AU9826898A - Hair care compositions providing hair conditioning and style retention - Google Patents

Description

:i: RFlegzbba 3.2v-)

AUSTRALIA

Patents Act 19.90

ORIGINAL

COMPLETE

SPECIFICATION

STANDARD

PATENT

Application Number: Lodged Invention Title: HAIR CARE COMPOSITIONS PROVIDING HAIR CONDITIONING

AND

STYLE RETENTICN *44 The following statement Is a full description of this Invention, Including the best method ot pettornlng It known to us RciOEVE 1 A; L 1 A r:i*

;I

:B

HAIR CARE COMPOSITIONS PROVIDING l-lAR CONDITIONING AND STYLE RETENTION TECHNICAL FIELD The present inventior relates to hair care compositons comprising a silicone conditioning agent, an emulsifying agent, a cationic cosmetic agent, a hair setting agent, and an aqueous carrier.

BACKGROUND OF TH4E INVENTION The desire to have hair retain a pairticular shape is widely held. Two corrmon methodologies of accomplishing this are permanent chemical alteration of the hair and temporary alteration. A temporary alteration is ore which can be removed by water or by shampooing, Temnporary alteration is commonly accomiplhied by means of the application of a hair care composition to dampenied hiair after shampooing andlor conditioning and prior to drying and/or styling. The materials used to provide hair styling benelits in these compositions have generally been film formring or adhesive resins and have been typically applied in the form of mousses. tonics, lotions, hairsprays, and gels, In typical hair cae compositions. ha'r styling is achieved by the use of resins, such as AMPHOMER, supplied by National Starch CtNemical Co., and GANTREZ SP 225R, supplied by GAF Corp.

1When such hair styling resins a incorporated into hair care compositions.

to provide style hold, the tactile feel of the hair becomes stiff and hence less *..desirabe., Rt is therefore, desirable to also add a conditioner to impart softer hair feel up~on drying of the styling resin. Silicone materials have been trigt for use in hair cawn compositions and can be highly effective at conditioning the hair. Especially preferred for imparting a soft hair feel are high molecula" weight silico~nes. comtmonly referred to as silicone gums.

However, these silicone gums are extremly difficult to formulate into water -or ethanol based hair care compcsitions. This is because the silicone gum is too viscous to Incorporate or disperse into typical hair care ompositions.

The high viscosity of the silicone gurn leads to difficulties in handling and mbftin in tha mak-nufacturing process- All One conventional way to reduce the vi scosity of silicone gum s is by adding a volatile solvent, such as cycloqmAhicone. -The use of volatile solvents reduces the viscosity of the silicone gum to a point wt,_re it can be easily incorporated into ani emulsion Meoro- addition to the hair care composition. However. the volatile solveoits can result in negaft've aesthetic and hair feel properties. .Cyr~lomethicone, for kt-,r ple, can cause Vie hair to, appear and feel oily and less desirable. It i.a also be desirable to limit thie use of the volatile solvents to et~sure compliance with respect to vamvus regulatory laws. limiting the use or amount of such materials.

Another, method to reduce the viscosity of fth silicone gum is to add a non-volatile solvent, such as a silicone fluid to the silicone gum. Silicone fluids. such -is pol-dimethylsiioxane, are known to reduce the viscosity of the high molecular weight silicone gum without incurring the negative-hair appearance and feel properties asscciated with volatile solvents.

Typically. silianin gum as- well as mixtures of silicone gum and fluid are emulsified usin, naioic surfactant as the emulsifying agent.

Although the use of anionic surfactants is desirable in shampoo compositions. it is no!-desirable to use anionic surfactants in hair care compositions containing cationic cosmetic agents. &ich as mousses, tonics, lotions, hairsprays and gels. Cationic, cosmretic; agents can include, for example, cationic conditioning agents and adhesive polymers. hair ~:styling agents). The use of anionic, surfaclants can result in ionic inte fion w~hsuchcationic cosmetic agents- It is therefore desirable to provide a way to emulsify the silicone gum that is essentially free of anionic surfactants.

It is the object of the present invention W~ formulate hair care compostioans such as such as mousses. tonics, lotions, hairsprays and gels, which provide style retention and improved conditioned hai r feel benefits- It is desirable to achieve improved conditioning and hair feel benefits by utilizing relatively high levels of silicone gums incorporated into hair care compostiofs contaiiing a hair setting polymer. It is further desirable that these hair care compositions red.,ce the negative aesthetic and hair feel properties associated with hair setting polymers.

*These and other benefits as may be discussed or .apparent to one, of ordiniary sWil in the art can be provided according to the invention which is desibed below.

API percentages herein are by weight of the composition unless other--ise indicated. All ratios are weight ratios trnle-ss ioth-erwise indicate& Unless otherwise indicated. all percentages, ratios. and levels of ingredients r-eferred to herein are based on the actual amount of the ingredient. and do not include solvents, filters. other materials with which the ingrediient may be combined as commercially available products, -The invention hereof can comprise, consist of. or consist ssetntially of the essenti -elements described herein as well as any of thia preferred or other optional ingredients described herein.

SUMMARY OF THE INVE1NTION The present invention comprises hair care ccrpostions such as mousses. tonics. lotions. hairsprays and gels, which provide style retention and improved onditioned hair feel benefits- Said compositions achieve the improved conditioning and hair feel benefits by emulsifying a silicone conditioning agerAt containing silicone gumis. These emulsions are incorporated into hair care compositions which additionally contain a hair setting polymer or another cationic cosmetic agent: wherein the hair care compositions are essentialdly free of volatile solvents and contain no more than about by weight of the composition, of anionic surfactants, preferably no more than about more preferably no more than aboul, most preferably 0%.

More specifically, the present invent'*on provides a hair care =rimposition thtcomplises: (afrom about 0.1% to abiout 75% by. weight of the composition. Off an emulsified siliconel conditioning agent cobmprising: from about 20% to 100%, by weight of the s"icone conditioning agent.

of a nonvolatile insoluble silicone gumn having a co~nplex viscosity at 2 50 C Of at least 1,000,000 centistoke

(CSTK):

(ii) from 0% to about.80%. by weight of the silicone conditioning agent.

of a nonvolatile insokt~e siticoN fluid having a viscosity at 25*C of ;ess than 1,000,000 clertoise" from abot 0.1% to abou jj'6_ weight of the composition, of an emulsifying .Agent for said Silicone =Mutioning agent; setting polrw.

4t~4.

Pr la~sr~P ls~-r~-4 WM-~ C4WA -DIIL 4 from about 0.1% to about 25%, by weight of the composition, of a hair setting polymer.

from 0% to about 25%. by weight of the composition, of an additional cationic cosmetic agent.

from about 24.8% to about 99.7%. by weight of the composition, of an aqueous carrer; wherein said hair care composition is essentially free of volatile solvents and said composition contains no more than about by weight of the composition, of anionic surfactants; and said composition must contain at least 0.1% of a cationic cosmetic agent selected from the group consisting of cationic surfactants or cationic polymers for providing style retention and improved conditioning.

The present invention also relates to a method of providing conditioning and style retention by applying the compositions hereof to the hair.

The compositions and methods of the present invention are advantageous for utilization in connection with a wide variety of hair care products including hair mousses, tonics, lotions, hairsprays and gels.

The terms "comprises', "comprising', "includes" and "including" when used in this specification are to be taken to specify the presence of stated 20 features, integers, steps or components but does not preclude the presence or addition of one or more features, integers, steps, components or groups tnereof.

The present invention including various optional and preferred embodiments thereof, is described in more detail below.

DETAILED DESCRIPTION OF THE INVENTION The essential, as well as various optional, components of the present invention are described below.

Non-Volatile Silicone Conditioning Agent An essential component of the present invention is a nonvolatile silicone hair conditioning agent which is insoluble in the hair care compositions hereof.

The silcone hair conditioning agent is emulsified so as to be in the form of dispersed, insoluble particles, or droplets. The silicone hair conditioning agent comprises relatively high levels of nonvolatile insoluble silicone gum and 4a optionally a lower viscosity nonvolafile silicone fluid. The silicone gumn is insoluble in the hair care composition as a whole but is soluble in the silicone fluid. The silicone hair conditioning agent can additionaly comprise a silicone resin.

The silicon gum will be present in the silicone conditioning agent hereof at levels of from about 20% to 100%. preferably from about 35% to about more preferably from about 30% to aboul Nonvolatile insoluble silicone miaterial t0hat is essential in the silicone conditioning agent is silicone gum The term "silicone gun-. as used herein. means polyixrganoilaane materials: havin~g a viscosity at 25"C of at least 1,000.000 centistokes. The term -nonvolatile as used herein shall mean that the silicone material exhibits very law or no significant vapor pressure at ambient conditions, as is understood by those in the art Silicone gums are described in U.S. Patent 4.152,416, Spitzer et al-, issued May 1. 1979 and Noll, Waiter, Chemistry and Technology of Siicones. New York: Academic Press 1968. Also descibing silicone gums are General Electric Silicone Rubber Product Data Sheets SE 30. SE 33. SE 54 and SE 76. Al of these described references are incorporated herein ny reference.

