CA2117264A1 - Hair setting composition with combination of cationic conditioners - Google Patents

Abstract

2117264 9307848 PCTABS00021 Disclosed is a hair setting composition having a thickening system which comprises a nonionic long-chain alkylated water-soluble polymer and a specifid cationic quaternary ammonium surfactant component in a compatible diluent. The quaternary surfactant component has an iodine value of less than 15. The composition additionally contains a hair setting agent, a distributing aid, and a mono-long chain, tri-short chain quaternary ammonium surfactant. The compositions are particularly useful in rinse-off hair conditioning and styling compositions.

Description

CA21 1 726~
WO,~/07848 Pcr/usg2/o8~75 H~IR SE~TING COMPOSITIO~I ~tITH
COMBIHATIOtl OF CATlONIC CONDITIOHERS

~ECHNICAL FIELD
5~he present inventton relates to hatr styl1ng compos1ttons based on non10ntc long ch~1n alkylated water-soluble polymer der1vattves and qu~ternary ~mmon1u~ sur~actants 1n ~ comp~tlble dtluent. A part~cul~rly useful appl1c~t~on of the present 1nven-t10n 1s 1n rtnse-off hatr cond1t10n1ng and styl~ng eompos~t10ns.
BACKGROUNQ Of ~E_lNVE~TION
~ypical r1nse-off h~ir cond1t~on1ng products have a part1cu~
l~r th1ck rhe~logy that 1s des1rable for such products. These products are based on the comb1nation of a surfactant wh1ch ts gener~lly a quaternary a~monium compound and a fatty alcohol.
15Thls combination results 1n a gel-network structure wh1ch provtdes the compostt10n w1th ~ thick rhèology. However wh11e such compostttons tel1ver cond1t10n1ng benef1ts to the hair sueh compos~tions ~1so deposit on ha1r ak1ng hatr look and feel d1rty.
Alternative thickening~systems have been used in ha1r c~re 20compos1tions but none have been found to date wh1eh provide th1s same desirable rheology. ~hough ha1r care products th1ckenet with polymer th~ckeners can be ~ade to have a thtck rheology, these . products generally ~are chan cterlzed by an undesirable ~s11~y~
feel and do not hold their poured~shape.
25Non~on1c water-solub1e~cellulose ethers are employed tn var~ety of appl1cat10ns inc1uding ha1r care compos~tions. ~1dely used commerc~ally-available~ nonionic cellulose ethers ~nclude methyl cellulose hydroxy ~propyl methyl cellulose hydroxyethyl ~cellulose hydroxypropyl icellulose and ethyl hydroxyet~jl ~ ~ 30cel!ulose.
Better tbickening effic1ency 1s real1zet w1th h1gher molec-ular we~ght cellulose ethers. However product10n of such mate-r1~1s ts d1~fficu1t~-nd ~expens1ve. ~hough crossl1nk1ng of these polymers ts ~an~;a1ternat1ve~ means to ach~eve h1gh v1scos~ty solu-35t10ns good crosslink1ag techn1ques are not known. Of course ~WAO23l/Ol 7 2 6 ~ pcr/us92/o847s ~,

- 2 -h1gh concentrat10ns of polymers w111 also prov1de h1gh v1scostty but such ~n 3pproach 1s tneff1c1ent and 1mpract1cal partlcularly due to the h1gh expense 1nvolved. Furthermore use of h1ghly crossl1nked po1ymers or h1gh levels of polymer1c th1ckeners may result 1n a veh1cle system that 1s too elasttc for the present uses.
Alternat1ve water-soluble polymer1c th1ckeners somet1mes used to th~cken ha1r care compos1t10ns are natural polysacchar1tes such as guar gum xanthan gum ~nd locust bean gum.
A number of references teach the use of non~on1c cellu10se ethers and water-solub1e gums for th~cken1ng h~1r care compos1-t10ns. See for example U.S. Patent ~ 557 92B Glover 1ssued December lO 1985 teach1ng a ha1r cond1t10ner compr~sing suspens10n system wh1ch eons1sts of one of glucan gum guar gum and hydroxyethylcellulose; and U.S. Patent ~ 581~230 Groll1er et al. tssued Apr11 8 1986 wh1ch teaches cosmet1c compos1t~ons for treat1ng ha1r wh1ch compr1se as th1cken1ng ~gents hydroxyethyl-cellulose or water-soluble vegetable th1ekening agents such as guar gum. Japanese P~tent Publtcatton ~1-053211 pubt1shed March 7 1986 d1scloses a hatr colorant contain1ng an aromat1c alcohol - xanthan gum and hydroxyethylcellulose.
Certa1n cellulose ethers have been d1sclosed in U.S. Patent 4 228 2~7 Landoll 1ssued October 14 1980 wh1ch are relat1vely low molecular weight but wh1ch are capable of produc~ng highly vtscous aqueous solut10ns 1n practtc~l concentrat10ns. These matertals are nonionic cellulose ethers haYtng a suffictent degree of noniontc substttut10n selected from the group conststing of methyl hydroxyethyl and hydroxypropyl to cause them to be ~ water-soluble anq whltch areifurther subst1tuted w~th a hydrocarbon rad1cal hav~ng from about lO to 24 carbon atoms tn an amount between about 0.2~weight percent and the amount wh1ch renders satd cellu!ose ether less than lX by we1ght soluble tn water. The cellulose ether to be mod1f1ed 1s preferably one of low to med1um , ; molecular we19ht; 1.e. less than about 800 000 and preferably ~ ~ 35 between about 20 000 nd 700 000 ~about 75 to 2500 D~P.).

: : `

CA 2 1 1 72~4 W0"''~07848 PCr/US92/08475 ~hese modifled cellulose ethers have been d~sclosed for use 1n a var1ety of compos1t10n types. Landoll ('277) teaches the use of these mater1als ln shampoo formulat10ns. ~ercules trade 11terature teaches the use of these materials 1n shampoos llqu1d soaps and lottons. U.S. Patent ~ 683 004, Godd~rd, tssuet Jul~
28 1987 d1scloses the use of these mater1als 1n mousse compos1-t10ns for the hair. U.S. Patent ~ 485,089 Le~pold ~ssued November 27 1984 teaches dent1fr~ce composttlons conta1n1ng these matertals.
These mater1als have now been found to prov1de a rheology very much ltke the desirable gel-network structure of typ1cal ha1r condtttoners (wtthout the sl1my feel ~ssoc1ated w1th most poly-meric th1ckeners) when they are combined w1th surf-ctants at certain cr1t1cal levels. Such compos1t10ns are disclosed in U.S.
lS Serial Nos. 07/551 118 07/551 119 and 07/551 120 all filed July 16 l990 by Bol~ch Norton and Russell. Improved systems contain1ng unsaturated ammon~um q~aternary surf~ctants and op-t10nally contain1ng add1t10nal quaternary compounds for 1mproved perceived spreadab~1ity of the compos1t10ns upon app1icat10n b~
the user to the ha1r or skin are d1sclosed 1n ~U.S. Appl~cation Serial No. 07/6~1 576 Coffindaffer et al. and 1ts cont1nuat10n-in-part app1icat10n f~led~on the same date as the present paten~t appl1cat10n Ser1al No. 07~7~6 960 It 1s an ob~ect to prov1de hair styllng/condlt~on1ng compos1-t10ns hav1ng 1mproved wet~halr feel. Such compos1t10ns conta1n hair setting agents wh1ch typ1cally are accompan1ed by distr1but1ng a1d to fac~l1tate spreading o~ the hair setting agent upon appl1cation to hair. The use of d1str~but~ng aids such as xanthan gum unfortunately can negat1vely 1mpact wet hair !feel.
Thus ~t is an object o- this invention to prov1de a hair styltng and cond1ttoning com40sition contain1ng a d1str1but1ng a1d ~or the ;~ hair sett1ng agent ~that has excellent wet hatr feel character1stlcs.~
Th1s and other ob~ects wil1 become readily apparent from the deta11ed descr1pt10n wh1ch follows.
; :

WO g3/07848 PCI'/US92/(~8475 ~iUMMARY OF THE INVENTION
The present 1nvent10n relates to ha1r styl1ng compos1t10ns conta1n1ng veh1c1e systems wh1ch are polymer-based but wh1ch prov~de a rheology to the cosmetlc compos1t10ns wh1ch m1mlcs gel^network systems. These ~eh1cle systems compr1se a two compo-nent th1ckenlng system ~n a comp~tlble d~luent where~n the pr~mary th1ckener component 1s hydrophobtcally ~odlf1ed non10ntc long cha1n ~lkoxylated polymer that 1s soluble 1n the d~luent ~nd the second th1ckener component 1s selected from quaternary ammon-1um surfactants having the formula in salt for~:

R~ - b R~ X-a wherein X is a salt-for~1ng an10n a 1s the ion~c charge of X the quaternary ammon1um radioals Rl R2 R~ and R~ ndependently are Cl - C22 alkyl CI, - C22 alkyl amido C2 - C~ alkylene or benzyl ~nd from two to three of sa~d quaternary ammonium rad1cals preferably two are C~-C22 alkyl or Cl~-C22 alkyl amido C2-C~
~lkylene (prefer-bly C2-C~ alkylene) preferably Cl~-C22 lkyl more preferably Cl~-C~ ~lkgl or m~xtures thereof no more than two of said radlcals are e1ther~C~4-C2t alkyl amido C2-C~ alkylene or a combination of Ct~-C22 alkyl and Cl~ - C22 alkgl amtdo C2-C~
alkylene from one to two of sa1d quaternary ammon1um~rad1cals preferab!y two are Cl-C~ al bl preferably Cl-C~ alkyl more preferably methyl and no more than one of sa~d radicals 1s benzyl; or _ _ +
, ,~N CH2 L~l ~N--LH2 ~

~ where1n X and a~are as def1ned above the rad1cals Rl R2 and R~
:
~ndependently -re Cl-C2~ al bl or benzyl preferably Cl-C22 alkyl and two or three of sa1d rad1cals are Ct,-C22 alkyls preferably ca2 1 1 726~.
WO '`~/07848 PCl/US92/08475 C~-C22 alkyl or Cl~-C22 alkyl amtdo C~-C~ ~lkylene (preferably C2-C~ ~tkylene) or a m1x~ure thereof zero or one of sa1d rad1-cals ~re CI-C~ alkyl preferably Cl-C~ alkyl more preferably methyl zero or one of sa1d radicals ls benzyl; or a mlxture of S Formula I and II surfactants; where1n the quaternary ammoni~
surfactant component of the bove descript10n has a level unsatu-rat10n in the Cl4-C22 alkyl or C~-C~2 ~lkyl a~1do C2-C~ alky1ene rat1cals or mlxtures thereof such that ~verage 10d1ne value of sa1d component ts less than 15.
~he compos1t10ns hereof further comprtse halr sett1ng agent a d1str1buting ald for the h~1r sett1ng agent nd as an essent1al addit10nal quatern~ry ammonium surfactant; a mono-long cha1n tri-short ehain cationic ammonium quaternary surfaetant wherein the long cha1n 1s selected from C~-C22 alkyl or Cl~-C22 }5 alkyl amido C2-C~ alkylene and the short chains independently are select~d from the group consisting of Cl-C~ alkyl and benzyl w1th the number of benzyl radicals per molecule being zero or 1 More specif1c embodiments of these ha1r styling and cond1-tioning compositions comprise:
(a) from about 80X to about 99.5% of a vehicle system comprising (A) from about O lX to about lO.OX by weight of the cosmet~c composltion of a hydrophobically mod1f1ed nonion1c ~ater-soluble polymer ~h1ch compr1ses -water-soluble polymer backbone and h~drophob1c groups selected from the group conslstlng of C~-Ct~
alkyl~ aryl al bl a1kyl aryl groups and mixtures thereof; wherein the ratio of the hydrophil1c portion to the'hydrophob1c portion of the polym'er ~1s from about IO l to about 1000:1; and (B) from about 0 02X to about 10 0% by weight of the cosmetic composition of unsaturated quaternary .
~ ammon1um~surfactant component of the formula:
:~ 3S

CA~l 1 7264 WO 93/07848 P~/US92/llfl475 ~,.,~

Rl +
~I) R3 - N -R~ X'~

wherein X ~ s a salt-form ng anion, a ~s the ~ontc S ch~rge of X, the qlJaternary an~non~um radlcals Rl7 R2 ~ R3, and R4 tndependen~-ly ar~ Cl ~ C2 2 ~1 kyl, Cl~ - C2~ ~lkyl ~m~do C2 - C6 alkylene, or benzyl, ~nd from two to three u~ sa~d quate~nary ammon11lm rad~cals, are C~ C22 alkyl or Cl~e22 alkyl amldo C2-C~ alkylen~ or m~xtures there~f, no more than two of sald r~d~cals be~ng C~-C22 dlkyl am~do C2-C6 alkylene or a comb~nat~on of GIJ-G22 alkyl and C14-C22 alkyl amtdo C2-C~ ~lkylene~ from one to two of sa~d quaterna~ an~nonium r~d~cals are Cl-C~ alkyls, and no more than one o~ sa~d ~ad~cals is benzyl; or (II) r ~--cH2l ~

~ - CH2 ~
Ra R3, a wherein X 1s a s~lt-forming an~on, a ~s the lon1c charge of X~ radicals R~ R2, and R3 ~n~epend~ntly are Cl -C2 2 al kyl or benzyl, and two or three o~
sald rad~cals are C~^C22 alkyl, or Cl~'t22 alkyl a~ido C2 C~ alkylen~ or a m~xture thereof, zero or one of said radicals are Cl-C6 alkyl, zero or one o~ said radicals is benzyl, or a mlxture of Formula I and II surf~ctants; where~n sa~d the quaterrlary an~non~um surfactant component has ~ suf~lcient l~vel of unsaturation ~n the C~4-t 22 alkyl or Cl~-C22 alkyl amldo C2-C6 ~lkylene rad~cals, or m~xture thereof, such that average ~odine value of sa1d component 1s at ls~st lS; and .

