citric acid, and sodium citrate are added and mixed until homogeneous. The Natrosol and xanthan gum are added and mixed until homogeneous. The composition is cooled to about 38'C.
The styling polymer premix, Kathon CG and perfume are added. The 3~

w o 92/16l87 ~ PCT/US92/00805 compos1tton ls m1xed and homogenized wtth a homogenlzer such as a Tekmar homogenizer (preferably ~n-l~ne).
The remalning DRO water is heated to about a8 C, '.he ~r~r~H
470 is added and mixed until homogeneous. The mlxture Is then cooled to about 43-C. The silicone gum pr~mix is ~dded 'lnd ~h?
composition homogenized wlth a homogenizer (in-7ine pre~arr~,i).
~ he two premixes are then combined ~nd m~a~l ur "' homogeneous to form the styling rinsP composition.
~xam~
The following is a hair styling rins,~ compos.'~.-.n n ?~r^.-~?n .a tive of the present invention.
Com~onent Natrosol Plus CS Grade D-o7; 1.15 ADOGEN 4705 ~ ~-lS Stearyl Alcohol ~ ~
Cetyl Alcohol o 3 Citric Acid O OJ
Sodium Citrate O l7 Styling Polymer Premix -Styling Polymer2 - 2.5 Decamethyl Cyclopentasiloxane l.875 Octamethyl Cyclotetrasiloxane 5.625 Silicone Gum Premix -Polydimethyl Siloxane Gum3 0.3s Decamethyl Cyclopentaslloxane l.98 Kathon CG O 033 Perfume 0.2 Xanthan Gum' 0.25 DRO ~ater q.s. to 100%
30 l Hydrophobically modified hydroxyethyl cellulose available from Aqualon Corp.
2 80/20 t-Butylacrylate/PDMS macromer, the macromer having a molecular weight of about lO,OOO, prepared in a manner similar to Example C-2b of U.S. Patent 4,728,571, Clemens, issued March l, lg88 WO 92/16187 2 1 ~ 6 ~ ~ O PCI`/US92/00805 S.E.-76 gu~ ava~lable fron 6ener~1 Electrtc Readlly ~spPrslble xanthan gum Parti311y hydrogenated dltallow d;methyl am~onium chlorlde, co~merrially available from Sherex Chemlcal Company, Dublln, Ohio~ USA.
The composi~ion is prepared as follows.
Th? styl,ng polymer prem~x is prepared by combinlng the styling polymer, àecamethyl cyclopentasiloxane, and the octamethyl c ~ c l o ~ r ~
Ihe ~ ale yum premix ls prepared by combining, in a separ~te ~es~l anà mixing the silicone gum and the decamethyl cyclo~eir~ i,lv~an~ until homogeneous About one-half of the DRO water is first heated to about C5'C ~h~ e~ ~ acid, ~nd sodium citrate are ~dded and ~ixed unt i 1 homog-aneous . The Natrosol and xanthan gum are added and mixed until homogeneous. The composition is cooled to about 38-C.
The styling polymer premix, Kathon CG and perfume are added. The composition i5 mixed and homogenized with a homogenizer such as a Tekmar homogeni2er (preferably in-line).
The remaining DRO water is heated to about 88-C, the ADOGEN
470 stearyl alcohol and cetyl alcohol are added and mixed until homogeneous~ The mixture is then cooled to about 43-C. The silicone gum premix ;s added and the composition homogenized with a homogeniLer (in-line preferred).
The two premixes are then combined and mixed until homo-geneous to form the styling rinse composition.
ExamDle ~
The following is a hair styling rinse composition representa-tive of the present inYention.
Componen~ ~eigh~_~
Natrosol Plus CS Grade D-671 1.15 ADOGEN 4705 0.7s Citric Acid 0.07 Sodium Citrate 0.17 3~ Styling Pol,~mer Premix -W O 92/16187 ~ PcT/usg2too80s Styl1ng Polymer~ 2.5 Phenyl Ethyl Pentamethyl Disiloxane 1. Q~
Octamethyl Cyclotetraslloxane 5.5~5 Silicone Gum/Fluld Premix Polydimethyl S~loxane Gum3 0.20 350 centistoke Polydimethyl Siloxane ;luit 0.30 Kathon CG o Perfu~e g Xanthan Gum~ ~.2j DRO Water ~.s. ~ Y, HydropnobicallY modif;ed hydroxyethy1 cellulose ~ail~blo ~r^m Aqualon Corp.
2 80/20 t-8utylacrylate/PDMS macromor, the macromer haYing molecular ~eight of about lO,OQO, oropar~d i~ ^ m~nne; i~ m~
to Example C-2b of U.S. Patent ~,~28,571, Clemens, issued darch 1, 1988 3 S.E.-76 gum available from General Electric Readily dispersible xanthan gum S Partially hydrogenated ditallow dimethyl ammonium chloride, commercially available from Sherex Chemical Company, Dublin, Ohio, USA.
The composition is prepared as follows.
The styling polymer premix is prepared by combining the styling polymer, phenyl ethyl pentamethyl dis;loxane, and the octamethyl cyclotetrasiloxane.
The silicone gum~fluid premix is prepared by combining in a separate Yessel and mixing the silicone gum and silicone fluid until homogeneous.
About one-half of the DRO water is first heated to about 66'C. The citric acid, and sodium citrate are added and mixed until homogeneous. The Natrosol and xanthan gum are added and mixed until homogeneous. The composition is cooled to about 38'C.
The styling polymer premix, Kathon CC and perfume are added. The composition is mixed and homogenized with a homogenizer such as a 3~ Tekmar homogenizer (preferably in-line).

