CA2309701A1

CA2309701A1 - Conditioning shampoo compositions

Info

Publication number: CA2309701A1
Application number: CA002309701A
Authority: CA
Inventors: Takashi Sako; Yasuhiro Egoshi
Original assignee: Procter and Gamble Co
Current assignee: Individual
Priority date: 1997-11-12
Filing date: 1997-11-12
Publication date: 1999-05-20
Also published as: EP1032354A1; AU5436698A; WO1999024004A1; JP2000513379A

Abstract

Disclosed is a conditioning shampoo composition comprising by weight: (a) from about 0.05 % to about 50 % of a polyhydrophilic anionic surfactant; (b) from about 0.05 % to about 20 % of a cationic conditioning agent selected from the group consisting of cationic surfactants, cationic polymers, and mixtures thereof; (c) from about 0.01 % to about 20 % of a silicone compound; and (d) an aqueous carrier.

Description

WO 99124004 PCT/US97l20735 CONDITIONING SHAMPOO COMPOSITIONS
TECHNICAL FIELD
The present invention relates to conditioning shampoo compositions which ~ o both cleanse the hair and condition the hair.
BACKGROUND
Human hair becomes soiled due to its contact with the surrounding environment and from the sebum secreted by the scalp. The soiling of hair ~ 5 causes it to have a dirty feel and an unattractive appearance. The soiling of the hair necessitates shampooing with frequent regularity.
Shampooing cleans the hair by removing excess soil and sebum.
However, shampooing can leave the hair in a wet, tangled, and generally unmanageable state. Once the hair dries, it is often left in a dry, rough, Zo lusterless, or frizzy condition due to removal of the hair's natural oils and other natural conditioning and moisturizing components. The hair can further be left with increased levels of static upon drying, which can interfere with combing and result in a condition commonly referred to as "fly-away hair."
A variety of approaches have been developed to alleviate these after Zs shampoo problems. These approaches range from post-shampoo application of hair conditioners such as leave-on and rinse-off products, to hair conditioning shampoos which attempt to both cleanse and condition the hair from a single prod uct.
In order to provide hair conditioning benefits in a cleansing shampoo base, so a wide variety of conditioning actives have been proposed. However, many of these actives have the disadvantage of leaving the hair feeling soiled or coated, of interfering with the cleansing efficacy of the shampoo.
Coacervate formation in a shampoo composition is known to be advantageous for providing conditioning benefits to the hair. The use of cationic 35 polymers to form coacervates are known in the art, such as in PCT
publications W093/08787 and W095/01152. However, these shampoo compositions are not capable of delivering satisfactory conditioning benefit while the hair is wet.
Based on the foregoing, there is a need for a conditioning shampoo which can provide improved conditioning benefit when the hair is wet, while not s interfering with the cleansing efficacy, nor providing negative feel to the hair when it is dried.
None of the existing art provides all of the advantages and benefits of the present invention.
~ o SUMMARY
The present invention is directed to a conditioning shampoo composition comprising by weight: (a) from about 0.05% to about 50% of a poiyhydrophilic anionic surfactant; (b) from about 0.05% to about 20% of a cationic conditioning agent selected from the group consisting of cationic surfactants, cationic i s polymers, and mixtures thereof; (c) from about 0.01 % to about 20% of a silicone compound; and (d) an aqueous carrier.
These and other features, aspects, and advantages of the present invention will become evident to those skilled in the art from a reading of the present disclosure.
Zo DETAILED DESCRIPTION
While the specfication concludes with claims particularly pointing and distinctly claiming the invention, it is believed that the present invention will be better understood from the following description.
25 All percentages are by weight of the total composition unless otherwise indicated. All ratios are weight ratios unless otherwise indicated. All percentages, ratios, and levels of ingredients referred to herein are based on the actual amount of the ingredient, and do not include solvents, fillers, or other materials with which the ingredient may be combined as commercially available ao products, unless otherwise indicated.
As used herein, "comprising" means that other steps and other ingredients which do not affect the end result can be added. This term encompasses the terms "consisting of and "consisting essentially of'.