W~ r~o784~ Pcr/us92io847s ~ 7 -(C) from about 65% to about 99X by we1ght of the cosmetic compos~tlon of a compat~ble d~luent; and tb) from 0.05X to about 10%, by we~ght o~ the compos~tlon, of a ha~r setting agent;
(c) from about 0~01X to about 5% of a distr1butlng ald; and (d) from about 0.05% to about 1.0%, by we1ght o~ the compo-slt~on, of a mono-long cha~n~ trl-short chaln quaternary ammonlum surfactant of the formula:

¦ R~ l +
(IlI) R3 - N - R~ X a R2 a wherein X is a salt Forming anion, a is the ionic charge of X, the quaternar~ ammonium radlcal Rl is C~-C22 alk~l or C~-C22 a1kyl amido Ct-C6 alkylene, and q~aternary ammonlum radicals R2, R3, and R, independently are Cl-C, alkyl or benzyl, wherein zero or one of~said R2, R~, and R4 radicals is benzyl;
wherein said composition comprises no more than about 1.0% of water-sol~ble surfactants.
The compositions hereo~ compr~se or, alternately, cin cons~st essentially of or conslst of the essential ingredients, as well as the opttonal ingred~ents, descrlbed herein.
DE~AILED DESCRIPTION OF ~HE INVENTIOH
The essential as well as various optional components of the present composltions are~dèscribed below. All !solubllit~es are determined at 25-C, unless otherwise indicated. All percentages and ratios are ~ by weight~ unless otherwise indicated. All percentages are by ~weight of the total compositlon, unless otherwlse lnd~cated.
HYdroDhob~callY Modified Water~oluble Pol~m~
The vehlcle systems of the present invent~on contaln, as an ::

:

w2 131 o7 2 6 4 PCI'/US~2/08475 essent1a1 thlckener component a water soluble polymer. Th1s th1cken1ng ~ater1al 1s a hydrophob1cal1y modif1ed non10n1c water-soluble polymer. By ~hydrophob1cally modif1ed non10n1c water-so1uble polymer~ 1s meant a nonion1c water-soluble polymer wh1ch has been modified by the subst1tution with a suffic1ent amount of hydrophob1c groups to make the polymer less soluble 1n water.
Hence the polymer backbone can be essent~ally an~ water-soluble polymer. ~or the compos1t10ns hereof the unmod1f1ed polymer backbone should be suffic~ently soluble such that forms substant1ally clear 501ut10n when dissolved in water at a level of lX by weight of the solut10n at 25-C. The hydrophob1c groups can be C~ to C22 alkyl aryl alkyl alkyl aryl groups and mixtures thereof. The degree of hydrophobic subst~tution on the polymer backbone should be from about 0.10% to about 1.0% by total we19ht of the polymer preferabl~ from about .4% to about .7%. More generally the ratio of hydroph11~c port10n to h~drophobic port10n of the polymer 1s from about 10:1 to about 1000:1.
A number of ex1st1ng patents disclose non10n1c polymer materials which meet the above requirements and which are useful in the present; invent10n. U.S. Patent 4 496 ~08 Dehm et al.
1ssued January 29 1985 teaches water-soluble polyurethanes having hydrophil1c polyether backbones and pendant monovalent ; hydrophobic groups to result 1n a hydrophil1c/11poph111c balancê
of between about 14~and about l9.5. U.S. Patent 4 426 485 Ho~ et al. 1ssued January l7 l984 d~scloses a water-soluble thermo-plast1c organ1c polymer hav1ng segments of bunched monovalent hydrophob1c groups;. U.S. Patent 4 415 701 Bauer 1ssued November lS 1983 discloses ~copol~mers conta~ning a monoepoxide and a d10xolane. ~ ~ -The most preferred hydrophobically modified water soluble `~ ~ polymer1c thickener mater1~1s for use 1n the present invent10n are dlsclosed 1n U.S. Patent ~ 228 277 Landoll issued October 14 ~- 1980 wh1ch 1s 1ncorporated here1n by reference. The mater1als d1sclosed there1n are th1ckeners compr1s~ng a non10n1c long cha1n alkylated cel~l~ulose ether.

CA2 1 1 -/~6ll W0 ~3/0784~ PCI~/US92/08475 g The cellulose ethers have a suff1clent degree of non1On1c subst1tut1On selected from the group cons1st1ng of methyl hydroxyethgl and hydroxypropyl to cause the~ to be water-soluble.
The cellulose ethers are further subst1tuted w~th a hydrocarbon radtcal having about lO to 2~ carbon atoms 1n ~n amount between about 0~2 we~ght percent ant the amount wh1ch renders s~d cellu-lose ether less than 0.2X preferably less th~n lX by we1ght soluble ln water. ~h~ cellulose ether to be mod1f1ed 1s preferab1y one of low to medium molecular we1ght 1.e. less than about 800 000 and preferably between about 20 000 and 700 000 (about 75 to 2500 D.P.).
The Landoll patent teaches that any non1On1c water-soluble cellulose ether can be employed as the cellulose ether substrate.
~hus e.g. hydroxyethyl cellulose hydroxypropyl cellulose ~ethyl cellulose hydroxypropyl methyl cellulose~ ethyl hydroxy-ethyl cellulose and methyl hydroxyethyl cellulose can all be modif1ed. ~he amount of nonionic subst1tuent such as methyl hydroxyethyl or hydroxypropyl is taught not to be cr1t1cal so long as there 1s an amount suffictent to assure that the ether 1s water-solu~le.
~ he preferred cellulose ether substrate 1s hydroxyethyl cellulose (HEC) of about S0 000 to J00 000 molecular weight.
Hydroxyethyl cellulose of this molecular weight level ~s the mo9st hydroph111c of the mater1als contemplated. It can thus be ~odi-fied to a greater extent than can other ~ater-soluble cellulose ether substrates before 1nsolubility is ach1eved. Accordingly control of the mod1f1cat1On process and control of the propert1es of the modified product can be more precise w1th th1s substrate.
Hydrophilicitg of the most commonly used nonionlc cellulose ethers varies in the general direction: hydroxyethyl ~ hydroxypropyl hydroxypropyl methyl - methyl.
The long~chain aikyl~mod~fier can be attached to the cellu-lose ether substrate~vli~n ether ester or urethane linkage. The ether 11nkage 1`s preferred.
Although the mater1als taught 1n Landoll are referred to as , . ~ .

''~';~',310~ 6 4 PCI~/US92/08475 ','~

be~ng ~long chaln alkyl group mod1f1ed~ 1t w111 be recogn1zed that except ~n the ease where mod~ftcat10n 1s effected wlth ~n alkyl hal1de the ~odifier is not a simple lonq cha1n alkyl group.
The group is actually an alphahydroxyalkyl radical 1n the case of ~n epox1de a urethane rad1cal 1n the case of an isocyanate or an acyl rad1cal 1n the case of an ac1d or acyl chlor1de. Nonethe~
less, the term1nology ~long cha1n alky1 group~ 1s used s1nce the s1ze and effect of the hydrocarbon port~on of the mod1fy~ng molecule completely obscure ny not1ceable effect from the con-nect1ng group. Propert1es are not sign1f1c~nt1y d1fferent from those of the product modtf1ed with the s~mple lQng cha~n alkyl group.
Methods for making these modlfied cellulose ethers are taught~n Landoll ~ 277) at column 2 11nes 36-65.
lS These materials h-ve been found to be part kularly des~rable for use 1n the vehlcle systems of the cosmetic compos1tlons of the present ~nvention. The mater1ats are able to stab111ze suspensions of dispersed phases and when used w1th the add~tional components ~n the veh~cle systems of the present 1nvention they produce rheolog~eally thick produtts which lack the slimy feel character-lst1c of most polymer1c th!ckeners.
One commerc1ally ava11able materlal whlch meets these re-~uirements 1s NATROSOL PLUS Grade 330 a hydrophoblcally modif1ed~
hydroxyethylcellulose avallable from Aqualon ~ompany ~lmington Delaware. Th~s ~ter~al has a C~ alkyl subst~tut~on of from about 0.4% to -bout 0.8% by weight. The hydroxyethyl ~olar subst~tut~on for this materlal ~s from about 3.0 to about 3.7.
~he average ~olecular weight for the water-soluble cellulose pr10r to modlfkation~i~s a~prox~mate}y 300 000. Another matert-l of ; 30 thls type has a C~ alkyl subst~tut~on of from about O.~OX to about 0.95% ~by~weight. ~he hydroxyethyl molar subst1tution for th1s mater~al ls from about 2.3 to about 3.3 and may be as h~gh ~ ~ as about 3.7. ~The average molecular we~ght for the water sol~ble `~ cellulose pr10r to modlf1cat10n 1s approx1mately 700 000.
~ 35 The hydrophoblcally mod1M ed water soluble polymer thlckener :~ :`

c ~o~ PCI`/USg2/08475 component 1s present ln the cosmet~c composlt~ons of the present lnvent10n at from about O IX to about lO.OX preferably from about 0 2X to about 5 0%.
Saturated OuaternarY Ammon~um Surfactant The present veh~cle systems further compr1se as a second essent~a1 component a second thickener wh~ch 1s ~ saturated water-1nsoluble Ct~C2 2 al kyl~subst~tuted quaternary ammon1um surfactant By ~water~1nsoluble surfactant~ 1s msant surfact~nt mater1als wh1ch do not form clear ~sotrop1c solut10ns when d~ssolved ~n water at greater than 0 2 we~ght percent at 25 C. By ~saturated~ as appl1ed to the C~C22 alkyl substttuted quaternary ammon1um surfactant is meant quaternary ammon~um surf-ctants that are suff~ciently saturated such that it has an average ~od~ne value of less than I5 It should be understood that the ~od~ne }5 value is meant to describe the average level of unsaturat~on of the essential C~,-C22 alkyl substituted quaternary ammonium surfactant ~hus ~alkyl- as used here~n can ~nclude unsaturated radicals as well as saturated.
~he essential ~ C22 alkyl-subst~tuted quaternary ammon1um surfactant component hereof constitutes materials of the for~ula in salt form: _ ~ N - R,~ X-~

~ R2 where~n X ls;a sa1t-hnm~ng anion a is the ion~c charge of X the quaternary ammonium r-d~c~ls Rl R2 R~ and R~ 1ndependently are Cl - C22 alkyl Cl~ - C22 alkyl amido C2 - C~ alkylene or benzyl and from two to three of~ sa1d quaternary ammon~um raJ~cals preferably two are C~C22 alkyl or C~-C22 alkyl amido C2-C~
alkylene (preferably~Ct-C~ alkylene) pre~ferably Cl,-C22 alkyl more preferab!y C~-Cl~ alkyl ~or mixtures thereof no more than two of sald rad~e-ls are e~ther C~4-C22 alkyl am~do C2-C6 alkylene or a~ comb1nat~on of t~-022 alkyl and Ca~-Ctt alkyl am1do C2-C~
alkylene from one to two of sa~d quaternary ammon~um rad~cals .