w o 92/16187 2 1 ~ PCT/US92/00805 The remaining DRO water ls heated to bout 88'C, the ADOGEN
~70 ls added and mixed until homogeneous. ~he ~xture ~s then cool~d to about 43-C. The s~licone gum/flu~d prem~x 1s added and ~he co,nposi-ion homogenized with a homogen ker (ln-l~ne preferred).
`The ~wo rrqmixqs -~rq then combined and mixed until homo-geneous to form the styling rinse composltion.
xample ~11 The following is a hair 5tyling rinse composition r~p,asai,`~ h~ present invention.
npo,~
`la~, Oâi), .~l~.s CS Grade D-S7~ 1.15 Hy~rogenated Tallo~ Betalne 0 30 ~ethYl-1-sova amido ethyl-2-soya 0.75 imid~olinium (MSAESI) Citric Acid o 0~
Sodium Citrate 0.17 Styling Polymer Premix -Styling Polymer2 2.5 Octamethyl Cyclotetrasiloxane 5.25 Decamethyl Cyclopentasiloxane 2.25 Silicone Gum Premix -Polydimethyl Siloxane Gum3 0.35 Decamethyl Cyclopentasiloxane 1.98 Kathon CG O 033 Perfume 0.2 Xanthan Gum' 0.25 DRQ ~ater q.s. to 100%
~ Hydrophobically modified hydroxyethyl cellulose available from Aqualon Corp.
2 80!20 t-8utylacrylate/PDMS macromer, the macromer having a molecular weight of about 10,000, prepared in a manner similar to Example 2b of U~S. Patent 4,728,571, Clemens, issued March 1, 1988 3~ 3 S.E.-76 gum aYailable from General Electric w o 92/16187 ~ PCT/US92/00805 Read~ly d~sperslble xanthan gu~
The composition is prepared as follo~s.
The styling polymer premix is prepar~d by comb~ning ~he styling polymer, the octamethyl tetrasiloxane, and the d~camethyl pentasiloxane.
The silicone gum premix is prepared by combining, in separate vessel and mixing the silicono ~um and the deca" 'hy1 cyclopentasiloxane until homogeneous.
About one-hal~ of the DRO ~at~r is ~irs' heat~d ~o abou~
66'C. The hydrogenatod tallo~ b~taine, cit,ic acid, and iOdiU',l citrate are 3dded and mixed until homogeneous. The N2trosol an~
xanthan gum are added and mixed until homogeneoui~ Ih~
composition is cooled to about 38-C. The stylina ~olymer ~remtV
Kathon CS and perfume ~ra addod~ T~e cem~l`ivn ,, m,u - 31.U
homogenized wlth a homogenizer such as a lekmar homogeni2er (preferably in-line).
The remaining DRO water is heated to about 88-C, the MSAESI
is added and mixed until homogeneous. The mixture is then cooled to about 43'C. The si1icone gum premix is added and the composition homogenized with a homogenizer (in-line preferred).
The two premixes are then combined and mixed until homogeneous to form the styling rinse composition.
` Exampl~s XIIT-XVI
The fol70wing are hair styling~conditioning rinse compositions representative of the present invention.
Composi~ion XIII XTy ~Y ~1 Citric Acid 0.02 0.02 0.02 0.02 Sodium Citrate O 09 0.09 0.09 0 09 Cetyl Alcohol 0~12 0~12 0~12 0.12 Stearyl Alcohol 0.08 0.08 0.08 0.08 Natrosol Plus CS Grade D-6~1 1.25 l.qO O.9S 1.10 Xanthan Cum2 0.25 0~25 0.25 0.25 Styling Polymer Premix Styling Polymer3 1.75 1.75 1.75 1.75 Octamethyl Tetrasiloxane 5.98 5.98 5.98 5.98 w o 92~16l87 21 n ~ ~ 6 0 Pcr/us92too8o5 - 63 ^
~ecamethyl Pentasiloxane 2.56 2.56 2.56 2.56 3ut~1 Stqa.at~ ~.15 0.15 0.15 0.15 ~a~.hon CG 0.03 0.03 0.03 0.03 ?erru."e 0.33 0.33 0.33 0.33 Thic~ener Premix ~,~0 ~ac2r 11.67 11.9011.93 11.63 .k~?~ 70~ 0.57 1.33 1.00 1.00 ~emamine~ O~C 0.33 .
~ .. _ ., 7J ~ O 30 ----~ cr~u~: C~)1ori;i.e ~o~ - -- -- 0.60 UI~ .3`t-:'iil i ;~
Decamethyl Pentasiloxane 1.98 !.42 1.42 1.42 ~ l S~ , 3.~i ~.25 ~.2~ 0.25 lj A~odi"e~,licon~ (Dow Corning Q2-8220) -- 0.10 0.10 0.10 DR0 ~ater q.s. q.s. q.s. q.s.

