CA2097836C - Shampoo compositions with silicone and cationic organic polymeric conditioning agents - Google Patents

Abstract

Disclosed are hair conditioning shampoo composition comprising: (a) from about 5 % to about 50 % by weight of an anionic surfactant component; (b) from about 0.1 % to about 10 % by weight of a dispersed, insoluble, nonvolatile, nonionic silicone hair conditioning agent; (c) from about 0.05 % to about 10 % by weight of soluble, organic, polymeric cationic hair conditioning agent, said polymeric, cationic hair conditioning agent consisting essentially of one or more cationic, hair conditioning polymers, said cationic hair conditioning polymers having quaternary ammonium or cationic amino moieties, or a mixture thereof, an open chain backbone, and a charge density of about + 3.0 meq/gram or less; and (d) an aqueous carrier. The shampoo compositions hereof can provide excellent overall hair conditioning benefits, in conjunction with excellent cleaning performance, to a variety of hair types including treated hair such as permed and color-treated hair, as well as undamaged hair.

Description

' O 92/10162 2 v 9 7 ~ 3 6 PCr/US91/08927 SHAMPOO COMPOSITIO~!S '.~ITH SILIC~E AND
CATIONIC ORGANIC POLY,'lERIC CC~DITIO~ING AGENTS

FIELD OF IHE IINVENTION
5This invention rQ1 lt~C t~ shampo~ c~m?csitions comprising anionic detersive surfactants, silicone hair conditioning agents, and cationic polymeric hair con~ tioning agants.
B,~C,~G~OU~i~ u'~ ,'I'J~ ON
Human hair beccmas soil~o ~ue to its cont~act with the surrounding atmosDhere ~nd~ ~a ~ g,eat~i~ e~tent from sebum secreted by the head. The build-uD Ot the seDum causes the hair to h~vQ ~ di~ty f~ d ?~ ''n'~ . ' ''~ -t''~'~ 'pp~ C~. ThQ soiling of the hair necessita~s i' b~ing shampdoed wi~h frequent regularity.
15Shampooing the hair cleans by removing excess soil and sebum.
However, the shampooing process has disadvantages in that the hair is left in a wet, tangled and generally unmanageable state.
Shampooing can also result in the hair becoming dry or "frizzy"
due to removal of natural oils or other hair moisturizing mate-rials. After shampooing, the hair can also suffer from a loss of "softness" perceived by the user upon drying. A variety ofapproaches have been developed to alîeviate the after-shampoo problems. These range from the inclusion of hair conditioning aids in shampoos to post-shampoo application of hair conditioners, i.e., hair rinses. Hair rinses are senerally liquid in nature and must be applied in a separate step following the shampooing, left on the hair for a length of time, and rinsed with fresh water.
This, of course, is time consuming and is not convenient.
While a wide variety of shampoos have been disclosed which contain conditioning aids, they have not been totally satisfactory for a variety of reasons. One problem relates to compatibility problems between good cleaning anionic surfactants and the many conventional cationic agents which historically have been used as conditioning agents, includins b~th cationic surfactants and cationic polymers.

2 PCl/US91/08 'ih~reas ef,orts have been made to minimize adverse incaracLion -i~nrough tlle use or aiternate surfactants and improved catio,tic condiiioning anents~ it remains highly desirable to u~liiAa ari-ioitio iù.fac~aîn~, n sh~mpvo com~osttions. Furthermor~, cationic cnndi~ionin~ agents commonly do not provide optimal OV~r~ oo~i ioniils ~ene,~'i~s, ~a,~tic~Alarl~ ln th~ area of "soft-ness"~ e~~t ctall~ hen delivered as an ingredient in a shampoo ;;, a ~ a~ ~ ~me~s~ ?cditionally, tPnd to build U '~t ~ l d ~, ' L V i ' ~ i '- S ~ ~I U ~ C l e~ll co~d ie~l.
;o~ ;-t,~ ;t ,~~ C~ A sot'i~ness a~ noni~nic silicon~s. S;l,cJnes in sh~i"p;to compositions have been àisclosed in ~ ult~ùr ?~ iiffe,~ent oubiications. Such publications include U,S~ D~n' ~~Q~ een, lssued March 11, 1958; U.S. Patent 3,3O~ , Dra~off, issued June 22, 1976; U.S. Patent 4,36~,837, 15Pader, issued December 21, 1982; and 8ritish Patent 849,433, Woolston, issued September 28, 1960. While these patents disclose silicone containing compositions, they also did not provide a totally satisfactory product in that it was difficult to maintain the silicone well dispersed and suspended in the product.
Recently, stable, insoluble silicone-containing hair conditioning shampoo compositions have been desc.ibed in U.S. Patent 4,741,855, Grote ~nd Russell, issued May 3, 1q88 and U.S. Patent 4,788,066, Bolich and Williams, issued November 29, 1988. These shampoo compositions can deliver excellent overall conditioning benefits to the hair while maintaining excellent cleaning performance, even with the use Ct ~nionic detersive surfactants, for a wide variety of hair types. However~ it would be desirable to improve these types of shampoos such that they provided improved conditioning benefits to one type of hair in particular, that type being hair damaged by permanent treatments (i.e.~ "perms"), color treatments, and bleâch t,~atm,2nts, appli2d ait"er at hair salons or at home.
Unfortunately, silicone hair conditioner efficacy for permed hair appears to be lower than tha~ for most undamaged hair. It would be desirable to orovide a shamDoo composition that would provide excall-nt overall clean,r,g ar.d canditioning benefits for such ~o 92/10162 ~JI.~ 7 ~ ~ ~ PCT/~'S91/08927 hair, as well as other types of hair not subjected to such treat-ments. This would reduce the need for ,~amilies or other residents to purchase separate hair conditioning shampoo products for persons with damaged and undainaged hai;.
It is an object of this invention to provide shampoo compo-sitions, which can provide excellen~ clea,)ing pér~ormance and excéllent overall hair condit,oning for such damaged hair as well as for hair not subjected ~o ~UC'1 rea~ a"~ "';;,.'m"aga~ 'na,r~
It is a further object o,' cnii in~ n~ion ;o pro~,id~ an improved anionic sur,actanb-call a,nlil5 iiiai,~av cv;n;)u~ blUnS b;la~
can proviàe excellent cleaning performance and conditioning performance for both damaged and undam~?ed hair tvces~ such that the shampooed hair can havo ~o5jrahlo lavols of m~n~geabilitv, combability, softness, and low or reduced levels of dryness.
These objects will become apparent from the description which follows, as many other objects become apparent upon a reading of said description.
Unless otherwise indicated, all percentages are calculated by weight of the total composition, and all ratios are calculated on a weight basis.
SUMMARY OF THE INVENTION
This invention provid2s an,onic detersive surfactznt-containing liquid shampoo compositions that can provide both_ excellent cleaning performance and ha;r conditioning benefits to a wide variety of hair types. including treatment damaged and undamaged hair. This can be attained by incorporating into the shampoo composition a nonionic, insoluble, nonvolatile silicone hair conditioning agent and, additior.ally, a critically selected soluble, organic, cationic, polymeric conditioning agent. The shampoo compositions hereof will also comprise an aqueous carrier.
The cationic polymer conditioning agents of the present invention are organic polymers having quaternary ammonium or amino moieties (said amino moieties being cationic at the pH of the shampoo composition)about pH 9~ more preferably from about pH 4 to WO 92/10162 "~ PCI/US91/08' -~
- ''; . ' . 3 ~ ' -i~ ', and op~n r.hain bac~bone. Furth2rmore~ these polymers essentially ha~Je a e;la ~e densi y oi~ about ~3.d me~/gram or less, preferably about 2.?~ "meq~gram ~r l_ss. The precise cationic charge density is n~ 1 i2~'2~ ~o ~e cr, ~1~ a, ~s lon~ ~s it is less than those statQd ~ssential and ~r~ferred limits~ ~owever, for practical reasoi~s~ ~ihe ehal~3e del~ hùu~ be uf â le~el such that effi-cie.nt .~n'''~ i't.i'.';'~ be~'!e'-~n ~.lnQ pol~mer and the hair can be .~;.;'.'~''.i''':';. ~'~n''. ' m''~ i'r,'a d ~,ha~ ca~ionic charge density i'J. ~ iJ~ à~. '~as. ~I)out û.~

