CA2071637A1 - Hair treatments utilizing polymethylalkyl-siloxanes - Google Patents

Abstract

These improved compositions include a polymethylalkylsiloxane hair conditioning agent dispersed in a cosmetically acceptable carrier medium such as a hair shampoo, hair conditioner or aerosol spray composition. The polymethylalkylsiloxane is from 0.1 % to about 10 % by weight of the total composition and is of the general formula:
R2(CH3)Si(OSi(CH3)2)x(OSiR'CH3)yOSi(CH3)R2, wherein each R is selected from the group consisting of methyl, ethyl and phenyl groups, R' is an alkyl group of from 8 to about 60 carbon atoms where the total number of R' groups present has an average of at least 12 carbon atoms, the values of x and y are such that the ratio of x:y is in the range of from 97:3 to 55:45, the sum of x+y is greater than or equal to about 60 and less than or equal to about 1,333 and the polymethylalkylsiloxane has a melting transition, as measured by a differential scanning calorimeter, between about -25 ·C to +27 ·C. Also claimed is a method of conditioning the hair by applying such a composition to the hair and a method of improving the hair conditioning ability of a cosmetically acceptable hair treating composition by adding such a polymethylalkylsiloxane to such a composition.

Description

~''') 91/09586 PCr/l,'S90/071~
a ~

IMPROVED HAIR T~AT~ i~S UTILI-ING POL`i~ETH~LALKYLSILOXANES

This is a c-n. n~ a~~~ cf _~ e..ding U.S. Se~ial No- 0 /~ ?.~

_ ._ ~ AA
This in~en.i~n r~`a.es ~o a~. i.m~r_ved o",position for rea lng ~
pol~met~ S ~ ~. C ~ t~ S ?~ - .. ~. .~i i-- _ 0 !1 * ^ - ~ ll a hair -on~ cosr~er~ llv accepta~ie c_~^ria~- ms~ s ~~ . shc e~ ion. ~he in~enti~ s~ t~ ai-which cv~p^~s2s a~_ _y~s~ m~a~s~ _~ .o the halr anà
also to a r,e~ho~`~ o i~ vi.~ ~-.e ;-a~ n~i.ioning ability of a cosmetical ~ a__e~ e ..~ rea_in~ _omposi.ic.. by adding such a poiyr~ethylalkyls.loxane lo the hair treating composition.

Background Art Silicone polymers such as those having the Cosmetic Toiletries and Fragrance Association Adopted Names of "dimethicone" (i.e., t-ime-hy'ciloxy-end~locked polydimethylsiioxa-.es, an~. "cy_`odim2~.^_c3n-" (i.e., 2S polydimethylcyclosiloxanes) have been used in cosmetic formulations fo- he haAir such as shampoos and hair conditioners to enhance ~he gl^ss, sheen and drying time of the hair. Because of their si`icone nature, these compounds also lubricate the hair and make i' easier to comb. However, use of an excessive amount of silicone polymer can result in hair which has a coated or gre_sy appearance. The relatively short ~ethyl gro~ps a~.ached ~_ the silicon atoms in polydime~hylsiloxanes enhance _:.e character of the polymer.
Polydimethy1silo~:anes are alsG -el_~ively insoluble in water 3. anà in many water-con.cin ..g s__v_n_s.
~ o provide a blen~ o- s :--on_ ch_racter and substantive hair conditioning proner~ies, a` licone organic polymers containing amine-, qua~ernary- or carboxy-functional groups extending from the silicon atc..s -_rming the backbone of the -2- 2 ~ 7 ~i ~ J~ 7PCT/~'S90/071~

polymer have been proposed as can be seen fror ~.S. ~a~. ~'cs.
~,S63,347 to Starch (polyorganosilo~anes having func~ional substituents providing attachment to the hair ~her2 ~he a'`~:y_ substituents can have 1-8 carbon atoms); ~t ~ 5~6,518 to Cornwall e~ al. (hair setting using arinoal~yl-subs;: u_e_ polydiorganosiloxanes); 4,559,227 to Chandra et al.
(conditloning shampoos ~ith amine- u~ctional polydiorganosiloxanes); ~,74~,97~ to Homan e~ al. (hair treat~.en~s using carboxy-functional polydimethylsilc~:~n2s ~
i~ a cationic, o~gan~c polymer); ~,6~ ,3G^~ .o r.ldd e~. a~ .a :
treat~ents usir.g silanes or po~y~ic ganosilo~ane~ h~.v~:1g qua~ernary amr,c~iu~ groups alony ~'.-h amine-fu.._~ic.,al polydiorc2nosilo~2nes~ and ~ ,96-. to 2iemelis e~ al. (ha1r treatrents ~;ith c~~ionic polydio~ganosilo~:anes~ and ~,7~9,/3 i~ to ~ohl e~ al. (hair care compositivns erpicying polydiorganosilo~anes containing arinoal~yl groups modified by alkoxycarbonylalkyl groups). Thus, there has been a trend to employ silicone polymers which contain functional groups to treat and condition the hair.
Column 1 of the '732 Patent states that the addition of functional groups to polydiorganosiloxanes has a disadvantage in that the chemical reactivity of aminoalkyl groups may ~resent a problem in regard to compatibilitv ~ith other common componen.s of hair care forr.,ulations.
~5 Other types of polyorganosiloxane polymers have been used in conjunc;ion ~;ith the treat-~-nt of furs and h~ir as well as textiles.
British Pat. ~o. 992,0~7 to Dc;; Corning Corporation teaches a process for treating hair with an aqueous emulsion of an organosiloxane polymer having an average of from 1.9 to 2.1 crcanic radicals per silico-. atom`in the polymer. The silicon-vonded organic radicals are selected from monovalent hydrocarbons and halogenated hyd-ocarbons such as methyl, ethyl and octaàec,l, vinyl, cyc:oh_~:yl, phenyl, chloropheny 3~ and 3,3,3-trifluoropropyl and can even include hydrogen although methyl radicals are prefe-red. The emulsions are said to be especially useful fc- r:nsing the hair after sha.~pccing ~o i-.,prove ~he manaa_-b ity of the hair and to SU~ST~TUl ~: S~lE~

~91/09586 PCT/~;S90/071 -3- ~ ~rJ

impart a marked softness and feeling of sil~iness to the touch.
U.S. Pat. No. ,~307,557 to Carne~ teaches a method Oc treating furs, preferabl~ using a combi.lation of an polyorganosilo~ane -2S` n and a polyorganosilo~ane oil i.. ar.
oil-in-water emulsion: The alkyl radical in the polyorganosilo~ane oil can be rethy', ethyl, p-opyl or octadec~l. These compositions are said to impYOVe the luster and the ~eneral feel o~ fu- treated ;;i.h them.
.C~ Pal . ~0. ~,2~o,gll ~0 Opplige- teaches a me~h.cd fo~
~rea.ing "air i~i.h io;.ic cil-i~ ;a._r amu's'^ns cc polyor~anosilo~anes ~o ge~ ~c-e ~loss and shir.e as ~ell as superior ranageabi`_~ an~ a s_-- f 2e . _^ '' U`.~ nes ~
~each that the R group in ~he `_~mula glve;. can be re.:~l or , octadecvl. .~ ide -ange c- visc_si~i2s for the silicone compounds is given, t~ith 1~-lO,GOO cen-isto~es (1 ~ 10 ~ to 1 X 10 2 square meter per second) being preferred.
U.S. Pat. No. 3,185,627 to Kass teaches the use of a solvent to make incompatible silicones compatible with cosmetic ingredients. Column 4, lines 10-12 teach that some examples of useful silicones are laurylmethylsiloxane fluid (DC 1300 Fluid) and dilaurylpolysiloxane fluid (DC 1500 Fluid).
U.S. Pat. `~o. 3,~2,~2~ ~o ~cquaviva teaches a hair 2~ polish composition comprising a liquid silicane which can be applied to the coa_ of an anima~ and ~ill later dry to the desired superior shiny finish. It teaches the use of polyal~ylsiloxanes although di.~ethylpolysilo~anes are specifically taught to be usefu`. Column ~, lines 44-45 teach that ~hile the compositions can be used for hairy anirmals, it also states that ~ s ~ade from humans can be treated to provide -he im~proved shiny finish.
U.S. Pat. ~o. ,~23,032 tc ~be et al. teaches hair treatments co.mp~sed o keratin decom?osition products and 3~ certain derivalives based on pclyorganosilo~anes. Useful silicone derivatives are described in columns 6 and /, particularly Ihe al~v'-rmodifie^~ siliccne oils ~hich are described ir, colu~n " lines 1-~-30.

SU8S~TU~: SHFE~

WO 91/09~86 2 ~ ~ ~ 3 7Pcr/~s90/7l~4 U.S. Pat. 1;^. -,:), ,0S2 to Tietjen et al. teaches one-phase silicone-based cos~etic products containing wax. The wax is ~ ed ;; _n a i_i_o ~ ma~- ~al :.nich _2n con.alr an R
group tha~ cail b~ _n! _r o ~adecy~ ples i~ and B in colum;~ .ese formulations are called "foundations" ~hich appear to be formulat~ s~*~ . ?. ha~
treatment. ~he o~ ~os .ions ~du~n~ 2`'e in s_ic~ ca};e or cream fo-i .
lQN~n~ '` -' _ ? `~ .' ? ~ ? ~ `?~' ' . ; ( inventi_... - r~ aa__._s s;._w_n_ _:._ ;,_a~ `Ae-a~t concerning ~~e -c` s - ~ -o-~e ~ `s i~n ~arioùs compositicns S~A~. as s~ciisuoos ar_ COAnd;~ rS as well as 15 other cos-e~ic --po-~i~io?.s a~ . -?.-. `~OS. ~,6~8,839 to Dallal e. al.; -,3.~-,S3 to Pade:; 3,C~_,500 to Dra};ofr;

4,704,272 to Oh e~ al.; 4,72S,45, to Fieler et al.; 3,641,239 to Mohrlo}i and 4,725,658 to Thayer et al.