~Hydrophobically modified hydroxyethyl cellulose from Aqualon Corp.
2Readily dispersible xantham gum 380/20 t-Buty1acrylate/PDMS macromer, the macromer having a molecular weight of about 10,000, prepared in a manner similar to Example C-2b of U.S- Patent 4,728,5?1, Clemens, issued March 1, 1988.
'SE-J6 gum available From General Electric sSolution of 75X surfactant and 25X isopropyl alcohol/water for Examples XV and XYI; 100X surfactant for xamples XIII and XI~.
~Tallow trimethyl ammonium chloride (Sherex Chemical Co.J
The styling polymer premix is prepared by combining the styling polymer, the octamethyl tetrasiloxane and decamethyl pentasiloxane, and butyl stearate.
The silicone gum premix is prepared by combining and mixing (in a separate vessel) the silicone gum and decamethyl penta-siloxane until homogeneous.

W o 92/16187 ~ Pcr/US92/oo805 ~Q~ - 6~ -The thlckener premix ls prepared by co~b~ntng and ~ixtng (1n a separa e vessel) DR0 water, and an~ primary and secondary thic~en~,s (promeltPd if n~cessary to ensur~ homogenlty) at 82'C, and the silicone gum premix and the amodimethicone at 71'C, unt~l 5 . homogeneous.
In ~nother vessel, the DR0 water is heated to 71'C. Citrtc acid, sod.um c,trato, c~tyl alcohol, stearyl alcohol and Natrosol Plus CS grade D-~7 are added and mixed until homogeneous. ~e ~anthan ~um is added and mixed until homogeneous. The styling I~ polymer ~remiV~ ~athon CG and perfume are aàded and mixed until homogenonus. Tho composition is further dispersed ~ith an ~n-line homoqa,lizer ~uch as Tekmar homogenizer) and then cooled to 3~'C.
The thickener premix is also further dispersed .~th an in-1ine ~^-oS~ ar and cooled to 3~`C and a~ded ~o the fina7 ij vesse1, mixins until homogeneous to form the styling rinse composition.
The compositions hereof comprise or, alternatively, can consist essentially of or consist of the essential ingredients, as well as the various optional ingredients, described herein.
WHA~ IS CLAIMED IS:

Claims (60)

THE EMBODIMENTS OF THE INVENTION IN WHICH AN EXCLUSIVE
PROPERTY OR PRIVILEGE IS CLAIMED ARE DEFINED AS FOLLOWS:

1. A cosmetic composition useful for application to the hair or skin, comprising:
(a) from about 30% to about 100% of a vehicle system which comprises:
(A) from about 0.1% to about 10.0% by weight of the cosmetic composition of a hydrophobically modified nonionic water-soluble polymer which comprises a water-soluble polymer backbone and hydrophobic groups selected from the group consisting of C9-C22 alkyl, aryl alkyl, alkyl aryl groups and mixtures thereof; wherein the ratio of the hydrophilic portion to the hydrophobic portion of the polymer is from about 10:1 to about 1000:1; and (B) from about 0.02% to about 10.0% by weight of the cosmetic composition of unsaturated quaternary ammonium surfactant component of the formula:

(I) wherein X is a salt-forming anion, a is the ionic charge of X, the quaternary ammonium radicals R1, R2, R3, and R4 independently are C1 - C22 alkyl, C14 - C22 alkyl amido C2 - C6 alkylene, or benzyl, and from two to three of said quaternary ammonium radicals, are C14-C22 alkyl or C14-C22 alkyl amido C2-C6 alkylene or mixtures thereof, no more than two of said radicals being C14-C22 alkyl amido C2-C6 alkylene or a combination of C14-C22 alkyl and C14-C22 alkyl amido C2-C6 alkylene, from one to two of said quaternary ammonium radicals are C1-C6 alkyls, and no more than one of said radicals is benzyl; or (II) wherein X is a salt-forming anion, d is the ionic charge of X, radicals R1, R2, and R3 independently are C1-C22 alkyl or benzyl, and two or three of said radicals are C14-C22 alkyl, or C14-C22 alkyl amido C1-C? alkylene or a mixture thereof, zero or one of said radicals are C1-C3 alkyl, zero or one of said radicals is benzyl, or a mixture of Formula I and II surfactants; wherein said the quaternary ammonium surfactant component has a sufficient level of unsaturation in the C14-C22 alkyl or C14-C22 alkyl amido C2-C6 alkylene radicals, or mixture thereof, such that average iodine value of said component is at least about 15; and (C) from about 65% to about 99% by weight of the cosmetic composition of a compatible solvent; and (b) from 0% to about 20% of an additional cosmetic compo-nent; wherein said cosmetic compositions comprise no more than about 1.0% of water-soluble surfactants.

2. The composition of Claim 1, wherein said radicals of Formula I are selected from the group consisting of C14-C22 alkyl, C1-C6 alkyl, benzyl, and C14-C22 alkyl amido C2-C5 alkylene, and said radicals of Formula II are selected from the group consisting of C14-C22 alkyl, C1-C5 alkyl, benzyl, and C14-C22 alkyl amido C2-C6 alkylene.

3. The composition of Claim 2, wherein the cationic quater-nary ammonium surfactant is selected from the group consisting of compounds of Formula I wherein two of said radicals are C16-C22 alkyl, from one to two of said radicals are C1-C3 alkyl, and zero or one of said radicals is benzyl, and compounds of Formula II wherein two of said radicals are C16-C22 alkyl, and one of said radicals is C1-C3 alkyl or benzyl.

4. The composition of claim 3, wherein said unsaturated quaternary ammonium surfactant component is selected from Formula I and comprises from one to two methyl radicals, zero or one benzyl radical, and two C16-C18 alkyls.

5. The composition of Claim 1, wherein said cationic quaternary ammonium surfactant comprises: salts of dimethyl di(unsaturated) tallow ammonium, dimethyl di(unsaturated) arachidyl ammonium, dioleyl dimethylammonium, di-rapeseed alkyl dimethyl ammonium, diricinoleyl dimethyl ammonium, and disoyadimonium, olealkonium, methyl-1-oleyl amido ethyl-2-oleyl imidazolimium, dierucyl dimethyl ammonium, and methl-1-soya amido ethyl-2-soya imidazolimium.

6. The composition of Claim 1 wherein said hydrophobically modified nonionic water-soluble polymer comprises a nonionic cellulose ether having a sufficient degree of nonionic substitu-tion, selected from the group consisting of methyl, hydroxyethyl, and hydroxypropyl, to cause it to be water soluble and being further substituted with a long chain alkyl radical having 10 to 24 carbon atoms in an amount between about 0.2 weight percent and the amount which renders said cellulose ether less than 0.2% by weight soluble in water.

7. The composition of Claim 6 wherein the vehicle system provides a rheology to the cosmetic composition that is charac-terized by a shear stress of from 0 to about 50 pascal over a shear rate range of from about 0.04 sec-1 to about 25 sec-1.

8. The composition of Claim 7 wherein the nonionic cellulose ether comprises the long-chain alkyl radical attached via an ether linkage.

9. The composition of Claim 8 wherein the nonionic cellulose ether comprises a water-soluble hydroxypropyl cellulose substi-tuted with a long-chain alkyl radical having 10 to 24 carbon atoms in an amount between about 0.2 weight percent and the amount which renders the hydroxypropyl cellulose less than 1% by weight soluble in water.