'~hen co"lbined wi~" ~ne nùlliùnic silicone cûndttiolling agents in ~ h~ 3,~ 51'ini,~ Q; ~his invention~ these cationic v,~a'.is ~olyme~s can ?-e~"~3 surp~isincly good hair conditioning benefits ror permed or o~her àamaged hair characterized by in-creased anionic char~cter, such as bleached hair and color treatedhair. These types of hair that have been damaged and are charac-terized by increased anionic character shall hereinafter be collectively referred to as "damaged hair". Nonionic silicone conditioning agents suffer from reduced deposition, and therefore reduced efficacy, for these hair types. On the other hand, the use of the cationic organic polymers as the sole type of hair cond,tiûning ~gents to damaced hair and especially to undamaged hair when delivered from shampoo compositions may not provide sufficient overall conditioning benefits, especially in the area of sortness. The combination of hair conditioning agents, how-ever, results in shampoo ccm~positions with high levels of con-ditioning for damaged hair, and retains excellent conditioning for undama~ d hair and cleaning performance for all hair types. As used herein, undamaged refers to hair that is not damaged by perms or other hair treatments which increase the anionic character of the ha,r, and u02s not exclu~e, f3l ~xample, oily hair, dry hair, etc., or hair damaged in some other respect, unless such other damage is specificallv and expressl~ indicated. These performance benefits are especiallv important because merely increasing the ~"l0 92/tO162 2 0 9 ~ ~ 3 ~ PCT/US91/08927 level of silicone conditioning agent in a particular shampoo that - is effective for treating undamaged hair ~o improve conditioning of damaged hair can result in too high a lev~ Ot silico1le deposi-tion for undamaged hair. This can impara an un~esir~b~e greasy feel. On the other hand, the cationic organic polymer~ by itself, does not provide efficient conditioning ~r undamaged hair. .h~
present invention provides anionic detersive surfactant-containing shampoo compositions that can provide e~c~1lent c~rdi~,ning ~o both damaged and normal hair ~hrougn ~ ,e o,~ nol~~loilic s,'ica,~,e and particularly selected soluble~ o~gani~ r~ol~ e ~ iC
conditioning agents hereof.
Although it is not intended to limit tne ~resen~ inYention by theory, it is believed that the cationic oolymers of the present invention are particularly advantageous for use in anionic deter-sive surfactant-containing shampoos as a result of a combination of factors. First is the absence of ring structures and saturated carbon-carbon covalent bonds in the polymer backbone. This type of backbone results ;n a more flexible polymer which, along with their relatively low charge density, reduces the tendency of many cationic polymers to undesirably build up on the hair upon re-peated usage. The use of these cationic, organic polymers as conditioning agents along with the silicone conditioning agents hereof can provide excellent cleaning shampoos useful for condi-tioning a wide variety of damaged and undamaged hair types.
In a preferred embodiment, the present invention provices hair conditioning shampoo compositions comprising:
(a) from about 5% to about 50~,'0, by weight, of an anionic detersive surfactant component;
(b) from about 0.1% to about 10%, by weight, of a dispersed, insoluble, nonvolatile, nonionic silicone conditioning agent;
(c) from about 0.05% to about 10%, by weight, of soluble, organic, polymeric, cationic hair conditioning agent, said polymeric, cationic hair conditioning agent consisting essentially of one or more cationic hair conditioning polymers, said cationic hair conditioning polymers having wo 9'/10162 PCr/US91/OY '' ~ '~~ '!, ' ' ~.;
' ' 6 quaternary ammonium or cationic amino moieties, or a mixture thereof, an open chain backbone, and a charge density of about +3~0 i~eq/~ram Ot' less; and (d) an a~ueous car,i~,~
As used herein, the terms "soluble" and "insoluble" used in reference ~o ~arti;ulai~ ~"I~.n ~ia,i~s 3,~ 'he shampoo co~positions r~f~-tr to solubtl;t~y or insolubility, res~ectlvely, of that ingre-dien~ s',~",~

compositlon uniess ~n~:~w~ ~a~ ino,ct~e~
The inven~ion, 1ncludtn~ p,~el'crred em,uodil,,ents thereof, is described in fu,ther detail ,, the Oetailed Oescription of the Invention~ whlch follo~
DETAILED DESCR;rlION OF T~E INVE~TION
The essential as well as a variety of preferred and optional components of the compositions of the present invention are described below.
Anionic Detersive Surfactant - The hair conditioning shampoo compositions of the present invention comprise an anionic detersive surfactant to provide cleaning performance to the com"position.
The anionic detersive surf~ctant s~ill generally be from about 5% to about 50YO, preferably from about 8% to about 30%, more preferably from about 10% to about 25%, of the composition. The anionic detersive surfactant of the compositions hereof can be a single species of surfactant or a combination of different surfactants~
Synthetic anionic detersive detergents useful herein include alkyl and alkyl ether sulfates. These materials have the respec-tive formulae ROS03M and RO(C2H40)XS03M, wherein R is alkyl or alkenyl of from about 8 to ab~ut 24 carbon atoms, x is 1 to 10, and M is a water-soluble cation such as ammonium, sodium, ~0 9~/10162 PCT/~'S91/089'/
2037~

potassium and triethanolamine. The al~yl ether sulfates are typically made as condensation products ol- evhylene c~ide and monohydric alcohols having from about 3 to a~o,v ~ carbon a oms.
Preferably, R has from about 12 ~o abou; 8 oalL~oil a o,ilS iil oo~l~
the alkyl and alkyl ether sulfates. The alcohols can be derived from fats, e.g., coconut oil or t~llo~, or ~n he syn'he~,o.
Lauryl alcohol and straight chain alcohols derived from coconut oil are preferred herein~ Such alcohols ~re '~e'~.teli ~ eeu~ ', to about ;0, and espeeially abou~ 3~ m,ol~r ~ v'a;. ~r -vh~
oxide and the resulting mixture or' r,loleculan j~ o'~
example, an average of 3 molas or vthylene ~Yi"e p~r mo~e or ~ co-hol, is sulfated and neutralize~.
Specific examples of alkyl ether sulfates which may be used in the present invention are soàium and ammonium salts or coconut alkyl triethylene glycol ether sulfate; tallow alkyl triethylene glycol ether sulfate, and tallow alkyl hexaoxyethylene sulfate.
Highly preferred alkyl ether sulfates are those comprising a mixture of individual compounds, said mixture having an average alkyl chain length of from about 12 to about 16 carbon atoms and an average degree of ethoxylation of from about 1 to about 4 moles of ethylene oxide. Such a mixture also comprises from about 0 to about 20% by weight C12 13 compounds; from about 60 to about 100%
by weight of C14 15 16 compounds, from about 0 to about 20% by_ weight of C17 18 19 compounds; from about 3 to about 30% by weight of compounds having a degree of ethoxylation of 0; from about 45 to about 90% by weight of compoun~s having a degree of ethoxyla-tion of from about 1 to about 4; from about 10 to about 25% by weight of compounds having a degree of ethoxylation of from about 4 to about 8; and from about 0.1 to about 15% by weight of com-pounds having a degree of ethoxylation greater than about 8.
Another suitable class of anionic detersive surfactants arethe water-soluble salts of the organic, sulfuric acid reaction products of the general formula:
Rl-S03-M

WO 92/10162 PCT/US91/08~ ' t.~ i - 8 -wherein Rl is chosen 'rcm the group cansisting of a straight or branched chain, satunaLed ?.;~ n~ n.c~r'70n ;~ad,cal having from about 3 -co abou~ 4~ nel'O.''~ aou~ anOUL lP~ c~rbon atolns; and ii is ~ "
organic sulfuric acid reactii7n product o; ~ hydrocarbon of the meth~ni~ s~qri~ ? ~ ?.i~Cl~s, having about 8 to abcut 2-'~ ;~a~~~70n l~7mls~ ,re,~erab1y about 1~ to about 18 c~r~on o,eum, bleacRing ~ d lyd~
sulronated ~i2-iS n-para~ is i~dditional examDi~j oi ~n ,le ~,c an~ioilic de~ensive surrac-tants which come witiin the ter,s c.' ~he oresenL inventioll are the reaction products of ,-at~y aci s e,-~ri,i d wlth isethionic acid and neutralized ~ith sodium hydroxide where, for examDle, the fatty acids are derived from coconut oil; sodium or potassium salts of fatty acid amides of methyl tauride in which the fatty acids, for example, are derived from coconut oil. Other synthetic anionic detersive surfactants of this variety are set forth in U.S. Patents 2,486,921; 2,486,922; and 2,396,278.
Still other synthetic anionic detersive surfactants are in the class designated as sllccinama~es~ Inis class includes such surface active agents as disodium N-octadecylsulfosuccinamate;
tetrasodTum N-(1,2-dicarboxyethyl)-N-octadecylsulfosuccinamate;
diamyl ester of sodium sulfosucrinic acid; dihexyl ester of sodium sulfosuccinic acid; dioctyl ei~ers o. sod~.um sulfosuccinic acid.
Other suitable anionic detersive surfactants utilizable olefin sulfonates having about 12 to about 24 carbon atoms. The term "olefin sulfonates" ;s used herein to mean compounds which can be produced by the sulfonat on of ~-olefins by means of uncomple~ed sulfur trioxide, -ollowed by neutr~lization of the acid reaction mixture in cond~tions such that any sulfones which have been formed in the reâction are hydrolyzed to give the corresponding hydroxy-alkanesul;on2les~ Tne sulfur trioxide can be liquid or gaseous, ând is ~ual m~, but not necessarily, diluted ' '40 92/10162 2 ~ ~ 7 ~ 3 ~ PCT/US91/OX927 by inert diluents, for example by liquid S02, chlorinated hydro-- carbons, etc., when used in the liquid form, or by air, niLrogan, gaseous S02, etc., when used in the gaseous form.
The ~-olefins from which the ola;in su,r'ona~es are oen~v~
are mono-olefins having about 12 to about 24 carbon atoms, pre-ferably about 14 to about 16 carbon atoms. ~re,~a,ab7J, thay a.o straight chain olefins. Examples of suitable l-olefins include 1-dodecene; l-tetradecene; 1-hexadecene: l-OCt~aCe?le; I-~'.Sa:'?
and l-tetracosene.
In addition to the true al~ene sulrona~es an~ ~ or3!~0~ a hydroxy-alkanesulfonates, the oletin sultona~as can con~ain mir.v.
amounts of other materials, such 2s alkene disulfonatas aeDencing upon the reaction conditions, proportion of reactants, the nature of the starting olefins and impurities ~in the olefin stoc!~ and side reactions during the sulfonation process.
A specific ~-olefin sulfonate mixture of the above type is described more fully in the U.S. Patent 3,332,880, Pflaumer and Kessler, issued July 25, 1967, incorporated herein by reference.
Another class of anionic detersive surfactants are the ~-alkyloxy alkane sulfonates. These compounds have the following formula:

I
Rl - C - C - S03M
H H
where Rl is a straight chain alkyl group having from about 6 to about 20 carbon atoms, R2 is a lower alkyl group having from about 1 (preferred) to about 3 carbon atoms, and M is a water-soluble cation as hereinbefore described.
Specific examples of ~-alkyloxy-alkane-l-sulfonates, or alternatively 2-alkyloxy-alkane-1-sulfonates, having low hardness (calcium ion) sensitivity useful herein include: potassium-~-methoxydecanesulfonate, sodium 2-methoxy-tridecanesulfonate, potassium 2-ethoxytetradecylsu fonate, sodium 2-isopro-w o 92/10162 9~ '3 a PCT/~ISgl/08r poxyhexadecylsulfonate, lithium 2-t-butoxytetradecyl-sulfonate, sodium ~-methoxyoctadec~lsulroi~a~e~ and a~nonimn 3-n-propoxydo-decylsulfonate.
Many additional syr~n~ a1 on ~ c an~s an~ ~iortbe~
in McCutcheon's~ Emulsifi~rs and ~et~rqents~ l989 Annual, oub-lished by ~1. C. i'ubllsh-".s ~o., w,.,cn ~,s ,nco ,vo,~ate~ ~e,~." by reference. Also U.S. Patent 3~?~;J~, ~al!gl~lin et al~ issued December 30~ 1975, disclo ev ~snu ~ .n ~n~~ s~ s ~ r s~lrfacta~t ~ype~ aild i~ vl~ ù~ "
PrPferred anionlc ~ ar~ n~~ ~'U~
present shampoo co~posl~,o"s i"c,ù~e a"m",o,.1u", I.u,,~i .u " ate, ammonium laureth sulfate~ ;rie nYlamine 1auryl sui;are~ tri-ethylamine laureth sul t ate, ,riet~anolamine l~ur~l sulfate, triethanolamine laureth sulfat~, mono~thanolamine lauryl sulfate, monoethanolamine laureth sulfate, diethanolamine lauryl sulfate, diethanolamine laureth sulfate, lauric monoglyceride sodium sulfate, sodium lauryl sulfate, sodium laureth sulfate, potassium lauryl sulfate, potassium laureth sulfate, sodium lauryl sarcosi-nate, sodium lauroyl sarcosinate, lauryl sarcosine, cocoyl sar-cosine, ammonium cocoyl sulfate, ammonium lauroyl sulfate, sodiumcocoyl sulfate, sodium lauroyl sulfate, potassium cocoyl sulfate, potassium lauryl sulfate, triethanolamine lauryl sulfate~ tri-ethanolamine lauryl sulfate, monoethanolamine cocoyl sulfate, monoethanolamine lauryl sulfate, sodium tridecyl benzene sul-fonate, and sodium dodecyl benzene sulfonate.Ootional Detersi~e Surfactants In addition to the anionic detersive surfactant, the compositions of the present invention can optionally contain other detersive surfactants. These include nonionic surfactants, amphoteric surfactants, zwitterionic surfactants. Optional detersive surfact-~nts, whon used, ~re typically present at le~/els of from about 0.5% to about 20~o~ more typically from about 1% to about 10%. Also, the total amount of detersiYe surfactant in compositions containing optional àelersiYe surfactants in addition to the anionic surfactant will g~norally he frcm about 5.5% to YO 92/10162 2 B 9 7 ~ 3 ~ PCl /US91/08927 about 50%, preferably from about 8% to about 30%, more preferably from about 10% to about 25%. Cationic detersive surfactants can also be used, but are generally less preferred because they can adversely interact with the anionic detersive surfactant. Cat-ionic detersive surfactants, if used, are preferably used atlevels no greater than about 5%.
Nonionic detersive surfactants which can be used include those broadly defined as compounds produced by the condensation o~
alkylene oxide groups (hydrophilic in nature) with an orgalt,.
hydrophobic compound, which may be aliphatic or alkyl aromatic ,;
nature. Examples of preferred classes of nonionic detPrsive surfactants are 1. The polyethylene oxide condensates of alkyl phenols~
e.g., the concensation products of alkyl phenols having an alkyl group containing from about 6 to about 20 carbon atoms in either a straight chain or branched chain configuration, with ethylene oxide, the said ethylene oxide being present in amounts equal to from about 10 to about 60 moles of ethylene oxide per mole of alkyl phenol. The alkyl substituent in such compounds may be derived from polymerized propylene, diisobutylene, octane, or nonane, for example.
2. Those derived from the condensation of ethylene oxide with the product resulting from the reaction of propylene oxide_ and ethylene diamine products which may be varied in composition depending upon the balance between the hydrophobic and hydrophilic elements which is desired. For example, compounds containing from about 40% to about 80% polyoxyethylene by weight and having a molecular weight of from about 5,000 to about 11,000 resulting from the reaction of ethylene oxide groups with a hydrophobic base constituted of the reaction product of ethylene diamine and excess propylene oxide, said base having a molecular weight of the order of about 2,500 to about 3,000, are satisfactory.
3. The condensation product of aliphatic alcohols having from about 8 to about 18 carbon atoms, in either straight chain or branched chain configuration, with ethylene oxide, e.g., a coconut wog2/l0162 ~ 3~ 03a PC~/US91/08r-~

alcohol ethylene oxide condensate having from about 10 to about 30 moles of ethylene oxide per mole of coconu~ alcolol~ ~he c~conut alcohol fraction ha~ing from about 10 ~o ~icou~ !- cai~.o,l a~vms.
4. Long chain terti~ry amine o~-~h~es e'.':'e"~ 0 ~n-:
following general formula:
~1 R2~3N - ~ ~
wherein Rl contains an alkyl, al'~envl or mononv/lroxv ~l~yl radical o~ from about 8 to about 1~ e~on ~ , ~e~ ns 1?
ethylene oxide moietiej, and ,',~o;;~ v ~o ;~o;.; ~ e~r , ;~
and R2 and R3 contain from a~c~ eo ~ ~s sn~
from 0 to about 1 hyàroxy g,oup, e.y., me ,y,, elhy " p OpJ i, hydroxyethyl, or hydroxypropy'l ra~ica'is. '~he arro~ in tn~ rormula is a conventional representation of a semipolar hon~ ~xamples or amine oxides suitable for use in ;his invention include dimethyl-dodecylamine oxide, oleyldi(2-hydroxyethyl) amine oxide, dimethyl-octylamine oxide, dimethyl-decylamine oxide, dimethyl-tetradecyl-amine oxide, 3,6,9-trioxaheptadecyldiethylamine oxide, di(2-hydroxyethyl)-tetradecylamine oxide, 2-dodecoxyethyldimethylamine oxide, 3-dodecoxy-2-hydroxypropyldi(3-hydroxypropyl) amine oxide, dimethylhexadecylamine oxide.
5. Long chain tertiary phosphine oxides corresponding to the following general formula:
RR'R"P -> 0 wherein R contains an alkyl, alkenyl or monohydroxyalkyl radical ranging from about 8 to about 18 carbon atoms in chain length, from 0 to about 10 ethylene oxide moieties and from 0 to about 1 glyceryl moiety and R' and R" are each alkyl or monohydroxyalkyl groups containing from about 1 to about 3 carbon atoms. The arrow in the formula is a con~entional representation of a semipolar bond. Examples of suitable phosphine oxides are: dodecyldi-methylphosphine oxide, tetradecyldimethylphos?hine oxide, tetra-decylmethylethylphosphine oxide. 3,6,9,-trioxaoctadecyldimethyl-phosphine oxide, cetyldimethylphosphine oxide, 3-dodecoxy-2-hydroxypropyldi(2-hydroxyethyl) phosphine oxide, stearyldimethyl-phosphine oxide, cetylethylpropylphosphine cxide, oleyldiethyl-phosphine oxide, dodecyldiethylphosphine oxide, tetradecyldiethyl-vo 92/t0162 2 ~ ~ 7 ~ 3 ~ PCT/US91/08927 phosphine oxide, dodecyldipropylphosphine oxide, dodecyldi(hy-droxymethyl)phosphine oxide, dodecyldi(2-hydroxyethyl)phosphine oxide, tetradecylmethyl-2-hydroxypropylphosphine oxide, oleydi-methylphosphine oxide, 2-hydroxydodecyldimethylphosphine oxide.