SummarY Disclosure of Invention The present inventior, resides in the discovery that certain polymethylalkylsilo~anes can provide hair with iAm~provec shi,.e a..d g~ OSa as '.;2il' as a~apei-ic- -~anageability and a soft feel in _he same manrne- a, polvdime~hylsiloxanes, 25 but which also leave the hair feeling less coated and greasy in appearance. ~elati-;e .o pol~di-;ethylsilo:~:ane fluids, the polymethylalkylsiloxanes of Ihe present invention also leave the hair WitAl .u_~ ê body, ~ullness ar.d softness. A further advantage is tha. the hair detangles and combs easier when 30 dry. The hair feels less coated and has less tendency to flyat~ay.
These and o~her obiects an~ advantages of the present invention are p-ovided '-y an im--oved composition for treating ~he nai- which com--` S2- _ ~`.2i- conditioning agent 3- disperse~i wi~hi.. a cosme_ically _-c_--abl2 ca-.ier medium which can be an aqueous mediu.,. ~`h_ improve. en. comprises including roi~ about 0.~ tO ab~ _ O--O~ more preferably from about 0.'~ ~^ 5~, and '-^St preferab`y from about 0.5% to 2.5%, by weight of the compositi_.-, based on the total weight ~;U!2,S~U~ F~

~091/09S86 PCT/US90/0715~
, _ 2 ~ v 7 of the hair conditionina agerls and car-ier medium, of a polymethylal~ylsiloxane haviny the averagP formula R2~C~3)~ Si(C~i3~ 'c~3)yos'(cH3)R2 -wherein each ~ is selected frcm the aroup consisting of methyl, ~ is a r~e~~
group, and each R' is a!l al~y 1 C`-OUp C' frcm ~ to about ~0 carbon atoms ;;he~a the~ ~.o--a nu~re~ o .-" g-oups present has 13 an a~ar~ ! - tt~ `_ `' ^ ^ ' '~? `~ n average ~ and are suc~rt ~_n~t ~le ~r ic ~ i!' _r~_t ~-a~ of fro~ ~7:3 to 55:~-3, more crefera~ t~`~` a_ou~ _0 ~O 20, ~he sum of ~ - y is areate- than c~^ e~~Aa` t_ arou~ 60 and less than i~ or equal to abou~ 1~.3., ro~-e pr-fe.-_~iy be.ween about 250 and 800, and the polymelhyl21}~!1silo~ane has a ~eltin~
transition, as measured by differential scanning calorimeter, between about -25C. to +27C. In such improved compositions, the polymethylalkylsiloxane can be the sole 20 hair conditioning agent or can be one of several present in the composition.
The carrier medium can be an àqueous hair shampoo composition containina àetergents sucn as anionic surfactants; an aqueous hair con_itioner such as an emulsion containing cationic surfactants; or a carrier medium in the form of an aerosol s~ composi~ic-. ;:r.ich contains one or more solvents in addition to the pol~..me~hylal~lsiloxane of the present invention, optionally, along ~.:ith a propellant, to produce an aerosol spray composi.ion for treating the 3~ hair.
The present inver.~ion also -elates to a method of conditioning hair which comprises ~he step of applying to the hair a composition containing from abou~ 0.1% to about 10% by weight, based upon ~he to~al weig:-._ Oc _he composition, of 3~ the above polymethylal~ylsiloxanes ~ispersed in a cosmeticall~ acceptasle car-ier .e_ ur..
Finally, the present inven. or. further relates to a method cf improving the hai- co..-i_:oning akili_y of a cosmetically acceptable hair treating composition which .. .

WO91/09586 -6- ~ PCT/~S9 comprises at least one hair treating agent dispersed in a carrier medium such as a hair shampoo, conditioner or aerosol spray composition, wherein the method comp-ises adding tc that composi~ion a polymethylalkylsiloxane of ~he ty_e -. described above.

Best Mode for Car vlna Out the In~ntion The polyr,ethylalkylsiloxane employed in ~he compositionC;
and method of the present invention has the average c-~ula ~ ~ ( C'~ ~, \ C i ( '~S ` ' CLt ~ / C~ S ` ( ~U ' \ `~

:ihe.~i., e~_h ~ ~s s2'e_~e~ y~ s.~.., _`
~e~hyl, ethil and pheny gr^upâ ~;~_h ~e~hyl beiny p~2f~rred.
1~ ln that formula, R' is an alkyi group o` fro.~ S to about 6~
carbon ator,s which can be octyl, decvl, dodecyl, tetradecyl, hexadecyl, octadecyl, eicosyl, docosyl, hexacosyl, octacosyl, triacontyl, tetratriacontyl, hexatriacontyl, octatriacontyl, tetracontyl, dotetracontyl, tetratetracontyl, 20 hexatetracontyl, octatetracontyl, pentacontyl, dopentacontyl, tetrapentacontyl, hexapentacontyl, octapentacontyl and hexacontyl. Although branched chain alkyl groups can be e~.ployed, it is preferred that the al~l groups be linear slnce the organic character Ot these alkyl groups is what contributes to the effectiveness of the po!ymethylal~ylsilo~anes in the compositions of the present invention. The organic character mo~ifies the silicone character imparted by ~he siloxane`units present in the back bone of the polymethylalkylsiloxanes by permitting those 30 groups to associate with hydrophobic materials. To provide sufficient organic character to the polymethylalkylsiloxane, the total number of R' groups and the number of carbon atoms contained therein is selected so tha. the average number of carbon ato~s in all R~ groups presen. is at least 12. Below ,_ an average of i2 carbon ator.s in the total R' groups presen_, the overall hair .reating perrorran-- of compositions containing such polymethylal~ylsiioxanes decreases.
Therefore, it is even more preferred that the average number SU~3ST~TUTE SHEEl~

,'O 91/09~86 PCr/l~S90/0715 ~a7~ ~?rl of carbon atoms in the total R' groups present be at leas, 16 and most preferably between 16 and 24 carbon ator,s.
The polymethylalkylsiloxanes used in the present invention are made according to conventional procedures ~!hich i are ~;ell kno~;n to those of ordinary skill in the.prepara_ion of polydiorganosiloxanes. The bac~bone prepolymers are prepared according to conventional rethods involvina the equilibration of dimeth~lsiloxanes and organosilanes or organosiloxanes containing at least one silicon hydride unit s~ch as me~h~ldichlorosiiane or 1,2,,,~-tetramethyicyoio-rerrasilo~:ane in the presence of a l~asic ca,alyst.
Pol~organosiloxanes ccn~a~ning dimethylsiloxane ur..~C as ;:e'!
as ~e~ si;~ r.-~ ùrlit~ r~erc~
availakie r_~ various sources suc!l as tne Gene~-al ~le_~ric l~ Company, Sil,cone Produc~- ~i;ision of l~aterford, Nei Yor}:
anv the Do;~; Corning Corporation of ;-:idlanà, ~lichigan.
Using conventional and well-known techniques, 1-alkenes can be added to the silicon hydride-functional polyorganosiloxane prepolymer through the platinum-catalyzed addition of such alkenes to the hydride group. Thus, a polymethylalkylsiloxane of the present invention containing an R' group with lo carbon atoms can be obtained by the piatinum-ca~alyzed addition of 1-octadecene to a ~o yorga.r.osiloxane prepolymer ~;hich is a Irimethylsiloxy-2~ endblocked copolymer of dimethylsiloxane units andmethylhydrivesiloxane uni,s. To ob~ain alkyl groups with an average of r.ore than 20 carbon ator.s, it is generally more economical to use mixtures or these higher l-alkenes. A
typical mixture is a mixture of C30- 1-alkenes is described in U.S. Pat. No. 3,553,177. Another commercially available ~ixture of higher l-alkenes is a mixture of C20 to C24 1-alkenes. It is preferred tha. the higher 1-alkenes be essentially monoolefinic since diolefins can cause gel formation and cross-linking. ~nother commercially available ,, so~rce o~ i-al~enes is ~Aa~ con~ai.-_ng a mixlure of C2~ - C2O
~-alkene ,ix.ures. The i-alkenes a-e comrercially available fror.. E~Ayl Corporation cf Bator. Rou~e, Louisiana and Chevron CAemical Company of Houston, Texas.

SUBSTITUTE SHE~

WO91/09586 ~ 3 i3 ~

In Formula I above, the polymethylal~ylsiloxane is composed of units of ~ol~dimeth~lsiloxane randomly interspersed ;:ith me h.V' al~ ' ' O':alle ``n` _S ;.here 'he a`~y1 group correspords _o th2 ~ c^ou~ ro_e;~ above. ~ecausc the polymers are ~ a^ ~ ~. u:` ._ `., _n?i ~ ` ^ :`. .-~ _ - .' ~d, the polymers are composed of an averaae number of each such unit. To ob~ here must be a minimum nu.ibe~i- o~~ ~ac`- cype o` ~iini_ to ba`2r.ce ~he essentiall~ 2 ~ ?.;le l0 units ag~irst ~ ?~ e meth~lal~ ls~
in the range c~ a~ `: a orc preferr~ e.~ e~
groups hav~ng ar. o;_r _ a~^-r_i__ _~^_m ; _~ a-~_..i?i_ors.
li~ More preferably, ~ is a -~,e~ .` ~rou~. _n su_h co.p~s:-ions, it is preferred .ha_ the ratio e~ ~:y be îrom ~6 Y to ~:20.
In a still more preferred embodiment, the ratio of x:y is from 97:3 to 93:7 so that the polymethylalXylsiloxane has sufficient siloxane character contributed by the polydimethylsiloxane units to offset the organic character contributed by the methylal~ylsiloxane units. These polymethylal~ylsiloxanes would find utility in formulations used to treat normal ha~- sin.ce -.~e~ ha~e 'ess al~:y' conte~t.
On the othe~ hand, ror d-y hai~ o- hai- damaged b~
bleaching, permanent waving, hea., etc., compositions employing a highe- al~yl ^on~en_ ca-. be e--loyed such as those where the ratio of ~:y is LrO-m ~8:12 to about 80:20.
The amount of polysiloxane hair conditioning agent in that case ranges from 0.l~ to ~ b~ ~;eigr.~ of the composition with from 0.5~ to 2.5~ beir.g ~ore preferred.
Thus, the ratios of the organosiloxane units present can be altered IO sui. the needs of ~`ne par~icular hair which the hair treating com~osition is designed to treat.
To be effec ive, the sum o-^ .~ should be greater than 3~ about 60 and leass .han or equal _J a~ou~ i~3.~. ` ve-- lo;:
molecular weigh~ polvme.hylal}:y`a_`ls~:ar;e ~;:i'i have tOO little silicone charac~er ~o condition _ne hair. ~. very high molecular weigh. poly~er ~..ill ten~ ~o be difficult to synthesize as ~;ell as being too nig- in viscosity and ;ill SU~3STITU~ SHEE~

~,091/09586 PCT/~S90/071 _? ?
~ ~ 7 ~ ~ ~? .