10. The composition of Claim 9 wherein the hydroxyethyl cellulose prior to substitution with the long chain alkyl group has a molecular weight of about 50,000 to 700,000.

11. The composition of Claim 10 wherein the water soluble hydroxyethyl cellulose is substituted with a long chain alkyl radical having about 16 carbon atoms in an amount between about 0.40% to about 0.95%, by weight; the hydroxyethyl molar substitution is from about 2.3 to about 3.7; and the average molecular weight of the unsubstituted cellulose is from about 300,000 to about 700,000

12. The composition of Claim 3 which comprises from about 0.05% to about 3.0% of said unsaturated quaternary ammonium surfactant component.

13. The composition of Claim 6, wherein said radicals of Formula I are selected from the group consisting of C14-C22 alkyls, C1-C4 alkyls, benzyl, and C14-C22 alkyl amido C2-C6 alkylene, and said radicals of Formula II are selected from the group consisting of C14-C22 alkyls, C1-C6 alkyls, benzyl, and C14-C22 alkyl amido C2-C6 alkylene.

14. The composition of Claim 13, wherein the cationic quaternary ammonium surfactant is selected from the group consisting of compounds of Formula I wherein two of said radicals are C16-C22 alkyls, from one to two of said radicals are C1-C3 alkyls, and zero or one of said radicals is benzyl and compounds of Formula II wherein two of said radicals are C16-C22 alkyls, and one of said radicals is C1-C3 alkyl or benzyl.

15. The composition of Claim 14 wherein said surfactants of Formula I comprises from one to two methyl radicals and zero or one benzyl radical.

16. The composition of Claim 1 wherein the composition comprises no more than about 1% of fatty alcohol materials.

17. The cosmetic composition of Claim 1 which is a hair care composition comprising at least about 0.1% of an additional active cosmetic compositions and wherein said additional active cosmetic component comprises a hair conditioning component selected from the group consisting of a volatile silicone fluid having a viscosity of less than about 10 centipoise at 25°C; a non-volatile silicone fluid having a viscosity of less than about 100,000 centipoise at 25°C; a silicone gum having a viscosity greater than about 1,000,000 centipoise at 25°C; and mixtures thereof.

18. The cosmetic composition of Claim 1 wherein said additional active cosmetic component comprises a hair styling polymer present in said composition at a level of about .1% by weight.

19. A hair care composition according to Claim 1 which further comprises as an active cosmetic component a hair styling/conditioning agent at a level of 0.1% to about 10% of said composition.

20. A hair care composition according to Claim 17 which further comprises as an active cosmetic component a hair styling/conditioning agent at a level of 0.1% to about 10% of said composition.

21. The composition of Claim 19 wherein the hair styling/conditioning agent comprises a copolymer which has vinyl polymeric backbone having grafted to it monovalent siloxane polymeric moieties, said copolymer comprising C monomers and components selected from the group consisting of A monomers, B
monomers, and mixtures thereof, wherein:
A is at least one free radically polymerizable monomer, the amount by weight of A monomer, when used, being up to about 98% by weight of the total weight of all monomers in said copolymer;
B is at least one monomer copolymerizable with A, the amount by weight of B monomer, when used, being up to about 98% of the total weight of all monomers in said copolymer, said B monomer being selected from monomers that are polar relative to A; and C is a polymeric monomer having a molecular weight of from about 1,000 to about 50,000 and the general formula X(Y)nSi(R)3-m(Z)m wherein X is a vinyl group copolymerizable with the A and B monomers Y is a divalent linking group R is a hydrogen, lower alkyl, aryl or alkoxy Z is a monovalent siloxane polymeric moiety having a number average molecular weight of at least about 500, is essen-tially unreactive under copolymerization conditions, and is pendant from said vinyl polymeric backbone after polymeri-zation n is 0 or 1 m is an integer from 1 to 3 wherein C comprises from about 0.01% to about 50% of the copolymer.

22. The composition of Claim 21 wherein the copolymer comprises from about 5% to about 98% A monomer, from about 0.1% to about 50% C monomer, and from 0% to about 98% B monomer.