CA2~ 11204 WO g3/1~7~4~ PCI/U592/08~75 preferably two, are Cl-C~ ~lkyls, preferably Cl-C~ alkyl, more preferably methyl, and no more than one of sa1d radicals 1s benzyl; or S ~ c~NeCH2 I t where~n X and a are as def1ned above, the radlcals R~, R2, and R~
1ndependently are Cl~C22 alkyl or benzyl, preferably Cl-C22 lkyl, ~nd two or three of sald radlcals, preferably two, are Cl~-C22 alkyl, preferably Cl,-C22 alkyl, or C1~-C22 alkyl am~do C2-C~
alkylene ~preferably C2-C3 alkylene), or a m1xture thereof, zero or one of sa1d radisals are C1-C~ alkyl, prefer~bly Cl-Cl alkyl, more preferably methyl, zero or one of said radicals ls benzyl, or a m1xture of Formula 3 and lI surfactants; where~n the quaternary ammonium surfactant ~omponent of the above description has an average iodine value of less than 15.
~he an~on X can be any salt-forming anion su1table for use 1n cosmet1c compositions. Su~table an1:ons include~halogens (espe-: c1ally chloride and bromldej, acetate, phosphate, nitrate, sul-fate, and alkyl sulfate. Preferred anions g~nerally are chlor1de, acetate, sulfate, and methyl sulfate.
Speclf~c ~quaternary :am~on~um salts include dialkyld1methyl-ammon~um chlor1des, ~hereln the alkyl groups have from about 1~ to about 22 carbon:atoms:and are derived from long-cha1n fatty ae.1ds, such as hydrogenated tallow fdtty ac~d (taltow fatty ac1ds y~eld quaternary compounds wherein Rl and R2 have predominately from 16 to 18 carbon atoms)~ Exampl:~s of quaternary ammonium salts useful in the present invent1On include dl(hydrogenated) tallowdimethyl : ammon1um chlor1de and/or methyl sulfate, dihexadecyl d1methyl ammon1um chlor~de, d~octadecyl d1methyl ammon~um chlor1de, :~ d1docosyl dlmethyl ammoo1u-~ chlor1de, di(hydrogenated tallow) :: 35 d~methyl ammon~um acetdte, dlhexddecyl d1methyl ammon1um chlor1de, ~: :

~ I I /264 w ~ 93/07848 PCT/USg2/08475 - l3 -d1hexadecyl d1methyl ammon1um acetate d1tallow d1propyl ~mmon1um phosphate dl(hydrogenated) tallow d1methyl ammonlum n1tr~te~ ~nd stearyl dimethyl benzyl ammonium chlor1de.
It w111 be recogn ked by those sk111ed ln the ~rt that various saturated ~uaternary ammon1um surfact~nts when purch~sed commerci~llg will norm-lly also conta1n uns~turated qu~ternary ammon1um surfactants of otherw1se s1m11ar structure. Compos1t1Ons contaln1ng such mater~a1s ~re tncluded w1thln the scope of th1s inventton as long as they conta1n the m1nlm~m level of surfact~nt def1ned here1n hav1ng an 10d1ne val~e of less than 15.
Th~s quaternary am~,-;nium surfactant hereof 1s used ~t a level of from about 0.02% to about 10.0% prefera~ly from about 0.05X to about 3.0% more preferably from about 0.05X to about 2.C% by weight of the compos1tion.
~hereas the water 1nsoluble saturated quaternary ~mmon1um surfactant component hereof is referred to as ~ thickener mater1~1 1t should also be recogn~zed that 1t can also ~ct ~s a cond1tioner for the hair and/or sk1n.
uent A third essent1al component in the veh1cle systems of the present invention is a d1luent which is a solvent for the hydro-phobic~lly mod1fied water-soluble polymer and 1s comp~tible w~th the other components 1n the present compos~tions. Gener~lly the d11uent w111 comprtse w~ter or a~water-lower alkanol (e;g. C2-C, alcohols) mixture; preferably 1t w111 lnclude ~t least ~bout 25%
more preferably at least about 50% even more preferably ~t le~st about 75X by ~total weight of the d~luent of water. Rinse-off compos1t10ns such as ha1r rinses preferably ut11 ke water as the diluent. The ;d1l1uent ;1s Ipresent 1n the composttions of the present invention at a 1evel of from about 65% to about 9g% by weight of the cosmet1c compos1tion.
The other vehicl~e~components are d1spersed or 01xed in the diluent to prov1de~an opt1mum th1ck rheology to cosmetlc compo-s1t10ns formulated therewlth whlch m1m1cs the gel-network rheology ` 3s of typlc~l h~1r;~condlt10nlng compos1t10ns. Th1s rheology 1s ~ :

CA21 1 726~
WO 93/07848 PCI'/US92/1~8475 ,J~

charactertzed by a shear stress of from O to about 50 pascal over a shear rate range of 0.04 sec-l to 25 sec~ he rheology 1s measured us1ng a Bohl1n Rheometer VOR w1th the followtng cone and plate set-up: cone has a 2~5 degree angle plate ~s 30mm 1n d~ameter the gap between the truncated cone and plate 1s set at 70~m and the torque bar used ls 20.148 g-cm. The sample amount ls 0.35ml and the sample 1s syrtnged onto the center of the plate.
~he system us¢d ts as follows: there 1s no tnit1al delay t1me the stra1n delay time 1s 25 sec the tnteyration t1me 1s 5 sec the sens1ttv1ty ts set at lX the shear sweep 1s up the shear range ts from about 0.0405 sec~t to 25.53 sec~ (shear No. ~ 11 to 39)~
and the temperature 1s ma`~ntained constant between ser1es at amb1ent temperature (20-C to 25 C).
Additional ~hickener The present vehicle systems can also comprise an add1tional thtcken1ng component such as water-soluble polymer1c mater1als other than the hydrophoblcally modtfied water soluble polymers descr1bed above. Examples of water-soluble polymers wh1ch may desirably be used as an addtttonal thicken1ng component ~n the present vehicle systems re hydroxyethylcellulose hydroxypropyl cellulose hydroxypropyl methylcellulose polyethylene glycol polyacrylamide polyacryl1c acid polyvinyl alcohol polyvinyl pyrrol1done K-120 dextrans for example Dextran purtfied crude Grade 2P avatlab1e from ~D~ Chemicals carboxymethyl -cellulose plant exudates such as ac-c1a ghatt1 and tragac-nth seaweed extracts such as sod1um alg~nate propylene glycol alg1nate and sod1um carrageen-n and UCARE JR-polymer (a cat10n1c modtf1ed hydroxyethyl~cellulose ava11able from Un10n Carb1de). Preferred as the opt~ona!l add1t10nal !th1ckener for the present vehiele systems are natural polysaccharide mater1als. Examples of such ; matertals are guar gum locust bean gum and xanthan gum. Also preferred as the add1t10nal th1ckener 1n the present compos1t10ns ts hydroxyethyl ;cellulose hav1ng a molecular wetght of about 700 000. It 1s pre~f`erred that these polymer mater1als not conta1n W0.!~3/07848 PCI'/llS9~/08475 cellulase as this ~ay 1nterfere w1th obta1n1ng opt1mum v1scos1t1es.
~ he add1ttonal th~cken1ng component 1f present in the cosmet1c composit10ns of the present invent10n ls pre~erably used at a 1evel of from about ~.3X to about 5.0% preferably from about O.~X to about 3.0X.
Dtstr1butlnq A1d An essent~al component 1n the vehicle systems of the present 1nventton 1s a mater1al wh1ch acts as a dtstr~butlng aid for the 10 ha1r setting a~entSuch a material helps to d1stribute the ha1r setting agent onto the hair and avoid local ked deposition.
~ithout such a component in a compos1tion the hair setting agent would not be deposited and spread out as evenly and hence would not be qu1te as effect1ve or aesthetically pleasing and would be more d1fficult to thoroughly apply to the ha1r.
D1str1buting aid mat?rials useful in the present inventton are ~ctually;a subclass of the class of mater~als that can be used as the opt10nal water-soluble polymer ~dd1t10nal thickener in the present 1nvent~on. Th1s subclass is def1ned as follows: water-soluble polymer mater1als hav1ng h1gb molecular weight 1.e.
greater than l;OOO OOO;;and/or strong 10n1c character. By s~rong ionic character is meant that the material conducts electricity at greater than~30 m1111volts. ~Th1s can be measured by evaluat1ng conductance of a lX solut~on~of polymer in DRO (double reverse os~os1s) water~pr-served with~ 0.03X Kathon CG (methylchloroiso-th1 uol1none~and ~methylisothialolinone a preservative available from Rohm` ~ Naas) using ~a~ cal1brated Corning 130 pH ~eter. The probes used~were as follows: the reference electrode ts an Orion Model 9001 single junction. ~he pH electrode 1s an Orion Model 9161 s11ver-silver chloride. The probes are set 3/8 of an inch apart. The pH~meter is~s-t to milllvolt read1ngs. ~he absolute ` measurement ts recorded after~4 minutes immers10n.
Examples o- w-ter~soluble polymer mater1als ~h1ch meet these requ1rements nd~ h-nce ~can act as d1str1but1ng a1ds ln the present compos~1t10ns 1nclude xanthan gum; Dextran pur1f1ed crude :

~A21 1 7264 W O 93/~7848 P ~ russ2/0847s Grade 2P ~va11able from D~0 chem1cals; carboxymethyl ce11uloses;
for example CMC s ~HlF ~M6F 7HF 7M8Sf 7LF 9H~F 9M8 12M8P
I6M31 tall avallable from Aq~alon); plant exudates such as acac1at ghatti and tragacanth; seaweed extr-cts such as sod1um alg1nate propylene glycol alg1nate and sod1um carrageenan; h1gh molecul~r we1ght hydroxyethrl celluloses such ~s Natrosol 250H ~nd N~trosol 250HHR (-và11able fro~ Aqualon); and pect1n.
8ecause the class of materials wh1ch ma~ ct as dtstribut1ng a1ds in the present 1nvent10n 1s subset of the opt10nal water-soluble addit10nal thickener the matertals 1n th1s subclass may be used to provide both benef1ts to the compos1t10n. for ex~mple xanthan gum is a water-soluble natural pol~s~cchartde m~terial wh1ch add~tionally has a h~gh molecular wetght. Hence th1s mater1al could be used by 1tself to prov1de both additional th1cken1ng benef~ts ~nd d1stributing benefits. However it ~ay be necessary to use~ such materials at slightly higher levels to prov1de both benefits.
It ts also poss1ble to use two sep~rate mater1als as the optional water~soluble polymer add1tion~1 th1ckener and the dtstributtng ~td of the present 1nvention. ~h1s would be done when the water-~soluble polymer additional thickener was not ~ high molecular weight material or of strong ion1c character. Locust bean gum 1s such a material. A d~strtbuting aid such as x~ntha~
gum could be used wtth~locust be~n gum to prov1de the add1tional d1str1but1ng benef1ts.
The distr1b~uttng aid 1s present in the compostt10ns of the present 1nvent10n;at ;a level~ of from about 0.02X to about 5%
prèferably from about 0.05% to about 2.5X of the cosmetic compo-sition more preferably about .OSX to about l.0~. If the distr1-~;~ 30 buting atd 1s btfunctional i.e. acttng as both thé optional addtt10nal th~ckener ~and the distributing a1d 1t should be present at a level of from about 0.2X to about SX of the , compos1t10n.~
The present~vehlcle systems and cosmet1c composlt~ons formu-lated therew1th~ should be substant1ally free of water-soluble ` : ' ::
:~:

C~l 1 /264 W ~23/07848 PCr/USg2/~847~
,", ..

surfactants. These mater1als are not compat1ble ~lth the vehlcle systems of the present compos~t10n. By ~subst~nt1~ free of water-soluble ~urfactants~ 1s meant that the co~pos1t10ns compr1se less than an amount of such surfactants that wlll destroy the present ~n1que destrable rheology that ts the obJect of the preYent 1nvent10n. 6enera11y, this ~111 mean th~t the present compos1t~ons compr~se no more than about lX preferably no more than about 0.5% of such mater1als. Examples of spec1f1c water-soluble surfactant mater1als that can be part1cul~rly hanmful to the present vehtcle systems are ~lkyl sulfates ~nd ethoxylated alkyl sulfates such as mmon1um lauryl sulf~te; amphoter1c surfactants which are dertvat1ves of altphat1c secondary and tertiary amines; nonionic surfactants produced by the condensat10n of alkylene oxide groups w1th an organ1c hydrophtltc compound lS such as laureth-23 (sold under the trademark Bri~ 35 by ICI
Americas); and high alkyl betaines sulfo beta1nes am1do beta1nes and amido sulfobetaines such as cetyl bet~tne.
The present vehicle systems and cosmet1c compos1ttons formu-lated therewith are also preferably substantially free of fàtty alcohol materials such as stearyl- cetyl- myr1styl- behenyl-lauryl- and oléyl alcohol. By ~substantially free of fatty alcohol materials~ ts~meant that the composit10ns of the present invention comprise no more than about lX of these materials.
These matertals are commonly used 1n vehtcle systems--for h~1r condttloner products.~ However~ these mater1als tend to depos1t on the hair and leave the ha1r feeltng dirty after use. ~hese materials are not required 1n the present veh1cle systems as they are th1ckened with alternative materials which do not depostt on hatr.
Mono-~ona ~hain. Tri-Short Chain QuaternarY Ammon~um Surfactant A mono-long~cha1n tr)-short chain ammonium quaternary surfactant 1ngred1ent ts~requtred as~ an essent1~1 tngredient here1n. Su1table surfactants of th1s category are those havlng the formula ;tn salt~form:

: ~:

W o 93/07848 PcT/uss2/0&47 ~III1 R~ - N - R~ X~~

R2 a where~n X 1s a salt-forming an10n as prev~ously describet ~ ls the charge of the ~nion X Rl 1s a Cl~-C~2 alkyl or C~-Ct2 lkyl amido C2-C~ 1kylene preferably C~-C22, and R2 R~ ~nd R~
lndependent1y are Cl-C~ a1kyl or benzyl, preferably C~-C~ or benzyl more preferably methyl or benzyl whereln only one of the short ch~1n radlcals 1s benzyl The long chaln radical can be either satur~ted or unsaturated ~he Formula III surf~ctant utillzed preferably is more water-so1uble than the quaternary surfactants of Formulas I and II that are present in the compos1tion These cat10n1c surfactants are particularly useful for 1mprovlng wet feel of the composit10ns 1n formulations also contaln1ng a d1str1but~ng id In part1cular they are adYantageously util1zed~in composit10ns cont~1ning h~1r sty11ng agents or other tacky materials which require a distr1buting a1d for adequate distribution of the hair sett1ng agent or other tacky addit1ve ~ ~
Preferred surfactants;of Formula (III) include C"-C22 alkyl ~saturated or unsaturated) dimethyl benz~l ammonium chlorides such~
~` as stear~l benz~i d1methyl~ammon~um chlorlde and Cl~-C22 lkyl ~saturated or unsatur-ted) trimethyl ammon1um chlor1des.
Surfactants of Formula (IV) are generally used ~t levels of from about 0.05% to about~ 1.0% by weight of the eompos1t10n ;~ preferably from about 0 1% to about 0 75X more preferably from about O.lX to;about 0;4X Also preferably the ratio of formula ~: 3a I plus II surfactants~to formula IV surfactants 1s from about 1 20 ~` to about 20 1 more~preferably from about l:l to about 15 1 more preferably from about 2 l to about lO l Ra1r Sett1ng Aaent The composii10ns~ of the present 1nvent10n also cont~in an 3s effectlve amount of a ha1r sett~ng agent to 1mpart styl~ng bene-:: :