The -silicone gums' will typically have a mass molecular weight. in excess ct about 300.000. generally between about 300.000 and about .000,000 Silicone gums useful herein can include polyalkyl siioxaries, polyar-y! siloxanes. polyalkyaryl siloxanes. polyalkylarrinO siloxaries. polyether siloxanes and the like. Other insoluble, nonvolatile silicone gums having hair conditioning properties cant also be used- Silicone gums hereof include potyalkyl of' polyaryll siloxanes with '.he following structure(l)7 wtierein R is alkyi or aryt arid x is an integer from at least 4,000. preferably from about 4.000 to aboLt 60,000. more preferably from aboutA 8,000 to about 40.000. most preferably from about 12.000 to abot 30.000. WA represents groups wtuch' bloc the ends of the silicone diins.

The at.y" oraryl groups substituted on them siloxarie chaiin or a!l the ends of the siloxane chains may have any structure as long as theresulting siticories remain fluid at room temperature. are hydrophobic, are neither intiN, toxc nor othewse hafrfu wh~en ap~ied to the hair. wre c~~=r4patlbe with the other cwmponerts of the conpcsiion. are chemically $table, unider ruomal use and storage conditions and are capare of being deposited on and of axuitioring; hair-.

Suitable A groups include methyl, nethoxy. ethoxy, propoxy. and aiyloxy. The two R groups on the silicone atom may represent the same group or different groups. Preferably. the two R gf oups represent !he sa-me group. Suitable R groups include methyl, ethyl. propyl. phenyl, methylphenyl and phenylmethyl. The preferred silicones are polydimethyl siloxane, polydiethylsiloxane, and polymethylphenyisiloxafle.

Polydimethylsiloxane is especialty preferred.

Suitable insoluble, nonvolatile silicone fluids can have the same chemical structures as the previously described silicone gumns, but will be of lower viscosity, as described below. and consequently will have correspondingly lower molecular weight. The termn "silicone fluid' shall mean flowable silicone materials having a viscosity of less than 1.000.000 centistokes at 25"C. Generally, the viscnsity of the fluid will be between from about 5 and about 1.000.000 centistokes at 250C. preferably between from about 10 and about 6&0.000 centistckes. moe preferably between from about 100 and about 100,000 certotkes. In Formula I above, the lowe molecular weight silicone fluids hereof will typically have C* values of less than 400. generally from about 8 to about 3.000.

The nonvolatile polyalkylsilox.-ne flukiis that may be used include. for example. polydirnethylsiloxaries. These sifoxanes are available, for example. from the General Electric Companry it, their Viscasil.! arnd SF -0 seis n rr Dew Coigntheir Dow The palyalkylaryl siloxane fluids that may be used, atso include. for example. polymethyiphenylsiloxanes. These siloxanes are available, for example, from the General Electric Company as SF 1075 methyl phenyl fluid or from Dow Corning as 556 Cosmetic Grade FlUd The po4yethe stloxane copolymers that may be used include, for examnple. a Polypropylene oxide modified polydimethylsitoxarie Dow Corrwag DC-1248) although ethylene oxide or- mixtures of ethylee oxide anid propylente oxide may also be used The ettiylente oxide and polypropylen oxide level must be si.Actently low to prevent solutility in water and fth cwmpositiox1 hoereof.

Othe references disclosing sut abl icone fluids include Patent 2.82.S51. Geen; U.S- Patent 3.964.5W0. Drakoff. issue June 22. 1976: U. S- Patent 4.364.837, Fader, and British Patent 849.433, Woolston. All of these patents are incorporated herein by reference.

Typic-:-ly the silicone Fuid will te Presecot in tne silicone c;hditionQagent hereofl at Ieveis-Of from 0% to about 80%, reefaWNY frum about to about 75%, more preferably4from about 30% to about 70%, Specifi examples f. silicone fluid Iinclude pqiydimnethylsziole (polvdimethylslaxane) (methyvtnylsloxafl) ccpolymer.

ooly(dimethysiloxane) (diphenyl 5 ji 0 oane)(mrety'vilYlsiloxane) colYMAef and mixtures thereof.

The siliccone hair conditioning acient for use herein will preferably have an average viscosity of fhum about 1,"0 to abcut 2.1000,00 centistokes at more preferably from about 10.000 to about I ,600,000. even More preferably from about 100,000 to about 1,500,000- The viscosity can be measured by means of a glass capillary visccmeter as set forth in Dow Corning Corporate Test Method CTMOOC4, July 20. 1970.

Another optional ingredient that can be included in the silicone conditioniN agent is silicone resin. Silicone resins are highly crosslinked polymeric siloxane systems- The crosslinking is introduced throuqh the incorporation of trifunctional and tetrafunctioflal silanes with manoturwicfal or diftmctcnll or both. silanes during manufacture of the siliconte resin- -As is well understood in the art the degree of crosslinkirig that is required in order to result in a siicone resin will vary according to the specific slane units incorporated into th"-e silicone resin. In general, silicone materials whuich have a sLfficient level of trifuincitionail and tetrafuxfldiOrkV siloxane monor units (and henr=, a sufficient levei of crosslinki-ng) such that they dry down to a rigid, or hard. film are considered to be silicone resins- TWeratino f oxygen atomns to silicon atom is indicative of tthe level of aaossliikiflg in a particular silicone aterwial. Silicone materias which have at least about 1-1 oxyge atorrs per silicon atom will generally be silicone resins herein- Preferably, the ratio of axygerEsilicon atoms is at least about 121.0. Sitanes used in tde manufacture of SIlicone resins include mcwmrehN-. diriethyt- trim~ettlyl-. mrQ~hen*l. dipneflYI-. meth"YiphenYt-.

manoVinyl. and ratyNilykloSdwves and tetrdioroSiane. *ith the methyl-substtued silanes being mnost convmonly utilized.

Background material on silicones incuding sectiotns dscassing sihocooe fluids, gums. and resins. as well as maruffacture of silKx1~s. can be fou'id in Encyclopda of Poiyme Science, and Engkuneering. Volutne Second EdltUMa pp 204-308. Jotn VVley &Sons. nc.1989. RincorCate~d herein by reference.

Silicocne materials and silicone resins if- ParticuLJ-f. can cc"'eerY be identified acrzorduingto a shrriiad nomn0CIat syse, weheto~ft thjose skilled in the art as VOTO" norendabire- Une thi system,, tL silicone descrT!:ed according 110 preserce 04' various silOxaemo7 unis -ich mnake up the siliccone. Briely, the symbol M denoteS the monofuOmdioflal unit (CH 3 3 Sio) 5: D deno;es the difurictional unit deinotes the trifuncfi~ral unit (CH 3 )SiO 1.5 and a djem.!es the quaddi- or tet-a-fufclofal unit S10 2 Prmes of the Lni sytnbol!s. eg,.

AX. ,and aY denote suibstituefliS cther than methyl, and must be specificali defined for each occurrence. Typical alternlate substitueflis include groGupS such as vinyl. phenyts. arriines. hymioxyls, etc. The molac ratios of th,3 variouis units, either in terms C' subscripts to the symbols indlicating the total numiber of each type of unit in 'he silicone (or an average Ihref or as specificaily, indicateRd ratis cctnhn with Molecular wegh cmplete the descipti-or ot the s-licn mteriar under th-e MODTQ systenm. Higher relative molar amounts of T, G. T and/or Q' to D.,I0%

M

and/or or M' in a siliconte resin is indicativie of higher ievels ot crosslinkinq As discussed before, however, the overall levc4 d" crosslink~ng c-an also te indicated by the oxyfgen to silicon ratio.

The silicone resins for u-se herein *tuch are preferred are N110 WT.

MITQ, MO and MOTO resins- Thus, the, preferred icr~suttU s methyl Especially preferred are MO resins whe~rein tthe NtO ratio is from about 0.5:10 to about 1-5:1.0 and the average rrolec~ulaT weiqht of the resin is from about. 1000 to about 10,000.

If the silicone resin is present inv said comnposii, ity-rill typically b present at a level of from abot 0-5% to about 35%. preferabl'y fromn about 3% to about 30%. m preferably -fromn abOut 5% -w about 20% of th-e silicore condxboniflV ageMi The hair care composition aiz~ocding to the invention comprise as an essential compownt an ernuistilfl§ agent The emulsify'lg awln hereof is selected from the. group cmnisisfl of non onic sufffactts. catmnric surfadands, affphotezl spratalts, _*,tterioinc sjr'acafls and rrnodures x? thereof Preferaly, the emnutsfjlg agent is a rcronltc or cationic simfactarlt. rrwe preferatity. a rzrnioniic suraC!2rt Nor .ionic: sifffactant's which are useful in the present invention can be broadly defined as Lncluding compounds containing an arkkyle-ne oxide groups (hvd-ophiic in nature) witUh a hydrophobic compound, %hiclh may be aliphalvic or alkyt aromatic in nattwe- Examnples of preferred cfasses of nonionic surfactants are-- 1. The pOyethylefie oxide condensates of alkyl phen-ois. the condensabOn products of the alkyl phenols; having an alkyl! group containing from about 6 to about 20 carbon atomis in either a sUba~ght chain or branched chain configuration, with ethyene oxde, the said eOThyne oxide being prese&t in amounts; equal to from about 3 to about 60 mles of ethylene oxide per mote of all phenol.