23. The composition of Claim 19 wherein the active hair treatment component comprises a lipophilic low polarity free radically polymerizable vinyl monomer (A), a hydrophilic polar monomer which is copolymerizable with A (B), and a silicone-containing macromer having a weight average molecular weight of from about 1,000 to about 50,000 based on polydimethylsiloxane of the Formula:

wherein m is 1, 2 or 3; p is 0 or 1; R" is alkyl or hydrogen; q is an integer from 2 to 6; ? is an integer from 0 to 2; X is ;

R1 is hydrogen or -COOH; R2 is hydrogen, methyl or -CH2COOH; Z is ;

R4 is alkyl, alkoxy, alkylamino, aryl, or hydroxyl; and r is an integer from about 5 to about 700.

24. A hair care composition according to Claim 23 wherein monomer A is selected from the group consisting of acrylic acid esters of C1-C18 alcohols, methacrylic acid esters of C1-C18 alcohols, styrene, vinyl acetate, vinyl chloride, vinylidene chloride, acrylonitrile, alpha-methylstyrene, t-butylstyrene, butadiene, cyclohexadiene, ethylene, propylene, vinyl toluene, polystyrene macromer, and mixtures thereof.

25. A hair care composition according to Claim 24 wherein monomer B is selected from the group consisting of acrylic acid, methacrylic acid, N,N-dimethylacrylamide, dimethylaminoethyl methacrylate, quaternized dimethylaminoethyl methacrylate, methacrylonitrile, methacryloamide, maleic anhydride, half esters of maleic anhydride, itaconic acid, acrylamide, acrylate alcohols, hydroxyethyl methacrylate, diallyldimethyl ammonium chloride, vinyl pyrrolidone, vinyl ethers, maleimides, vinyl pyridine, vinyl imidazole, styrene sulfonate, and mixtures thereof.

26. A hair care composition according to Claim 25 wherein monomer A is selected from the group consisting of n-butylmeth-acrylate, isobutylmethacrylate, 2-ethylhexyl methacrylate, t-butylacrylate, t-butylmethacrylate, methylmethacrylate, and mixtures thereof.

27. A hair care composition according to Claim 19, comprising a cationic quaternary ammonium surfactant of the formula:

(III) wherein X is a salt-forming anion, a is the charge of X, the radicals R1, R2, R3, and R4 independently are C1-C5 alkyl, C20-C22 alkyl, or benzyl wherein one of said radicals is C20-C22 alkyl, preferably C22, from two to three of said radicals are C1-C6 alkyl, and zero or one of said radicals is benzyl.

28. A hair care composition as in Claim 27, wherein the weight ratio of the total of the surfactants of Formula I and Formula II to Formula III is from about 1:1 to about 4:1.

29. The composition of Claim 28, wherein said radicals of formula I are selected from the group consisting of C14-C22 alkyls, C1-C6 alkyls, benzyl, and C14-C22 alkyl amido C2-C6 alkylene, and said radicals of Formula II are selected from the group consisting of C14-C22 alkyls, C1-C4 alkyls, benzyl, and C14-C22 alkyl amido C2-C6 alkylene.

30. The composition of Claim 29, wherein the cationic quaternary ammonium surfactant is selected from the group consisting of compounds of Formula I wherein two of said radicals are C16-C22 alkyls, from one to two of said radicals are C1-C3 alkyls, and zero or one of said radicals is benzyl, and compounds of Formula II wherein two of said radicals are C1?-C22 alkyls, and one of said radicals is C1-C3 alkyl or benzyl.

31. The composition of Claim 30, wherein said unsaturated quaternary ammonium surfactant component is selected from Formula I and comprises from one to two methyl radicals, zero or one benzyl radical, and two C16-C18 alkyls.

32. A hair styling and conditioning composition comprising:
(a) from about 80% to about 99.8% of a vehicle system which comprises:
(A) from about 0.1% to about 10.0% by weight of the cosmetic composition of a hydrophobically modified nonionic water-soluble polymer which comprises a water-soluble polymer backbone and hydrophobic groups selected from the group consisting of C?-C22 alkyl, aryl alkyl, alkyl aryl groups and mixtures thereof; wherein the ratio of the hydrophilic portion to the hydrophobic portion of the polymer is from about 10:1 to about 1000:1; and (B) from about 0.02% to about 10.0% by weight of the cosmetic composition of unsaturated quaternary ammonium surfactant component of the formula:

(I) wherein X is a salt-forming anion, a is the ionic charge of X, the quaternary ammonium radicals R1, R2, R3, and R4 independently are C1 - C22 alkyl, C14 - C22 alkyl amido C2 - C6 alkylene, or benzyl, and from two to three of said quaternary ammonium radicals, are C14-C22 alkyl or C14-C22 alkyl amido C2-C6 alkylene or mixtures thereof, no more than two of said radicals being C14-C22 alkyl amido C2-C4 alkylene or a combination of C14-C22 alkyl and C14-C22 alkyl amido C2-C6 alkylene, from one to two of said quaternary ammonium radicals are C1-C6 alkyls, and no more than one of said radicals is benzyl; or (II) wherein X is a salt-forming anion, a is the ionic charge of X, radicals R1, R2, and R3 independently are C1-C22 alkyl or benzyl, and two or three of said radicals are C14-C22 alkyl, or C14-C22 alkyl amido C2-C6 alkylene or a mixture thereof, zero or one of said radicals is benzyl, or a mixture of Formula I and II surfactants; wherein said the quaternary ammonium surfactant component has a sufficient level of unsaturation in the C14-C22 alkyl or C14-C22 alkyl amido C2-C6 alkylene radicals, or mixture thereof, such that average iodine value of said component is at least 15; and (C) from about 65% to about 99% by weight of the cosmetic composition of a compatible diluent; and (b) from 0.1% to about 10%, by weight of the composition, of a hair setting agent;

(c) from about 0.01% to about 5% of a distributing aid; and (d) from about 0.05% to about 1.0%, by weight of the compo-sition, of a mono-long chain, tri-short chain quaternary ammonium surfactant of the formula:

wherein X is a salt forming anion, 3 is the ionic charge of X, the quaternary ammonium radical R1 is C14-C22 alkyl or C14-C22 alkyl amido C2-C6 alkylene and quaternary ammonium radicals R2, R3, and R4 independently are C1-C6 alkyl or benzyl, wherein zero or one of said R2, R1, and R4 radicals is benzyl;
wherein said composition comprises no more than about 1.0% of water-soluble surfactants.

33. A hair styling and conditioning composition, as in Claim Claim 32, wherein for the surfactant of component (d), R1 is C14-C22 alkyl, and R2, R3, and R, independently are benzyl or C1-C3 alkyl.

34. A hair styling and conditioning composition, as in Claim 33, wherein R2, R3, and R4 are methyl or benzyl.

35. A hair styling and conditioning composition, as in Claim 32, wherein said hair setting agent comprises a water-insoluble styling polymer solubilized or dispersed in a water-insoluble solvent.

36. A hair styling and conditioning composition, as in Claim 34, wherein said hair setting agent comprises a water-insoluble styling polymer solubilized or dispersed in a water-insoluble solvent.

37. A hair styling and conditioning composition, as in Claim 35, wherein said hair styling polymer is a silicone-containing polymer.

38. A hair styling and conditioning composition, as in Claim 35, wherein said hair styling polymer is a silicone-containing polymer.

39. A hair styling and conditioning composition, as in Claim 37, wherein said solvent of said hair setting agent is a volatile silicone fluid.

40. A hair styling and conditioning composition, as in Claim 38, wherein said solvent of said hair setting agent is a volatile silicone fluid.

41. A hair styling and conditioning composition, as in Claim 32, wherein said composition comprises from about 0.05% to about 3.0% of the unsaturated surfactant component of formula (I), said surfactant component being a di-long chain alkyl di-short chain ammonium quaternary surfactant wherein each of said long chain alkyls independently is C14-C22 alkyl and each of said short chain independently is C1-C3 alkyl or a mixture of C1-C3 alkyl and benzyl.

42. A hair styling and conditioning composition as in Claim 41, wherein each of said long chain alkyls independently are C16-C22 alkyl and said short chains are methyl or a combination of methyl and benzyl.

43. A hair styling and conditioning composition, as in Claim 33, wherein said composition comprises from about .05% to about 3.0% of the unsaturated surfactant component of formula (I), said surfactant component being a di-long chain alkyl di-short chain ammonium quaternary surfactant wherein each of said long chain alkyls independently is C14-C22 alkyl and each of said short chain independently is C1-C3 alkyl or a combination of C1-C3 alkyl and benzyl.

44. A hair styling and conditioning composition as in Claim 43, wherein each of said long chain alkyls independently are C16-C22 alkyl and said short chains are methyl or a combination of methyl and benzyl.

45. A hair styling and conditioning composition, as in Claim 44, wherein for the surfactant of component (d), R1 is C16-C22 alkyl, and R2, R3, and R, independently are benzyl or C1-C3 alkyl.

46. A hair styling and conditioning composition, as in Claim 45, wherein R2, R3, and R, are methyl or benzyl.

47. A hair styling and conditioning composition, as in Claim 41, wherein said hair styling agent comprises a water-insoluble styling polymer solubilized or dispersed in a water-insoluble solvent.