6. Long chain dialkyl sulfoxides containing one short chain alkyl or hydroxy alkyl radical of from about 1 to about 3 carbon atoms (usually methyl) and one long hydrophobic chain which include alkyl, alkenyl, hydroxy alkyl, or keto alkyl radicals containing from about 8 to about 20 carbon atoms, from 0 ~o about 10 ethylene oxide moieties and from 0 to about 1 glyceryl moiety.
Examples include: octadecyl methyl sulfoxide, 2-ketotridecyl methyl sulfoxide~ 3,6,9,-trixaoctadecyl 2-hydroxyethyl sulfoxide, dodecyl methyl sulfoxide, oleyl 3-hydroxypropyl sulfoxide, tetra-decyl methyl sulfoxide, 3-methoxytridecyl methyl sulfoxide, 3-hydroxytridecyl methyl sulfoxide, 3-hydroxy-4-dodecoxybuty methyl sulfoxide.
Zwitterionic detersive surfactants are exemplified by those which can be broadly described as derivatives of aliphatic qua-ternary ammonium, phosphonium, and sulfonium compounds, in which the aliphatic radicals can be straight or branched chain, and wherein one of the aliphatic substituents contains from about 8 to about 18 carbon atoms and one contains an anionic group, e.g., carboxy, sulfonate, sulfate, phosphate, or phosphonate. A general formula for these compounds is:
(R3)x R2 - Y(+) - CH2 - R4 - Z(~) wherein R2 contains an alkyl, alkenyl, or hydroxy alkyl radical of from about 8 to about 18 carbon atoms, from 0 to about 10 ethylene oxide'moieties and from 0 to about 1 glyceryl moiety; Y is se-lected from the group consisting of nitrogen, phosphorus, and sulfur atoms; R3 is an alkyl or monohydroxyalkyl group containing about 1 to about 3 carbon atomsi X is 1 when Y is a sulfur atom, W O 92/tO162 ~3~ ~ ~3 3 PCT/~S91/OY

and 2 when Y is ~ nitrogen or phosphorus atom; R4 is an al~len2 or hydroxyalkylene of from about 1 t~ .~bou; ~ car~on a;cms and L
is a radical selected from the group coRsisti;,s o, car.o~;~,a.e, sulfonate, sulfate, phosphonate, nd phospha e gnollpi.
Examples of such surfactants include:
4-~N,N-di(2-hydroxyethyl)-,'l-octadec~ m~o.ie - ''!~;'e- !-c~na~xy-late;
S-~S-3-hydroxypropyl-S-hexadecylsulfoniol-3-~n~ ypen-~an ate;
3-[P,P-diethyl-P-3,6,9-~rioxa~e~rad~.~ocy.pn,~jn,.~ n~- n~-opane-l-phosphate;
3-[N,N-dipropyl-N-3-dodecoxy-2-hydroxyoroD~Yi~mm~nio; -o, ooane- ! -on-osphonate;
3-(N,N-dimethyl-N-hexadecylammonio)propane-l-sul,onate;
3-(N,N-dimethyl-N-hexadecylammonio)-2- hydroxypropane-1-sulfonate;
4-~N,N-di(2-hydroxyethyl)-N-(2-hydroxydodecyl)ammonio]-butane-1-carboxylate;
3-[S-ethyl-S-(3-dodecoxy-2-hydroxypropyl)sulfonio]-propane-1-phos-phate;
3-~P,P-dimethyl-P-dodecylphosphonio]-propane-l-phosphonate; and 5-~N,N-di(3-hydroxypropyl)-N-hexadecylammonio]-2-hydroxy-pentane-l-sulfate.
Other zwitterionics such as betaines can also useful in the present invention. Examples of betaines useful herein include the high alkyl betaines, such as coco dimethyl carboxymethyl betaine, cocoamidopropyl betaine, cocobetaine, lauryl amidopropyl betaine, oleyl betaine, lauryl dimethyl carboxymethyl betaine, lauryl dimethyl alphacarboxyethyl betaine, cetyl dimethyl carboxymethyl betaine, lauryl bis-(2-hydroxyethyl) carboxymethyl betaine, stearyl bis-(2-hydroxypropyl) carboxymethyl betaine, oleyl di-methyl gamma-carboxypropyl betaine, and lauryl bis-(2-hydrovy-propyl)alpha-carboxyethyl betaine. The sulfobetaines may be represented by coco dimethyl sulfoDropyl betaine, stearyl dim~thyl sulfopropyl betaine, lauryl dimethyl sulfoethyl betaine. lauryl bis-(2-hydroxyethyl) sulfopropyl betaine and the like;

'O 92/10162 ~ 0 9 7 3 3 ~ PCT/US91/0892 am;dobetaines and amidosulfobetaines, wherein the RCONH(CH2)3 radical is attached to the nitrogen atom of the betaine are also useful in ~his invention. Preferred beta;nes for use in the presen~ compositions are cocoamidopropyl betaine, cocobetaine, lauryl amidopropyl betaine, and oleyl betaine.
Exâmples of amphoteric detersive surfactants which can be used in the compositions of the present invention are those which a~,~a b.o~dlJ d~scribed as derivatives of aliphatic secondary and ~erti~ y ~miiles ,n ~hich the aliphatic radical can be straight or branc e~ c~ain and wherein one of the aliphatic substituents con~ains f,om about 8 to about 18 carbon atoms and one contains an anionic water solubilizing group, e.g., carboxy, sulronate, sulfate, phosphate, or phosphonate. Examples of compounds falling within this definition are sodium 3-dodecyl-aminopropionate, sodium 3-dodecylaminopropane sulfonate, sodium lauryl sarcosinate, N-alkyltaurines such as the one prepared by reacting dodecylamine with sodium isethionate according to the teaching of U.S. Patent 2,658,072, N-higher alkyl aspartic acids such as those produced according to the teaching of U.S. Patent 2,438,091, and the products sold under the trade name "MIRANOL"TM and described in U.S. Patent 2,528,378.
The most preferred shampoos of the present invention contain specific combinations of anionic surfactants, zwitterionic sur-factants, and amphoteric surfactants. The preferred shampoos contain from about 2% to about 16% of alkyl sulfates, from 0% to about 14% of ethoxylated alkyl sulfates, and from about 0~~O to about 10% of an optional detersive surfactant selected from the nonionic, amphoteric, and zwitterionic detersive surfactants, with a total surfactant level of from about 10% to about 25%.
Silicone Hair Conditioninq Aqent An essential component of the present invention is a vola-tile, nonionic silicone hair conditioning agent which is insoluble in the shampoo compositions hereof. The silicone conditioning agent comprises a silicone fluid component which contains a 3~ nonvolatile, insoluble, silicone fluid and optionally comprises a W o 92/10162 PCTtUS91/08' ~
2f 3~33~ - 16 -silicone gum which is insoluble in the shampoo composition as a whole but is soluble in the silicone fluid. The silicone nair conditioning agent can also comprise a silicone resin to enhanca silicone fluid component deposition efficiency.
The silicone hair conditioning agent may comprise low levels of volatile silicone components; however, s~vch volatile s~.l.cvnes will preferably e~ceed no more than about 0.5~Ot by weight, o, the shampoo composition. Typically, if volatile sil;cones ~r~ ~res-ent, it will be for prac.ical reason~ ine,deil~al ~o ~hein u~"'~
as a solvent and carrier for commercia'i'iv avaiiali~ S! I ',C_:'?
resins.
The silicone hair conditioning agent tor use herein wiii preferably have viscosity of from about 1,000 to about 2tooo,noo centistokes at 25'C, more preferably from about 10,000 to about 1,800,000, even more preferably from about 100,000 to about 1,500,000. The viscosity can be measured by means of a glass capillary viscometer as set forth in Dow Corning Corporate Test Method CTM0004, July 20, 1970.
The silicone hair conditioning agent will be used in the shampoo compositions hereof at levels of from about .1% to about 10% by weight of the composition, preferably from about 0.5% to about 8%, more preferably from about lYo ta about 5%.
Suitable insoluble, nonvolatile silicone fluids include polyalky~ siloxanes, polyaryl siloxanes, polyalkylaryl siloxanes, 2i polyether siloxane copolymer and mixtures thereof. However, other insoluble, nonvolatile silicone fluids having hair conditioning properties may be used. The term "nonvolatile" as used herein shall mean that the silicone material exhibits very low or no significant vapor pressure at ambient conditions, as is well understood in the art. The term "silicone fluid" shall mean flowable silicone materials having a viscosity of less than 1,000,000 centistokes at 25~C. Generally, the viscosity of the fluid will be between about 5 and 1,000,000 centistokes at 25~C, preferably between about 10 and about 100,000. The term 'O 92/10162 PCI/US91/08927 2~97~36 "silicone", as used herein, shall be synonomous with the term "polysiloxane".
The nonvolatile polyalkylsiloxane fluids that may be used include, ,~oi~ eAampl e, polydimPthyl siloxanes. These siloxanes are available, for example, from the General Electric Company as a Yiscas~.l series and ~rom Dow Corning as the Dow Corning 200 series.
~ na po~ lkylaryl siloxane fluids that may be used, also i"c ude~ ~e~A ex~mple, polymethylphenylsiloxanes. ~hese siloxanes iv ar~ a~ r~r example, from the General Electric Company as SF 10~5 me~ yl phenyl fluid or from Dow Corning as 556 Cosmetic ~raae Fluid.
The Dolyether siloxane copolymers that may be used include, for example, a polypropylene oxide modified dimethylpolysiloxane (e.g., Dow Corning DC-1248) although ethylene oxide or mixtures of ethylene oxide and propylene oxide may also be used. The ethylene oxide and polypropylene oxide level must be sufficiently low to prevent solubility in water and the composition hereof.
Silicone fluids hereof also include polyalkyl or polyaryl siloxanes with the following structure:

A r; _ 'O ~ "; - 0l - '; - A
~ _ x wherein R is alkyl or aryl~ and x is an integer from about 7 to about 8,000 may be used. "A" represents groups which block the ends of the silicone chains.
The alkyl or aryl groups substituted on the siloxane chain (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 harmful when applied to the hair, are compatible with the other components of the composition, are chemically stable w o 92/10162 ~ PCT/~'S91/08~
~1~3~ ~

under normal use and storage conditions, and are capable of being deposited on and of conditioning hair.
Suitable A groups include methyl, methoxy, ethoxy, propc~y, and aryloxy. The two R groups on the siliconQ atom may rep~e,--, the same group or different groups. Preferably, the two R groups represent the same group. Suitable R groups include methyl~
ethyl, propyl, phenyl, methylphenyl and phenylmethyl. The pre-ferred silicones are polydimethyl siloxane, polydiethylsilo~an~, and polymethylphenylsiloxane. Polydimethylsilnxane is espec,ally pre~enr~d.
References disclosing suitable silicone fluids inclu~e U.S.
Patent 2,~26,~6i, Geeni U.S. Paten~ 3,(~,5C0, Dra'~o~-,~, is.ued June 22, 1976; U.S. Patent 4,36~,837, Pader; and British ~a~Qnt 849,433, Woolston. All of these patents are incorporated herein by reference. Also incorporated herein by reference is Si1icon Compounds distributed by Petrarch Systems, Inc., 1984. This reference provides an extensive (though not exclusive) listing of suitable silicone fluids.
Another silicone material that can be especially useful in the silicone conditioning agents is insoluble silicone gum. The term "silicone gum", as used herein, means polyorganosiloxane materials having a viscosity at 25-C of greater than or equal to 1,000,000 centistokes. Silicone gums are described by Petrarch and others including U.S. Patent 4,152,416, Spitzer et al., issued May 1, 1979 and Noll, Walter, Chemistry and Techno10gy of Si7i-cones, New York: Academic Press 1968. Also describing silicone gums are General Electric Silicone Rubber Product Data Sheets SE
30, SE 33, SE 54 and SE 76. All of these described references are incorporated herein by reference. The "silicone gums" will typically have a mass molecular weight in excess of about 200,000, generally between about 200,000 and about 1,000,000. Specific examples include polydimethylsiloxane, (polydimethylsiloxane) tmethylvinylsiloxane) copolymer, poly(dimethylsiloxane) (diphenyl siloxane~(methylvinylsiloxane) copolymer and mixtures thereof.

~O 92tl0162 2 ~ 3 7 8 3 ~ PCT/US91/08927 - 19 .
Preferably the s;licone ha;r cond;t;on;ng agent compr;ses a mi~ture of a polyd;methylsiloxane gum, hav;ng a viscosity greater than about 1,000,000 c~ntistokes and polyd;methyls;loxane flu;d havie~ osit~ o' From about 10 centisto~es to about I00,000 centistokes, wherein the rat;o of gum to fluid ;s from about 30:70 to abou~ 70:30~ preferably from about 40:60 to about 60:40.
Another opt;onal ingred;ent that can be included ;n the s;licon~ c~nditioning a~ent is silicone res;n. Sil;cone res;ns a~e ~;~hl~ o~~ossl,n~ed polyme,tc s;loxane systems. The cross-l,"'i~ noduo~l ~hi~vusli ~he inc~rporation of trifunctional and ~e~ ,ù~c~ional silanes with monofunctional or d;functional, or vO~n~ mOnOMer units during manu'acture of the silicone resin.
As is well understood in the art, the degree of crosslinking that ;s required in order to result in a sil;cone res;n w;ll vary according to the specific silane units incorporated into the silicone resin. In general, silicone materials which have a sufficient level of trifunctional and tetrafunctional siloxane monomer units (and hence, a sufficient level of crosslinking) such that they dry down to a rigid, or hard, film are considered to be silicone resins. The ràtio of oxygen atoms to silicon atoms is indicative of the level of crosslinking in a particular silicone material. Sil.cone materials which have at least about 1.1 oxygen atoms per silicon atom will generally be silicone resins herein.
Preferably, the ratio of oxygen:silicon atoms is at least about 2~ 1.2:1Ø Silanes used in the manufacture of silicone resins include monomethyl-, dimethyl-, monophenyl-, diphenyl-, methyl-phenyl-, monovinyl-, and methylvinyl-chlorosilanes, and tetra-chlorosilane, with the methyl-substituted silanes being most commonly utilized. Preferred resins are offered by General Electric as GE SS4230 and SS4267. Commercially available silicone resins will generally be suppl;ed in an unhardened form in a low viscosity volatile or nonvolatile silicone fluid. The silicone resins fcr use herein should be supplied and incorporated into the preseni compositions in such unhardened form, as will be readily 3~ apparent to those skilled in the art.

w o 92/10162 PCT/US91/08r ~ 9 ~ V ~ - 20 -Background material on silicones including sections dis-cussing silicone fluids, gums, and resins, as well as manufacture of silicones, can be found in Encyc10pedi~ of Po1~er Science ~nd ~nsineering, 'lolume 15, Second ~dition, pp 20~-308, 'o~n '.~ilay ' Sons, Inc., 1989, incorporated herein by reference.
Sil;cone materials and silicone resins in particular~ can conveniently be identified according to a shorthand nomenclaturP
system well known to those skilled in the art as "MDTQ" nom2n-clatl1re. Under this system, the s~,licone is described acon,~"lg 0 to pr'ienCP of various silo~ano ",o"omer un~,ts whioh ma'~ u~ th~
silicone. 8riefly, tho symbol M denotos the monofur.ctional uni (CH3)35iOo s; D denot~s ~he d,fvnctional unlt ~''H3)25iO; , deilo~c, the trifunctional unit (CH3)SiO1 s; and Q denotes the quadri- or tetra-functional unit SiO2. Primes of the unit symbols~ e.g., M', D', T', and Q' denote substituents other than methyl, and must be specifically defined for each occurrence. Typical alternate substituents include groups such as vinyl, phenyls, amines, hydroxyls, etc. The molar ratios of the various units, either in terms of subscripts to the symbols indicating the total number of each type of unit in the silicone (or an average thereof) or as specifically indicated ratios in combination with molecular weight complete the description of the silicone material under the MDTQ
system. Higher relative molar amounts of T, Q, T' and/or Q' to D, D', M an~/or -or M' in a silicone resin is indicative of higher levels of crosslinking. As discussed before, however, the overall level of crosslinking can also be indicated by the oxygen to silicon ratio.
The silicone resins for use herein which are preferred are MQ, MT, MTQ, MQ and MDTQ resins. Thus, the preferred silicone substituent is methyl. Especially preferred are MQ resins wherein the M:Q ratio is from about 0.5:1.0 to about 1.5:1.0 and the average molecular weight of the resin is from about 1000 to about 10,000.
The weight ratio of the nonvoiatile silicone fluid component to the silicone resin component is from about 4:1 to about 400:1, '10 92/10162 PCI'/US91/0892-7 2~197,~)3~