lose the fluid or gel-like character that we find contributes to the hair conditioning ability OI the polymethylal~ylsilo~anes useci in cur inve~ icn.
In addi,ion to a molecula- weigh~ lim~a.ion, the _? polymethy~ ~\!s-io~i Ci !1`~ _ 3 ~ I S ~ aisto have a melting transition, as .;~easured by i differential scanning calori?,me~er. be~ween a~ u~ o -~7CC.
Polymethylal}~ti~lsilo~anes ~`alli:~-3 cu~side o. this range do not have all of the adv;~nta~ecus ~c~e~ e~t ~eo~-tsessed bv those 1~? fallina within this ~a.l~. r~ ;a~ _ ei_`yi~ime~hylsiloxane fluid cf t;eia~l~ a~ ra~ ;`t~ J~ .t~ alt ~
2 0 0 0 i ,t t~ a~'t~ _ ?~ - r~-s ti~ t is less tlla~ 1?~ (I) above genera_ly aa;e â n~ _`~ S~.~ ` _ic;~ . ` S o~a~side Oî
this range ;;~,en ~he tc_a'. a~ -m~ chain length of the R' groups present ^ails ~elo;; :2~ eren~i 2~ sc2nning calorimeters are well ~nown in ~he art and are available from sources such as the DuPont 910 Differential Scanning Calorimeter from E. I. DuPont de Nemours & Co., Instrument Products Division, of Wilmington, DE used in the following examples.
A further requirement for utility in the present invention is that .he pol~mêthyla`~lsilo~ane be in the form~
of a fluià c- a gel-li};e -_~e~^i_` -__he~ .a.- a solid or a 2~ wax at room temperature or a ve-~ low viscosity fluid.
Polymethylal~ylsilo~anes mee-ing the above requirements will be in the form o~ the desired fluid or gel~ e material at room temperatures.
The abo~e poly~e'hylal~lsiloxan.es act as hair conditioning agents and can be dispersed within a cosmetically acceptable carrier medium. The term "cosmetically acceptable" is in~en~ed IO mean that it is suitable for contact with the hu.mar. body and, more specificall~, in conjunction wit.. human hair. As is well 3~ ~;nown ir. ~he a-~, an a~uecua ca--_e- mediu- is t~picall~ used and the polv.,ethylal}~ylsi~ ar.es ~ -he p-ese-~ invention can be used 1.. hai- shampoos such _a ~h~sê taugh- in ~.S. Pat.
No. Y,321,~6 to 3ushman whicn cc.p-ises an anionic detergent and inorgani_ sal~, a pH adjus~ ^mount of an acid and SUBSTITUTE SHEET

WO91/09586 -lO- ~ 7 PcT/~s90/071~1 water. As is well known in the art, shampoos for the hair can include anionic surfactants such as sodium and ammonium lauryl sulfate and sodiur and ammoniur. lauryl ether sulfates, fatty al~yl ether carboxylates and fatty al~yl ether sulfosuccinates; nonionic surfactants such as fatty a~ yl ethers and sorbitan esters of fatty acids; ar,photeric surfactan~s such as ratty al~yl betaines, sulfobetaines ar.d imidazol~nes and, in sorme cases, cationlc surfactants such as fatty al~yl amidoamines and fat~y al~yl quaternary amronium lC compounds~ ~he .erm "~`atty al};yl' is intended ~o mean a long .hain all;~.' ~a~ _al havinq ;^ro~, abo~t l~ .3 ~ carhon ato~s.
In shar~,poos, the polyme~hyial`~y'silo~ane can be the sole hair con~itioning a~ent present in the composition. Tt is l~ such as organic cationic hai~- conditioning aaents could be added to 'he shampoos. ~owever, il is more corron to have a cationic hair conditioning agent present in a composition wherein the carrier medium is a hair conditioner which can be used as a leave-on treatment or it can be rinsed off the 20 hair. For example, polymethylalkylsiloxanes of the present invention could be added to a cream rinse conditioner of the type described in U.S. Pat. No. 4,421,7~0 to Burton which cor.,prises an aqueous emulsion of cet~l alcohol and a fatty al~yl qua~e-nary ammoniur compound as a crea. rinse product.
2~ It is placed on the hair after shampooing, allowed to remain on the hair for a period of ti~e, and is then rinsed a~;ay.
Examples Oc conditioning co.~?ounds e~ployed in the '7~0 compositions are stearyl dimethyl ~enzyl ammonium chloride and cetyi dimethyl ar.ine oxide. A further ingredient is a ~O thic~ener or protective colloid which can be hydroxyethylcellulose or guar gum. O.her examples of suitable hair conditioner carrier media ~ill be apparent to those of ordinary s~ill in the art.
Ancther example of a carrier me-ium is a composition ~- ~hich is aispensed from an aerosol col..ainer in the form of a _ollapsible foal aerosol hair produc_ often called a "mousse"
product. The foam produced from a mousse product reaaily collapses onto the hair after dis?er.sing upon being touched or mechanically agitated. One su~h oar., mousse produc_ is WO9l/09~86 PCT/US90/071~
'~ ~ 7 ~
described in U.S. Pat. No. 4,536,390 to Padden and comprises from 3 to 956 by weight of a volatile propellant such as propane or bu.ane and from 97 to lO~z by weigh, of an aqueous intermedia~e containing from 0.25 to 2~ by t~eight of a . qu~e-nary 2m..'0!-iUm compound conditioning agen~ such as cetyltrimethyl ammonium chloride as well as from about 0.25 to 5% Oc a hih molecular weight polymer selec~ed from the group consisting of cationic polymers, amine functional polymers and ri~tures thereof with the balance being water and ~herein the composition contains le~s than 10~ of an ~' chol h.av~-.~ Cr~,~, ^ne 'o ou~ carh^n atoms.
.~no~he- e~:ample of a carrie- me~iu.m ;:hich can be used to rea~ ha ~ h ~_ly.me_hy`21':yls `o~:a-.es o~ p-esen_ invention is .o use a cos.~etically a__ep~abie solven~ such as ethanol as an ae~osol spray car-ier -edium and to spray a lo~;
viscosity solution or the polymethyl-l~ylsilo~ane on the hair. Other examples or solvents are isoproponol, volatile polydimethylsiloxane and polydimethylcyclosiloxane fluids, and other solvents commonly used in hair spray formulations 20 which are compatible with the polymethylalkylsiloxane chosen.
These types of compositions can then be applied to the hair using a conventional pump spray container.
` T_ a self-p-essurized aerosol spray is desired, then conv2n.iollal propellants such as vo`atile nydrocarbons such 2~ as n-propane, isopropane,-n-butane and isobutane can be used as ~ell as comp-essed gasses such as nitrogen and carbon dioxide. In some cases, ~he hydroca-bon propellants can act as the soivent for the polymethylal.~ylsiloxane. These composi~ions are pac~aged in conventional aerosol containers having an aerosol valve and an actuator button to permit dispensing as a self-pressurized ae-osol spray.
Other carrier media ~iill be apparent to those of ordinary s.~ill in the art. It .;ill be readily apparent that the type and amcunt of polymethylal~ lsiloxane employed must .~ ~e sucA t;a_ the co.~posi~ions remai;-. stable and do not separate into se~eral phases which ;:ould cause them to be more difficult ~o apply evenly to t.e hair. Conventional dispersing aids may be used to impr-ve the compatibility of the polymethylal~ylsiloxane with a --?ecific composition.

~;U~STlTUTE SHE~T

W091/09~86 -1~- 2 ~ '! PCT/~S90/071~4 Examples of such aids are ce-tain long chain (C.6 to C22) acyl compounds of the t~'pe ~escribed i~ ~.S. Pa~. No.
4,741,855 to ~-~o-e, e_ a. v~)e a~~aa~.a~-s c ~ne use c- the polymeth~lal~ lc~ a ~l ? ~ i s - ~ a they are more ;~ ini~~ 2-~a.
groups because the~ con~a_n iong cna n alky; groups. As a result, these ~ol~am2; ;~yla. ~y`s~ .o~a~ ?S a-e Cap<?~le 0' treàting the hai~ and are aC``` ''~'h a _ m` ''`e `~ ?~ le ir. hair treating cor~pcsi~icns ~ `` e ^~' ~5`.` `~ ` n~.
polydimethylsii3:~;an_s ~ t;~e ~:ia;::i? ~ =`ai;:e ~o^~ u`iar ~eicht.

art, the ~ ;a~e~

op~ion~; ~ l à ~` ?~ ~~. ~ O O S
l~ hair condi~ionin~ _a-~_csi.i_n~ u--s-s ari ~`he 'ike~ For example, fr2c~-an_es, an~icxida.-_c, ~__a~s~._na, _hickeni-.-agents, cosmetically accep.abie sol~en.a, preservatives, dyes, inorganic salts for viscosity control, and the like which are commonly employed in such compositions can be included in compositions of the present invention in amounts which are generally less than about 5% of the total composition.

ln~us~-`a` ~
Thus, the carrier media empio~y-e~ t^ deliver the polymethylalkylsiloxane o the prese-lt invention can range from ~shampoos, hair conditioners such as cream rinses and lea~e-on products, mousse produc _â _n.d hairsprays. One advantage of the preser.t in~er.~icn is that the amounts of the polymethylalkylsiloxanes as well as the ratio of the polydimethylsiloxane units to the me~hylal~ylsiloxane units can be altered so that ~a-ious type- o hair can be t-eated with good results.
As part of the total composi~i_n, from about 0.~ - 7% is ~-, preferred w.ith ~ eirg -~ e~e--ed and -_s_ prererred is ~.. - 2. c p^ly-_-h _--_:~lsilox2r,e ~ased u-on the total composition in per_en= _y .;eight. Fcr use -:ith normal hair, it is preferable to us- polymethylalkyl-SU~STITUTE SHEET