All cited references are incorporated herein by reference in their entireties.
Citation of any reference is not an admission regarding any determination as to its availability as prior art to the claimed invention.
POLYHYDROPHILIC ANIONIC SURFACTANT
The present invention comprises by weight from about 0.05% to about 50%, preferably from about 0.1 % to about 30%, more preferably from about 0.5%
to about 20% of a polyhydrophiiic anionic surfactant. Polyhydrophilic anionic surfactants useful herein are those having at least two anionic hydrophilic groups in the molecule. One molecule of a polyhydrophilic anionic surfactant may io comprise the same hydrophilic groups, or different hydrophilic groups.
Preferably, the hydrophilic group is selected from the group consisting of carboxy, sulfate, sulfonate, and phosphate groups, more preferably at least one carboxy group, still preferably at least two carboxy groups.
Without being bound by theory, it is believed that pofyhydrophilic anionic i 5 surfactants herein, with the presence of cationic conditioning agents, are capable of providing a coacervate with a large region which can trap and deliver an increased amount of conditioning agents to the hair surface. It is also believed that coacervates made with polyhydrophilic anionic surfactants herein are readily separated ftom the water phase, thus also resulting in delivery of an increased Zo amount of conditioning agents to the hair surface.
Nonlimiting examples of polyhydrophilic anionic surfactants include N-acyl-L-glutamates such as N-cocoyl-L-glutamate and, N-lauroyl-L-glutamate, sodium lauryl aminodiacetic acid, laurimino diproprionate, and N-lauryl-~i-imino-dipropionate, N-acyl-L-aspartate, polyoxyethylene laurylsulfosuccinate, disodium 25 N-octadecylsulfosuccinate; disodium lauryl sulfosuccinate; diammonium lauryl sulfosuccinate; tetra sodium N-(1,2-dicarboxyethyl)-N-octadecylsulfosuccinate;
the diamyl ester of sodium sulfosuccinic acid; the dihexyl ester of sodium sulfosuccinic acid; and the dioctyl ester of sodium sulfosuccinic acid, and 2-cocoalkyl N-carboxyethyl N-carboxyethoxyethyl imidazolinium betaine.
3o Other suitable polyhydrophilic anionic surfactants include those of the following formula (I) and (II):
H02CH2C-N-CH2CH2N(CH2COOH)2 35 C=O ( I ) R

wherein R is an alkyl of 12 to 18 carbons; and ~~ ~CH2CH2NCOOM1 R'-C-N (II) ~CH2CH2NCOOM2 wherein R' is a straight or branched alkyl or alkenyl of 5 to 21 carbons; and and M2, independently, are hydrogen, alkaline metal, alkaline earth metal, ~ o ammonium, alkyl or alkenyl ammonium of 1 to 22 carbons, alkyl or alkenyl substituted pyridinium of 1 to 18 carbons, or basic amino acids. Suitable examples of formula (1) include acid salts of N-acyl-N,N'-ethyienediaminetriacetic acid, such as sodium, triethanolamine and ammonium salts of lauroyl-N,N'-ethylenediaminetriacetic acid, myristoyl-N,N'-ethylenediaminetriacetic acid, ~5 cocoyl-N,N'-ethyienediaminetriacetic acid, and oleoyl-N,N'-ethylenediaminetriacetic acid. Suitable examples of formula (II) include acid and salt forms of N-hexanoyl-N-carboxyethyl-(3-alanine, N-octanoyl-N-carboxyethyl-~-alanine, N-decanoyl-N-carboxyethyl-~i-alanine, N-lauroyl-N-carboxyethyl-~i-aianine, N-tetradecanoyl-N-hydroxyethyl-~-alanine, N-hexadecanoyl-N-Zo carboxyethyl-~i-alanine, N-isostearoyl-N-carboxyethyl-~-alanine, and N-oleoyl-N-carboxyethyl-~-alanine.
Commercially available polyhydrophilic anionic surfactants suitable in the present invention are N-acyl-L-glutamate with a tradename AMISOFT CT-12S, N-cocoyl-L-glutamate with a tradename EMCOL 4400-1 supplied by Wtco, 25 lauroyl glutamate with a tradename AMISOFT LS-11, and acylaspartate with tradenames ASPARACK and AAS supplied by Mitsubishi Chemical, sodium lauryl aminodiacetic acid with a tradename NISSAN ANON LA supplied by Nippon Oil and Fat; and N-acyl-N,N'-ethylenediaminetriacetic acid derivaties with tradename ED3A supplied by Hampshire Chemical Corp.
ao CATIONIC CONDITIONING AGENT
The present invention comprises by weight from about 0.05% to about 20% of a cationic conditioning agent. The cationic conditioning agents are selected from the group consisting of cationic surfactants, cationic polymers, and mixtures thereof.
35 Cationic Surfactant The cationic surfactants useful herein are any known to the artisan.