preferably this ratio is from about 9:1 to about 200:1, more preferably ,~~om about 19:1 to about 100:1, particularly when the silicone fluid component is a polydimethylsiloxane fluid or a ini.~ dimethylsilo~ln fluid and polydimethylsiloxane gum as described above.
Pol~meric. Gltionic Hair Conditioninq Aqent The shampoo compositions of the present invention comprise a solubl~ ~rg;lilic~ polymeric cationic hair conditioning agent as an ~Sâe.n~iSl ele~e~ The ~ol~meric. cationic hair conditioning aaent 0 h~;''- .''.i'~ .?.'_r?.~'' b~ ol~e~-nt at 1 ev~ls of from about 0.05~,' to abcu~ pre~ r-bl,! from about ~.1~~ to about 5~, more preferably fro", vovv-~ ~.3". ~o i~out ~, by weight, of the shampoo composi~ion.
The ca~ionic organic polymers useful in the hair conditioning agent nereof are organic polymers that can provide conditioning benefits to hair and that are soluble in the shampoo composition;
Structurally, these polymers are characterized by open chain backbone, with quaternary ammonium or cationic amino moieties, or a mixture thereof, and a charge density which is no greater than about +3.0 meq/gram. Preferably, charge density is less than about +2.75 meq/gram. The precise cationic charge density is not believed to be critical so lonp as it is less than those stated essential and preferred limits. However, for practical reasons, the charge density should be of a level such that efficient substantivity between the polymer and the hair can be attained.
Generally, it is preferred that cationic charge density be at least about 0.2 meq/gram, more preferably at least about 0.4 meq/gram.Generally, the shampoo pH will be between about 3 and about 9, preferably between about 4 and about 8. Those skilled in the art will recognize that the charge density of amino-containing polymers may vary depending upon pH and the isoelectric point of the amino groups. Additionally, it is preferred that the charge density be within the above limits at the pH of intended use which will, in general, be from about pH 4 to about pH 9, most generally from about pH 3 to about pH 8. The polymer, of course, must WO 92/10162 PCI'/US91/08' -' ' - 22 -remain cationic upon application to the hair in order for there to be adequate substantivity between the conditioning agent and the hair.
The cationic hair conditioning polymers hereof have a ,~lex-ible, open chain organic backbone comprising saturated carbon-carbon covalent bonds. The polymer backbones are preferably substantially free of carbon-carbon triple bonds, which can aoversely affect polymer flexibility~ ~lore preferably, the polymer backbone will be complQt~ly fr~e of carbon-car~on triole i O bon(', .
ThP cationic nitrogPn-containing moiety will be presen~
senerally as a substituent, on a .~racticn a,~ the tot21 moncm~.
units of the cationic hair conditioning polymers. Thus, the cationic can comprise copolymers, terpolymers, etc. of quaternary ammonium or cationic amine-substituted monomer units and other non-cationic units referred to herein as spacer monomer units.
Such materials are known in the art, and a variety of such mate-rials can be found in the CTFA Cosmetic Ingred~'ent Dictionary, 3rd edition, edited by Estrin, Crosley, and Haynes, (The Cosmetic, Toiletry, and Fragrance Association, Inc., Washington, D.C., 1982). As used herein, the term "polymer" shall include materials whether made by polymerization of one type of monomer as well as materials made by two (i.e., copolymers) or more types of monomers.
Suitable cationic polymers include, for example, copolymers of vinyl monomers having cationic amine or quaternary ammonium functionalities with water soluble spacer monomers such as acyl-amide, methacrylamide, alkyl and dialkyl acrylamides, alkyl and dialkyl methacrylamides, alkyl acrylate, alkyl methacrylate, vinyl caprolactone, and N-vinyl pyrrolidone. The alkyl and dialkyl substituted monomers preferably have Cl-C, alkyl groups, more preferably Cl-C3 alkyl groups. Other suitable spacer monomers include vinyl esters, vinyl alcohol (made by hydralysis of polyvinyl acetate), maleic anhydride, propylene glycol, and ethylene glycol.

~O 92/10162 2 ~3 ~ 7 ~ 3 ~ PCr/US91/08927 Tertiary amine-substituted vinyl monomers can be polymerized in th2 amine form, or can be converted to ammonium by a qua~a,niza-tion reaction. The amines can also be similarly q~ nl ~e~ su3sequ~rt " Coril~'ion of the polymer.
Tertiary amine functionalities can be quaternized by reaction wil.ll a sal~ of the formula ~'X wherein R' is a short chain alkyl, preferably a C1-C, alkyl, more preferably a C1-C3 alkyl, and X is an ~i~io~ wilich forms a water soluble salt with the quaternized am'i~ l. X can be~ l or exampl ~! a halide (e.g., Cl, Br, I, or F, Su,~a~la cationic amtno and quaternary ammonium monomers incluu , ,-or exampla. ~inyl co",~ounds subs.ituted with dialkyl-aminoal~yl acrylate, dialkylaminoalkyl methacrylate, monoalkyl-aminoalkyl acrylate, monoalkylaminoalkyl methacrylate, trialkyl methacryloxyalkyl ammonium salt, trialkyl acryloxyalkyl ammonium salt, vinyl quaternary ammonium monomers having cyclic cationic nitrogen-containing rings such as pyridinium and imidazolium, e.g., alkyl vinyl imidazolium and alkyl vinyl pyridinium salts.
The alkyl portions of these monomers are preferably lower alkyls such as the C1-C3 alkyls, more preferably C1 and C2 alkyls. The quaternary ammonium salts must, of course, be solùble, and the anionic counterions referred to above are suitable.
The amine-substituted monomers useful for cationic organic_ polymers hereof will preferably be secondary or tertiary amines, more preferably tertiary amines. Suitable amine-substituted vinyl monomers for use herein include dialkylaminoalkyl acrylate, dialkylaminoalkyl methacrylate, dialkylaminoalkyl acrylamide, dialkylaminoalkyl and methacrylamide wherein the alkyl groups are preferably C1-C7, more preferably C1-C 3, alkyls.
The cationic polymers hereof can also comprise mixtures of monomer units derived from amine and/or quaternary ammonium-substituted oxyalkylene, vinyl, or other polymerizable monomer and compatible spacer monomers.
The charge density, i.e., the meq/gram of cationic charge, can be controlled and adjusted in accordance with techniques will w o 92/10162 ~ PCT/US91/0 '3 known in the art. In general, adjustment of the proportions of amine or qua~ernary ammonium moieties in the polymer, as well as pH of the shampoo composition in the case of the amines, will affec ~ charge density.
Specific examples of suitable cationic hair conditioning polymers include, for example, copolymers of l-vinyl-2-pyrrolidone and I-vinyl-3-methylimidazolium salt (e.g., chloride salt) (re~erred to in the industry as Polyquaterniu~-16), such as those comm~,ci~ vailable from 8ASF Wyandotte Corp~ (Parsippany, NJ, 'JSA! un'er !"'!I~UAT ~radenama ~-S-. L"'IIQ~AT FC 370, and c~-poly".ers c,' t-vinyl-2-pyrrolidone and dimethylaminoethyl meth-acryla~2 i~ ~'err~d ~o in Lhe i"dus~,y as ~olyquatern,um-1I) suc,S
as those com~ercially available from Gaf Corporation ~Wayne, NJ, USA) under the GAFQUAT tradename (e.g., GAFQUAT 755N).
Aaueous Carrier The shampoo compositions of the present invention are liquids which, preferably are pourable at room temperature. The composi-tions hereof will comprise an aqueous carrier, i.e., water, which will generally be present at a level of about 20% to about 95% by weiqht of the composition, preferably from about 60Yo to about 85%
for pourable, liquid formulations. The compositions of the present invention can also be in other forms, such as gels, mouse, etc. In such cases, appropriate components known in the art such as gelling agents (e.g., hydroxyethyl cellulose), etc. can be included in the compositions. Gels will typically contain from about 20~ to about 90% water. Mousses will contain aerosol propellent in a low viscosity composition qnd are packaged in an aerosol can, according to techniques well known in the art.
SusDendinq Aqent for Silicone Conditioninq Aqent Since the silicone conditioning agent used in the present compositions is an insoluble silicone dispersed in the composi-tions, it 'is preferred to utilize a suspending agent for the silicone. Suitable sùspending agents are long chain acyl deriva-tives, long chain amine oxides, and mixtures thereof, wherein such suspending agents are present in the shampoo compositions in Vo 92/10162 PCT/US91/08927 crystalline form. A variety of such suspending agents are de-scribed in U.S. Pat~nt ~,7~ 55, GrotP ~t al., issued May 3, 1988. Espec,~llJ~ preferr~d is eth~lene glycol distearate.
~,io m;cllided amon~ ~;r lc ~ ch~in acyl derivatives usPful as suspending agents are the N,N-di(hydrogenated) C16-C18 amido ben el ~cld, or soluhle salt (e~g.~ K, ~a salts) thereof parti-cularly N~N-di(hydrogenated)tallow amido benzoic acid which is cQmm~rc; ~l 1 y m~rliet?d b~ 5~eo ~n com3anY tNo,th~ield, Illinois, USA).
10'~ e cGilditioni~g ager,ts or~ ~he pt''ese~lt CQmlpOsi'~iQils i j xa"than ~um as described in U.S. Patent ~ ?OOo~ ~lich e~ al.~ iisued June 5, 198~. The combination Ot long chain acyl derivatives and xanthan gum as a suspending system for silicone is described in U.S. Patent 154,704,272, Oh et al., issued November 3, 1987, and may also be used in the present compostions.
Generally, the shampoo compositions will comprise from about 0.1% to about 5.Q%, preferably from about 0.5% to about 3.0%, of the suspending agent to suspend the silicone conditioning agent.
O~tional ComDonents The present compositions may also comprise a variety of non-essential~ optional shampoo components suitable for rendering such compositions more cosmetically or aesthetically acceptable or to provide them with additional usage benef;ts. A variety of such ingredients are well-known to those skilled in the art, and these include without limiting the invention thereto: pearlescent aids, such as tiO2 coated mica, ethylene glycol distearate; opacifiers;
preservatives, such as benzyl alcohol, l,3-bis(hydroxymethyl)-5,5-dimethyl-2,3-imidazolidinedione (e.g., Glydant~, Glyco, Inc., Greenw;ch, CT, USA), methylchloroisothiazolinone (e.g., Kathon~, Rohm & Haas Co., Philadelphia, PA~ USA), methyl paraben, propyl paraben, and imidazolidinyl urea; fatty alcohols, such as cetearyl alcohol, cetyl alcohol, and stearyl alcohol; sodium chloride;
sodium sulfate; ethyl alcohol; pH adjusting aids, such as citric acid, sodium citrate. succinic acid~ phosphoric acid, monosodium \~'0 92/10162 , , PCr/US91/OX' 2 3 3'~