WO91/09586 PCT/~vS9O/071 ~ c~,7 siloxanes having lo~.er al~vl content such that the ratio of x:y is from 97:3 to 93:,. In ~he polymethy~al~ylsiloxanes of the present inver~icn, high*~ 1 C~?.~en~ could give treated hai~ -2aS`_- _pt'e?`-'~n^e.
Thus f~ c-~ ?. ~ U'; `. ~ h~ ;'s.~isiioxanes having a higher al~i content is ~,o-e desiravie such as ~.~here the ratio C t- ~ i s f -c-. ^` '`. '~ ' ' `? C . i~i`he polymethylal~lsilo~;ar.es ha~ n-i_io:li..g ac3ent is from 0.1 to 5% b~ ;;eig~.t c~ th~ posi~i-~ `-^m a~out 0.~% to 10 about 2.5~ e'~!'C' n^.~e erre~ nair ~ damac3ed hair requires ~ `?`~ '?~^ na~uraiiv deficien~ -~ . a ;~
previous 5.. -~ s ~ s bene~its ~-c.~ a_m2'`~e_n ~ lsi IO~a;leâ G.
the presen~ in;~en_ion.
Thus, one aspec~ he ~resen_ in;en_ion is a rethvd of treating the hair through the application of the po~ymethylalXy~siloxanes of the present inventi~n to t~e ~air by means of a shampoo, hair conditioner, mousse, aerosol 20 spray, or other carrier media. rrhe polymethylalkylsiloxane does not have to be the only hair conditioning agent present.
Conventional hair conditioning agents such as quaternary am~onium compoun~.C can be furtner included to provide specific benefi~s t^ the h2i~ use cf _..e quaternarv ammonium groups present in ~he orgar.ic cationic hair conditioning agen-s, the~ w~ll tend tO be ~ore substantive to the hair t~an the essentiall,v ncn?c`ar polymeth~lal~y~silo~anes of the _reser.~ inven_ion. In this manner, a s}~nersist~c ef ect car. ke obtained i;here the -benefits of the siloxane polymer enhance the benefitsobtained b~ an organic hair con~itionin~ agent.
The polymethylalXylsiloxane, c_ the present invention can thus improve the properties ot a cosmetically acceptable hair treating compcsiti^n such as G conventional hair 3-, shampoo, hair condi~ione- c- ae-_s_~ f__.ulc~_cn.
The fol'owing r~a.m?i-s are ~ .-ide~ __ sho~ v2rious aspects o- the p,esent inven~ior. ..:_hou~ de?ar~ing from the scope and spirit of the inventicn. Uniess other~ise lndicate_, ail pa-~s and percen~-__s used in the Exa~ples are SU~STITUT~ SHEE~

~5 q0 1~7ISL
-14- ~3 ~C,/7ql by weight. In the Examples, the molecular weights were measured by Gel Permeation Chromatography using polystyrene molecular weight standards. nRoom temperature~ is between 200C. and 250c.

Exam~le 1 This Example demonstrates the production of a hair condition~r composition containing a polymethylal~ylsilo~ans of the present invention which is appliad ~o the hair and 10 then rlnsad off with water.
A ~olt~ebhylal~ylsiloxane was conv2ntionally pra~ar~d ~v the pla~ m-ca~ali~d addition o 1-oc~ad2csna ~o a trimethylsilyl-endblockad copoly~e- of dimethylsiloxans and methylhydrid~qiloxane units to obtain a polymer of the typa shown in Formula I, supra, wherein R was a methyl group, R~
was an octadecyl group, x had an average value of 400 and y had an average value of 18. The weight average molecular weight of the resulting polymer was 56,974 and it had a number average molecular weight of 3,157 with a peak 20 molecular weight of 36,627. This polymer was a viscous liguid at room temperature, had a melting transition as measured by the DuPont 910 Differential Scanning Calorimeter of -15.4C, and will be re~erred to as ~Silicone I~.
Silicone I was used in the preparation of the hair 25 conditioner formulation described in Table I below.
Table I
Cetyl Alcohol 2.00 30 ADOGEN 432ETl O.70 Citric Acid 0.05 SCHERC~DINEo s2 0.40 Tricetyl Amine O.40 Silicone I 0.50 35 KATHON~ CG3 0.032 Fragrance 0.50 ---Ammonium Chloride (20~ in water) 1.25 Deionized Water 94.168 100 . 00% . -lDicetyl dimethyl ammonium chloride in ethanol at 67-69 solids from Sherex Chemical Co., Inc. o~ Dublin, OH.

~,.-s~s~ ~ s~

~'091/09586 PCT/~'S90/07154 -15- 2~7~7 2Stearamidopropyl Dimethylamine from Scher Cher,icals, Inc., of Clifton, NJ.
35-Chloro-2-me~h~ `L--.-._SO~;'ia~ .-3-_'e ~ h~l an_ Yiaas Company of Philadelphi ~?~, P.~..

To prepare tnis com~os _~oi" _l.e ~2 ~ a wa~er is heated to 76.67C (170r~. ~he etyl alc^`~.c' is then added with sliqht agi~ation alld ~e~mi-__e~ so d~ss_ ~e. Lhe following ingredients a~^a ~.hen -~ d ~:n o-de~s ;;_th _i.m~ being given for eacil ~o dlssc~.* `~ n~ i 2..- __ add~d: ADOG~

and the foiio~iing are added ii C`-deL -~;;.!. ag_~a~ion:
Si~icone I ~-.~ ~u'~ s then coole~ ^c~ - ?~ *~ ?. h~h shear mi~er (I~A ~ior~s ~LTR~-T~ r~o n~gl. shea- ro.ary mixer from I~A l~ior~s o- S~au_en, ~;es= Gerrar.y with ar. S50-G45G generator and shaft at 4,000-10,000 R.P.M.) until the formulation has a thic~ creamy appearance. The ammonium chloride solution is then added with mixing until a viscosity of from 3,000-7,000 centipoise (3-7 pascal seconds) is reached.
To use the resulting hair condi,ion2r co~?osition, the ~, user is inst~uc~e~ -^ sha~p~_ th~ ~a~- and s~uee7e out e~cess water. A generous amount of the hai- conditioner corposition is then wor~ed through the hai~. The hair conditioner composition is tnen rinsed ~hcr_~h:; fro. .he hair ~ tn water and ~he hair is ther, se~ ~5 us~aal.
Example 2 In this Example, the ability o_ Silicone I to act as a hai~ conditioning agent by itsel- waa evalua~ed using t~-c trained hair s~ylists who applie` 2.. aerosc' s~ray composition containing Silicone ~ tc the hai. of a panel of 1~ women volunteers.
The aerosol sprav comc^siti^n used was cor,posed cf 2%
Silicone I, ,9~ SF-1202 Sil:ccn^ ~ (prin.cipally decamethylcycloDentasilo~anê fr_- C-eneral Ele_tric) and ~9 ~0 SD Alcohol 3A '190 proof elhanc_ de-aturec w--h ,e~~

~U~STIl ~T~ SHEE~

WO9l/09586 .~ n r ~ ~ ~ 7PCT/~S90/071 alcohol). A number of standard 202 X 509 lined tin-plated steel aerosol containers were filled with lOO grams each of this composition and then sealed with a Seaquist NC-31 O.O'~"
(0.033 c~) aerosol container valve fror~ Seaquis. Pu~ps, division of ?it~;~ay Cc-poration, of Cary, IL. Each sea:e_ container was pressurized through the valve using about 6 milliliters ~3~ gra~s) of isobutane as a propell~nt. Th~
actuator bu;ton used on the valve was an E~CEL-lOO Mis.y button t~ith an orifice si~e of C.Ol." (C.03. c.-,) mis~y fro~
Seaquist.
~ `he cc~pc~ or. r-^~ the pre~suri ed c^nta~e-s ~`:a~=
spra~ed on~ tha ha;~ o^ 1 vo'u._eer panelis.s b~ trained halr st~ is s ~us~ ~ ach pa~.eiis_'s ..~ ha~ ~ee~.
sha~pooe_ a~._ was s~ .;et. The cor~pcsi~icr. ;:~s le~_ _n ~..e 1~ hair ;;hile i- :;as it ;;as combed and detangled foilowed b~
blow drying and styling.
The stylists were as~ed to evaluate various aspects of the treated hair by how they rated statements such as "wets easily/', "easily combed", nfeels coated", "feels conditioned"
and the like as applying to the treated hair using a rating scale of from 1 to 5 for both wet and dry hair as well as after the hair was dry and styled. The panelists were asked for a verbal evaluation OI their hair after stylinq.
~he resul.s o~ .he .esting -.;ere that ~he spray was 2~ relatively highly rated by both the hair stylists and the panelists. Silicone I w2s judged to be very good for conditioning without a loss of b_dy, fullness, or bounce.
The product was not judged to leave the hair matted flat or weighted down in appearance. The dry treated hair was soft, silky and its shine was greatly enhanced. After styling, the curls on the treated side were tight with good to excellent spring.
The cor.ditioning benefits we-e less noticeable for some panelists who didn't nee~ a condi ioner. In that case, the __ addition of .he polyme_rylal~yls_loxane to the hair possibly resulted in overconditioning. Ir. such cases, the curling iron used ir. s ~ling r,ay not have been able to grip the hai~
because the poly~ethyl21~ylsilox_ne rendered the hair relativel~ fric~ionless.

SU8STITUTE SHEE~ `

5~6 p(~/l~S90/071: 1 2~ ~ 6~ ,' One negative noted during testing was an objectionable odor presumably caused by the ethanol present. This can be overcome by simply substituting SF-1~02 Silicone Fluid (principally decamethylcyclopentasiloxane) or SFl173 Si'icone Fluid (pri..cipaily octamethylcyclotetrasiloxane) fror Genera Electric in place of the ethanol in the composition.

E~amples 3-In these Examples, a liquid an~A a gel form of the l~ polvmethylal~vlsiloxanes of the present invention ~ere co~"pa~ed ~o ~a_h other. Li~uiA ~oly-me`!lyl?.l~yls~loxares ::e-_ also com-ared to a li~uid polydi.ethylsiloxane. ~hey were tested fcr e~~ c~ivenesa as a ha~r _ond~o.ing age.,~ in a hair conditioning carrier r.ediu.m when applied ~c ~he hai, cf l~ a panel cf ;~c~en volunteers. The panelists used in these tests had a variety of hair types ranging from, normal to dry to slightly damaged due to hair dyeing, bleaching, etc.
The liquid polymethylalkylsiloxane used (hereinafter NSilicone II") was conventionally prepared by the platinum-catalyzed addition of 1-eicosene to a trimethylsilyl-endblocked copolymer of dimethylsiloxane and methylhydridesiloxane units to obtain a polymer of the type shown in For~ula I, suPra, wherein R was a methyl group, R' was an eicosyl group, x had an average value of 273 and y had an average value of 13. The weight average molecular weight of the copolymer prior to addition of the l-eicosene was 20,971 and it had a numbèr average molecular weight of 2,115.
Silicone II was a mediur to high viscosity liquid at room temperature and had a melting transition as measured by the DuPont 910 Differential Scanning Calorimeter of 13C.
The gel polymethylal~ylsiloxane used (hereinafter "Silicone lII") was conventionally prepared by the platinum-catalyzed addition of l-eicosene to a trimethylsilyl-endblocked copolymer of dimethylsi'oxane and 3~ meth~lhyàridesiloxane units to c~tain a polymer of the type shown in Formula I, suPra, wherein R was a methyl group, R' was an elcosyl group, x had an ave-age value of 222 and y had an average value of ~1. The weigh~ average molecular weight of the copolymer prio- to additior. of the l-eicosene was - SU8STITUTF SHEE~