7- Those derived from the cxincensalion df ethylene oxide with the product resulting from the reaction of propylene oxide and ethylen-a diainine products.

3. The condensation produc of aliaphalic alcotiols having frorn about 3 to about 16a carb on atoms. in ethe-r straight chain or branched chain configuration, with ethylene oxide. a coconut abcohol ethylene oxide condensate hiaving from about 2 to about 340 males of ethylene o 1 e per, mote of coconuit alcohol, the oomnut alcohol fraction having froqz abou-xt to about 14 carbon atom 4. Long clhain tertiary amir-e oxides such as those corresponding to the folkirqn ge eral foanla:

RIR

2

R

3 N 0 wtwerein R, contains an alkyK- alkftyl or rnonohydroxy alkyl redical of from about 8 to about 18 carbon atoms, from 0 to about 10 ethylene oxide moieties, anid from 0 to aboutI qllycefy mciety. and R 2 and R 3 contain from about I to about 3 carbon atorris and from 0 to about 1 hydroxy group.

methyl edryl, propyl hydoxety. or hy&oxypropyl radicals (the arrow in fte f=O~ja represents a semipolar bond).

Long chain tertiar j~Osmiin oxdes corresPOrtding to the fo~owing genr~al form RRCR-P >0 wherein R contains an ailcyl. alkenyt or mono ,hydroxcyalkyl radical ranging from abou-t a to aboxt IS carbon atoms in chain ength. from 0 to about ethylene oxde moieties and from 0 to about 1 glyceryl moiety ard Fr and. r' are each alkyt or monihydroxyalky grOup-s cantaiin from abou 1 to about 3 caebon atoms. The arrow in the fonmdua represerts a semipolar bond 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 carbon atoms. from 0 to about 10 ethylene oxide moieties and from 0 to about 1 glyceryl moiety.

7, Polysorbates, sucrose esters of fatty acids, Such materials are described in U.S. Patent 3,480,616, sucrose cocoate (a mixture of sucrose esters of a coconut acid, consisting primarily of monoesters, and sold under the tradenames GRILLOTEN LSE 87K from RITA, and CRODESTA SL-40 from Croda).

8. Alkyl polysaccharide nonionic surfactants are disclosed in U.S.

Patent 4,565,647, Ltenado. issued January 21, 1986, having a hydrophobic group containing from about 6 to about 30 carbon atoms, preferably from about 10 to about 16 carbon atoms and a polysaccharide, a polyglycoside, hydrophilic group. The polysaccharide can contain from about 1.0 to about 10, preferably from about 1.3 to about 3. most preferably from about 1.3 to about 2.7 saccharide units, Any reducing saccharide containing 5 or 6 carbon atoms can be used, glucose, galactose and galactosyl moieties can be substituted for the glucosyl moieties. (Optionally the hydrophobic group is attached at the eta~ positions thus giving glucose or, galactose as opposed to a glucoside or galactoside.) The intersaccharide bonds can be, between the one position of the additional sacchardd units and the andlor 6-positions on the 4 preceding saccharide. units. Optionally there can be a polyalkyleneoxide chain joining the hydrophobic moiety and ft polysaccharide moiety. The aikyl group preferably contains up to about 3 hydroxy groups and/or the polyalkyleneoxicle chain can contain up to about 10, preferably less than ***alkylene moieties. Suitable alkyl polysaccharides arep;ctyl, nonyldecyl, :undecyldodecyl, tridecyl, tetradecyl, pentadecyt, hexadecyl. heptadecyl, and octadecyl, di-. ti-, tetra-. penit&-, and hexaglucosides, galactosides.

tactosides, glucoses. fructosides, fructoses andfor galactoses.

9. Polyethylene glycol (PEG) glycetyl fatty esters, as depicted by the formula RC(O)OCH 2

CH(OH)CH

2

(OCH

2

CH

2 )nOH wherein n is from about S. 5 to about 200, preferably fom about 20 to about 100, mora preferably from '.:about 30 to about 85, and RC(O)- is an ester wherein R comprises an alilhtic radical having from about 7 to 19 carbon atoms, preferably from about 9 to 17 carbon atoms. more preferably from about 11 to 17 carbon aloms, most preferably from about 11 to 14 carbon atoms. The combinations of n from about 20 to about 10)0, wYth C 12

-C

18 preferably ic 12 c 1 fatty esters, for minimized adverse effect on foaming, is preferred.

Cationic surfactants useful, in hair care compositions of the present invention. contain amino or quatematY ammonium hydrophilic moieties which are positively charged when dissolved in the aqueous compostion of the present invention. Cationlic surfactants among those useful herein are disclosed in the following documents, all incorporated by reference herein: M.C. Publishing Co., cce'. DeeLns&EM.ulsifers, (North American edition 1979); Schwartz. et Surface, Active AentS, Delir Chgmij~tf and TecholOY New Yotk lnterscience Publishers, 1949;

U.S.

Patent 3,155,591, Hilfer, issued November 3, 1964;, U.S. Patent 3,929,67B, Laughlin, et at., issued December 30, 1975; U.S. Patent 3.959,461, Bailey, et at.. issued May 25, 1976; and US. Patent 4.387.090, Bolich, Jr.. issued June 7, 1983.

Among the quaternary ammonium-n~taifling catioflic surfactant materials useful herein are those of the general formula- RIP.\ R 3 e N,

X

wherein

R

1 -R4 Pre Independently an aliphatic group of from about A to about 22 carbon atoms, or an aromatic, alkox(y, polyoxyalkylene, alkylamido, hydroxyalkyl, aryl or alkylaryl group having from about 12 to about 22 carbon atoms;, and X is an anion selected from halogen, acetate, phosphate, nitrate and alkylsutfate radicals. The aliphatic groups may contain, in addition to carbon and hydrogen atoms, ether linkages, and other groups such as3 amino groups. The longer chain aliphatic groups, eg., 4,4* *those of about 12 carbons, or higher, can be saturated or unsaturated.

4 4 Salts of Ormary, seconday and tertiary fatty amines are also suitable catiornic surfadatit materials. Thie alkyl groups of such amines preferably have from about 12 to about 22 carbon atoms, and may be sbsituedorurtsubstituted. Such amines. useful herein, include stearamlido propyl imhy mine, diethyl amino ethyl stearamide, dimethyl stearaiife, dimnethyl soyamrirle, -soyarne, mnrstyl amine. tIidecyl amine.

ethyl stearylam~ifle, Ntallowpropafl diamine, ethoxylated (5 moles

E.O.)

stearylamifle. dihydroxy ethyl stearylamirte,, and arachidylbeheflylarmine.

12 Suitable amine salts include the halogen, acetate, phosphate, nitrate.

citrate, lactate an~d alkyl sulfate salts. Such salts include stearylaMifle hydrochloride, soyamine chloride, stearylamine formnate, N-tallowpropafle diamine dichloride and stearamidopropyl dirrnethylamine citrate. Cationfic amine surfactants included airong those useful in the present invention are disclosed in U.S. Patent 4.275.055. Nachtigal, et at, issued June 23. 1981, incorporated by reference herein.

Examples of amphoteric sutfactants whtich can be used in the compositions of the present invention are those which are broadly described as derivatives of aliphatic secondary and tertiary aminez; in which the aliphatic radical 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 water solubilizing group. carboxy.

sulfonate, sulfate, phosphate, or phosphonate. Examnples of compounds failing within this definition are sodium 3-dodecyl-afilopropiofate, sodium 3-dodecylamilopropafe sulfanate, N-alkyltaurines such as the one prepared by reacting dodecytamifle wvith sodium isethionate according to the leaching 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" and desc'ibed in U-S. Patent 2,528,378, both of which patents are incorporated herein by reference.

Z~iterwicsurfactants, ussfui-in the present invention, are exe-nplified by those which can be broadly described as derivatives of aliphatic quaternary ammronium. phosphonium, and sutfonilur 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 water-solubilizing group, e.g., carboxy, sulfonte, suffate, phosphate, or phosphonate. A general formula for these corqiundSa is.