CA21 1 726~
W 0 ~3/07848 PcT/uss2/08q7s f1ts upon appl1cat10n to ha1r. The term ~ha1r sett1ng agent~
means a ha1r setttng polymer and any carrter or dlluent not 1ncluding the diluent of the veh1cle system descrlbed above that may be used in con~unct10n w1th the polymer. As used here1n ~hair styl1ng polymer~ means any po1ymer, natural or synthet1c that can provlde h-1r sett1ng benef~ts. Polymers of th1s type are well known 1n the rt. 6enerally, the le~el of halr styl1ng polymer used will be at least about 0.05% by wetght of the compos~t~on. Typtcally, 1t wtll be present at a teYe1 of from about 0.1% to abaut 10% preferably from about 0.5% to about 8%.
The halr styltng polymers hereof can be homopolymers CQ-lS polymers terpolymers etc. As used heretn the term ~polymer~
shall enoompass all of such types of polymeric mater1-1s. For conventence tn describlng the polymers hereof monomer1c untts present tn the polymers may be referred to as the monomers from whtch they can be derived. The monomers can be 10ntc (e.g.
antonic catlontc amphotertc zwitteriontc) or nontonlc.
Examples of antontc monomers tnclude:
(1) unsaturated carboxyllc acid monomers such as acryltc ac1d methacryltc actd maletc ~ac~d malelc acld half ester ltacontc actd fumaric ac1d and croton k acld;
(tt) half esters of an unsaturated polybask actd anhydr1de such as succ~nio anhydrlde phthalic anhydr~de or the llke wlth a hydroxyl group-cont-inlng ~acryl-te and/or methacrylate such as hydroxyethyl~ ~crylate and hydroxyethyl methacrylate hydroxy-propyl acrylate and the l1ke;
~11) monomers h-ving a sulfon1c acld group such as styrene-sulfonic acid sulfoethyl~acrylate and methacrylate and the llke;
and (~v) monomers having a phosphoric acid group such as acid phosphooxyethyl~ acrylate nd ~methacrylate 3-chloro-2-acid phos-phooxypropyl ~crylate~and methacrylate and the llke.
- Examples of catlontc monomers lnclude:
(1) monomers~ derlved~from: acryllc acld or methacryl1c ac~d whlch ls referred to herelnafter collectlvely as (meth)acryl~c C ~ ~3~o~86 4 PCI`/US~2/08475 ~, -. 20 -ac1d, and a quaternar1zed ep1halohydr1n product of a tr1alkylam1ne hav1ng I to 5 carbon atoms 1n the ~lkyl such as (meth)acr~l-oxypropyltr1methylammon1um chlor1de and (meth)acryloxypropyl-tr1ethylammonium bromide;
(11) am1ne derivat1ves of (meth)acryl1c ac1d or am1ne der~vat1ves of tmeth)acrylam1de derlved from (meth)acryltc c1d or ~meth)acrylam1de and a d1alkylalkanolamine havlng CI-C~ alkyl groups such as d1methylam1noethyl (meth)acrylate, diethylam1no~
ethyl (meth)acrylate, d1methylam1nopropyl (meth)acrylate, or I0 d1methylaminopropyl (meth)acry1am~de; and (111) der1vat1ves of the products of the group (11) above by (I) neutral1zat10n with an ac1d such as hydrochloric ac1d, or lactic ac1d, ~2) mod1ficat10n w1th a halogenated alkyl, such as methyl chlor1de, ethyl chloride, methyl bromide, or ethyl 10d1de, IS (3) modificat10n with a halogenated fatty ac1d ester such as ethyl m~nochloroacetate, or methyl monochloropropionate, and (~) madlficat10n w1th a d1alkyl sulfate such as d1methyl sulfate, or d1ethyl sulf~te.
Further cationic unsaturated monomers include amine der~va-t1ves of allyl compounds~such as d1allyldimethylammonium chlor1de and the 11ke.
The cat10n1c unsaturated monomers can be polymer1zed 1n cat10n1c form. As an alternat1ve, they can be polymerized in the form of the1r non10n1c precursors, which are opt10nally- mod1f1ed to be c~t10n1c, for example~, by a quatern1z1ng agent (e.g. ethyl monochloroacetate, d1methyl sulfate, etc.).
~xamples of the amphoter1c monomers 1nclude zwitter10n1zed derivat1ves of the aforementioned amine dertvat~ves of tmeth)-acryl1c acids or the amine d!er1vat1ves of ~meth)acrylamide such as dimethylaminoethyl (meth)~crylate, dimeth~laminopropyl(meth)acryl-amide by a halogenated fatty ac1d salt such as potass1um mono-chloroacetate,~ sod1um monobromoprop10nate, am1nomethylpropanol salt of monochloroacet1c ~ac1d, tr1ethanolamine salts of mono-chloroacet1c ac1d and the 11ke; and am1ne derivat1ves of ~meth)-:: ` : : :
acryl1c ac1d or (meth)acrylam1de, as d~scussed above, mod1f1ed ::

C ~ o~4 PCI'/US92/0847s with propanesultone These ~mphoter1c monomers 11ke the aforement10ned cation1c monomers can be polymer1zed 1n amphoteric form or as an alterna-ti~e they can also be polymerized in the form of the~r precursors wh~ch are then opt10nally converted into the amphoter1c state Preferred 10nic monomers 1nclude acrylic ac1d ~eth~cryl1c ~c1d dimethylaminoethyl methacrylate qu~tern1zed d1~ethyl am~noethyl methacrylat~ male1c ac~d male1c anhydr1de h~lf esters crotonic ac1d 1tacon1c ac1d dtallyld1methyl ammon1um chlor1de polar vinyl heterocycl1cs such as v~nyl 1midazole v1nyl pyrid1ne styrene sulfonate ~nd mixtures thereof Espec1ally preferred ionic monomers ~nclude acrylic acid d~methylaminoethyl methacrylate quaternized dimethylaminoethyl methacrylate ~nd mixtures thereof ~ he hair setting polymers hereof will generally oompr1se from OX to IOOX ion~c monomers ~nd from OX to 100% noniontc monomers prefer~bly from about 2X to about 75X ionic monomers and from about 25% to about 98% nonionic monomers more preferably from about 5X to about SOX ionic monomers and from about 50% to aboùt 95% nonionic monomers Represent~tive examples of low polarity nonionlc monomers are acryl1c or meth-cryl1c acid esters of Cl-C~ alcohols such as methanol ethanol l-propanol ~2-propanol l-butanol 2~~ethyl-l-propanol l-pentanol 2-pentanol 3-pentanol 2-methyl-1-but~nol l-methyl-l-butanol 3-methyl-1-butanol l-methyl-l-pentanol 2-methyl-l-pentanol 3-methyl-1-pentanol t-butanol cyclohexanol ;` ~ 2-ethyl-l-butanol 3-heptanol benzyl alcohol 2-octanol 6-methyl-l-heptanol 2-ethyl-l-hexanol 3 5-dtmethyl-1-hexanot

3 5 5-t~imethyl-1-hexanol ~l-decanol i-dodecanol l-hexadecanol l-octadecanol and the like the alcohols hav1ng from about 1-24 carbon atoms with the average number of carbon atoms preferably ` ` being from about 4-18 more~preferably from about 4-12; styrene;
chlorostyrene; v1nyl esters~such as v1nyl acetate; vinyl chlor1de;
v1nylidene chloride; acrylon1trile; alpha-methylstyrene; t-butyl-.~

~ :

WO 93/07848 PCI`/US92/08~7 styrene; butad1ene; cyclohexad1ene; ethylene; propylene; v1nyl toluene; alkoxy~lkyl (meth)acrylate such as methoxy ethyl (meth)-acrylate butoxyethyl (meth)acrylite; and mixtures thereof Other non10n1c monomers 1nclude acrylate and methacrylate der1vat1ves such as allyl acrylate and methacrylate cyclohexyl acrylate and methacrylate and methacrylate, oleyl acrylate and methacrylate benzyl acrylate and methacrylate tetrahydrofurfuryl ~crylate and methacrylate ethylene glycol d1-acryl~te ~nd ~methacrylate 1 3-butyleneglycol d1-acrylate and -methacrylate, d1acetonacryl-amide 1sobornyl (meth)acrylate " nd the 11ke Preferred non10n1c monomers 1nclude n-butyl methacrylate 1sobutyl methacry1ate 2-ethylhexyl methacrylate methyl meth-acrylate t-butylacrylate t-butylmethacrylate and mixtures thereof Representative polar non10nic monomers 1nclude acrylam1de N N-d~methylacrylamide methacrylam1de ~-t-butyl acrylam1de meth~crylon1tr11e acrylate methacrylate alcohols (e g C2-C~
acrylate nd methacrylate alcohols such as hydroxyethyl acrylate hytroxyproxyl acrylate hydroxyethyl methacrylate and hydroxypropyl methacrylate) v1nyl~ pyrrol1done vinyl ethers such as methyl v1nyl ether acyl lactones v~nyl pyrid1ne allyl alcohols vinyl alcohols and v1nyl caprolactam Examp ks of anionic hair styl1ng polymers are copolymers of v1nyl acetate~and croton1c ac1d terpolymers of v1nyl- acetate crotonic acid and a v1nyl~ester of an alpha-branched saturated al1phat1c monocarboxyl1c ac1d~ such as vtnyl neodecanoate; and copol~mers of ethyl v1nyl eth-r and maletc anhydr1de (molar rat10 about 1:1) where1n such copolymers are 50% ester1f1ed w1th a saturated alipha~ttc~allcohol containing from 1 to 4 carbon ato~s such as ethanol or butanol; and acryl1c copolymers and terpolymers conta1n1ng acryl1c actd or methacryl k ac1d as the an10n1c rad1cal conta1n1ng molety~such~as copolymers w1th ~ethacryl1c ac1d butyl acryl~te ethyl methacryiate etc Another example of an acryl1c polymer wh~ch can be employed 1n the compos1t10ns of the present 1nvent10n 1s a polymer of tert1-ry-butyl acrylam1de acryl1c ac1d C~21 1 7264 WC~3/07848 PCI/US92/0~47~
j: , and ethyl acry1ate.
An ex~mple of an amphoterlc polymer whtch can be used ln the present lnventlon ls Octylacrylamtde/Acr~lates/Butylaminoethyl Methacrylate Copo1ymer descr~bed generally tn U.S. P-t. No.

4 192 861 as belng a polymer of N-tert~octyl acrylamlde ~ethyl methacrylate, hydroxypropyl methacrylate, cryl1c actd and t-butyl am1noethyl ~ethacrylate of approprtate molecular we1ght for purposes hereof.
Examples of cat~on~c ha1r styltng poly~ers are copolymers of am1no-functional acrylate monomers such as lower alkylamlno alkyl acrylate or meth-crylate monomers such as dlmethyl amlnoethyt-methacrylate ~lth compattble monomers such as N-vinylpyrrol~done or alkyl methacrylates such as methyl methacrylate and ethyl methacrylate nd alkyl acrylates such as methyl acrylate and butyl acrylate. Cationic polymers containing N-vtnylpyrrolidone are commerciallg ava11able from GAF Corp.
St111 other organ1c halr styllng polymers 1nclude carboxy-methyl cellulose copolymers of PVA and crotontc acld copolymers of PVA and male1c anhydrlde sod1um polystyrene sulfonate PVPt ethylmethacrylate/methacryltc ac1d terpolymer vlnyl acetate/cro-tonic acld/v~inyl neodecanoate copolymer octylacrylamtde/acrylates copolymer monoethyl ester of poly~methyl v1nyl ether-malele acid) and octylacrylamide/a~rylate/butylaminoethyl methacrylate copol~mers. ~ixtures of~polymers ~ay also be used. - -Hlghly preferred actlve hatr c~re materlals for use with the vehtcle systems of ~he present lnventlon are hair holdlng/styltng polymers. Any of the ~stllcone-contalning hair styltng polymers known ~n the ~rt for thts purpose can be used.
In its bro-dest sense the s11icone-containing polymers useful ~n the compositlons of the present invention lnclude all copolymers of silicone wtth a non-sil~cone ~dhesive polymer which:
~) when dried~ the copoiymer phase-separates 1nto a dlscont~nuous phase whtch includes the s~ltcone portlon and a contlnuous phase wh1ch lncl~tes tbe non-stllcone portlon; and (b) the slllcone 3S portlon ts cov-lently attached to the non-s11tcone portlon. The C ~ ~3~o~8~6 4 PCI /USg2/~8475 r~l s11icone-conta1n1ng polymers hereof are such that when formulated tnto the f~n1shed hair care compostt10n when dr1ed the polymer phase separates ~nto a dtscont1nuous phase wh1ch tncludes the polydimethyls110xane macromer and a cont1nuous phase wh1ch includes the backbone. The phase-separattng nature of the compostt10ns of the present ~nventton may be determ1ned as follows:
The polymer 1s cast as ~ sol1d f11m out of a good solvent (1.e. ~ solvent wh1ch dtssolves both the backbone and the s111-cone). th1s f11m ~s then sectioned and examined by transmisstonelectron m1crography. M1crophase separat10n 1s demonstr~ted by the observatton of tnclustons 1n the cont1nuous phase. These tnclus10ns should have the proper size to match the size of the stl1cone chatn (typtcally a few hundred nm or less) and the proper denstty to ~atch the amount of s11icone present. This behavior ts well documented tn the llterature for polymers w~th th1s structure (see for example S. D. Sm1th PhØ Thests Unlversity of Vtrgtnia 1987 and references ctted therein).
A second method for determtning phase-sep~rattng character~
tstics tnvolves exami:ning the enrtchment of the concentration of ~; s11icone at the surface of a polymer f11m rel~t1v`e to the concen-tration in -the bulk po1ymer. S1nce the silicone prefers the low energy a1r 1nterface 1t preferentially orients on the polymer surface. Tht~s~ produces ~ surface which is ent~rely covered by stl1cone even when the concentratton of the stl1cone by wetght tn the whole ~polymner is~ low ~(2% to 20%). Th1s ~s demonstrated exper1mentalty~by ESCA (electron spectroscopy for chemtcal analy-sis) of the ~dr~ed film surface. Such an analysts shows a high level of~s~l~cone~and ajgrea!tly reduced level of backbone polymer when the ftlm~surface ts analyzed. ~Surface here means the ftrst few tens of Angstroms of f~lm thickness.) By varying the angle of the ~nterrog-ttng~be~am the ~surface can be analyzed to varytng depths. ~
The~most~preferred stl1cone^contatnlng polymers comprlse a v1nyl poly~er1c backbone preferably hav1ng a ~9 or a Tm above ::` ` :