phosphate, disodium phosphate, sodium hydroxide, and sodium carbonate; coloring agents or dyes; perfumes; and sequestering agen~,, such as disodium ethylenediamine tetra-acetate.
~,ochcl ~pticnal ing,~di~r.~ 'hat can be advantageously used is an anti-static agent. The anti-static agent should not unduly interfe ~ wi~h the in-use performance and end-benefits of the shampoo: oarticularly~ the anti-static agent should not interfere wi-'h ;he anionic detersive surfactant. Suitable anti-static agen~, cluia~ , e~;a,ple, tr cet~l methyl ammonium chlorlde.
u ~ ,C;i, ~V~ OU~ O.i,~ td dbOUt ;,o of sucl~ anti-static agen is incorpor~ed into 'he shampoo compositions.
ihough che silicone suspending agent component may act to thic~en the present compositions to some degree, the present composi~ions may also optionally contain other thickeners and viscosity modifiers such as an ethanolamide of a long chain fatty acid (e.g., polyethylene (3) glycol lauramide and coconut mono-ethanolamide).
These optional components generally are used individually in the compositions of the present invention at a level of from about 0.01% to about 10%, preferably from about 0.05% to about 5.0% of the shampoo composition.
The pH of the present compositions will generally be in the range of from about 2 to about 10, preferably from about 3 to about 9.
Method of ~anufacture The compositions of the present invention, in general, can be made by mixing the materials together at elevated temperature, e.g., about 72'C. The silicone resin, if any, and silicone fluid component are first mixed together before being mixed with the other ingredients. The complete mixture is mixed thoroughly at the elevated temperature and is then pumped through a high shear mill and then through a heat exchanger to cool it to ambient temperature. The average particle size of the silicone is preferably from about 0.5 microns to about 20 microns. Alter-3~ nately, the silicone conditioning agent can be mixed with anionic 'O 92/10162 2 i~ Vl i ~ ?~ ~ PCT/US91/08927 surfactant and fatty alcohol, such as cetyl and stearyl alcohols, at elevated ~emperature~ to r~orm a premix containing dispersed silicone. The premix can ~h-n be added to and mixed with the remaining ,îa~-anials o,~ ~h~ .ilia.rlvoo~ aump_ "n,~ugh a hish shear mill, and cooled~
Method ~f Use The shampoo compositions or the present in~ention are uti-lized c~nve~tionally, i a ~ hair is shamDooed b~y applying an effectm~ am,c it ~.~ th~ ,.amp.~ oma~si~ion ~~ th- scalp, and then 1~ rinsl,~g i~ ju~ e i;alp i~
general, encompassei m~ssag',ilg o, worklilg ~he sha~poo in the hair such Ihat ail ~r most or ~i~e n~ir o1l the jcal? is contacted. The term an "efTective amount" as used herein~ is an amount which is effective in cleaning and conditioning the hair. Generally, from about 1 9 to about 20 9 of the composition is applied for cleaning and conditioning the hair.
EXAMPLES
The following examples illustrate the present invention. It will be appreciated that other modifications of the present invention within the skill of those in the hair care formulation art can be undertaken without departing from the spirit and scope of this invention.
All parts, percentages, and ratios herein are by weight_ unless otherwise specified. Some components may come from sup-pliers as dilute solutions. The levels given reflect the activeweight percent of such materials.
ExamDle I
The following is a shampoo composition of the present invention.
Comoonent Weiqht %
Ammonium Lauryl Sulfate 13.5 Ammonium Laureth (3) Sulfate 4.0 LUVIQUAT EC 370 ~ 0.5 Coconut Monoethanol Amide 1.0 Ethylene Glycol Distearate 1.5 WO 92/10162 . _ ~ 3 ,~, PCI'/US91/0 Ammonium Xylene Sulfonate l.0 Xanthan Gum 0.5 Polydim~'hylsilo;c2ne ~ 3.0 C~ O.~
Stearyl Alcohol 0.2 Perf.li1e l.2 Color Solution 0.6 Pre~rv~ e 0.2 s 72~
0~ A'.~ ndJ~te Corpora~,on \Parsippany, NJ, USA) ,o,~ eQpoly"en o, vtnyl p~n~rolidone and methyl vinyl imidazo-liuln ei11~ri~e.
~ A ~OjoO weight ratio blend of polydimethylsiloxane gum (GE
SE 76, available from General Electric Co., Silicone Products Div., Waterford, NY, USA) and polydimethylsiloxane fluid (about 350 centistokes).
The composition can provide excellent in-use hair cleaning and conditioning, for both damaged and undamaged, or normal, hair types.
Examole II
The following is an example of a shampoo compos;tion of the present invention.
Comoonent Weiqht %
Ammonium-Lauryl Sulfate 13.0 Ammonium Laureth (3) Sulfate _ 5.0 GAFQ~AT 755N l 0.5 Coconut Monoethanol Amide 1.5 Ethylene Glycol Distearate 2.0 Ammonium Xylene Sulfonate l.0 Polydimethylsiloxane 2 2.5 Cetyl Alcohol 0 4 Stearyl Alconol 0.2 Perfume 1.2 Color Solution 0.6 Preservative 0.2 Water and Minors 71.9 Vo 92/10162 '~ 3 ~ PCT/US91/08927 1 Tradename of Gaf Corporation (Wayne, New Jersey, USA) for copolymer of vinyl pyrrolidone a~d ethyl dimethyl m~thacryoxyethyl ammonium metho~ulfate~
~ A iO/~ ,eig,l-; rac~,-) v,e,id o,~ polyd.~""e~'aylsilo~ane gum (GE
SE 76, ava;lable from General Electric Co., Silicone Products Div., Waterfcrd, NY, USA\ and polydimethvlsiloxane fluid (about 350 centistokes).
The compositioll can provi~i? excellen~ in-lJse~ hair cleaning and co~d~ v~ ,. f~ ?~s~d, ~r nor~ air types~
.~a~le I1I
Ihe foi7Owing is an ~xalnpie or d shampoo corlpo~i~ion of the present invention.
Com~onent ~eight %
Ammonium Lauryl Sulfate 13.5 Ammonium Laureth (3) Sulfate 4.0 LUVIQUAT FC 370 1 0.5 Coconut Monoethanol Amide 1.5 Ethylene Glycol Distearate 2.0 Trimethylsiloxysilicate 0.1 Polydimethylsiloxane 2 2.0 Cetyl Alcohol 0.4 Stearyl Alcohol 0.2 Perfume 1.2 Color Solution 0.6 Preservative 0.2 Water and Minors 73.~
1 Tradename of BASF Wyandotte Corporation (Parsippany, NJ, USA) for copolymer of vinyl pyrrolidone and methyl vinyl imidazo-lium chloride.
2 A 40/60 weight ratio blend of polydimethylsiloxane gum (GE
SE 76, available from General Electric Co., Silicone Products Div., Waterford, NY, USA) and polydimethylsiloxane fluid (about 350 centistokes).

w o 92/10162 ~ 3 ~ PCT/US91/0 The composition can provide excellent in-use hair cleaning and condi~ioning, for both damaged and undamaged, or normal, hair types.
~amDle IV
The ,ollowing is an example of a shampoo composition of the p r a S 'a ~ ~ ; ,' ',' Q ~ t j ~ n Comoonent Weiqht ~~O
.~t~ L~ l Sl!lf~e 4 0 ~ i) C O ~ O ,V '' v i~ a iltOil .~ Ui ~ a~ g 0 Soàiun ~.Y-L~uryi ~-Imitlodipropionat~ ~ o LU~iQUAî PC 370 ~ 0.3 Coconut ~onoethanol Amide 2.0 Ethylene Glycol Distearate 2.0 Xanthan Gum 0.5 Polydimethylsiloxane 2 2.0 Cetyl Alcohol 0.4 Stearyl Alcohol 0.2 Perfume 1.2 Color Solution 0.6 Preservative 0.2 Water and Minors 70.4 ~ Tradename of BASF Wyandotte Corporation (Parsippany, NJ, USA) for copolymer of vinyl pyrrolidone and methyl vinyl imida~o-lium chloride~
2 A 40~60 weight ratio blend of polydimethylsiloxane gum (GE
SE 76, available from General Electric Co., Silicone Products Div., Waterford, NY, USA) and polydimethylsiloxane fluid (about 350 centistokes).
ExamDle V
The follo~ing is a shampoo composition of the present invention.
ComDonent Weiqht %
Ammonium Lauryl Sulfate 13.5 Ammonium Laureth (3) Sulfate 4.0 . .