Among the cationic surtactants useful herein are those corresponding to the general formula (I):
R
R-N~ R3 X
R

wherein at least one of R1, R2, R3, and R4 is selected from an aliphatic group of from 8 to 30 carbon atoms or an aromatic, alkoxy, polyoxyalkylene, alkylamido, hydroxyalkyl, aryl or alkylaryl group having up to about 22 carbon atoms, the remainder of R1, R2, R3, and R4 are independently selected from an aliphatic ~ o group of from 1 to about 22 carbon atoms or an aromatic, alkoxy, polyoxyalkylene, alkylamido, hydroxyalkyl, aryl or alkylaryl group having up to about 22 carbon atoms; and X is a salt-forming anion such as those selected from halogen, (e.g. chloride, bromide), acetate, citrate, lactate, giycolate, phosphate, nitrate, sulfonate, sulfate, alkylsuifate, and alkyl sulfonate radicals.
~ 5 The aliphatic groups can contain, in addition to carbon and hydrogen atoms, ether linkages, and other groups such as amino groups. The longer chain aliphatic groups, e.g., those of about 12 carbons, or higher, can be saturated or unsaturated. Preferred is when R1, R2, R3, and R4 are independently selected from C1 to about C22 alkyl. Nonlimiting examples of cationic surfactants useful Zo in the present invention include the materials having the following CTFA
designations: quatemium-8, quatemium-14, quaternium-18, quaternium-18 methosulfate, quatemium-24, and mixtures thereof.
Among the cationic surfactants of general formula (I), preferred are those containing in the molecule at least one alkyl chain having at least 16 carbons.
25 Nonlimiting examples of such preferred cationic surfactants include:
behenyl trimethyl ammonium chloride available, for example, with tradename INCROQUAT TMC-80 from Croda and ECONOL TM22 from Sanyo Kasei; cetyi trimethyl ammonium chloride available, for example, with tradename CA-2350 from Nikko Chemicals, hydrogenated tallow alkyl trimethyl ammonium chloride, ao dialkyl {14-18) dimethyl ammonium chloride, ditallow alkyl dimethyi ammonium chloride, dehydrogenated tallow alkyl dimethyl ammonium chloride, distearyl dimethyl ammonium chloride, dicetyl dimethyl ammonium chloride, di(behenyl/arachidyl) dimethyl ammonium chloride, dibehenyl dimethyl ammonium chloride, stearyl dimethyl benzyl ammonium chloride, stearyl propylenegiycol phosphate dimethyl ammonium chloride, stearoyl amidopropyl dimethyl benzyl ammonium chloride, stearoyl amidopropyl dimethyl (myristylacetate) ammonium chloride, and N-(stearoyl coiamino formyl methy) pyridinium chloride.
s Also preferred are hydrophilically substituted cationic surfactants in which at least one of the substituents contain one or more aromatic, ether, ester, amido, or amino moieties present as substituents or as linkages in the radical chain, wherein at least one of the R1 - R4 radicals contain one or more hydrophilic moieties selected from alkoxy (preferably C1 - C3 alkoxy), ~o poiyoxyalkylene (preferably C1 - Cg polyoxyalkylene), alkylamido, hydroxyalkyl, alkylester, and combinations thereof. Preferably, the hydrophilically substituted cationic conditioning surfactant contains from 2 to about 10 nonionic hydrophile moieties located within the above stated ranges. Preferred hydrophilically substituted cationic surfactants include those of the formula (II) through (VIII) i s below:
CH3(CH2)n-CH2-N~ (CH2CH20)xH X
(CH2CH~0)yH ( wherein n is from 8 to about 28, x+y is from 2 to about 40, Z1 is a short chain alkyl, preferably a C1 - C3 alkyl, more preferably methyl, or (CH2CH20)zH
Zo wherein x+y+z is up to 60, and X is a salt forming anion as defined above;