(R))k S.R-P-CHr-R4-P wherein R 2 contains an alkyt, alkenyl, or hydroxy alkyl radical of from about 8 to abou 18a carbon atoms, from 0 to about 10 .thylene oxide moieties and from 0 to about.1 glyceryl moiety; Y is selected from the group consisting of nitrogen. pOvspholus, and sulfur atoms-, R 3 is an alkyl or monohydroxyalkyl group containig about I to about 3 carbon atoms, X is 1 when Y is a sulfur atom and 2wtleYi itoenorphsphrsatom is at.kyleneo 13 hydroxyalkylene of from about 1 to about 4 carbon atoms and Z is a radical selected from the group consisting of carboxylate. sulfonate, sulfate, phosphonate,. and phosphate groups, Other zwitterionics such as betaines are also useful in the present invention. Examples of betaines useful herein include the high alkyl betairies, such as coco dimethyl carboxymethyl betaine. lauryl dimethyl carboxymethyl betaine, lauryl dimethyl alphacarboxyethyl betaina, cetyl dimethyt carboxymethyl betaine, lauryl bis-{2-hydroxyethyl) cadbxiymethyl betaine, stearyl bis-{2-hydroxypropyl) carboxyrnethyl betaine, oleyl dimethyl garnma-carboxypropyl betaine, and lauryl bis-(2-hydoxypropyl)lpha-carboxCyethyl betaine. The sutfobetaines may be represented by coco dimethyt suffopropyl betaine. stearyl dirnethyl sulfopropyl betaine. lauryl dimethyl suit oethyl betaine.- lauryl bis-(2-hydroxyethyl) sulfopropyl betaine and the like; amidobetaines and amidosulfobetaines, wherein the RCONH(CH 2 3 radical is attached to the nitrogen atom of the betaine are also useful in this invention.

Other surfactants that can be used include fluorosurfactants. or other halogenated surfactants, which can be nonionic, cation-6c, amphoteric. or zwitterionic, Fluorosurfactants include perfluorinated compounds such as those represented by the forrn~a

CF

3 cH4z S where Z is a water solubilizing group of either organic or inorganic char acter, x is an integer which is generally from 2 to 17, particularly from 7 to 1, nd isan integer from 0 to 4, and said compounds may be nonionic, cationic. amphoteric or zwitterionic. depending upcn the nature of the grouping or groupings encompassed by Z. The Z groups may be or may conprse sulfate. sulfonate. carboxylate, amine salt, quaternary ammonium.

*.*phosphate. phosphonate. and combin-ations thereof. heperfluorinated cempounds are known in the aet These compounds are described in U.S& Patent 4.176,176, Cella et al., issued November 27, 1979, U.S. Patent 3,993.745, Celia at aL, issued November 23, 1976, and U.S. Patent 3,993,744, Cella et al.. issued November 23, 1976. each being incorporated he-rein by reference. Fluorosutfactants. when used, will typically be used at Icow levels ftan mast othe emulsifying agents.

ft.

W

14 Another surfactant which can be present in the invention are polyether siloxane copolymners, or silicone "copolyols7 as they are sometimes referred to. Silicone copolyols are surfactants charecterized by a hydrophobic polysiloxarie chain and a hydrophilic alkoxy portion.

Silicone topolyols which may be used include polyalkylefle oxide modified polydimethylsiloxafles of the following fcrmnulae: [CH31

CHW

3 WSOCH.Ich 4 iO- sitHm 1 2 1 4 O )<c 3 Hj 6 o)b-R and R:-Si r OSi(CH 3 2 x-(CZfi43(OCH)bOR'3 wherein R is hydrogen, an alkyl group havin~g from I to about 12 carbor. atoms, an alkoxy group having from I to about 6 carbon atoms or a hydroxyl group; IT and R" are alkyl groups having from I to about 12 carbon atoms, x is an integer of from I to 100. prefer.Ably from 20 to 30; y is an integer of 1 to 20. preferably from 2 to 1 0; and a and b are integers of from 0 to 50, preferably from 20 to Silicone copolyols among those useful herein are also disclosed in the following patent documents, all incorporated by reference herein: U.S.

Patent 4,122.029, Geen, et aL, issued October 24, 1978: U.S. -Patent 4,265,878, Kell. issued May 5, 1981; arnd Patent 4,421.769, Dixon. et issued December 20. 1983. Such silicone copolyol materials are also disclosed, in hair compositions, in British Patent Application 2.066,659, Abe, pulished July 15, 1981 (incorporated by reference herein) and Canadian Patet 727,588, Kuehns. issued February 8, 1966 (wicorporated by reference herein). Commrercially available silicone cqopoyols which can be used herein, incude Sillwet Surface Active Copolymers. (manufactured by the Union Carbide Corporation); and Dow Coming Silicone Surfactants (mranufactured by the Dow Coming Carporatico).

Emulsionl The hair care owpostion according to the invention comprises an aquous emulsion of the siflicone conditioning agent The emulsion of the present invention is prepared by combining the silicone gtumn in the optional silicone puid, adding the emulsifying agent and forming the emulsion with the addition of the aqueous carrier (which is described in further detail below) and mixing to form an emulsion.

The silicone conditioning agent is present in the hair care compositions in an amount of from about 0.1% to about 75%. preferably from about to about 50%, more preferably ftrm about 1% to about 15%. most preferably from about 2% to about 10%. The weight ratio of the emulsifying agent to emulisfy the silicone conditioning agent, as described above, to slicone conditioning agent is preferably from about 1:25. preferably from about 2: 1. more preferably from about 1:*10, most preferably from about 1: 1.

The emulsified particles of the silicone conditioning agent. will preferably have an average diameter less than 25pim, more preferably from about 0.1 to about 10 g.m. The average particle size may be measured for example by laser light scattering technique such as a Particle Size Analyzer from Malvern Instruments.

Hair Setinc Polymers The hair care compoitions5 of the present invention contain, as an essential component a hair setting polymer. Any hair setting polymer soluble or dispersible in the aqueous carrier may be used. Solub ility is determined at amibient conditions temperature about 25mC and atmospheric pressure). Hair setting polymers provide style retention benefits upon application to the hair and drying to form an adhesive film A wide variety of hair setting polymers are known in the art. Suitable types of hair setting polymrs include anionic, nonionic. amphoteric, and cation ic, Prefeted hair setting polymrers; are cationic: or amphoteric, especially pteferrecl are cationic; har setting polymr, Specific hair setting polymers k-4ude: vinyl pyrrolidonevinyt acetate copolymers; vinylacetate hconopotyrmer. t..butyl acrylate homopolyrw.e t-butyl ,syrnehyhel mnethaoylate copolyme dimethyl acrylamide/ t-butyl icrylate/ethyl "Ixy methacrylat* cop~lyii'e thylerne/VnyI acetate copG"yme alty alcohollstyrelO copolymr vinyl chloide~,inyl acetate copolymer, vinyl pyrrolidotwAflr actate"Ibuy acrylate copolymfer, vinyl pyrrobidoneill acetate/butyt aylate/stryrene sulfonate copolymer. vinyl pyrrolidonevitl prop~onata copolymef vinyl caprolatanhiflyl acetate copoylme-, and.

stying resins sold under the trade names Ultrahold CA 805 by Ciba, Geigy (ethyl acryltel acrylic acidN-t-bityl acrylamride copolymer): Resyn 26-1310 ft.

ft.

ft. ft ft. ft ft .ft ft. ft ft S.

ft.

'Ct' 0 by National Starch and Luviset CA 660 by BASF (vinyl acetateirectonic add copolymer 90/10)1; Luviset CAP® by BASF (vinyl acetatevinyl pwopionatelcrotonic acid): Resyn 253-2920® by National Starch (vinyl acetatelvinyl neodecancialelcrotorvic acid copolymer); Ganti-ez AN® by GAF (polyvinyl methyl etherlrnaleic anhydrid4 copolyri); AMPH-OMERM by National Starch (octytacrylamidelacrylatelbutylailoethyl methacryiate copolymer); Ceiquat H-i100 and Celquat L200 by National Starch (dialtyldimoniumlhydroxyethycellase copolymer). and mixtures thereof.

With certain of the polymers it may be des-"rable to neutralize some acidic groups to promote solubility PVA/crotonic adid). Examples of suitable neutralizing agents include 2-amino-2-methyl-1 ,3 propanediol (AMP 2-amino-2-ethyl-1 ,3-propanedioi (AEPD): 2-amino-2--methyl-1 propanol (AMP); 2-amrino-1-butanol monoethanolarrine (MEA)*.

diethanolamine (DEA); triethanolainine (TEA); monoisopropanolamine (MIPA)-. didsopropanol amine (DIPA), triiseopropanolamine (TIPA); and dirnethyl stearamine (DMS).

The hair setting polymer is present in the hair care compositions of the present invention at a level of from about 0.1% to about 25%. preferably from about 0.5% to about 15%. more preferably from about 1% to about by weight of the composition.

Cationic Cosmetic AgQent The compositionis of the present invention must contain a cationic cosmetic agent of cationic emulsifier. The cationi cosmetic agent may be a cationic hair setting polymer or a cationic emulsifier if present at a sufficient level to provide a conditioning bnefit, as descdbed above. However. if neither the hair setting agent nor the emulsifer is cationic. the composilons must contain one or miore other cationic cosmetic agents, Such additional cationic cosmetic agefts useful in the present invention can be any cationic material which Provides a cosmnetic benefit to the hair conditioning, shi MI heir colorig and the like). Preferably such cationiic materials are -selected from the group consisting of cationic surfactants, cationic polyrs, and mixttes thereof. These cationic materials can also be persent i wrbirnatiixi with catiot*i hair settng polymers andloc cationic emulsifers.