~ ~;
:~ :
:

CA21 1 726~
w 0~3/07848 PcT/US92/08475 about -20 C and grafted to the backbonej ~ polyd1methylslloxane macromer hav1ng a weight average molecular ~e1ght of from about I 000 to about 50 000 preferably from about 5 000 to about 40 000 most preferably about I0 000 to about 20 000 As used here~n the abbrèv~at~on ~Tg~ refers to the glass trans1t1On temperature of the non-s111cone b~ckbone, ~nd the abbrev1at1On ~Tm~ refers to the crystalllne melting po1nt of the non-s111cone backbone 1~ such a trans1t10n ex1sts for a glven polymer Highly preferred examples of such m~ter1als are the s111-I0 cone-cont~in1ng copolymers as described 1n the followlng patent appl1cations: Serlal Number 07/758 3I9 Torgerson Bol1ch and Garbe filed August 27 1991; ~nd Serlal Number 07/758 320 Bolich and Torgerson f11ed August 2~ 1991; both of whlch are ~ncorporated by reference here1n and 1n European Patent I5 Appl1cation 90307528 1 Hayama et al (Publ1cation No 0 408 311 January 16 1991). Such pol~mers typical1y have a weight average molecular weight of ~t least about I0 000 generally from about 75~000 to about 3 000 000 and also preferably have a Tg of at least about -20 C
In addit1On to the gr~ft copolymers descr1bed above useful copolymers ~nclude block copolymers containing up to about 50%
(preferably from about I0% to about 20%) by weight of one or more polydimethyl slloxane blocks and one or more non-s111cone blocks~
(preferably acrylates or v1nyls) ;
Preferred pol~mers compr1se~a vinyl polymeric backbone havlng a Tg or a Tm above about -20 C and grafted to the backbone a polydimethy1s11Ox-ne m-cromer having a we~ght average molecul~r we~ght of from about I OOO to about 50 000 preferably from about

5 000 to about 40~000 most preferably about 20 000 ~he sil1cone-containing poly~ers util1zed as styling/condi-tion1ng agents generally comprise C monomers together w1th mono-mers selected from the~group constst1ng of A monomers B monomers and m1xtures thereof ~-s descr1bed in more detail below These .
copolymers contain~ at least A or B monomers together w1th C
~ 35 monomers and preferred copolymers contain A B and C monomers : , : ;

WO ~3/07~48 PCI`/US92/08475 ~
, Examples of useful copo1ymers and how they ~re m-de are descr~bed 1n deta~l 1n U.S. Patent ~ 693 935 Hazurek 1ssued September lS, 1987 and U.S. Patent ~ 728 S71 Clemens et al.
1ssued March 1 1988 both of wh kh are 1ncorporated here1n by reference. These copolymers are compr1sed of monomers A C and opt10nally, B, wh1ch are def1ned as foltows. A when used 1s at least one free r~d1cally polymer1zable monomer or monomers. B, when used, compr~ses at least one monomer copolymerizable w1th A
and 1s selected from the group cons1st1ng of polar trelat~ve to A) monomers and macromers hav~ng a ~9 or a Tm above about -20-C.
When used B may be up to ~bout 98X preferably up to about 80X
~ore preferab1y up to about 20% of the total monomers ~n the co-polymer. Polar monomers include ionic monomers as well as polar nontonic monomers. Monomer C comprises from about O.OlX to about 50.0% of the total monomers ln the copolymer.
Representative examples of A monomers are acryl1c or meth-acrylic ac~d esters of C~-Cl~ alcohols such ~s methanol ethanol l-propanol 2-propanol l-butanol 2-methyl-1-propanol l-penta-nol 2-pentanol 3-pentanol 2-meth~ butanol 1-methyl-1-butanol 3-N thyl-l-butanol l-methyl-l-pentanol 2-methyl-1-pentanol 3-methyl-1-pent-nol t-butanol cyclohexanol 2-ethyl-l-butanol 3-heptanol benz~l` alcohol 2-octanol 6-methyl-1-heptanol 2-ethyl-1-hexanol 3 5-dimethyl-1-hexanol 3 5 5-tr1-~methyl-l-hexanol l-dec~nol ~ l-ddecanol l-hex~decanol l-octa-decanol and the l~ke the alcohols hav1ng from about 1-18 carbon atoms w1th thé average number of carbon atoms be1ng from about 4-12; styrene~i~vln~l acetate; vinyl chlor1de; v1nylidene chlor1de;
acrylonitrile~; alpha-methylstyrene; t-butylstyrene; butadiene;
cyclohexadiene; ethylene; propylene; v~nyl toluene; and mixtures thereof. `Preférred A monomers include n-butyl methacrylate 1sobutyl methacrylate 2-ethylhexyl methacrylate methyl meth-~; acrylate t-butylacrylate ~;~ t-butylmethacrylate and mixtures thereof. ~ ~ ~
Representat;1ve examples of B monomers 1nclude acryl k ac1d methacryl1c ac1d N N-dtmethylacrylam1de dimethylaminoethyl C~21 1 7264 W ~,,g~07848 PCr/USg2/08475 methacrylate, quatern1zed d1methylam1noethyl methacrylate, meth-acrylon1tr11e, polystyrene macromer, methacrylamlde, ~ale1c anhydr1de and 1ts half esters, 1tacon1c ac1d, ~crylam1de, acrylate alcohols, hydroxyethyl methacrylate, d1allyld1methyl ammon1um chloride, vtnyl pyrrolidone, vlnyl ethers (such as ~ethyl v1nyl ether), male1m~des, acylactones, v~ny1 pyr~d~ne, vtnyl tmtdazole, other polar v1nyl heterocycl1cs, styrene sulfonate, and mtxtures thereof~ Preferred B monomers 1nclude acryl~c ac1d, N,N-d1methyl-acrylam1de, dtmethylam1noethyl methacrylate, quatern1zed dtmethyl-aninoethyl methacrylate, v1nyl pyrrol1done, and m1xtures thereof.
Add1tional su1table A and B monomers are descr1bed aboYe 1n the d1scuss1On of non-s11 k one-conta1n1ng polymers.
~he C monomer has the general formula:
%(Y)ns1(R)3-mz~
IS wherein X is a vinyl group copolymerlzable with the A and B
monomers; Y is a divalent link1ng group; R ts a hydrogen, lower alkyl " ryl or alkaxy; Z 1s ~ monovalent s11Oxane polymer1c mo1ety having a number average molecular weight of at least about 500, 1s essent1ally unreact1ve under copolymer1zation cond1tions and 1s pendant from the v~nyl polymeric backbone, descrtbed above; n ts 0 or l; and m ts n integer ~rom I to 3. C has a wetght average molecular we~ght of from about 1,000 to about 50,000, preferably from about ~S,000 to abo~t 40,000, most preferably from about 10,000 to about 20,000. Preferably, the C monomer has the hrmula: ~ -Q
X~ O-(CH~)q-(O)p~St(R~ m 2m ~ In those structures, m is 1, 2 or 3 ~preferably m 1); p is 0 or l; R~ ~s alkyl or hydrogen; q 1s an 1nteger from 2 to 6; s 1s an tnteger from 0 to 2; X 1s CN-C- ;
Rl R2 ~
Rl ts hydrogen or -COOH (preferably Rl 1s hydrogen); R2 1s hydro-gen, methyl or -CH2COOH (preferably R2 1s methyt); Z 1s .

CA21 1 726~
WO g3/07848 PCI`/US92/08475 , ~.

CH~
R~ 1-0-)r;
CH~
S R~ 1s alkyl alkoxy alkylam1no aryl or hydroxyl (preferably R~
1s alkyl); and r 1s an 1nteger from about 5 to ~bout 700 (prefer-ably r 1s about 130 to about 250). Part1cularly preferred 1s when p~0 and q-3.
The preferred polymers useful 1n the present 1nvent10n generally comprtse from OX to about 98% (preferably from about 5X
to about 98X more preferably from about 50% to about 90X) of monomer A from QX to about~98% (preferably from about 7.5X to about 8QX) of monomer B and from about O.IX to about 50% (prefer-ably from about 0.5% to about ~OX most preferablr from about 2X
to about 25 ) of monomer C. ~he comb1nat10n of the A and B
monomers preferably comprises from about 50.0% to about 99.9X
(more preferably about 60X to about 99X most preferably from about 75X to about 95X~ of the pol~mer. ~he compos~t10n of any p~rt~cular copolymer will help determine its formulat10nal pro-pert1es. For~ example polymers wh1ch are soluble tn an aqueous formulat10n preferably have the compos~tton: from 0% to about 70X
preferabl~ from about 5X to about 70%) monomer A from about 30%
to about 98X (preferabiy~from about 3% to about 80X) monomer B
and fro~ ~bout lX to about 40% monomer C. Polymers- whtch are dlspers1ble~have the preferred;compos~t10n: from OX to about 70%
(more~prèferably~from about 5X~to~about 70X~ monomer A from about 20% to~ ahut~80X (more preferably from about 20X to about 60Z) ~; monomer B and from about lX to about 40X monomer C.
:` ~
Pçlymers for use 1;n~lthe present invent~on 1nclud@ the fol~
lowing (the~weight percents below refer to the ~mount of reactants added ~n the~ polymer~zat~on react~on not necessartly the amount tn the finlshed~pol~ymer)~: ~
acryl~c ac~d/n-butylmethacrylate/polyd~methyls~loxane (PDMS) macro~er-20 OOO~molecular we~ght (e.g. lO/70/20 w/w/w) (I) N N-dlmethyl~acry1am1de/~sobutyl methacrylate/PDMS macromer -~: :