48. A hair styling and conditioning composition, as in Claim 42, wherein said hair setting agent comprises a water-insoluble styling polymer solubilized or dispersed in a water-insoluble solvent.

49. A hair styling and conditioning composition, as in Claim 43, wherein said hair setting agent comprises a water-insoluble styling polymer solubilized or dispersed in a water-insoluble solvent.

50. A hair styling and conditioning composition, as in Claim 44, wherein said hair setting agent comprises a water-insoluble styling polymer solubilized or dispersed in a water-insoluble solvent.

51. A hair styling and conditioning composition, as in Claim 49, wherein said hair styling polymer is a silicone-containing polymer.

52. A hair styling and conditioning composition, as in Claim 37, wherein said hair styling polymer is a silicone-containing polymer.

53. A hair styling and conditioning composition, as in Claim 51, wherein said solvent of said hair setting agent is a volatile silicone fluid.

54. A hair styling and conditioning composition, as in Claim 52, wherein said solvent of said hair styling agent is a volatile silicone fluid.

55. The composition of Claim 42 wherein said hydrophobi-cally modified nonionic water-soluble polymer comprises a nonionic cellulose ether having a sufficient degree of nonionic substitu-tion, selected from the group consisting of methyl, hydroxyethyl, and hydroxypropyl, to cause it to be water-soluble and being further substituted with a long chain alkyl radical having 10 to 24 carbon atoms in an amount between about 0.2 weight percent and the amount which renders said cellulose ether less than 0.2% by weight soluble in water.

56. The cosmetic composition of Claim 55 which is a hair care composition comprising at least about 0.1% of an additional active cosmetic compositions and wherein said additional active cosmetic component comprises a hair conditioning component selected from the group consisting of a volatile silicone fluid having a viscosity of less than about 10 centipoise at 25°C; a non-volatile silicone fluid having a viscosity of less than about 100,000 centipoise at 25°C; a silicone gum having a viscosity greater than about 1,000,000 centipoise at 25°C; and mixtures thereof.

57. The composition of Claim 54 wherein the hair styling/conditioning agent comprises a copolymer which has a vinyl polymeric backbone having grafted to it monovalent siloxane polymeric moieties, said copolymer comprising C monomers and components selected from the group consisting of A monomers, B
monomers, and mixtures thereof, wherein:
A is at least one free radically polymerizable monomer, the amount by weight of A monomer, when used, being up to about 98% by weight of the total weight of all monomers in said copolymer;
B is at least one monomer copolymerizable with A, the amount by weight of B monomer, when used, being up to about 98% of the total weight of all monomers in said copolymer, said B monomer being selected from monomers that are polar relative to A; and C is a polymeric monomer having a molecular weight of from about 1,000 to about 50,000 and the general formula X(Y)nSi(R)3-m(Z)m wherein X is a vinyl group copolymerizable with the A and B monomers Y is a divalent linking group R is a hydrogen, lower alkyl, aryl or alkoxy Z is a monovalent siloxane polymeric moiety having a number average molecular weight of at least about 500, is essen-tially unreactive under copolymerization conditions, and is pendant from said vinyl polymeric backbone after polymeri-zation n is 0 or 1 m is an integer from 1 to 3 wherein C comprises from about 0.01% to about 50% of the copolymer.

58. The composition of Claim 55 wherein the copolymer comprises from about 5% to about 98% A monomer, from about 0.1% to about 50% C monomer, and from 0% to about 98% B monomer.

59. A hair care composition according to Claim 56 wherein monomer A is selected from the group consisting of n-butylmeth-acrylate, isobutylmethacrylate, 2-ethylhexyl methacrylate, t-butylacrylate, t-butylmethacrylate, methylmethacrylate, and mixtures thereof.

60. A hair care composition according to Claim 57 wherein monomer B is selected from the group consisting of acrylic acid, methacrylic acid, N,N-dimethylacrylamide, dimethylaminoethyl methacrylate, quaternized dimethylaminoethyl methacrylate, meth-acrylonitrile, methacrylamide, maleic anhydride, half esters of maleic anhydride, itaconic acid, acrylamide, acrylate alcohols, hydroxyethyl methacrylate, diallyldimethyl ammonium chloride, vinyl pyrrolidone, vinyl ethers, maleimides, vinyl pyridine, vinyl imidazole, styrene sulfonate, and mixtures thereof.