Thvs, the comipositions hereo will contain an additional cationic *cosmeti;; agent at a levei of from 0% to about 25%, by weight of the corr~osit fI the Compositionl does not contain a cationic hair setting potymner or a Caticrn-c enmulsifier, as described above. such cOMP~sit iOn' will cOmpnise frkom about 0.1% to about 25% of one or more other types Of cation c cosnetCr agents, preferably from. about 01. 1% to about 15%, more preferably from about 05j% to about 10%- in the event that the compOsiiOfl does contain cationic hair setting polymer or ernulsifer, such components are only to be included in the calculation of hair setting polymer Or emulsifier, respectiveli, and are not to be included as part of the additional cationic, cosmetic agenLi Additionally. the emulsifier componenlt as described abov.e includes only that tyeand amoun Of surfactant that is used to emulsify the silicone con-ditioflifl agent. Cationic suftactant that is added or used otthe (Such as after the emulsion is formed) would conistitute part of the adddicinal cationlic cosmetic agent.

Cationic surfactants. as described previouSlY, are used to provide additional Wnlnring benefits in the present copOsitioris. The cationlic surfactanlts used herein can be used at higher level than the catiortic surfactantls used as an emulsifying agent. Preferably, the cationicsurfactants of the Present invention contain amino or q~uate mary anMrrOfium moiees.Catoflc sufacaflS aongthose useful herein are disclosed in the following docureflts. all *incrPr)arted herein by reference:

MC

Publishing Co_. McCjutheon'S. Detergents EmulsifierS. (North Amiericanl edition 19T9)-; Sd~ft. Surface Active Agents. Their ChemiStrY an~d TechlotgfNewYork Interscience Publishers. 1949; Patent ~3,155.591, HOWite ssue November 3. 1964; U- S- aet39968 4.-Laughlin et al., issued December 30, 1975;, U. S- patent 3959461. Bailey 9t aL issued May 25. 1976: and U. S. patent 43870W0. Bolich. issued The Cff Sifon of the Present iniveiOn can Ilso, comprise one or moO caiarlc plyfiS- Te c~iank~ arsr used in the present irvnon canl pmiMds boh concdioin and styling benefits. The catoi V*Wwil Preferably be water eubte. Catiornic polym'5 are typically usedin he sme angesias diSClos-ed above for catieic surfctan~t.

Byei wte Sm t~ r~ nt plmr what is meant is a polyme whcn ~s suficientlYsokibtein water to fat-o a jbsmfritally clear solutiont h naked eeat; a cnerflinatIlo 0.1% in water (di~tlltd of equwvalert) at 2S* C- PrwbY the Po,1le will be sudficiently soluble to forma usntty cle slui~a~t 050A cw#;etiom~ romf piferbly at 1 COneRIt tion As used herein, the term 'pokyme' shahi include materials wtiether made by polymerization of one type of monomer or made by two copolymners) or more types of monomers.

The cationic polymers hereof witl generally have a weight average molecular weight which is at Ileast about 5.000, typically at least about 10.000, and is less than about 10 million. Prefeeably, the molecular weight is from about 100.0iQO to about 2 milliona The cationic polymers will generally have cationic nitrogen-containing moieties such as quaterarl ammnoniumn or cationic amino moieties, or a mixture thereof.

Any anionic counterions can be utilized for the cationic polymers so long as the water solubility criteria is met. Suitable aounterions include halides Cl. Br, 1, or F. preferably Cl, Br, or sulfate, and methylsulfate- Others5- an also be used, as this list is not exclusive.

The catioriic Piitroslen-containing moiety will be present generally as a substituent, on a fracion tif the total monomer units of the cationic: hair conditioning potymts- -thus, the cationic polymer can comprise copolymers. terpolmers. etc- of- quaternary ammonium or cationic aimine-substitute? mnomer unfits and uther non-cationic units refer-ed to herein as spacer.. p# bromer units, Such polymers are known in the art. and a variety can be.tound in the CThA Cosmetic Ingredient Dictionary. 3rd.

edition, edited by. Estrin. Crosley, and Haynes, (The Cosmnetic, Toiletry. and -Fragrance Association, Inc., Washington, 1982).

-Suitable f~ationic; polymers include, fvo' exarsple. copolymers of vinyl SMonomerws having cationic amine or quateimary amrmonium fur.ctiorialiies with water soluxAe spacer monomers such as aarylarude. inetiiacylamide.

atkyl and dialkyl ao'ylamides. aflyf and dialkyl methacrylainides. alkyl acrytate, alkyl methataylate, vinyl caprolactorie, and vinyl pyrrolidone. The alkyl and dialkyl substituted mfonomers prefeirably have Cl-C 7 alky groups, mre preferably Cj-C 3 alk groulms.1- Other suitable~ spacer mcgonnels include vinyl esters, vinyi alcihol (made by hydrolysis of polyvinyl acetate).

maleir- aaitydride ppylene giycol. and ethylene glyco 'The, cationic amnines can be pomaTry, secondary. o ter!ir ains, *depend'tig upw.~ the particular species and the pH of the shan-poo In generaL. secondary and tertiary arrirres. especially tertiary amnes. are preferred.

~fsfde vinyl mionomers cart be polynirized in 0the ar'ie.

form, and 9hen optionally cn be cornverted to ammronin by a quatemnization reatian. Amines can alsc) be similarly quaternized subsequent to foration of the polymer. For example. teftiary arntne functionalities can be quatemnized by reaction with a salt o! the formula RVX Atherein R is a s&Wr chain alkyl, preferably a Cj-C 7 alkyl, more preferably a C, -C 3 aikyl. and X is an anion which f orms a w.ater soluble salt with the quatemnized ammonium.

Suitable cationic amino and quaternary ami-rinium moncomers in-Jude. for example, vinyl compounds sutistitued with dialkylaminoalkyl acrylate. dijalkylamincakyl methacrylate. moncajk annoaly cya~ mncarkylrnincalkyt inetiacrylaze, trialkyl mnetiacryloxyalkyl arnmcniumn salt triagtkyi acryloxyalkill amrmonium salt diallyl quaternary anmniumn salts, and vinyl quaternary ammonium monomers having cycccalionic nit )gen--cntainiriq rns such as pynidiniiurn. intdazaliurn. and quaternized pyrrolidone. alk! yin'.! imidazolium, arkyl vinyl pyridinium, alkyl vinryl pyrrolidorie salts. alkyl portions of these monomers are prefer-ably lower alkyls such a-sthe C 1

-C

3 alkyls, more preferably C 1 and C. akyls.

Suitable arain-subOtuted vinyl monomers for use herein include dialkarninoalkyl acrylate dialkylarninoalkyl methacrylate. diatikylamroalkyl acrylamide. anid diaikylaminoaky methacrylarnide. wherein the alkyl groups are preferably C (I--7hdrocarbyls, more preferably C I-C alkyls.

-ie cationic polymers hereof can corise mixtures of monomer units -zermed V~ora -,aine-, ancd1or quaternary arnmoiurni-substituted monor and/lor compabible space' aonomrs S4, tbie catibv'ic hair coi-4iftxnin poT-ers include, for example: poLb'grs of 1-vinyI-2-pyrrolidone and 1t-Vlny!-3-nethyiiniazoliumr salt ctlaiide sAil) (referred to. in the iriuisy by the Cosmetic Toiletry, and Fragrw; Msociafion. *C1TA'X as Polyquatomi-16}. such as fthse =on i~ally a-vailable fromn EASF Wyandotte Corp. (Parsppay, NJ. USA) .2Lr~lef -tie I!QUAT tradenarne (eq Ujn WALT FC 310): -copolymners of 1~~-viny2-pyrro-done and deytin.tI e! tae(referred to in the indust. by CTIFA as Po~pquaienim--1 .11sudh as thoe cr;rnrnrcia~iy avaable ti rn Gaf Corporation (.Va VJ UISA) L'ider the GAFOUAT tradenrne ja&g. GAFIUA.T v! caliokc da1I qua-,-rnafy ammoraum*-cOnaini polymar-- inclding for exatmple, dimthydia&yn=-- c -id homopolymer and copolymers o ~acrylarnide and d iymrix choride, ref erred to in the irks~ (CTFA) as PalyquAtemttn 6 and Polyuatemnitu 7. respectivey, and g mineral acid salts of afpir"!~kyi estes of homo-a and co-poyrrers of unsaturated carboxylic acids haying from 3 to 5 carbon atoms. as described in U.S. Patent 4,009.256. incorporated herein by reference.

Othe cto poyrstat can be used include poiysaccharide polymebrs. such as cation ic cellulose derivatives and cationic starch deriatives.