R
R ~+ CH m-N~ R X
17 ( 2> I (~) R Rlo wherein m is 1 to 5, one or more of R8, R6, and R~ are independently an C1 -25 C30 alkyl, the remainder are CH2CH20H, one or two of R8, R9, and R10 are independently an C1 - C30 alkyl, and remainder are CH2CH20H, and X is a salt forming anion as mentioned above;

R> > ~ _ CH - ~+ ~ 1 z ( 2)P I3 (CH2)q-NHCR x Z

R ~ ~-O- CH
( 2)P ~ 3 (CH2)9-O-C-R X-Z
wherein, independently for formulae (IV) and (V), Z2 is an alkyl, preferably a C~ -C3 alkyl, more preferably methyl, and Z3 is a short chain hydroxyalkyl, preferably hydroxymethyl or hydroxyethyl, p and q independently are integers from 2 to 4, inclusive, preferably from 2 to 3, inclusive, more preferably 2, R~~ and R~2 , independently, are substituted or unsubstituted hydrocarbyls, preferably C~2 -~o C20 alkyl or alkenyl, and X is a salt forming anion as defined above;

Z
R 3 NS (CH~CHO)aH x wherein R~3 is a hydrocarbyl, preferably a C~ - C3 alkyl, more preferably methyl, i 5 Z4 and Z5 are, independently, short chain hydrocarbyls, preferably C2 - C4 alkyl or alkenyl, more preferably ethyl, a is from 2 to about 40, preferably from about 7 to about 30, and X is a salt forming anion as defined above;

~N~ CH2~HCH2 A X (VII) Rls OH
wherein R~4 and RCS, independently, are C~ - C3 alkyl, preferably methyl, Z6 is a C~2 - C22 hydrocarbyl, alkyl carboxy or alkylamido, and A is a protein, preferably a collagen, keratin, milk protein, silk, soy protein, wheat protein, or hydrolyzed forms thereof; and X is a salt forming anion as defined above;