W091/09586 PCr/-S90/071~4 -lS- ~ v ~ ~

18,86~ and it had a number avera~e molecular weight of 1,80~.
Silicone III was a gel (thic.~ and ~-a~) at room te~perature and had a meltir.~ ~~ana~ ior. ~s m~aa`l~_d ~' th~ DuPor.~ 910 Differen~l S~

endbloc~ed polydimethylsiloxalle wi~h a viscositv of ~00 centisto~â '~ ,c^~t~ ?. _ room temperature ~-~0~; ~O~`;;.;C~ ~, 't-luid, ~V ce-.~is~o~e fror.
Dow Corning) and `à ~e'~~ a~`~e~ d ;0 2S "Sil.oor.e ~"', a comparative 2~;a~~ 1 e m~~.e.r~ a `~ .

preparin, ~ ;y~ r J~
(S.earal~ c~ c~ a;~, Inc. of ~urne_, :;" ~ ;_S~
1~ (hydroxye~ c~ c~ ~ aJ~ o-` ~ ing~cn, DL) and 9~'0 deionized ~.a~er (he~-ina~ter "Base 1"). One part of Silicone II, Silicone III and Silicone IV, respectively, was dispersed into 100 parts of Base 1 using a TEKMAR RW20 DZM rotary mixer with a 4-blade stirrer from IKA Works of Staufen, West Germany at 250 to 2,000 R.P.M. to form Examples 3, 4 and 5, respectively.
A "half-head" procedure t~as used in this evaluation.
Two trained h^lr -^-yl sls sham.r_^e th_ entire head ^f each of 13 volunteer panelis.s ar.d _..^-. ~inaed .he sha~poo fro.
the panelist's hair. The stylis_s then applied a measured amount of rxample ~ ~o the hai~ _n _ne side of a panelist's head usinq a syringe. The stylis. immediately worked the conditioner into the hai- cn tha- side of the head and then rinsed it immedia-ely from ~he ..air using tap t~ater. The same procedure t~as used on the hair on the opposite side of the panelist's head, but Exa~ple ~ t.as used on that side.
The identitv of each polyme_hylal~ylsiloxane was not revealed to either the hair sylia_ or the panelists. The hair stylis~ was iven an evalua~i^.. form giving statements 3~ of the type no~ed in rx2..mple 1 a~_ve and ~oid to evaluate the tviet, dry and af~er-s~yling cAar---_e-ist~cs of the treated hair on each side of tAe paneiis 's head by ran};ing those state~ents using a scale of ' t^ _. Before the panelist left the salon, she was also given a ~ar--home evaluation form SU~3STITIJ~ SHEE~

6 PCI`/l,S90/071~4 -l9- 2a~ ~3 ~
which she was as~ed to com~lete 'he next morning and to telephone the results to the tes_ facility.
Due t~ _he small sa.~n~_le s~ used in the salon testing reported in m^s- a ~-.e _:a-.m~_`_s -^re~ _he diCcerences in scale ranl~`nsJs W'_ ` ~ s~ g~ ng. ' ~:o~ever, significant physical properties were roticeable upon visual inspection. ~as_d en ~ r~su`_s c t~is ~_sting, ~xample 3 (liquid polymeth~,lal'r:~lsilo~alle) ;aà nc. judged to be superior lo E:~amala ~ ~e`~ - ly.m-^-_h la'`s~'ai.lox~ane), but both lQ delivered ve-y gc.e.d ~~ e~c~:` c.~.~ e-~`^r~-nc_ ^n ~ey condi~icr.^~
The r~s_'_c ~ s-_, _~

higher average ,a_~ s ^n ~ 5;~ ..' r~ ris~_s _han 1~ that treated ;;i~h Exam~;e ~: r..`.~.~ els less coated when wet; detangles and combs eaaier ~ihen dry; t~eighs hair down less (dry); feels softer, smoother and more conditioned;
leaves hair more manageable, cleaner loo~ing, and with more shine; and PANELISTS (next day evaluation): slightly more easily combed with less flyaway; feels less coated; leaves hair more manageable, cleaner looking and with more body and shine.
The results cf the hai- stylis-c~ ev21uation was that hair trea~ed wirh Exar.pi2 ~ .eceivêd hlghe~ average ratings in the following characteristics ~han tha~ treated with Example 3: less _l~away; feels l-ss drv: and less matted/flat.
The same "half-head" procedure was hen repeated on a different day by t~o hai- stylic_s on '/ volunteer panelists.
Example 3 was placed on the hair on one side of the panelist's head and Exam?le 5 was placed on the other side.
Example 3 was found to have defi~i _e performance advantages over the comparative polydimethylsiloxane-containing Example ~. ~he results of the h_i- stylists' and panelists' 3~ evaluation was ~hat hair .rêa~ê^ ;~ h Exa,..pl_ 3 received higher average ra~ings in ~he f^:l_;.ing charac~eristics than that trea~ed with Example ~ STiLISTS: feels less coated when wet and dry; weighs -a:- down less (drv); leaves hair more manageable with more r~d,~ fullness, bounce and SU~ST~TUTE SHEE7' WO91/09586 ~ ,r r ~ J PCI`/I~S90/0/151 --2 0-- ~ ~r ~

shine; and PANELISTS (next day evaluation): feels less coated with less flyaway; feels soft; leaves hair more manageable with r.ore body. Exarple 5 was very slightly superior to E~ample 3 in that it was more easilv comked wr.en _ wet and fel~ more condi~ioned wherl dry ac_ord~.lg ~o ~..?, stylists.
Example 6 was prepa-ed usinc~ Silicone ~` in ~he same manner as described for E~ample 3 and was evaluated using ~-~.e half-head procedure described abcve versus compara.ive ~a~ple ~ e~.t^e~ usin Sil'c~e ~ ~?~ n~
as ~es.~.bed, c~ am~ ss_n~ia'ly thi sa.e ~`ësa~ ~S a:
were repcr~ed fo. E~ample 3 versus ~am~ple . were ob~ailled.
E~:a~pl~ 6 ;~s SU~e~iC'^ t_ E~;a.`.`l'.~ie / ii~ S'.~ d_.ri~U~éS
note~ for E~ample 3 over Example ~ above e~cept the s~ylis~s reported that the manageability c ~he hair a .er s~`ing ;;as essentially the same for both Exar,ples 6 and , and the panelists reported that the flyaway for both Examples 6 and i was equivalent.
Silicone V was conventionally prepared by the platinum-catalyzed addition of 1-octadecene to a trimethylsilyl-endblocked copolymer of dimethylsiloxane and methylhydridesiloxane units to obtain a polymer of the type shown in Formula I, supra, ~herein ~ was a rmethyl group, R' was an octadecyl group, x had an average value of 80G and y 2~ had an average value of 36. The weight average and number average molecular weights of the polymer could not be measured because the polymer crosslin~ed prior to the time that measurements were to be ta~en. Silicone ~' was a medium tO high viscosity liquid at room te~perature shortly after it 30 was made and evaluated as a hair conditioning agent and had a melting transition as measured by the DuPont 910 Differential Scanning Calorimeter of -1~.1C. ~`?on storage at roorm temperature, it eventually crosslin.~ed into a gel.
Sili_one ~I was SF-96-100 Si'i-one Flui_ fror, General 3. Electric which was a trimethylsiio~.-endbloc~;eà
polydimethylsiloxane fluid of 10^ centisto~e (l x 10 ~ square meter per second) viscosity at room temperature.

SU~3ST~U~rE SHEE~

W091/09~86 -21- PCT/~S90/071 ~,r~ r Examples 8~
In these Examples, the hair conditioning effect of a series of polymethylal~ylsiloxanes having the same bac~bone polymer, but different al~yl chain lengths, was instrumentali~ measured.
The base silicone prepolymer used was a copolymer of the type shown as Formula I, su~ra, where R was a methyl group, x had an average value of 273, y had an average value of 13, R' was hydroger., the weight average molecular weight was 20,9,i, the number averaqe molecular weioht was ^~,115 and the percen~
Si~ con~en~ was 0.6~ mol/g ~ ilicones ~'II, ~I~l, li;
and ~, respec~i~ely, were prepared ky ~he pla~inum-c~.alyzed addi~ion ~ ^c ,er.e, ^-~ecene, :-do~e_-n-- ar.i l-e _os~
respective_~, ~o ~ha. prepoiyme~m 1~ Silic~nes ~ ?I_- and I~ ~;ere ea^h relalively lo;
viscosity liquids at roo.~ tempera~ure. S~liccne ~ was a medium to high viscosity liquid at room temperature and had a melting transition as measured by the DuPont 91O Differential Scanning Calorimeter of 13C.
Comparative Example 8 was prepared by adding 0.5% of Silicone VII to Base 1 as described for Examples 3-7.
Examples 9-11, respectively, were prepared in the same manner by addina 0.5% of Silicone VIII, I~ and X, respectively, to Base 1. ,~a~ple 9 was also a ccmpara~ive example.
2~ The first test done was a body test which used clean dry swatches of DeMeo European Virgin Hair from DeMeo Brothers of Ne~ York, NY, 8 inches ~20.3 c~) long weighing about 10 grams each. Five swatches were used to ev2'u2te each of Examples 8-11 .
3Q To obtain a base hair volume reading, each swatch was shampooed and rinsed with tap wa~er. The water was squeezed out between the fingers and the swa~ch was hung on a rac~. to air dry over a ~ hour period at ~oo. temperature. Each swatch was ~eriodically combed and carefully brushed while it 3~ was àryin~ ~_ g~ve the s;atch a __r.~entric cone shape.
~ fter drying, the s-.atch was hu..g on a rotatable ho^}; ir.
front of a videocamera. The videoc2-era W25 interfaced with computer analysis equipment to allo- the cross-sectional area of the swatch to be calculated f-om .wo images which is SU~STITUTE SHEET