Cationic poly3ccharide polymer materials suitable for use herein include those of the formula'

R,

A-O(R.-NR3X) whereifl A is an anhydroglucose residual group. such as' a starch or Cellulose anhydroiucase residual. R is an al'kylefle oxyaUkylerte, payaUkyLerie, or hydroxyalicylene group. or combination thereof. Ri,

R

2 and R.3 depflentiy are alkyl. aryl. alkyaryl. arylalkyl. alkoxyalkyl.

or alkoxyaril groups, each gcoup containing up to abiout 18 carbo aturris. arid the total number of carbon atom for each caiomio moiety te sum of carbon atoms in R 1

R

2 and R 3 Preferably being about or less. and X is an aniaruc counterion as previmUmly describedJ Cationic cellulose is aviailable from Arnerchol1 Corp- (Edson

NJ,

USA) in their Polyme JR& and LR@ series of polymers. as salts of 7 2 hydr=ethY1 cellulose reacted with trirrittyl ammfoniltxl substituted epoide. referred to in the industry (CIFA) as PolyquatemaiMff Anoter yp of cationic cellulosei includes the polymeic quatemvary anralrium salts cf hydkoxyethyl .cellulose reacted with laLryl dimethyl ft f~J1~.SljtsbhW~t opoxid. refered to in the industry (CTFA) as Patyquaterni'rn 24 These materials am available from. Amerchol Corp.

*0 (Edison. NJ. USA) =uuior the Wradenwfl Polyrri LM-200.

Other catioti polymers toat can be used indie caftorc guar gur derivati"S. sucha guar hy ylro ttrflyiil' (*nialty availabte from Celanese Crp in their JaguarR series).

Other materials "vhd utern-,Ial' nibrog n-cntailf cellulose ethers e-asdes bed in U.S Patent 3,9 Z.in 18orte by ref ence ri) herein), and copolyrners of etewtied ellulOse arnd starCh as deaie inUS ft.988.b eerrehri) I Aqueous -Carr-ier the present hair care compositions also comprise an aqiueous carrier. This can comprise any of those aqueous carriers ccnventicnaly used in hair care compositions. Generally. -water is present in the aqueous carrier of the present hair care composaticml of fron about 50% to about 99-17%, preferably of from about 65% to about 95%, more preferably of fromr about 80% to about 95%. by weight of the compasifica. Optionally. other water miscible fluids can also be used in the aqrueous carrier such as, (but not limited to) ethanol, propaoL and the like .Comnpositions of the present invention contain no more than abeut by weight of the cornpositior'. of an anionic surfactanit, preferably rio more than about more preferably no more than most preferably no more than Additionally, said composiionS, wilt containt no more than about by weight of the comnpasition. of volatile solvents (e.g.

cyclomethicotne). perferably no more than about more preferably no more thian about most preferably no more than about 01 ThickeninQ Acents Hair care compositions cian additionally include thickening agents or viscocity modifiers- Such thickening agents and viscosiy modiliers, are generally described in the following doacirnents. ali incoporated by reference herein: Barry. "The. Self Bodying Action of the Mied Emulsifier Sodiurn Dodecyt SuffatelCety-I Aicom 28 1. of Co~t&W and Interface Scie 82-91 (1968): Barmey. et at-. "The Self-Bodying9 Action of imethylammdrflnI~ Bromidest-Cetostearyl Alcohol Mixed Ermulsifiers- InfLwe of Quaterriwry Chain Leagtrr.- 3S, I of Coffa and Interface S6eive 689-708 (1971), and Barry. et aL. -Rheotogy of Systems Contairnig Ceta~fflO9Ol 1000 Cetostearyt Ak*loo. L Self Bodying Action". 38 J. of Coffiold and kdedace Sce 61fp-63 (1 972).

4. The hair care CWnaostwri C4f te presert invetnfi may incorporale OMe or mome lipid erWWs (twein referred to as crirprisirig a 'Tip veharxle 4' materia(t. singly or in combination). which are essentially water-insoluble.

Lipid veide materialsinclude nara4 or yrtheticalty4Wiv ed aeids, acid derivativeS. akcg*Kl esters ethers ketones, and arnkdes with carbonl chs ftmn 12 to 22. preferaby from 16 to 18. carbon atomrs in length.

Fatty esters ame prefred: faty acidos aire particulairly prefered Lipid vehicle materials among tno-se useful herein are diclcsed in Sadeys findustial 09i and Fzt Products. (3rd edition, 0. Swerr, ed. 1979) (irporaed by rference herein)- Fatty alcohols icluded an-og those useful iricorporated by reference heei U.S. Pat. No. 3.155.591. HLfr issued Nov. 3. 1964- U.S- Pat No- 4.165,369, Watanabe. et aL. issued AS 21, 1979. U.S- PaL No- 4,269,824. Villamarisi. et issurd May 26, 1%81; &it-sh .Specffcaioar No- 1.532.58-S, puhliskted Nov- 15. 1978:. and Fukushirna. et aL. The Effect of Cetostearyl Alacohol In Cosmetic Emlsions". 98Cosmetics &Toiletries 59-112(19863). Fatty eate&s incliuded among those useful herein are disclosed in U-S. Pat. No. 3.341,45 Kauftman, et at. issued Sept. 12, 1976 (incorporated by reference heemn)- If included in the hair care compositions off the present invention, the lipid vehicle material is cresent at a level of from about 0. 1% to about 1 0%4 Another typt: of thickentng agerst that-can be used are cationic crosslinked polyners. Suitable aotsslinked polymers fw use herein are generally described in U.S- Patent 5,100.660, to Hawe et al., ssued March 31. 1992; U.S. Patent 4.&49.454. to Heard, issued Jul~y 18. 1989: U.S. Patent 4,83,206. to Farrar et at. iszue M6ay 30. 1SH99 U.S.

Patent 4.628,078 to Glover et aL issued December 9. 1966: U.S. Patent 4,599.379 to Fleshef et at- issued July B. 1966i: and EP 228.668. to Farar et at. pubtished July 15. 1987; all of wtich are inrpoated by reference herein in their entirety. The polymes hereof can be c tle zed by the generl ftirrm. (AeBnCpW lfif is a dialkylaminealk acrylate fmorow or its quatemary ammrnonim or acid *,'~*addition salt is a dialkylaminoakyl methacrylate moner or its q"ternary ammoni~mr or aid addiin salt, is a nonionic moniomer diat is polymerizable wit or havirg a carbon-catanf double bond. that is polymerizable wth or m is an integer, of 0 or Teter. n is an integer of 0 or grenWr mi.e mor n, or both. must be 1 or Gmer. and pis a ideUofor greeW ~The maroww can be selected from any of the =nmx*l used SN~doriiriig exwfples of these, morwrfes inclde ethylerte.

pro~lefe~.but~en~. iobuylee. i~sne.maleic arh)-Irde.

-a~mi. meoylade. maleic acid. aarOks.k Cydo~r* ethy wqidy ethr. and rrethwyl i ether. in the cafionic polymers of the present invention is preferably cyaieThakipotnso ft*A ffaX~e ar stx (nkent:ayl uha prefemaby Cj-C 5 =ore preferably CI-C 3 r.-ot pceferably C 1

-C

2 When quaternizzed, the polyrners are preferably quartemiuzed 'Mth short chain allkyls. Lde_ C.-CS. preferably C 1 -CC. more preferably C 1

-C

3 mst preferably C 1 442 The acid addticn sallq refer to. polymers having Protonated affino groups. Acid addition salts can be performed through the Lse of halogen chloride), acefic. phosphoric. nitriM. citric. cc other acids- These (A6r(B)n(CI'p poiymners also contain a cosslinking agent.

which is typically a mnaterial conaining two or mome unsaturated furnctionat groups- The crosslinking agent is reacted with the morxorner units of the polyme and is incorporated into the polymer. forming eithe lirks or covalet bonds between two cr fmr indvidual polymrer chains or between two or rnorm~ sections of the same polymer chain- Nordirnitirq examples at suitable crosslinking agents idcude those selected front the group consisting of methytentebisacrylamides, diaa'ylates. dirrethacylates, di-vinyl azyl di-vinyl phenyl ring) carmpounds. polyalkery~l polyelhefs of polyhydric alcohos. altyt acrylates. vinyoxyalkylacrylates. and polyfutiona vinylidenies.

*Specific exarrnpies7 of crossu'xlng agents usefUt herein include those selected frorrt the grojup consisting of mrethyltenebisacrYlaide. ethylene glycol. propylene glycol. butylene gtycof. di-(mettl)aa~yate.

di-{meth)acKxyamnide, cyanomethylacxyae, v inyoxyethyicaylte.

vinyloxyethykmethacrylate. ally pertaerytitol, trimethylolpiopane dialyktet Wli ucnsebi~dieeisoprene. 1,4 e5-ethylene benizene.

divinyl, raptihakmn, ethyl vinyl ether. mevthyl viny ather arl afflyt acrytate Otew r osslir*em, include forwldetydo_ and qyoxal..