'O 92/10162 PCI/US91/08927 20~'75~

LUVIQUAT FC 370 1 0.5 Coconut Monoethanol Amide 1.0 Ethylene Glycol Distearate 2.0 Ammonium Xyl~ne Sulfonate 1.~
Polydimethylsiloxane Fluid Component 2 2.85 MQ Silicone ~esin/'lolatil~ Cyclomethicone 3 .15 Cetyl Alcohol 0.4 Stearyl Alcohol 0.2 Perrume 1.2 Color Soiu;ion ~.6 Preservative 0.03 Water and Minors --- to 100% ~~~
1 Tradename of ~ASF ~vandotte Corporation (Parsippany, NJ, USA) for copolymer of vinyl pyrrolidone and methyl vinyl imidazolium chloride.
2 A 40/60 weight ratio blend of polydimethylsiloxane gum (GE
SE 76, available from General Electric Co., Silicone Products Div., Waterford, NY, USA) and polydimethylsiloxane fluid (about 350 centistokes).
3 A 60/40 weight ratio belnd of the MQ resin in volatile silicone carrier. M:Q molar ratio of about 0.8:1Ø
The composition can provide excellent in-use hair cleaning and conditioning, for both damaged and undamaged, or normal, hair types.
The compositions hereof can be made by preparing a premix of the entire amount of silicone conditioning agent (i.e., the silicone fluid component and the silicone resin) to be incorporated into the shampoo, along with sufficient ammonium laureth sulfate and cetyl and stearyl alcohol such that the premix comprises about 30% silicone conditioning agent, about 69%
surfactant, and about 1% of the alcohols. The premix ingredients are heated and stirred at 72~C for about 10 minutes and the premix is then conventionally mixed with the remaining hot ingredients.
The composition is then pumped through a high shear mixer and cooled.
WHAT IS CLAIMED IS:

Claims (20)

1. A liquid hair conditioning shampoo composition comprising:
(a) from about 5% to about 50%, by weight, of an anionic surfactant component (b) from about 0.1% to about 10%, by weight, of a dispersed, insoluble, nonvolatile, nonionic silicone hair conditioning agent;
(c) from about 0.05% to about 10% by weight of soluble, organic, polymeric cationic hair conditioning agent, said polymeric, cationic hair conditioning agent consisting essentially of one or more cationic, hair conditioning polymers, said cationic hair conditioning polymers having quaternary ammonium or cationic amino moieties, or a mixture thereof, an open chain backbone, and a charge density of about +3.0 meq/gram or less; and (d) an aqueous carrier.

2. A liquid hair conditioning shampoo composition as in Claim 1, further comprising a suspending agent for said silicone hair conditioning agent.

3. A liquid hair conditioning shampoo composition, as in Claim 2, wherein said shampoo composition comprises from about .1%
to about -5% of said polymeric cationic hair conditioning agent, and said polymeric cationic hair conditioning _agent comprises cationic polymers having cationic vinyl monomers with ammonium quaternary or cationic amine substituents and water-soluble spacer monomers and having a charge density of about +2.75 meq/gram or less, said cationic polymers being free of carbon-carbon triple bonds.

4. A liquid hair conditioning shampoo composition, as in Claim 3, wherein said spacer monomers are selected from the group consisting of acylamide, methacrylamide, alkyl and dialkyl acrylamides, alkyl and dialkyl methacrylamides, alkyl acrylate, alkyl methacrylate, vinyl caprolactone, and N-vinyl pyrrolidone and said cationic vinyl monomers are selected from the group consisting of dialkylaminoalkyl acrylate, dialkylaminoalkyl methacrylate, dialkylaminoalkyl acrylamide, and dialkylaminoalkyl methacrylamide, monoalkylaminoalkyl acrylate, monoalkylaminoalkyl methacrylate, trialkyl methacryloxyalkyl ammonium salt, trialkyl acryloxyalkyl amommiun salt, vinyl quaternary ammonium monomers having cyclic cationic nitrogen-containing rings such as pyridinium and imidizolium, e.g., alkyl vinyl imidazolium and alkyl vinyl pyridinium salts.

5. A shampoo composition as in Claim 4, wherein said cationic polymeric hair conditioning agent is a copolymer or 1-vinyl-2-pyrrolidone and 1-vinyl-3-methylimidazolium salt or a copolymer of 1-vinyl-2-pyrrolidone and dimethylaminoethyl methacrylate, or a mixture thereof.

6. A shampoo composition as in Claim 2, further comprising from about 0.5% to about 20% of a detersive surfactant selected from the group consisting of nonionic, zwitterionic, and amphoteric surfactants, and mixtures thereof.

7. A shampoo composition as in Claim 2, wherein said anionic detersive surfactant component is selected from the group consisting of alkyl sulfates, ethoxylated alkyl sulfates, and mixtures thereof.

8. A shampoo composition as in Claim 3, wherein said anionic detersive surfactant component is selected from the group consisting of alkyl sulfates, ethoxylated alkyl sulfates, and mixtures thereof.

9. A shampoo composition as in Claim 8 wherein the surfactant is selected from the group consisting of ammonium lauryl sulfate, ammonium laureth sulfate, triethylamine lauryl sulfate, triethylamine laureth sulfate, triethanolamine lauryl sulfate, triethanolamine laureth sulfate, monoethanolamine lauryl sulfate, monoethanolamine laureth sulfate, diethanolamine lauryl sulfate, diethanolamine laureth sulfate, aluric monoglyceride sodium sulfate, sodium lauryl sulfate, sodium laureth sulfate, potassium lauryl sulfate, potassium laureth sulfate, lauryl sarcosine, cocoyl sarcosine, ammonium cocoyl sulfate, ammonium lauroyl sulfate, sodium cocoyl sulfate, sodium lauroyl sulfate, potassium cocoyl sulfate, potassium lauroyl sulfate, triethanolamine lauroyl sulfate, sodium tridecyl benzene sulfonate, sodium dodecyl benzene sulfonate, and mixtures thereof.

10. A shampoo composition as in Claim 8, further comprising from about .1% to about 20% of a detersive surfactant selected from the group consisting of nonionic, zwitterionic, and amphoteric surfactants, and mixtures thereof.

11. A shampoo composition as in Claim 10 wherein the surfactant additionally comprises a detersive surfactant selected from the group consisting of betaines, amido propyl betaines, sarcosinates, cocoamphocarboxy glycinate, and mixtures thereof.

12. A shampoo composition as in Claim 3 wherein the silicone conditioning agent is present at a level of from about .5% to about 10%.

13. A shampoo composition as in Claim 12 wherein the silicone conditioning agent is present at a level of from about 0.5%
to about 5% and comprises a silicone fluid component containing polydimethyl siloxane gum having a viscosity greater than about 1,000,000 centistokes, and a polydimethylsiloxane fluid having a viscosity of from about 10 centistokes to about 100,000 centistokes, wherein the ratio of gum to fluid is from about 30:70 to about 70:30.

14. A shampoo composition as in Claim 12, wherein said silicone conditioning agent comprises a silicone fluid component and a silicone resin component, said resin is soluble in said fluid, and the weight ratio of silicone fluid:silicone resin is from about 4:1 to about 400:1.

15. A shampoo composition as in Claim 13, wherein said silicone conditioning agent further comprises a silicone resin that is soluble in said silicone fluid component, and the weight ratio of silicone fluid component: silicone resin is from about 4:1 to about 400: 1.

16. A shampoo composition as in Claim 2 in the form of a pourable liquid.

17. A method for cleaning and conditioning the hair comprising applying an effective amount of the composition of Claim 1 to the hair and then rinsing said composition from the hair.

18. A method for cleaning and conditioning the hair comprising applying an effective amount of the composition of Claim 2 to the hair and then rinsing said composition from the hair.

19. A method for cleaning and conditioning the hair comprising applying an effective amount of the composition of Claim 14 to the hair and then rinsing said composition from the hair.

20. A liquid hair conditioning shampoo composition as in Claim1, further comprising an anti-static agent.