~JC\ ~ l O ~
-22- ~ ~ 9 ~ C \

directly related to the volume of the hair swatch and calibrated using a standard size image. A videocamera image of each swatch was taken from the front and then at 90 degrees f~om IhQ ron~. rh~ compute- generatQd a cross-sectional 2r~?~ mQ2surem~nt .^o- -ach Qf ~ho two imases.
The ~ ?~C~ ?~ h ~at~r. ~o milliliters or the conditioner co be testPd was applied to the swatch and vc,~ied inoc ~h~ hai~-. The conditioner was then rinsed out with ~p water anà ~rushQd and combed while air dryins as A~C~ ?.~ ?~`~C~ f-~r ~rying, the cross-sectional ar~ or` h~ ~-QSS ~ias c~q? ~ ~e-sllr ed usina the above ViA~ r~ t;~n21 2rQ2 obtained was sukt~ct~d ~cm the ( ~ss-sectional arPa obtainPd `c~ :._ sam~e m~_-_h h~ ~s_. ^us d y. Ei~ swatch2s 15 were done fcr ~ach OL Exa.upl~s q-l ana _h~ -~sults were averaged ~oset~er to ~'ain an a~ ao change in cross-sectional area (i.e., volume) af.er conditioning. The results are reported in Table II below.
Table II
Difference in Hair ExamDleCross-Sectional Area Duncan Grou~ing 8 -2.309 cm2 A
9 -3.417 cm A
-4.185 cm2 A
11 -8.156 cm2 B

Hair conditioners typically reduce hair volume and the negative number results in Table I show that all had some reduction in hair volume after trsatmsnt. The Duncan Grouping is a statistical analysis orocedure which groups results together based upon the level o~ confidence chosen which, in this case, was a 95~ confidence level. Under this 35 analysis, Examples 8-10 had about ~he same level of conditioning efîect at that confidence 12v21 while Example 11 was clearly statistically significantly different from the A
group. Thus, Example 11 had more _onditioning effect than the other three Examples t_st~d.
The second test done was a cc.-~bing orca t2st using tresses of the above type which weighed 6 grams each and were ~ s-r1~ S ~ t ,~T

-2~- 03 ~C lqq I

between 10 and 12 inches in length (25.4 - 30.5 cm). The tresses were wet with tap water, shampooed and again rinsed with tap water followed by application of 0.5 milliliters of one of the conditioners of Examples 8-11. The conditioner ~as worked into the hair swatch with the fingers and rinsed with 100~F. (37.S-2.2c.~ tap water for 15 seconds, the swatch was squeezed between the fingers to remove the water, and detangled with a comb. The swatch was hung from a hook attached to a Shavitz 100 gram load cell connectad to an analog-to-digital interface connected to a personal computer.
The instrument was used to measure .he ~verage forc~
resulting from combing the tress 10 consecutive times. The higher the average force reading, the more difficult it was to comb the hair and is ~hus an `ndication` th~t less c'onditioning had taken piace. Seven swatchas were done per Example and the average results for each seven are summarized in Table III below.
Table III
Exam~le Averaqe Combin~ ForceWaller Grou~ina 8 0.09639 Newtons B
9 0.10968 Newtons A
0.09641 Newtons B
25 11 0.08018 Newtons C
In Table III, the Waller-Duncan K-Ratio statistical analysis was used to evaluate whether the differences between readings were significant at a 95% confidence ratio. In this test, Example 9 (R' was decyl) was found to have a statistically significantly different and higher average combing force than Example B ~R' was octyl) and Exa~ple 10 (R' was dodecyl).
The lo~est combing force was exhibited by swatches treated with Example 11 (R' was eicosyl: C20H41-) which was statistically significantly diffQrent from the others (Group C).

Examples 12-13 These Examples show the use of a polymethylalkylsiloxane ~0 of the present invention in a shampoo formulation.

S~,s~ ~r~ S*~ ~r WO91/09~86 .~;.`~..,~G~/~S90/071 24 ~

Silico-ne XI was conventionally prepared by the platinum-catalyzed addition l-octadecene to a trimethylsilylendbloc~eà
copolymer of dimethylsiloxane and methylhydridesiloxane uni,s to obtain a polymer of the type shown in Formula I, su~ra, wherein R w,as a methvl group, R' w,as an oc~acecyl grou~
had an average value of 240 and y had an average value of 60.
The weigh' average molecular t-eigh_ of the resulting ~olyner ~as 113,57~ and it haà a number average molecular weigh~ c^
3, 323 with a pea~ molecular ~eigh_ of ~6,617. This pcly...er ;as a lot; `~ iu~ ~isc~sit~ c~ Q-?._~`-'`' ;`~``'`~
had a mel~ rarsi.ioil as meas~-ed b~ ~he ~ 3r Differen~.al Scanning ~alorime~ar c~ 6~C.
i~ shar,poo base composed 3' . `_ par~s o. _~Oi; r~`, (am.~onium laure.h-3 sulfa.e a. 2~ actives r`ro.m .~.lcolac, Inc.
1~ of Linthicum, ~'D), _-0 par_--, o^ '~~~O~ -2 ' (a.mmoniu. au-yl sulrate at 2~ ac~ivès fror" Alcolacj, 733.3 par.s of deionized water, 5.20 parts of citric acid and 29 grams of ammonium chloride was prepared (hereinafter "Base 2").
Example 12 was prepared by dispersing 1 part of Silicone XI into 100 parts of Base l using the TEKMAR rotary mixer used in Examples 3-7. Exampl~e 13 was prepared by dispersing 2 parts of Silicone XI into 100 parts of Base 1 using the TEXi~'~R ro~ary mixer.
Two trained hair stylists sham~pooed one half of the head of hair of 16 women volunteer panelists with the shampoo of Example 12 and the other side with Example 13. The stylists were asked to complete an evaluation of the hair both wet and dry and after styling. Overall, bo,h Examples 12 and 13 were found to have a positive conditioning effect on the hair, but Example 12 was preferred over Example 13, apparently because the higher level of Silicone ~I in Example 13 provided too much conditioning. The Silicone ~ left the hair sof.
without diminishing the clean feel ..hich is expected after shampooing. One stvlis. verbally -emarked that after 3~ rinsing, the hair had a squeaky cle n feel, but instead o.
being difficult to style and com~ as she had expected, the hair was very manageable.
Example 12 was rated as giving a higher level of fullness, body and bounce to the îc' r while E~ar,ple 13 SU8ST~T~TE SHEE-r WO91/09586 PCT/US90/071~1 -25- 2 ~

imparted a greater degree of shine to the hair and was easier to comb and detangle, both wet and dry, but felt more coated than the hair treated with Example 12. Afte- styling, hair treated with Example 13 was judged to feel softer and more conditioned than that treated bv Example 12 -~hile-Example i2 was judged to leave the hair more manageable.

Exam~les 14-17 In t~ese Examples, the conditioning effect of four polymeth~lal~ylsiloxanes was evaluated using a voluntee~
par,el of ~ WOmQ~ and one ~an t~ho were identiried as havinc3 dr~; hair cr damaged hai~ suc~ as ~~o.~ f~equent hair dyeing, per-~anen~ leac~.ing, hlo~ le ^-cm s;~mmirg pools, ex^~ss hea~ from ~.a~~ s_yliri~3 a~piianc_a such aa cu~~;ing ircr.s, e~_ 1~ Sili_one ~T-, was conventionally prepared bv the platinum-_atalyzed addi_ion of a com,me~cial mixture of 1-eicosene, l-docosene and 1-tetracosene to a trimethylsilyl-endblocked copolymer of dimethylsiloxane and methylhydridesiloxane units to obtain a polymer of the type shown in Formula I, supra, wherein R was a methyl group, R' was an eicosyl, docosyl or tetracosyl group, x had an average value of 240 and y had an average value of 16. The weight average molecular weight of the resulting polymer ~as 78,0~8 and it had a numer average molecular weigr.~ of 3,72~ ;.ith a 2~ peak molecular weigh. of 25,919. This polymer was a liquid to a gel at room temperature and had a melting transition as measured by the DuPont 910 Differential Scanning Calorimeter of lSC.
Silicone XIII t~as conventionally prepared by the platinum-catalyzed addition of a commercial mixture of 1-octadecene to a trimethylsilyl-endbloc~ed copolymer of dimethylsiloxane and methylhydridesiloxane units to obtain a polymer of the type shown in Formula I, su~ra, wherein R was a methyl aroup, R' t~as an octadecyl group, x had an average .~ value of 2~0 and y had an average ~alue of 16. The weight average rolecular ueigh_ ot- the -esulting polymer was ~0,10~
and it had a number average molecular weight of 3,311 with a pea~ molecular weight o_ 20,~8~. ~his polymer was a mediur viscosic~ liquid a~ room temperâ-u_e and had a melting SU~STITUTE SH~

-26- ~ ~ 3 ~

transition as measured by the Du~ont 910 Differential Scanning Calorimeter of -5C.
The condit~cn~- fo- ulatlon us~ a base composed of 2 parts cety1 alcc~ '.7 ~?~ s `~G~ par~s citric acid ~ r_s .~ r~s _-ice~
amine, 0.032 par_s ~.~'rHON~ CG, ard ~.4i8 pa~ts deionized water (hereir1aft~ ?.S_ ~ `X?~`.-~',` ' ~'`i '~ ! ~ / '` ~ 2nd ' 7, respectively, we~s~ prepa~ , a_~ng l~ one X _, XIII, XI an~ ^s ~ ' ~o ~ ?.S`- 3 usi~i~ a high shea~ mi~:e~-Eac.. ~ ?~
17) were a~ a .y ~:~ `? ``~ 'e' `~`-~"` i:` ~`'`i--i`` .' ':.^.'~ ~ _hei-evaluate- r_- a ~ eek ~ a-~ ;~s given l~ a new formula~io~ _c ~es~. The ~an~'is~ also cc~l e~2~ an evaluation for- ~v-2 beiny yiVen ano~h-r ,~ormu'a'ivn ~o test.
ôverall, the expected attributes of combing ease, soft `feel and conditioning were observed by the panelists for each of Examples 14-17. Additionally, the treated hair was judged overall to have the desirable characteristics of fullness, body, shine, manageability and a clean look without the conditioner beina judged as imp2-ling a coa~ed feel to the hair, ~eighing t:.e hai~ down c- _eavina a ma~.ed/-iat look.
2~ The latter was found to vary depending upon the specific polymethylal~ylsiloxane. Overal`, lyaway is typically noted as being a problem when polydime~hylsilo~anes are used, but was not perceive- to be a proble.~n from the ratings given to the compositions .ested.
One conclusion drawn from the results of this study is that for users with dry or damage~ hair, a polymethylalkylsiloxane wi~h larcer amounts or R' group, such as Siloxane XI is prererred. Fc- o,her hair types such as normal or oily hair, this type c- polyrethylalkylsiloxane may 3~ tend to leave th~ hai- m^r~ _oa~ nd :~e~ghed ~wn in appearance when i~ is used.
Example 17 con~aining Sili__-.e v was ra.ed very high in panelist number scale ratings ar._ in voluntarv comments submitted by the panelists. Th,s polymer was rather high in SU~3STITUTE SHEE'r WO91/09;86 PCT/US90/071~
-2/- ~ ~7~:~3~