Wo~2?/o7~ PCr/USg2/08475 - 29 ~
20,000 molecular we19ht (e.g., 20/60/20 w/w/w) (II) d1methylam1noethyl methacrylate/~sobut~l methacrylate/2-ethylhexyl-methacrylate/PDMS macromer-20,000 molecular we19ht (e.g., 25/40/15/20 w/w/w/w) (III) d1methylacrylamlde/PDSM ~acromer-20,000 molecular we1ght ~e.g., 80/20 w/w) (IV) t-butylacrylate/t-butylmethacrylate/POMS macromer~10,000 molecular we19ht ~e.g., 56/24/20 w/~/w) (V) t-butylacrylate/PDMS macromer-lO,000 molecular we19ht (e.g., 80/20 w/w) (VI) t-butylacrylate/N,N - d~methylacrylam1de/PDMS macromer-10,000 molecular we~ght ~e.g., 70/10/20 w/w/w) (VII) t-butylacrylate/acr~l~c ac1d/PDMS ~acromer-lO,000 molecular weight ~e.g., 75/5/20 w/w/w) (VIII).
The partlcle size of the halr setting agent of the present compostt1Ons may have some e~fect on performance in product.
Th1s, of course, will vary from polymer to polymer and from product to prod~ct.
The ha1r sett~ng polymers are prefer~bly provited in a solvent h r the polymer, generally pr~or to comb1nat1On w1th the veh~ele systems of the present 1nvent1On.
The solv*nt selected must be able to d1ssolve or d1sperse the particular hair styling p!olymer being used~ Sultable solvents for use 1n the present invent~on, in general, ~nclude, but are not 71mitPd to, alkyl alcohols (such as linalool and decyl alcohol), hydrocarbons (such as isobutane, hexane, decane, dodecane, and tr~dec3ne~, hydrocarbon ~esters (such ~s C~-CI2 alkanoates, e.g.
methyl decanoate, d~ (C2-C~) alkyl ad1pates, e.g. d1sopropyl adepatei, C~-C~0 alkyl acetates, e.g. octyl acetate, and benzoates, WO93/07848 P~/US92/08475 e.g. butyl benzoate,), volat11e sllicon der1vat1ves, espect~lly s110xanes (such as phenyl pentamethyl disiloxane, phenethyl pentamethyl d1slloxane, methoxypropyl hepta~ethyl cyclotetra-s1loxane, chloropropyl pentamethyl dis1loxane, hydroxypropyl pentamethyl dtstloxane, octamethyl cyclotetras110xane, decamethyl cyclopentas110xane), ethers, such as d1 ~Cs-C~J lkylethers, and mtxtures thereof. Preferred solvents 1nclude vol~t11e s111cone flu1ds, and ~1xtures of s111cone flulds w1th ester, ether, and or hydrocarbon solvents. The cho1ce of solvent w111 depend upon the particular h~1r sett1ng polymer chosen and the d11uent ut111zed for the veh1cle system, as descr1bed above. In general, 1t 1s preferred that the ha1r sett1ng polymer solvent be d1spers1ble, but lmnl1scible, wtth the veh1cle system d11uent. Also, the ha1r sett1ng poly~er solvent ls preferably volat11e and not soluble 1n water. For purposes hereof, ~volat11e~ means a bo111ng po1nt, at atmospher1c pressure, of less than about 300-C, preferably from about IOO-C to about 300-C, and ~not soluble 1n water~ means a water solubil1ty ~in water at 25-C of 0.2% or less, preferably about O.lX or less, on a water plus sol~ent weight basis.
The performance of the styling polymers can be 1mproved through the 1ncorporat10n of a nonvolatile plastic1zer 1nto the styl1ng pol~nner-so1vent solution. The preferred solvents 1n these systems are volat11e s111cone flu1ds in wh1ch the styl1ng polymer 1s soluble or dispe-s1ble.~ The plast1cizer w111 generally be present in the compos~t10ns at a plast1cizer: styl1ng polymer we1ght rat10 of about 1:20:~ to about 1:1, preferably from about 1:15 to about 1:2, nore preferably from about 1:12 to about 1:2.5.
As~ used herein, -nonvo1atile~ 1n regard to plast1cizers means that the plasticizer ~exhibits essent1ally no vapor pressure at atmos-pher1c pressure ;and 25-C. The polymer-volatile solvent solut10n should not suffer fro substant1al plast1c1zer weight loss while ; the volat11e solvent 1s evaporat1ng, s1nce th1s would reduce plast1c1zat10n~of- the ~styl~1ng polymer dur1ng use. ~he plast1-c1zers for use~here1n should generally have bo111ng po1nts of about 250-C~ or h19her. Such plast1c1zers 2re nonvolat11e for :: :
.

CA21 1 726~
W 0,~23/07848 Pr/USg2/0847 purposes hereof.
The plasticker should also be compat~ble w~th the ha1r styling polymer-volat11e solvent solutton. By "compatlble~ w~th respect t~ the plastlc ker and the polymer-volatile solvent solut10n, it is meant that the plastlc~zer does not adversely 1nteract w~th the hair styling/condlt~oning copolymer, and must be m~sc~ble in sa~d solut10n. In general, the nonvolatile pl~stl-c kers for use here~n will be of relatlvely low water solub111ty.
The solubility parameter of these plastlclzers w111 generally be between about 7 and about 10, pre~erably between about 8 and about g (un~ts equal(cal/cc)l/2). The solub~l~ty parameter ~s defined in the Polymer Handbook 3rd Ed. ~John W~ley and Sons, New York), J. Brankrup and E.H. Immergut, Chapter VII, pp. 519-5S99 as the square root of the cohesiYe energy density and describes the attract~ve strength between molecules of the mater~a1. Solubility parameters may be determined by direct measurement, correlations with other physical properties, or indirect calculat~on as set forth by Immergut.
Plasticizers are well known in the art and are generally described in Kirk-Othmer EncYcloDedia Qf Che~ical Technoloqv, second edltion, Volume 15, pp. 720-789 (John Wiley ~ Sons, In~.
New York, 1968) under the topic heading ~Plast~c~zers~, and by J.
Kern Sears and Joseph R. Darby in the text The Technoloqv ~f ~lasticizers ~ohn W~ley ~ Sons, Inc., New York, lg82), both tncorporated here~n by reference. See especially ~n the Append~x of Sears/Uarby Table A.9 at pages 983-1063 where a wide variety of plast~c kers are disclosed.
~ he plast~cizers for use herein include both cyclic and acyclic nonvolatile materials. Suitable categories of nonvolatile plast~cizers include ad~pates, phthalates, isophthalates, aze-lates, stea~tes, citrates, trimell~tates, s~licone copolyols iso 4-C22 alconols, methyl alkyl sllicones, carbonates, sebacates, ~sobutgrates, oleates, phosphates, myristates, rlc~nolestes, pelargonates, valerates, oleates, camphor, and castor o~l, and s~l1cone copolyols.

CQo~3~o77~864 P~/US l2~84~s Examples of ad1pate plast1c1zers 1nclude ad1p1c ac1d der1vat1ves such as d11sobutyl ad1pate, b1s(2-ethylhexyl) ~d1pate, dilso~ecyl ad1pate, b1s(2-butoxyethyl) ad1pate, and d1-n-hexyl ad1pate.
Examples of phthalate plastic1zers include phthal1c ac1d derivat1ves such as d1butyl phthalate, butyl octyl phthalate, ~1-n-octyl phthalate, d11sooctyl phthalate, b1s(2-ethylhexyl phthalate, n-octyl n-decyl phthalate, di-n-hexyl phthalate, isooctyl isodecyl phthalate, di1sodecyl phthalate, dltr1decyl phthalate, butyl cyclohexyl phthalatè, di1soctyl benzyl phthalate, butyl benzyl phthalate, dicyclohexyl phthalate, dlphenyl phtha-late, isodecyl benzyl phthalate, and bis~2~butoxyethyl) phthalate.
Isophthalate plastic1zers include bis(2-ethylhexyl) ~so-phthalate, and diisooctyl benzyl phthalate.
lS Exa~ples of azelate plast~cizers include azelaic ac1d der1-vatives such as di(2-ethylhexyl) azelate, and bls(2-ethylhexyl) azelate.
Examples of stearate plasticizers include stear1c ac1d derivatives such as n-butyl stearate, butyl acetoxystear-te, and butoxyethyl stearate.
Examples of citrate plasticizers include citric ac1d deriva-tives such as acety1 tri-n-b;utyl citrate, tri-n-butyl citrate, and acetal tri-2-eth~l hexyl citrate.
Examples of trimell1tate plasticizers include tri-(2-ethyl-` 25 hexyl) trimellitate, and tr11sooctyl trimell1tate.
Other examples of plast1cizers 1nclude dibutyl carbonate, butyl oleate, n-butyl, butyr-te, isobutyl butyrate, 1sopropyl butyrate, dibutyl carbonate,~ethyl palmltate, isooctyl palmitate, methyl ricinoleate, butyl r1cinoleate, diisooctyl sebacate, triisobutyl phosphate, isodecy pelargonate, ethyl valerate, isocetyl alcohol, octododecànoi, isopropyl myristate, isostearyl alcohol and methyl alkyl silicones having C2-C~O alkyl and from I
to about 500 silox-ne monomer units.
Silicone copolyols, ~described S~pr~, can also be used as 3s plastickers.

..

If a plastlc1zer 1s used, the molecular we19ht, we1ght average, of the styl1ng poly~er 1s preferably ~t le~st about 200,000, more preferably from about 300,000 to about 800,000, ~ost preferably from ~bout ~00,000 to about 600,000.
The present composit~ons can be used to del1ver a w1de var1ety of act1ve components onto the h~1r. Such compos1tlons wou1d 1nclude sk1n mo1stur1z1ng lot10ns, sunscreen compos1t10ns, and cleans1ng compos1t10ns. The compos1t10ns hereof most de-slrably are used as ha1r care products, especially rinse-off ha1r care products ~here some act1ve ha1r care component, 1nclud~ng the hair sett1ng agent, is tc be deposlted onto the ha1r but the vehicle carrying that component ~s desirably rlnsed off of the hair with little or no deposit10n of the veh1cle mater1al onto the halr. However, the present composttions may additlon-lly be applied to skin.
6enerally! the present vehicle systems wlll not be useful 1n typi~al shampoo compositions since these compositions contatn high le~els of water-soluble surfactants, wh1ch as dtscussed supr~, are incompatible with the present vehicle systems. However, the present compositions to encompass ha1r coloring compositions, hatr tonic or gel compositions, hair mousse compositions, and especial-ly hair stylinglconditioning compositions, especially rinse-off composittons.
Active Çosmetlc Component The cosmetic composltions of the present tnvent10n generally will comprise n additional acttve cosmetic component ~htch provtdes some benefit~to he hair or skin. The term ~addStlonal active component~ ls used s~nce the saturated quaternary ammonlum surfactant component hereof generally operates as a conditioner to hair or skin. Such materia!s may include moisturizing agents, sunscreen agents, cleaning agents (that are compatlble with the present vehicle systems),~and especially hair conditioning agents, hair styllng agents,~ antidandruff agents, hair growth promoters, hair dyes ~nd pigments, or perfumes.

WO 93/~784~ PCI /US92/08475 - 3~ -A ~1de var1et~ of convent10nal sunscreen1ng agents are su~table for use 1n the cosmet1c compos1t10ns of the present 1nvent10n. Segar1n et al. at Chapter VIII, pages 189 et seq.
of ~Q~metlcs Sciçnce and TechnoloaY disclose numerous su1table agents. Specif1c sultable sunscreenlng agents 1nclude, for example: p-am1nobenzo1c ac1d 1ts salts and 1ts der1vat1ves;
~nthrantl~tes; sal1c~1ates; c1nnam1c ac1d der1vat1ves; d1hydroxy-c1nnam1c ac1d derivatlves; tr1hydroxyc1nnam1c ac1d derlvattves;
hydrocarbons; dibenzalacetone and benzalacetophenone; naphthol-sulfonates; d1hydroxy-naphthol1c ac1d and 1ts salts; coumar1n derivatlvesi dtazoles; quin1ne salts; quinoline der1vatlYes;
hydroxy- or m~thoxy-s~bst1tuted benzophenones; ur1c and v110ur1c acids; tann1c ac1d and lts dertvat1ves; hydroquinone; and benzo-phenones.
Of these 2-ethylhexyl p-methoxycinnamate 4 4 -~-butyl methoxydibenzoylmethane. 2-hydroxy-4-methoxybenzophenone octyl-dimethyl p-aminobenzoic ac1d digalloyltr101eate 2 2-dlhydroxy-4-methoxybenzophenone ethyl-4-lbis(hydroxypropyl)]-aminobenzoate 2-ethylhexyl-2-cyano-3.3-diphenylacrylate 2-ethylhexylsalisylate glyceryl p-aminobenzoate 3 3 5-trimethylcyclohexylsallcyl~te methylanthranilate p-dimethyl-aminobenzo1c acid or am1nobenzoate 2-ethylhexyl p-dimethylaminobenzoate 2-phenylbenz1midazole-5-sulfonic acid 2-(p-dimethyl-aminophenyl)-5-sulfonlcbenzoxazo1c acid nd mixtures of these compounds are particularly useful.
Examples of antidandruff aids suitable for use with the veh1cle systems of the present 1nvention 1nclude zlnc pyr1th10ne sulphur and selenium sulfide. One example of a ha1r growth promoter suitable for use w1th the vehicle systems of the present invention is Minoxidil (6-amino-l 2-dihydro -l-hydroxy-2-imino-4-piperidino pyrimide) available from Upjohn.
Hair oxidizing (blleaching)~agents such as hydrogen peroxide perborate and persulfate salts and hair reducing agents such as thioglycolates~may also be used.

W0 ~3/07848 PCI'/US92/08475 ~dd1t10nal Cond~ttoners Examples of cond1t10n1ng ~ater1als su1table for use 1n the veh1cle systems of the present 1nvent10n re volat11e 11qu1d hydrocarbons. These are part1cularly useful for use ln ha1r treatments.
These materials preferably have a boiling po1nt 1n the r~nge of about 99 C to about 260 C and have a solub11it~ 1n water of less than about 0.1%. The hydrocarbons may be either stra1ght or branched cha1n and may contain from about lO to bout l6 prefer-ably from about 12 to about 16 carbon atoms. Examples of su1table hydrocarbons are decane dodecane tetradecane tr~decane and mixtures thereof.
Volat11e silicones useful as an active cond1tion1ng component in the compos~ttons of the present lnvention 1nclude s111cone lS flu1ds such as cycllc nd 11near polyd1~ethylslloxanes. The number of silicon atoms in the cycltc silicones is preferabl~ ~rom about 3 to about 7 more~preferably 4 or 5.
The general formula for the cycl1c silitones is Z ~$i~03n wherein n 3-~. The linear;polyd1methylsiloxanes have from about 3 to 9 silicon atoms and have the general fon~ula:
(CH~)~Si-o-[-Si(CH3)~-o-jn-Si(CH~)~ n 1~7.
Silicones of the~-bove type both cyclic and 11near are available from Dow Cornin~Corporation Oow Corning 3U 345 and 200 fluids;
Union Carbide Silicone 7202 and S11icone ~158; and Stauffer Chemical S~S-03314.
The 11near volatile silfcones generally have v1scosit1es of less than;~about 5 centipoise at 2S-C while the cycl~c materiaJs have viscosit~es~less than about lO centipoise at 25-C. A
description of~volatile s11icones is found in Todd and Byers ~Votatilc S11~cone ~ Fluids ~for Cosmetics- Cosmetics and Toiletries, Vol.~ 91 January 1976 pp. 27-32 1ncorporated here~n 3S by reference.