Preferred for use hetein as' a aossi*6ng agen is Wiely vaying' Arnmints, of thcrcpsskrikimg agent can be enployed depwm*Vn upon the jrvplie desied tq the finat poyr*1, e-g rVoSifin effect- The "iirngaetviitpcll ops from about I ppm to abot I 0OA-n Wpm, preferabl trn. about 5 ppm. to about 750 pM m m x prek-nrably fmrm abot 25 p~xto atcut 50 ppm, even ff ce Preferably frm abo,- '100 pm to abot 5W0 pPm, and ms MheaWk= about 250 pm ta alx" abWu SW0 ppm of the totaW weig; of the porw on a wihIe~bss

I

.24 An example of such a cationic polymer is one that. is: commercially available as a mineral oil dispersion (which can include vanous dispersing aids such as PPG-1 trideceth-6) under the--trademark SaIcareR SC92 from AlliOed Colloids Ltd. (Nuriolk Vkgnia), -This polymer has the proposed CTFA designation, "Polyquaternium 32 land) Mineral Oil" Another examnle er such a polymer is commercially available as a mineral oil disoersion also containing PPG-I tridecoth-6 as a dispersing aid, from AWqed Coiloids Ltd, (Norfolk VA) under the.

trademark SalcareR SC95. This product has been designated by the Cosrnetlcs Toiletries, and Fragrance Associa'ion (OTFA) as "PolyquaterniUm 37 (and) Mineral Oil (and) PPG-1 Trideceth-6 Ofthr thickening agents useful herein are chatacterized by the3 general formula:

H(OCH

2 %CH2)nOH or H(OCH 2

(CH

3 )CH)nOH j wherein n has an average value of from about 2,000 to about 14,000, preferably from about 5,000 to about 9,000, more preferably from about 8,000 to about 8,000.

Other polymers useful herein are PEG-2M wherein x equals 2 and n has an average value of about-2,000 (PEG 2-M is also known as Polyox -WSR@D N-10 from Union Carbide and as, PEG-2,000); PEG-SM wherein x equals 2.and n has ani average value of abouit 5,000 (PEG 54 is also known as Polyox WSRE N-35- and Polyox WSRES N-80; both from Union Carbide and as. PEG-5,000 and Polyethylene Glycol 300,M0); PEG-7M wherein x equals 2 and n has-an average value of about 7,000 (PEG 7-MIs also known as Polyox WSFe) N-750 from Union Carbide), PEG-SM wherein x equals?2 and n has an average value of -about 9,000 (PEG 9-Ni is also knowmn as Polyox W$RW N-3333 from Union Carbide); and PEG-IVA wherein x equals 2 ad in has a-n average value of about 14,000 (PEG 14-Ni 21 is also known as Polym WSR40 N-3=0 from Union Carbide.) Preferred esters for use herein include cetyl palrnitate and glycerylmornostearate, Cetyo alcohol an stearyl alcohol are preferred 4 alcohols. A. particarly11 preferred lipid vehicle material is comprised ofa mixture tyl a cohol an ay loo otining fom about 55% to ~about 65% -w~1eight of mixture) of cetyl achl Hair care comipow; 1cml for wh~ich the present invention can be useful inclujde, for example, MUS, toniics, lotions, hairsprays. andi gels.

Tonics, gels and non-aerOSOl hair sprays utilize a solvent such as water or alcohol while mouss and aerosoI hair sprays additionally utilize a propellant such as trichlorofluoromethane, dichlorodiluormethafle, difluorothfl@, dimethylether, propane, n-bulafl8 or isobutafle. The level of propellant can be adjusted as desired but is generally from~ about 3% to about Z0% of mousse compositions and from about 15% to about 50% of the aerosol hair spray cOITPOsitiOriS, Suitable spray containers are well known in the art and include coniventional, non-aerosol pump sprays "atornizers," aerosol containers or can having propellant, as described above, and also pump aerosol containers utilizing compressed air as the propellant. Pump aerosol containers are disclosed, for example, in U.S. Patents 4.077,441. March 7.

1978, Olofssofl and 4,850,577, July 25, 1989, TerStege, bolh incorporated by reference herein, and also in U.S. Serial No, 07I39,648, Gosselifl, Lund, Soika, and Lefebvre, filed February 21, 1992, "Consumfer Product Package Incorporating A Spray Device Utilizing Large Diameter Bubbles.

Pump aerosols hair sprays using compressed: air are also currently marketed by The Procter Gamble Company under their tradeflare

VIDAL

SASSOON AIRSPRAY@ hair sprays.

Optional ingredients The compositions herein can contain a variety of other optional components suitable for rndering such compositions more cosmetically or a. ~aesthetically acceptable or to provide them with additional usage benefits.

K Suchconventional optional nrdet r well-known to those skilled in A wide variety of additonal ingredients can be formulated into the preent composition., These include cohe conditioning agents, hair-hold, polymers, additilonal thickenin agents. aqueoS carriieri, and suspending agents, such as Xantiaf gum, guar gum, hydroxythyl cellulose, methyl cllulo@ hdoyehlltls sac and starch derivatives, viscosity modifiers such as methanolatnides of long chain fatty acids.

-COcOmoth w amnide. salts such as sodium -potassium chloride and ~sule arnd crystatlf suspending agents, and pearlSSCxflt aids such as ehyln lycl dstarae;aqemau carriers such as Ci-C6 alkanols* Waevais such as bWayl alcohol, methyl; parabrt propyl paaben and imidazolidny ~We oyvrinyl aloohml ethyl alcohO pH adjusting agents,

XI

26 such as citric acid, sodium citrate, succinic acid, phosphoric acid, sodium hydroxide, sodium carbonate'. salts. in general. such as potassium acetate and sodium chloride; coloring agents. such as any of the FD&C or D&C dyes; hair oxidizing (bleaching) agents, such as hydrogen peroxide.

perborate and persulffate salts;. hair reducing agents, such as the thloglycolates, perfumes, sequestering agents, such as disodiuni ethyleniediamine tetra-acetate, and polyr plasticizing agents, such as glycerin. disobutyl adipate. biyl stearata, and propylene glycol.

METHOD OF MAKING The hair care compositions of the present invention can be made using conventional formulation and mixing techniques. The emulsion of the presen' invention is prepared by combining the silicone gum in the optional silicone fluid, adding the emulsifying agent and forming the emulsion with the addition of the aqueous carrer. The resulting emulsion is added to the other. components of the hair care compositions and can be formulated into a variety of hair care products including mousses, tonics, lotions.

hairsprays, and gels. Preferably the pH of the final composition should be from about 4.5 to about 9, preferably from about 4.5 to about Methods of making various types of hair care compositions are described more specifically in the follo'vng examples.

ME~HOD OF USE The hair eare compositions of the present invention are used in ~convenional ways to provide the contioning and styl retenion benefits of .owth present inventn Such mnetho of use depends. up"n theto of composition, eWMpoyed Wu 9oerlly. involves application of an effective amolunt, of the product to the har. -which. may then be rinsd from te hair (as in the case of C0ndiionrs) Or allowed to remin on the hair (as in the cas of tonic, mousses gels, lotions. and hairsprey). By "effective iiouflt is means an uiount sufficient enough to provide a codiinifg 'P'.andstyle retention benfit. In geneal. frtrn about Ig to, abou SOO is applied to the hair, The corriposition is distrbute throughotA the hair, tyily by nabing ct massaig the hair and scalp with ones7 hanlds or by 27 another's hands. Preferably, the composition is applied to wet or damp hair prior to drying of the hair. After such compositions are applied to the hair, the hair is dried and styled in accordance with the desires of the user and in the usual ways of the user. Alternately, the composition is applied to dry hair, and the hair is then combed or styled in accordance with the desires of the user.

The following Examples further illustrate the preferred embodiment's within the scope of the present invention. The Examples are given solely for the purposes of illustration and are not to be constwred as limitations ofj the present invention as many variations of the invention are possible without departing from the scope.

EXAMPLE #1 Silicone Emulsion Premix Component Weight% Silicone blendl 60.13 Dimethicone Copolyol2 12.03 Water to 100.00, o 1 A 40160 blend of high viscosity silicone gum 1,000,000 CSTK) and silicone fluid such as SE-30 Gum and SF-18(350) Fluid available from GE Silicones.

2 Dow Coming 190 silicone surfactant.

The emulsion is prepared entirely at ambient temperature using only low speed mixing. The dimethicone copolyof is slowly added to the highly visous silicone blend and mixed to a ugiorm white opaque fluid using a :conventional. Owee bladed, axial flow impeller at lwrprT. Water is added slowly, in stepiise fashimn withi continued mixing to form an emulsion.

EXAMPLE#

Mousse Composition ComponentW-aiht A-46 propellant 1 6.00 Polyquatermtl4 1.41 Silicone Emulsion from Example 1 0.964 Lauramine Oxide 0.188 Cocamidoproply Betaine 0.188 Propylene Glycol 0.094 Preservative

OS.

Fragrance

Q.S'

Water

Q.S.

1 Available from Phillips Petroleum Company.

The aerosol mousses of the present invention are prepared by combining all ingredients except the aerosol propellant into a batch Called ,he concentrate. This concentrate is made by combining with agitation all of the ingredienis except for the preservative and the emulsion prepared as in Example 1. and mixing until well dispersed. The preservative and emulsion are finally added and mixing continued until these wre thoroughly dispersed., Aerosol moujsse cans are prepared by; placing 135 grams of concentrate into 5 oz. aluminum epoxy lined cans. placing mousse valves on can tops, drawing a vacaum to evacuate ran headspace (to remove air).

and crimping the valves into place The propellant is added by pressure ~filling tough the valve stem.