molecular weight relative to the other silicone polymers tested.
From th~ results, z ~,ore e-.e~d s_ruc-ure for the polymethylal`s~'lcil_xanes of ~he preàent inver.tion, as evidenced k~ :~~a_-: , ,--si.- ~ ~e`~ n, ?c~pe?.rs tO ~-' desirable from a conditioning perrormance s~andpoint.
Example 15 c^n_ains Silicon* "~ .ich is a mediur. vis_osity liquid with 13 carbon ztcm .'~ cup-~ _.xam~ple l-lt contained Silicone ~ h `aa~ .e sam.? si ~ cne ~ mer bac~:bone as in Example l~, ~ut t~iai- a ~ .l `.d ~ O Z ~.'L ;ii~ 20-2~'t ca-~on a tor~ ?~ ? '^ `` --~ r ~- orl~c~ ;lce than did ~

l4-l7, bu~ ~;zs --s~eci~ ne_~__?.~ as~le i:', .`~-highest r,olecula- weiyht polyrer ~es.ed~ ar,ageabilil~. is thought to resul~ because .he si'ic-ne p^lyme- chains .ield readily under a high force sucn as combing, but under lower forces, such as a light wind or normal head movement, they do not allow the hairstyle to relax.
Examples 18-22 In these Examples, a level study was conducted using the formulation lis~ed in Table I ~herein Ihe Siiicone I was or.~itted and rep aced by _he sa.- a-_un_ o_ ~.a~er in tr._ formulation (comparative Example l~,. The remaining Examples ~ere prepare- wi~h ~ilicone ~} added at 0.1% (Example l9), 0.5% (Example 20), l.0~ (Example 2l! and 2.0% (Example 22), respectively, le~els to 3ase l. The stu~y was done to determine if diîferences could be c_served among the various levels of polymethylalkylsiloxanes used as well as between Examples 19-22 and comparative Example lS.
In this evaluation, iO0 v_lun~-er panelists aged from l8-55 participa_ed in the test'ng ;;:^ich was conducted by trained hair stylists over a ~ day period. ~. "half-head~
procedure o.~ .h_ type d2sc- b2~ ir. =~e p evious Exampl~s wzs used with a -andom selec_ion c- tw_ _or,posi~ions to be applied, after =he hair was ShG_.PO-ed, to each one half of the panelist's hair in an amou.._ o_ up to 7.~ milliliters of produc~ per side. The stylists an_ panelists ~Jere not told SU~3STITUTE SHEE~

WO91/0g~86 PCT/~S90/071~
-28- 2~7.~

the identlty of any of the compositions being tested. ~he hair stylists rotated to a new panelist after application of the compositions and rinsing.
The panelists were as~ed to complete a 9 point ~n~e~va' evaluation containing statements of the type, note~ ir. -he above Examples while the hair stylists were as~ed to complete a 60 point structured line scale containing statem~n~ r.ich were ran~ed according to an assigned point scale.
The results were that while there was a dif~erence ~0 between Exar~ple 1~ w~th no polymeth~lal~ylsiloxane and rxa~~ples ~c~ he-~ ;ie-e few diCcet-er^es n^led ~_we_~
Exarples la-2~ .n imp~-tant di ^eren^~ bet;;een Exa.rle 18 ar.d rxa-p es '9~ as _h--_ E";a~~le '` __.._~i.,ed _ significan~ a~ou... O- .OUt' dirre-en~ organic ~.ai~
conditioning agents while Base ~ only containe~ ; o one organic hair conditioning agent plus the polymethylalkylsilo~ane.
Overall, the panelists perceived Example 19 to leave the hair feeling drier and less conditioned than did Examples 21 or 22. Example 18 was judged to leave the hair with a cleaner loo~ than Examples 19, 21 and 22, and left the hair with more shine than did Examples 19 and 21. Examples 19-22 were judged to have a thinner consistenc~ and to impart less lubricity to the hai- than did E~ample lo. The s~ylis~s 2~ rated Example 20 to be easier to rinse out of the hair than were Examples 18 anà la. After one àay, hair treated .ith Example 18 was judged to have a less clean feel than hair treated with Examples 19-22. Thus, Examples 19-22 were fairly comparable ~ith a conventional hair conditioner formulation (Example 18) with multiple hair conditioning agents.

Exam~les 2~-26 Since few differences were noted in the study done with .- Exa,~ples io-22, another study -~ias done using th~ same conditioner base throughout so that any conditioning effects due to the presence of the polymethylal~ylsiloxane would become more apparent.

SU~3STITUTE SHEE~T

W~91/09586 PCT/~IS90/071'~

2 ~ 3 7 This level study was conducted using Base 1 alone (comparative Example 23) and with Silicone XII added at 0.5%
(Example ?~ .0% (Example 25) and ~.0~ (Example 26) leveis, respectively, 'o Base 1 using the TEXMAR~ rotary mixer used in Examples ~- .
The stud~ was conducted over 5 days using 115 volunteer panelists aged 1~-55 in the same manner as described in Exa~ples lS-22 above, but with Examples 23-26.
The resul_s of the s~udy were that significant differences ke~ieen E~amples 2~-2~ with the three differen, l_~els cf ~ er.e ~YTI and co~parati~e Exar~le 23 ~ere observed. ~c n the stylists and .he panelists judged tha~
the addi~_n _~ _he pclyme-h~lal`~:yl_ilox~ o Base ' p-ovided 2 ;;e_ and dry hai~ co~.bing ad~an~age. ~xampl~s 2 1~ and 26 t~ere r__ed as pro~iding a less dry and more conditioned ~e-l to the hair than w2s provided by Exarples 23 or 24. A more coated feel to the hair after drying was observed with increasing amounts of polymethylalkylsiloxane and this was judged as being especially noticeable with Example 26.
The stylists rated Examples 25 and 26 as having a thinner consistency, as being more` easily distributed through the hair, ut less easily rinsed OUI than Example 23. One day after the hair was trea~ed, ~he panelists felt tha':
Example 24 tended to leave the hair less matted than did Example 2~; rxa~ple 26 ~as felt to leave the hair easier to comb than did Example 23; and Example 23 had a less dry feel on the hair relative to the feel of hair treated with Examples 2~ or 26.
Exa~le 2,~
This Example illustrates a pre^erred shampoo formulation using the present invention having ~ood stabilization of the polymethylalkylciloxane in the sham?oo.
The snarpoo formulaticn consis_s of two parts with a -ange of each ingredient being given in parentheses after the nominal amour.l in parts by weigh~ 'isted first (all ingredients a-e on a 100% solids basis):

WO91/09586 PCT/~'S90/07154 ~ u . _ 3~,.
Part I is Cetyl/Stearyl Alcohol in a 60/~0 weight~ eight ratio, 1% (0.5-16%); Silicone ~I, 2% (0.1-3?o~; and Coco-Betaine, 1.8 (~ o` ~n, to~al sur ac~an~ presen~).
Part II is Amroni~nm Laur~l Sull'at*~ -onium Laur~
Ether-3 Sulfa~-~ in ?.;' -`O ' ' ^; ~ `-.ig~i` `r-.~.` O" ;~ . -`, (;~7-22~); Cetyltrime~h~lamr~loniur,~ .hlo~-id-, L~.-77^7 (0.i-0.7~); and deionized wa~er, ~iS.;,~ balanc~e ro 00~
The shampoo r'ormu~lio.~ _,f ~.~ar~,le ;`, is prepare_ ~,y melting the Ce_vl,~^L*ar~ l.o~cl ~c~.~2~ihe~ h .he Siiicone ~I until a hom-~ogen~ou-, n~2 ~ is o"~a :._d. ~"~.e Coco-Be~ e is then added on ~~? e ra- .~e`.~ r.~ ` a~_e ~he meit is cocled ~ r~

~ ed ~oge.
1~ The mixture is all^;;ed ~o ~ti~r a~ r_am ~em--ê--a_urê ur_il i~
becomes clear ~~ c^~~plc_ê prê~a~^a_i^n -- ?ar. II.
Part II is then heated to 70C. with s~irring. Part I
is gently remelted until it becomes flu`id and Part II is then poured into Part I with stirring using the TEKMAR RW20 DZM
stirrer. The temperature is kept at 70~C. to allow the ingredients to mix well with vigorous stirring and then the heat source is removed and the formulation is allowed to cool to room temperature ~hilê -~igo-ous s~irrir.g is maintained.
- The resulling formul~.ion is Ex_mplê ,.
2~ A shampoo formulation ~as prêpz-ed by this metho~ and the formulation had a 3roo~rield vis_osit\ or ~,000 centipoise at 30 R.P.M., -4 spindle arter 30 seconds at room temperature.

Example 28 This Example illustrates an aoueous emulsion carrier for delivering pol~methylal~ylsilo~anes rom a pump spray container for use as a pump spray h2ir conditioner.
Example 2~ ~as prepared by slo~.~ly adding 3.00 grams of 3~ PEMULAN~ T~-2 (.~._-yl2~es~C~C-30 A~ Acryla~e Crosspolymer) from B.F. Coo~~ich C--ou~, ~pe_i21.y ~olymers ~ Cnemicals of Cleveland, OH) rLo 2912.0 grars of d_uble distilled waLer ~ith moderate stirring using ~he TEKM~.R R;~20 DZil rotary stirrer.
After the majority of the PEMULAN- -R-2 appeared to b-SU~STITUTE SHEE~

~91/09586 PCT/US90/071~4 -31- ~ 2 7 hydrated ~only a few small clurps were apparent), 24.00 grams of triethanolamine was added to the stirring mixture.
Stirring was continued un.il on'.y ore piece o.-^ undispersed PEMULAN~ TR-2 re~ained. Stirr~ n,~ WA~S stop e~ and the resulting i.-i-erm^~ C~A`'`'`A`'_.`^" ~.a- a`!`'o'~ 0- remain a.
room temperature overnight.
On the ne~ day, the ir..e~m?diAa_e cor~^si~ior. was stirred for 15-~0 rinu~es ar.d -.o -emainin-g uncispersed PEMULAN~ TR-~ ;;as _bS2r~
A sclution C^n~a'ning '~0,:`! '~ S 0'~ one I' ~ ~rO grar~s of Gener~ a r a i~l O i^
fragrance ;ias t,~-e~ s`~ .e intermedia~e c-.~n-_~ ;i_h ~ hen _~.e solution was c~ e~e_~ a~-.e~, _n~ s ~ a.e was lS increased to crea_e a sm2'l ~ x.
To prepare a bet~e. eruls~ mi'`i'i.ers of the resulting composition was sheared using the U~RA-TURRAX T50 rotary mixer used in Example l at 3,500 - 4,000 R.P.M. The resulting emulsion (Example 28) was placed in a conventional 20 pump spray bottle and sprayed onto the hair of models as a conditioner with good results.