~;~29~)o~ P~/US92/08475 The vol~tlle agent ~ay be present 1n the composlt10ns of th1s 1nvent10n at ~ level of from about lX to about 20X preferably from about 2X to about 15X. The vol~t11e s111cones are the preferred volat~le ~gents.
S Honvalat~le s~l1cone flu1ds are useful as the act1ve halr condit~oning component 1n the composit10ns of the present invent10n. They will generally have a v~scos1ty ln excess of 10 cent~poise at 25-C. Examples of such mater1als 1nclude polydimethyls~loxanes (flulds and gums) amlnos111cones ~nd phenyls111cones. ~hese 1nclude polyalkyl or polyaryl s110xanes w~th the following structure:
R R R

R R ~ x- li - A
wherein R is alkyl or aryl and x is an integer from about 7 to about 8 000 may be used. A represents g~oups which block the ends of the silicone chains.
The alkyl or aryl groups substituted on the s~loxane cha~n (R) or at the ends of the siloxane chains (A) may have any struc-ture as long as the resulting silicones remain fluid at room temperature are hydrophobic are neither irritating toxic nor otherwise har~ful when applied to the hair are compatible with A
` 25 the other components of the composition are chemtcally stable under normal use and storage cond~t~ons and are capable of being deposited on and of conditloning h~r.
Su~table A groups include methyl methoxy ethoxy propoxy and aryloxy. ~The~two R groups on the silicone atom may represent the same group or different groups. Preferably the two R groups rep~esent the same group. ~Su~table R groups include methyl ethyl propyl~ phenyl. methylphenyl and phenylmethyl. ~he pre-ferred silicones are polydimethyl siloxane polydiethyls~loxane and polymethylphenylsiloxane. Polydimethylsiloxane is especially preferred-CA 2 1 17;~64 W(~3/07848 PCI/US92/08475 Su1t~ble methods for prepar1ng these s111cone mater1als ~re disclosed 1n U.S. P~tents 2 826 551 and 3 964 500 ~nd references c1ted there1n. S111cones useful 1n the present 1nvent10n are ~lso com~e~cially ava11able. Su1table examples 1nclude V1scas11 trademark of the General Electric Company and s111cones offered by Dow Corning Corporat10n and by S~S Sil1cones a d1v1s10n of Stauffer Chemical Company.
Other useful s~licone materlals include materials of the formul~:
HO 1~ 0 1 fH H
H, x (CH2)~ y NH
(CH2)2 in which x and y are ,nteHger ; which depend on the molecular we19ht the average molecular we19ht being approx~mately betwe~n 5 000 and lO OOO. This polymer 1s also known as ^amodimeth1cone~.
Other silicone cationic polymers which can be used in the present composit10n correspond to the formula:
(Rl)aG3 a-Si ( OsiG2)n-(osiGb(R~)2-b)m-o-s~G~-a(Rl)a in which 6 is chosen from the group consist1ng of hydrogen phenyl OH Cl-C~ alkyl and preferably methyl; a denotes O or an integer ~rom l to 3 ant preferably equals 0;
b denotes 0 or l and preferably equats 1; the sum n~m 1s a number from l to 2 000 and preferably from SO to 150 n being able to denote a number from O to l 999 and preferably from 49 to 1~9 , and m being able to denote an integer from l to 2 000 and prefer-ably from l to lO;~ j Rl is a monovalent radical of formula CqH2qL 1n wh~ch q is an integer from 2 to~8 and L is chosen from the groups ~: ~ -N(R2 )CH2 -cH2 -N(R2 ) 2 -N(R2) 2 ~ ~ 35 -N+(R2)3A-:::
`::
: :: : ; :

WC) 93/07848 PCI/US92/08475 ~3 -~+(R2 ) 2CH2 -CH2 -N~ (R2 ) ~A
1n which R2 is chosen from the group cons1sting of hytrogen phenyl benzyl a saturated hydrocarbon radical preferably an alkyl radical containing from 1 tb 20 carbon atoms and A- denotes a halide 10n.
These compounds are described in greater deta11 in European Patent Appltcation EP 95 238. An espec1all; preferred polymer correspond~ng to this formula ~s the polymer known as ~trimethyl-si1y1amodimethicone~ of formula:

(CH,)~-Si- ~O-S~ O-S~ -OSI(CH,), CH3 n (IH2)~
NH

(CH~)~ m _ NH2 _ Compositlons of the prl sent invel ~t10n inc1uding this mater1a1 typical1y wil1 comprise up to about l.OX of the trimethylsilyl amodimethicone silicone conditioning material.
Other silicone cationic polymers may also be used in the present composittons such as those of the formula:
+
R~-CH2-CHOH-CH2-N(R,),Q-~ ; ] Si (R ) R3 r R~ s in which R, denotes a monovalent hydrocarbon radical having from 1 to l~ carbon atoms and ~orç especially an alkyl or alkenyl radical such as methyl7 R~ denotes a hydrocarbon radical such as preferably a Cl-Cl~
alkylene radical or a Cl-Cl~ ~and preferably Cl-C~ alkyleneoxy radical;
Q- is a halide ~on preferably~chloride;
, :

~3/07&~8 P~/US92/0~475 r denotes an verage statistic~l value fro~ 2 to 20 prefer~bly from 2 to 8;
s denotes ~n ~verage stat1st1c-1 value fro~ 20 to 200 ~nd prefer-ably from 20 to 50.
These compounds are descr1bed ln greater detail 1n U.S.
Patent 4 185 017.
A polymer of this class wh1ch ~s espectally preferred ls th~t sold by UNION CARBIDE unter the name ~UCAR SILICONE ALE 56~.
Sil kone condit~oning agents ~re used ln th~ present compo-sitions at levels of from about O.lX to about 18% preferabl~ from about 0.5% to about l5X.
Preferred silicone conditioning agents for use 1n the present compositlons comprise combinations of vol~tile sll1cone fluids having viscosities of less than about 10 centipoise and from lS about 0.015X to about 9.0X preferably from about 0.5X to about 2.0Z of sil~cone gums having vlscoslties of gr~ater than bout 1 000 000 centipoise at ratlos of volatile ftuid to gum of from about 90:10 to about lO:90 preferably from about 85:15 to about .
50: 50.
A1ternative preferable nonvol-tile silicone matert~ls for use in the present invention compr1se non-volatile sllicone fluids ~; having viscosities of less that about 100 000 cP ~centipolse) at 25-0 and from about O.aISX to ~about 9.0X preferabl~ from about 0.5% to about 2.0% of sillcone gums having v~scosit1es greater than about l OOO OOO cP ~t;25-C especially polyd1meth~1siloxane gums and pol~phenylmethyls1loxane ~gums t rat~os of non-volatile fluld to gum~of from about 70:30 to about 3~:70 preferably from about 60:40 to about 40:60.
The efficacy of nonvoi-tile silicone hair conditioning agents can be ~enhanced~throughl the use of silicone resin which is misc~le with the silicone hair conditioning agent. Silicone resi are highly cross1inked polymeric siloxane systems. The cross;i-.klng~ is introduced through the ~ncorporation of trifunct10nal and tetrafunctional sllanes with monofunct~onal or 3S difunctlonal ~ or both ~ monomer units during manufacture of the :

C~21 1 7264 Wo 93/07848 Pcl~/uss2/08475 ~

- ~0 -s111cone res1n. As ~s well understood ln the art, the degree of crossl1nk1ng th~t 1s requ1red 1n order to result 1n a sll1cone res1n w111 vary accordlng to the spec1f1c s11ane un1ts ~ncorporated 1nto the sll1cone res1n. In gener~l s111cone 5 mater1als whlch have a suffic~ent level of tr1funct1Onal and tetrafunct1Onal slloxane mononer un1ts (and hence a sufficlent level of crossl1nklng) such th~t they dry down to a r1q1d or hard f11m ~re cons1dered to be s111cone res1ns. The ratlo of oxygen atoms to sllicon ato~s 1s lnd1cat1ve of the level of crossllnk1ng 1n a p~rticular s11icone mater1-1. S111cone res1ns will generally have at least about 1.1 oxygen atoms per s111con atom. Preferably the rat1O of oxy~en: - s111con atoms 1s at least about 1.2:1Ø ~yp~cal silanes used in the manuf-cture of silicone resins are monomethyl- dimethyl- monophenyl- diphenyl-methylphenyl- monovinyl- and methyl-vinyl-chloros11anes and tetrachlorosilane. Preferred resins are the methyl substituted silicone reslns such as those offered by Gener~l Electr1c as GE
SS4230 and SS4267. Commerclally~ ~va11able sil1cone res1ns ~111 genenlly be supplied in an unhardened form in a low viscos~ty vol~tile or nonvolatile silicone fluid. The silicone resins for use herein should be supp11ed and incorporated lnto the present compositions 1n such non-hardened form r~ther than as a hardened resin as will be readily apparent to those skilled ~n the art.
The weight ratio of the nonvolatlle silicone flu1d cond1tlonlng component to the s111cone res1n component 1s preferably from about 4:1 to about 400:1. More preferably such ratio 1s from about 9:1 to about~200:1 most preferably from about 19:1 to about; IOO:l partieularly when the sil1cone flu1t component is a polydimethyls~loxane fluid or a mixture of pol~dimethy1siloxane 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 provlde both style retentlon and condltloning benefits to the hair. These ~nclude sllicone polymers that are r~gid silicone ~ ~31~o~ ~ ~ 6 ~ PCT/US92/08475 polymers. Such mater1als are descr1bed 1n U.S. Patent ~ 902 ~99 Bol1ch et al. 1ssued February 20 1990 1ncorpor~ted here1n by reference.
Add1t~onal c-t10n1c cond1t10nlng mater1als ~ be used 1n the present compositions. In general cat10n~c sur~-ctants useful as ha1r cond1tion1ng agents 1nclude both quaternary ammon1um and amine cation1c surfactant mater1als. If such a 0ater1~1 other than the secondary th~ckener eomponent 1s 1ncluded 1n the present compos~t10ns it w1tl generally be present at levels up to about 2.5% ~referably at from about 0.5X to about 2.0X by weight of the composition.
Cat~on1c surfactants thit can be used 1n gener~l conta1n amino or quaternary ammonium hydrophil1c mo1et1es wh1ch are positively charged when dissolved in the aqueous compos1t10n of the present invention. A wode varoetu pf cation k surfactants among those useful herein are dtsclosed 1n the Sollowing docu-ments all incorporated by re~erence herein: M.C. P~blish1ng Co~
McCutcheon s. Deteraen~s ~ Emulsifiers ~Horth Aneric~n Ed1t10n 1979); Schwartz et al. Surface Active Aaents The1r ChemistrY
and TechnoloaY New York: Interscience Publishers 1949; U.S.
Patént 3 155 591 Hilfer ~ssued November 3 1964; U.S. Patent 3 929 678 Laughlin et al. issued December 30 Ig75; U.S. Patent 3 959 461 Batley et al. issued May 25 1976; and U.S. Patent 4 387 090 801ich Jr. ~ssued June 7 1983.
Included ~as optlon~l cationic surfactants are unsaturated ~` vers~ons~ of the saturated surfactants described above 1.e.
cationic ammonlum quaternary surfactant with an average iodine value of at least lS.
.
Examples of unsaturated quaternary ammonium surfactants hereof include the salts of dimethyl d~(unsaturated) tallow ammonium dimethyl ; di(unsaturated)arachidyl ammonium dioleyl dimethylammonium ~ di-rapeseed alkyl dimethyl ammonium diricinoleyl dimethyl ammonium and disoyadimonium olealkonium.

~:
.

CA21 1 7~6~
WO g3/07 PCI'/US92/0847S

- ~2 -Other examples 1nclude the salts of methyl-l-oleyl a~1do ethyl-2-oleyl 1m~dazol1nium, d1erucyl d1methyl ammonium, and methyl-l-soya amido ethyl-2-soya 1m1dazolin1um.
Salts of pr~mary, secondary and tertiary fatty amines are also preferred cationic surfactant materials for use heretn. The alkgl groups of such amines preferably have from about 12 to about 22 carbon atoms, and may be subst1tuted or unsubst1tuted. Second-ary and tertiary amines are preferred, tert1ary am1nes ~re par-t kularly preferred. Such amines, useful here1n, include stear-am1do propyl dimethyl am~ne, diethy1 amino ethyl stearamide, d~methyl stearamine, dimethyl soyamine, soyam1ne, tri(decy1) amtne, ethyl stearylamine, ethoxylated (2 moles E.O.) stearylamine, dihydroxyethyl stearylamine, and arachidylbehenyl-amine. Suitable amine salts include the halogen, acetate, phos-phate, nitrate, citrate, lactate and alkyl sulfate salts. Such salts include stearylamine hydrochloride, soyamine chloride, stearylamine formate, N-tallowpropane diamine dichloride and stearamidopropyl dimethyl-mine eitrate. Cation1c amine surfac-tants included ~among those useful in the present invention re - disclosed in U.S. Patent 4,275,055, Nachtigal, et al., issued June 23, 1981, incorporated by reference herein.
A particular category of cat~onic quaternary~ammonium sur-fact~nts that can be advantageously incorporated into the present compositions in combination with the~ above-described essential ` 25 sat~rated quaternary ammonium surfactants, are water-insoluble materials having the formul-, in s-lt form:
~ R

(IV) L R, - - R, j X-~

wherein X is a salt-forming anion as previously descr1bed, is the charge of the anion X, the radicals Rl, R2, R3, and R~
independently are C~-C, alkyl, C20-C22 alkyl, or benzyl wherein .