-It, 29 EXAMPLE #3 Weiht Polyqjaewniurn4 1.00 Carborner 9% 0.20 Silicone Emulsion from Example 1 0.25 Potassiumn Hydroxide to adiust 6 PH 7 Preservative

OS

Fragrane

Q.S.

Water

Q.S.

A non-aerosol hair tonic spray produc Is Prepared as follows, The polYquatemiurn-4 is mixed with part 0of t water at a ratio of about 30 to 1 until fully dissolved The preseivative is added and mixed nil hoamgeneous The emulsion frOmi Example I iS added arid mixed uil homogenaou& The remainder of the water is put into a stainless siteei mixing vessel.

The Carborner 956 is mixed into the water Using. for example, a triblender or eductor mixer. Mixing is continued until the Carborner is completely dissolved The poassium hYdoe is added while mixing Then the emulsio premix is added wt~de mixing until horrogenemus.

Fragranc is added and mixing is cONInue !or an additional 10 minutes to yield fth final product.

~A

EXAMPLE #4 2; 1itiofifl -S c Comnpofent Stealwyl Quaternized ProteinI 1,69 NorOXYOOI- 9 4.00 Silicone Emulsion from Example 1 1.00 polyquaternLufl-1.

FragaEVOQ

S

preservative

Q

Water I HydrOtriticum QS-' used as solution supplied from Croda. 1nc 2 Available from GE Silicornes.

The conditionling spray product is prepared by first dissolving the polyquaterruum14 then mixilng the quatemnized protein into the water. Then.

the nongmurc.Preservative and fragrance are added. Lasitly, the emulsion is blended in to gi1O the final product EXAMPLE 44

S

4* 4 p2n!gtioner '4.

54 I Cetyl AlcdOko Quatmiuffi 18 Stoayl AlcOho SwWTeW1,OpPY' Dfohylami' Gceryt*h lO2W0 Fragraflc* Siri=*n Emt1sioIn frai Exar.le i CiftiAcid.

Watser~ai Werzh-t 1.0 0.85 0.75 0.50 0.35 0.25 2.00 0.25 0.75 0-13

Q.S.

1~*

I

31 Polyquaeflf.W- 4 is added to the distilled water at a temperature Of to 40oC. This mnixture is weldispersedt then heated to a temperature of from 600C to!90C. Matejias I throug 6o ame added to the batch while the temperature kS maintained in this range. The mixture is stirred for appr oxilatlY 10 minutes. then cooled to approximately 500C. The remaining materials are added at thi!-. temperature_ The mix Te is milled under high shear for approximately 2 minutes using a conventional milling apparatus. then cooled to room temperature. The finished composiions have a pH of from about 5 to about. EXAMPLE 6 Componentoh sLN Polyquaterium'-I 1 Carbomer W4 0.40 TriethanOtarnin 0.36 Silicone Emulsion from Example 1 0-60 Preservative

Q.S.

ft .Fragrance

Q.S.

.7 WaterQS The gel CoM9s tions of the present invention are prepared ulsiing the method otlinefd in Example 3 for the hair tonic except th~it the Carbomet 940 is &Lbstied for fth Carbomer 956-. Only about. "if of Mhe triethaflOnsmf is added to the cabom6( sok~Luin The remainirg portion is ineledd With the otae inredients iM the emulsion premix, These roIIoswofls have a PH of about 6 to?7, EXAMPLE #7 Hair Treatment Lotion Hydrogenated PotyisobtL~eriel Vitarmin E LinoleaO C 12-15 Alkyl Benzoate2 Quatem-ium 803 S.Ricone Emuflsion from Example 1 PVPNA Copotyrne Carbopol 9804 Sodium Hydroxide to adjust Preservative Fragrance Water I Available from Amoco Chemica GoldsluTW 2 Available from Fnetex Weight 34.00 5.00 6.00 0.30 0-60 1.00 0.15 5.S <PH 7

Q.S.

Q.S-

ci.s.

3 Used as supplied by.

4 Available krm BP Goodrich S. S Comiponents 1Itough 4 plus fr-agrancee are bleried n a premixt Separately. the Carbopol is dissolved in the water as desr~ribod, in Example 3 and preservative is added. About half the sodium hydraxie is added and mixed to unfoimity. The PVPNVA copolmer is added wIh mixing then the prmix is added slowly, with miing. Next, the siliowe ernu4sair is added with continued agitation-, Lastly, the remainder of sdoyn hydroxide solutio is added with stiring to produce a thick lotn i.SS 55 4

I

1- 33 EXAMPLE #6 Soft Feel Sculatinq Gel ComponerA FPVNA Coporymef Polyvinypyi7i1one.

Quterrium eal~ Isasteareth-2T- Silicone Emnulsion froir Example 1 Carborner 940 Triethanolamnine adjustA Preservative Fragrance Wa ter I Used as supplied by Goldschrnidt Weig~ht 3.50 2.50 0.20 0.s0 0.60 0.90 5.5 <pH

Q.S.

o)-s- 0-s.- -Disperse the carbomer in about half "h avalable water. Dissolve ingredients 1 through 4 in the remaining water-, add the silicone emulsicon, trithanolamine, preservative and fragrance and mixc until homogeneous, Add the carbomrer solution with wontinused agitation utill homnogeneous- .4.

.4 a 4 4.

Ii.

Claims (9)

1. 2- The composition or Claim I -characterized in that said emulsifying agent is seected from the group consisting ot n~onionic surfactants. cationic surtacian t s. arnphoteric surfaclants, zwitterionic Wurfactants. and mixtures thereof, 'The composition af Clam 2 chrctadezedjin that said emuWsfigaeti selected from thrrupcniig of a nonionic surfactant and mixtures of nonzoric suHataiL
2. 4. The composiio of Claim 2 characterized in that said emulsfying agnt is silicone copoto(- S. The composition of any one of Claims I to 4 char, tzed in that the nonvolatie silicone condiioning agent includes polydimethyt siloxane gum-.
3. 6- The composition of any one of Claims I to 4 characterized in that the nonvolatile silicone conditioning agent includes pclydimnethylsiloxanle fluid having a viscosity at 2500: of 10 centistokes to 600,000 centistokes- The compostion of Claim 6 characterized in that the nonvolatile silicone conditioning agent includes polydimethylsiloxafle fluid having a viscosity at 0 C of 100 centistokes to 100,000 centistokes. The composition of any one of ClaIms 5, 6 or 7 characterized in that the non volatile silicone conditioning agent was present at a level from 30% to
4. 9. The composiftion of any one of. Claims 1 to 8 characterized in that the hair setting polymer is selected from the group consisting of nonionic polymers. anionic polymers, ampihoterc polymers. cationic polymers and mixtures thereof. to.- The composition ot Claim 9 characterized in that the hair setting poiymer 2is selected trom the group consisting of a cationic polymer, arniphoteric polymer. .:~and mixtures 1hereof.
5. 11. The compositionl of Claim 10 chanacterized in that the hair setting polymer is a cationic polymer.
6. 12- The compostion, of any one of Claims 9 to 11 characterized in that the baV setting polymer is present at a level from 1% to
7. 13.- Th1opsto fCai 12 wherein the hair setting polymer is clallycivluffictoride~yroxyethycelulose copolymner- I%
8. 14- The composition of any one of Claims 1 to 13 characterized in that tho compositi includes aa additional cationic cosmetic agent The composition of Claimn 14 characterized in that the additional catiOr' c cosmetic agent is selected trom the group cons;!Stino ot cationlic surffactantS, cationic polymers, and mixtures 4hereot- 1.A hair care comPosiOn according to any one of Claims I to 15 in the form of a Iation which additionally includes f, mr 0-1% to 10-0% of a thickening agent, I7T A hair care composition according to any one ol Claims 1 to 15 in the form of a mousse. 8.A hair care composition according to a ny one of claims Ito 15 ift tine form of a geL
9. 19. A process for making the hair care composition accorifing to Claimn I which includes the steps of: combriig the silicone gumn in-optional silicone fluid to form a silicone conditioningq agent, combininrg the conditioning agent with the emulsifyIig agent and forming the emtglon with the addfition alf the aqueous Carriec; -miking the emulsion into a hair care composition selected from the group consisting ot mousses, tonic, lotions,. hairspray, and gels. wh-ich additionally includes a hair setting polymer. A 37 A hair Cari comPGSiti~rn according to Claim I subsafltiJlly aLS here inbefore descfit-ed witb, palticJlaf reference to the exaMPleS. QLTM .this 23rd day of December I99 THE pROC)TER AND CIANBLE COM-PANy WATER~MARK PATENT TRADEMARK ATTORNEYS 290 BUIRWOOD ROAD HAWVTHORN VICTORIA 3122 AUSTRALIA VAX DOC 0241 AU I SMS 95WP0 LCG'=JC'" 4.45 e~ C VA I I