Examples 29-A.Q
In tAese examples, the W.2_ COm_ ` r.g CA.2 -a_teristics of alkylsiloxanes containing several diîferen' R' groups as well as different silicone polymer bac~kcnes were compared against themselves and against a control wh~ch was Base l used in Examples 3-7. E~amples 29, 30, 33, 3 and 37-39 were comparative exarples. The wet ccm~ing characteristics were 30 measured as described in Examples ~-ll for the combing force test summarized in Table III.
Examples 29, 33 and 37 were Base l only and the remaining Exa~ples were prepared by adding 0.~% of the poly~ethylal~ylsiloxane being teste- to Base l. Example 30 3~ was a batch of Si'icone ~ e-- ~;' was 2 ~10 group and no melting point transi~ion was c 2=eC __~ . E~:amP1e 3l was Silicone XI~ wnich was prepared :n =ne same ranner as described for Sllicone IX, bu. ~i a~ding l-dodecene to a prepolymer of the type shown in ror~ula I, su~ra, where R' S'~8STITUTE` SHEE~

P~S qo ~ 5~

was a methyl group, x had an average value of 50, y had an average value of 36, R' was hydrogen, and the number average molecular weight was 5824. The resulting Silicone XIV had a melting point transition at -55C. Examples 32 and 36 were Silicone I where R' was a C18 group. Example 34 was Silicone VII. Example 35 was Silicone XV which was a medium to high viscosity liquid copolymer of the type described in Formula I, supra, wherQ R' was a methyl group, x had an average value of 300, y had an average value of 48, R' was a C18 group, the 10 melting transition was 7.9C., had a number average molecular weight of 2,798 and a weight ave~age molecular weight of 13,1~7. Example 38 was ~ilicone XVI which was made by adding l-octene to the prepolymer used to prepare Silicone XIV and the resulting polvmer had a melting point transition of 1~ -104C. ~ca-plQ 39 was Silicone XVII which ~as made by adding l-decene to the prepolymer used to prepare Silicone XIV and the resulting polymer had a melting point transition of -67C. Example 40 was Silicone IX and no melting point transition was detected for this polymer.
The wet combing tests were done in three separate groups and are summarized in Table IV below.
Table IV
Example R' Average Wet Co~bing Force Waller Grouping 29 -- 0.1485 Newtons A
C10 0.1024 Newtons B
31 C12 0 0997 Newtons B
32 C18 0.0758 Newtons C
33 -- 0.1386 Newtons A
34 C8 0.0899 Newtons B
C18 0.0706 Newtons C
36 C18 0.0724 Newtons C
37 -- 0.1482 Newtons A
38 C8 0.1091 Newtons B
39 C10 0.0962 Newtons B
C12 0.0972 Newtons B

From Table IV, it is apparent that the polymethylalkylsiloxanes with C18 as the R' group are clearly better in conditioning effect than the control or the other 45 polymers. Even though different silicone polymer backbones S~ ~ S~FT

~'~91/09586 PCT/US90/07151 ~71g?7 were used, the general trend is that conditioning of the hair, as measured bv a reduction in average ~et co~bing force, in~crease~ a5 t~.e length. o- -h~ ~' -~? oresen~ is increased.

SU~3STITIJTF SHEE~

Claims

What we claim is:
1. An improved composition for treating the hair comprising a hair conditioning agent dispersed within a cosmetically acceptable carrier medium wherein the improvement comprises inclusion of from about 0.1% to about 10% by weight of a polymethylalkylsiloxane as at least one of the hair conditioning agents, based upon the total weight of the agents and carrier medium, wherein the polymethylalkylsiloxane has the average formula R2(CH3)Si(OSi(CH3)2)x(OSiR'CH3)yOSi(CH3)R2 wherein each R is selected from the group consisting of methyl, ethyl and phenyl groups, R' is an alkyl group of from 8 to about 60 carbon atoms where the total number of R' groups present has an average of at least 12 carbon atoms, the values of x and y are such that the ratio of x:y is in the range of from 97:3 to 55:45, the sum of x+y is greater than or equal to about 60 and less than or equal to about 1,333 and the polymethylalkylsiloxane has a melting transition, as measured by a differential scanning calorimeter, between about -25°C to +27°C.
2. The composition as claimed in Claim 1 wherein the sum of x-y is g-eater than or equal to about 250 and less than or equal to about 800.
3. The composition as claimed in Claim 2 wherein R is a methyl group, and R' is a linear alkyl group of from 16 to 24 carbon atoms.
4. The composition as claimed in Claim 3 wherein the ratio of x:y is from 96:4 to 80:20 and the polymethylalkylsiloxane hair conditioning agent is from about 0.1% - 5% by weight of the composition.
5. The composition as claimed in Claim 3 wherein the ratio of x:y is from, 97:3 to 93:7 and the polymethylalkylsiloxane hair conditioning agent is from about 0.1% - 5% by weight of the composition.
6. The composition as claimed in Claim 3 wherein the ratio of x:y is from 88:12 to 80:20 and the polymethylalkylsiloxane hair conditioning agent is from 0.10 to 5% by weight of the composition.
7. The composition as claimed in Claim 1 wherein the polymethylalkylsiloxane hair conditioning agent is from 0.5%
LO 7% by weight of the composition.
S. The composition as claimed in Claim l wherein the carrier medium is a hair shampoo.
9. The composition as claimed in Claim 1 wherein the carrier medium is a hair conditioner.
10. The composition as claimed in Claim 1 wherein the carrier medium is an aerosol spray carrier medium.
11. A method of conditioning hair which comprises the step of applying to the hair a composition containing from about 0.1% to about 10% by weight, based on the total weight of the composition, of a polymethylalkylsiloxane of the average formula R2(CH3)Si(OSi(CH3)2)x(OSiR/CH3)yOSi(CH3)R2 as at least one hair conditioning agent present in the composition wherein each R is selected from the group consisting of methyl, ethyl and phenyl groups, R' is an alkyl group of from 8 to about 60 carbon atoms where the total number of R' groups present has an average of at least 12 carbon atoms, the values of x and y being such that the ratio of x:y is in the range of from 97:3 to 55:45, the sum of x+y is greater than or equal to about 60 and less than or equal to about 1,333 and the polymethylalkylsiloxane has a melting transition, as measured by a differential scanning calorimeter, between about -25°C. to +27°C., the polymer being dispersed in a cosmetically acceptable carrier medium.
12. The method as claimed in Claim 11 wherein the sum of x+y is greater than or equal to about 250 and less than or equal to about 800.
13. The method as claimed in Claim 12 wherein R is a methyl group, and R' is a linear alkyl group of from 16 to 2 carbon atoms.
14. The method as claimed in Claim 13 wherein the ratio of x:y is from 96:4 to 80:20 and the polymethylalkylsiloxane hair conditioning agent is from about 0.1% to 5% by weight of the composition.
15. The method as claimed in Claim 13 wherein the ratio of x:y is from 97:3 to 93:7 and the polymethylalkylsiloxane hair conditioning agent is from about 0.1% to 5% by weight of the composition.
16. The method as claimed in Claim 13 wherein the ratio of x:y is from 88:12 to 80:20 and the polymethylalkylsiloxane hair conditioning agent is from 0.1% to 5% by weight of the composition.
17. The method as claimed in Claim 12 wherein the polymethylalkylsiloxane hair conditioning agent is from 0.5%
to 7% by weight of the composition.
18. The method as claimed in Claim 11 wherein the carrier medium is a hair shampoo and the method further includes the step of rinsing the composition from the hair.
19. The method as claimed in Claim 11 wherein the carrier medium is a hair conditioner and the method further includes the step of rinsing the composition from the hair.
20. The method as claimed in Claim 11 wherein the carrier is an aerosol spray carrier medium.
21. A method of improving the hair conditioning ability of a cosmetically acceptable hair treating composition comprising at least one hair conditioning agent dispersed in a carrier medium, the improvement comprising adding to the hair treating composition a polymethylalkylsiloxane of the average formula R2(CH3)Si(OSi(CH3)2)X(OSiR'CH3)yOSi(CH3)R2 as at least one of the hair conditioning agents present in the composition wherein each R is selected from the group consisting of methyl, ethyl and phenyl groups, R' is an alkyl group of from 8 to about 60 carbon atoms where the total number of R' groups present has an average of at least 12 carbon atoms, the values of x and y being such that the ratio of x:y is in the range of from 97:3 to 55:45, the sum of x+y is greater than or equal to about 60 and less than or equal to about 1,333 and the polymethylalkylsiloxane has a melting transition, as measured by a differential scanning calorimeter, between about -25°C. to +27°C. wherein the amount of polymethylalkylsiloxane added is from about 0.1% to about 10% by weight based on the total weight of the hair treating composition and polymethylalkylsiloxane.
22. The method as claimed in Claim 21 wherein the sum of x+y is greater than or equal to about 250 and less than or equal to about 800.
23. The method as claimed in Claim 22 wherein R is a methyl group, and R' is a linear alkyl group or from 16 to 2 carbon atoms.
24. The method as claimed in Claim 23 wherein the ratio of x:y is from 96:4 to 80:20 and the polymethylalkylsiloxane hair conditioning agent is from about 0.1% to 5% by weight of the composition.
25. The method as claimed in Claim 23 wherein the ratio of x:y is from 97:3 to 93:7 and the polymethylalkylsiloxane hair conditioning agent is from about 0.1% to 5% by weight of the composition.
26. The method as claimed in Claim 23 wherein the ratio of x:y is from 88:12 to 80:20 and the polymethylalkylsiloxane hair conditioning agent is from 0.1% to 5% by weight of the composition.
27. The method as claimed in Claim 21 wherein the polymethylalkylsiloxane hair conditioning agent is from 0.5%
to 7% by weight of the composition.
28. The method as claimed in Claim 21 wherein the carrier medium is a hair shampoo and the method further includes the step of rinsing the composition from the hair.
29. The method as claimed in Claim 21 wherein the carrier medium is a hair conditioner and the method further includes the step of rinsing the composition from the hair.
30. The method as claimed in Claim 21 wherein the carrier medium is an aerosol spray carrier medium.