CA21 1 7~64 W(~ ~3/07848 PCI'/USg2/08475 . .
- ~3 -one of sald rad1cals 1s C20-C2~ alkyl preferably C2~ from t~o to three of sa1d rad1cals are C~-C~ alkyl prehrably C~C~ ~ore preferably methyl and zero or one of s-1d rad1cals 1s benzyl.
The long cha~n alkyl (1.e. the C20-C22 ~lkyl) c~n be e1ther saturated or unsaturated. If 1t 1s saturated the surfactant may also fall w1th~n the scope of the essent1al satur-ted quaternary ammon1um surfactant th1ckener descr1bed ~bove. If th~t 1s the case 1t should be lncluded as part of the saturated quatern~ry ammonium surfactant th1ckener in any assessment of the compos1-t10ns hereof.
A quaternarg ammonium surfactant of Fonmuta IV part1cularly contemp1ated here1n is: dimethyl behenyl benzyl ammon1um salt (alternately referred to as behenalkon1um salt) ava11able from ~itco Chemical Corp. (Memphis Tennessee USA) as a chloride salt under the trade name KEMAMINE BQ-2802C. Another particularly contemplated Formula IV material is dimethyl arach1dyl benzyl ammonium salt.
The quaternary mmonium surfactant of Formula IV 1s generally used at a level of from about 0.02% to about 10~0% preferably from about 0.05% to about 3.0X more preferably from about 0.05%
to about 2.0% by weight of the composltion.
Preferred combinations are compositions Containing the surfactant of formula ~IV especially in saturated fonm wherein the Formula I and II component comprises Cl~-C~ unsaturated alkyls preferably at a ~weight ratio of ~Formulas I and Formula IV) of about I:I~to about 4:1.
A particularly useful combinatlon of cationlc surfactants that can be used comprises a mixture of di(saturated) C~,-Cl, alkyl dimethyl ammonium salt and dimethyl (saturated or unsatu-rated behenyl and/or arachidyl preferably saturated) benzyl ammonium salt le.g. the c~loride salt at a weight ratlo of about I at about 4:1 more preferably about 1:1 to about 3:1.
These co-blnations of cationic surfactants can provide improved overall performance for hair styling/condltionlng prod-ucts especial;ly for as~ha`ir rinse products. Style hold can be C~913~ PCI /US92/08475 1mproved through the use of the long cha1n C20-C22 alkyl~substt-tuted mater1als of Fonmul~ III.
Hydrolyzed an1mal prote1n ha1r condltlon1ng agents may also' be included 1n the present composltions. Such mater1als are present ln the compos1t10ns at levels of from about O.IX to about 1.SX. An example of a commercially avai1able ~ater1al 1s sold under th0 tradename Crotein Q~ from Crod~ Inc.
Fatty alcohols are known hair cond1tion1ng agents and may be included 1n the present compositlons. ~owever as described supr~
lo such matertals tend to deposit on hair and leave halr feellng dirty after use. Hence it may be described that any fatty alcohol materials included ln the composltlons of the present invention be present at levels no greater than about lX.
Combinations of the aforementioned condit10ning agents may ' 'also be used in the present compositions.
These additional active cosmetlc materials are genera~ly present at a total level of from about 0% to about 20% preferably from about O.lX to about 20% by weight of the cosmetic composi-tion. For purposes hereof these additional active cosmet1c components shall~ not include the saturated quaternary ammonium surfactants which are encompassed by Formulas I and II even though such surf-ctants generally will h-ve cosmet1c efficacy eg.
as hair or skin conditioners. ~he 0% level reflects the situation when one of the vehicle component provides the halr care act1v~ty ~; ` 25 to the present composlt10ns. For example lf the veh1cl-e system compr1ses a water-~nsoluble quaternary ammon~um compound th1s ' mater1al will proYlde ha1r cond1t10nlng beneflts as well. The level of the act1Ye cosmetlc care mater1al varles depend1ng upon which active aterial is chosen the particular cosmet1c composi-tions to be formulated therewith and the level of benefit desired.' Other optional components that can be added to the cosmet1c compositions of the present invention do not prov1de any direct cosmetlc care benefit but~instead enhance the compos~t10n in some ~; ' 35 way. Examples;of such materials are coloring agents such as any . ~ .
.

W0,~3/07848 PCI'/US9~/08475 - ~5 -of the FD~C or D~C dyes; opac1f1ers, pearlescent a1ds, such as ethylene glycol dtstearate or ~102 coated m1ca; pH mod1f1ers, such as c1tr1c ac1d, succ1n1c ac1d, phosphorlc ~c1d, sod1um hydrox1de, and sod1um carbonate; perservat1~es, such as benzyl alcohol, ethyl paraben, propyl paraben, and 1m1dazolldonyl urea; and ant10x1-dants. Such agents generally are used individuatly at ~ level of from about O.OOlX to about 10%, preferably from about 0.01% to about SX, of the ha1r care compos1t~on.
The veh1cle systems and cos~et1c compos1t10ns of the present invent10n can be made us1ng convent10nal formulat10n and m1x1ng techniques. In one procedure for manu~acture, a sil1cone cond~-tioner, quaternary ammon1um surfactant, and at least a port10n of the solvent component are premixed prior to the add~t10n of the remaining components. Methods of making various types of cosmet1c lS compositions are described more specifically in the follow1ng examples.
The following examples illustrate the present ~nvention. It wi11 be apprec1ated that other modificat~ons of the present in~ention within the skill of those in the cosmetic compos1t10n fonmulation art can be undertaken without departing from the spirit and scope of this in~ent10n.~
All parts, percentages, and ratios herein ~are by weight unless otherwise specified.
ExamDles I~
` 25 ~he following are hair styling/condit10n1ng rinse compos~t10ns representat1ve~of the present invention.
ComDosit1on ~ I II
C~tr1c Acid ~ 0.02 0.02 Sodium Citr-te ~ o.og o.og Cetyl Alcohol~ j 0.12 0.12 Stearyl Alochol 0.08 0.08 ~: Natrosol Plus CS Grade D-67t l.OS 1.10 Xanthan Gum2; 0.25 0.25 Styling Polymer Premix ~
Styling Polymer~ ~ 1.75 l.75 , ~
~:

:: :

CWA 231018~82 6 4 PCr/US92/0~7s - ~6 -Octameth~l Tetrasiloxane 5.98 5.98 Decamethyl Pentasiloxane 2.56 2.56 Butyl Stearate 0.15 O.lS
Kathon CG 0.03 0.03 Perfume 0.33 0 33 Thtckener Prem1x ORO ~ater 12.18 11.88 Adogen 4~2-lOOP5 0.75 0.75 Adogen ~71~ -- 0.60 Stearyl Tr1methyl Ammonium Chlor1de 0.30 --Sllteone Gum Premix Oecamethyl Pentasiloxane 1.42 I.~2 Pol~dimethyl Siloxane Gum~ 0.25 0.25 Amodimethicone (Dow Corning Q2-8220) -- 0.10 ORO ~ater q.s. q.s.

~Hydrophobically modified hydroxyethyl cellulose from Aqualon Corp.
2Readtly dtspersible xantham gum ~80/20 t-Butylacrylate/PDMS~ macromer, the macromer having a molecular weight` of about 10,000, prepared in ~ manner similar to Example C-2b of U.S. Patent~4,728,571, Clemens, issued March 1, ;; 1988 ~ :
~SE-76 gum ava11able From 6eneral Eleetrie sDttallow dimethyl ammontum chloride, Sherex Chemtcal Co., Dublin, Ohio, USA. ~
'Tallow trimethyl~ ammonium chloride, Sherex Chemical Co.
The styli~ng polymer premix is prepared by comb~ning the styling polymer, the octamethyl tetrastloxane and decamethyl pentasiloxane, andlbutyl steairate.
The silicone gum premix is prepared by combintng and mixing (in a separate vessel)~the silicone gum and decamethyl penta-siloxane untll homogeneous.

. C~2117264 WO~g3/07B48 PCI'/US92/0847 The thlckener premlx 1s prep~red by comb1n~ng ~nd m1x1ng ~1n a separate vessel) DR0 water and ~ny pr1mary and secondary th1ckeners (premelted 1f necessary to ensure homogen1ty) at 82-and the s111cone gum prem1x ~nd amod10meth1cone ~t 71 C unt11 homogeneous.
In another vessel the DR0 water 1s heated to 71-C. C1tr1c ac~d sod1um c1tr~te cetyl ~lcohol stearyl ~lcohol and Natrosol Plus CS grade 0-67 are added and mixed unt11 homogeneous. The xanthan gum ts added and mixed unttl homogeneous. The styl~ng polymer premtx Kathon CG and perfume are added and mixed unt11 homogeneous~ ~he composltlon ls further dtspersed wlth an 1n-11ne homogenizer ~such as Tekmar homogenizer) and then cooled to 38-C.
The thickener premlx ~s ~lso further dispersed w~th an in-line homogenizer and cooled to 38-C and added to the final vessel mixing until homogeneous to form the styl~ng rinse composit~on.
: : :

` : , :;: :

` 25 ` ' , . , , I , ;:

`~ ~ 35 :
::

.

Claims (29)

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

1. 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 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 C8- 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 saturated 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 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 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, two or three of said radical are C14-C22 alkyl, or C14-C22 alkyl amido C2-C6 alkylene or a mixture thereof, zero or one of said radicals are C1-C6 alkyl, zero or one of said radicals is benzyl, or a mixture of Formula I and II surfactants; wherein said 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 less than 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 change, tri-short chain quaternary ammonium surfactant of the formula wherein X is a salt forming anion, a 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, R3, and R4 radicals is benzyl;
wherein said composition comprises no more than about 1.0% of water soluble surfactants.

2. A hair styling and conditioning composition, as in Claim Claim 1, wherein for the surfactant of component (d), R1 is C14-C22 alkyl, and R2, R3, and R4 independently are benzyl or C1-C3 alkyl.

3. A hair styling and conditioning composition, as in Claim 2, wherein R2, R3, and R4 are methyl or benzyl.

4. A hair styling and conditioning composition, as in Claim 1, wherein said hair setting agent comprises a water-insoluble styling polymer solubilized or dispersed in a water-insoluble solvent.

5. A hair styling and conditioning composition, as in Claim 3, wherein said hair setting agent comprises a water-insoluble styling polymer solubilized or dispersed in a water-insoluble solvent.

6. A hair styling and conditioning composition, as in Claim 4, wherein said hair styling polymer is a silicone-containing polymer.

7. A hair styling and conditioning composition, as in Claim 5, wherein said hair styling polymer is a silicone-containing polymer.

8. A hair styling and conditioning composition, as in Claim 6, wherein said solvent of said hair setting agent is a volatile silicone fluid.

9. A hair styling and conditioning composition, as in Claim 7 wherein said solvent of said hair setting agent is a volatile silicone fluid.

10. A hair styling and conditioning composition, as in Claim 1 wherein said composition comprises from about 0.05% 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.

11. A hair styling and conditioning composition, as in Claim 10, 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.

12. A hair styling and conditioning composition, as in Claim 2, 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 mixture of C1-C3 alkyl and benzyl.

13. A hair styling and conditioning composition as in Claim 12, 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.

11. A hair styling and conditioning composition, as in Claim 12, wherein for the surfactant of component (d), R1 is C14-C22 alkyl, and R2, R3, and R4 independently are benzyl or C1-C3 alkyl.

15. A hair styling and conditioning composition, as in Claim 14, wherein R2, R3, and R4 are methyl or benzyl.

16. A hair styling and conditioning composition, as in Claim 10, wherein said hair styling agent comprises a water-insoluble styling polymer solubilized or dispersed in a water-insoluble solvent.

17. A hair styling and conditioning composition, as in Claim 11, wherein said hair setting agent comprises a water-insoluble styling polymer solubilized or dispersed in a water-insoluble solvent.

18. A hair styling and conditioning composition, as in Claim 12, wherein said hair setting agent comprises a water-insoluble styling polymer solubilized or dispersed in a water-insoluble solvent.

19. A hair styling and conditioning composition, as in Claim 13, wherein said hair setting agent comprises a water-insoluble styling polymer solubilized or dispersed in a water-insoluble solvent.

20. A hair styling and conditioning composition, as in Claim 18, wherein said hair styling polymer is a silicone-containing polymer.

21. A hair styling and conditioning composition, as in Claim 6, wherein said hair styling polymer is a silicone-containing polymer.

22. A hair styling and conditioning composition, as in Claim 6, wherein said solvent of said hair setting agent is a volatile silicone fluid.

23. A hair styling and conditioning composition, as in Claim 7 wherein said solvent of said hair setting agent is a volatile silicone fluid.

24. The composition of Claim 11 wherein said hydrophobically modified nonionic water-insoluble 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.

25. The cosmetic composition of Claim 24 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 silicon gum having a viscosity greater than about 1,000,000 centipoise at 25°C; and mixtures thereof.

26. The composition of Claim 23 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.

27. The composition of Claim 24 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.

28. 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.

29. A hair care composition according to Claim 26 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.