WO 99/24004 p~~S97/20735 O R
HOCH2-(CHOH)4-CNH(CH2)b-N~ CH2CH20H X- ( ~17 wherein b is 2 or 3, R16 and R17, independently are C1 - C3 hydrocarbyls preferably methyl, and X is a salt forming anion as defined above. Nonlimiting s examples of hydrophilically substituted cationic surfactants useful in the present invention include the materials having the following CTFA designations:
quaternium-16, quaternium-26, quaternium-27, quaternium-30, quaternium-33, quaternium-43, quaternium-52, quatemium-53, quaternium-56, quaternium-60, quaternium-61, quaternium-62, quaternium-70, quaternium-71, quaternium-72, 1 o quaternium-75, quaternium-76 hydrolyzed collagen, quaternium-77, quaternium 78, quaternium-79 hydrolyzed collagen, quatemium-79 hydrolyzed keratin, quaternium-79 hydrolyzed milk protein, quaternium-79 hydrolyzed silk, quaternium-79 hydrolyzed soy protein, and quaternium-79 hydrolyzed wheat protein, quaternium-80, quaternium-81, quaternium-82, quaternium-83, ~ s quaternium-84, and mixtures thereof.
Highly preferred hydrophilically substituted cationic surfactants include dialkyfamido ethyl hydroxyethylmonium salt, dialkylamidoethyl dimonium salt, dialkyloyl ethyl hydroxyethylmonium salt, dialkyloyl ethyldimonium salt, and mixtures thereof; for example, commerically -available under the following Zo tradenames; VARISOFT 110, VARIQUAT K1215 and 638 from Witco Chemical, MACKPRO KLP, MACKPRO WLW, MACKPRO MLP, MACKPRO NSP, MACKPRO NLW, MACKPRO WWP, MACKPRO NLP, MACKPRO SLP from Mclntyre, ETHOQUAD 18/25, ETHOQUAD 0/12PG, ETHOQUAD C/25, ETHOQUAD S/25, and ETHODUOQUAD from Akzo, DEHYQUAT SP from 25 Henkel, and ATLAS 6265 from ICI Americas.
Salts of primary, secondary, and tertiary fatty amines are also suitable cationic surfactants. The alkyl groups of such amines preferably have from about 12 to about 22 carbon atoms, and can be substituted or unsubstituted.
Particularly useful are amido substituted tertiary fatty amines. Such amines, so useful herein, include stearamidopropyldimethylamine, stearamidopropyldiethylamine, stearamidoethyldiethylamine, stearamidoethyldimethylamine, palmitamidopropyldimethylamine, palmitar~nidopropyldiethylamine, palmitamidoethyldiethylamine, palmitamidoethyldimethylamine, behenamidopropyldimethylamine, behenamidopropyldiethylamine, behenamidoethyldiethyiamine, behenamidoethyldimethylamine, arachidamidopropyldimethylamine, arachidamidopropyldiethylamine, arachidamidoethyldiethylamine, s arachidamidoethyldimethylamine, diethyiaminoethyistearamide. Also useful are dimethylstearamine, dimethylsoyamine, soyamine, myristylamine, tridecylamine, ethylstearylarnine, N-tallowpropane diamine, ethoxyiated (with 5 moles of ethylene oxide) stearylamine, dihydroxyethylstearylamine, and arachidylbehenylamine. These amines can also be used in combination with ~o acids such as L-glutamic acid, lactic acid, hydrochloric acid, malic acid, succinic acid, acetic acid, fumaric acid, tartaric acid, citric acid, L-glutamic hydrochloride, and mixtures thereof; more preferably L-glutamic acid, IactiG acid, citric acid.
Cationic amine surfactants included among those useful in the present invention are disclosed in U.S. Patent 4,275,055, Nachtigal, et al., issued June 23, 1981, i s which is incorporated by reference herein in its entirety.
The cationic surfactants for use herein may also include a plurality of ammonium quaternary moieties or amino moieties, or a mixture thereof.
Cationic Pol The hair conditioning compositions of the present invention can further 2o comprise one or more cationic polymer as a cationic conditioning agent. As used herein, the term "polymer" shall include materials whether made by polymerization of one type of monomer or made by two (i.e., copolymers) or more types of monomers.
Preferably, the cationic polymer is a water-soluble cationic polymer. By 25 "water soluble" cationic polymer, what is meant is a polymer which is sufficiently soluble in water to form a substantially clear solution to the naked eye at a concentration of 0.1 % in water (distilled or equivalent) at 25°C. The preferred polymer will be sufficiently soluble to form a substantially clear solution at 0.5%
concentration, more preferably at 1.0% concentration.
3o The cationic polymers hereof will generally have a weight average molecular weight which is at least about 5,000, typically at least about 10,000, and is less than about 10 million. Preferably, the molecular weight is from about 100,000 to about 2 million. The cationic polymers will generally have cationic nitrogen-containing moieties such as quaternary ammonium or cationic amino ss moieties, and mixtures thereof.

The cationic charge density is preferably at least about 0.1 meq/gram, more preferably at least about 1.5 meq/gram, even more preferably at least about 1.1 meq/gram, still more preferably at least about 1.2 meq/gram.
Cationic charge density of the cationic polymer can be determined according to the s Kjeldahl Method. 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. The charge density should be within the above limits at the pH of intended use.
Any anionic counterions can be utilized for the cationic polymers so long ~o as the water solubility criteria is met. Suitable counterions include halides (e.g., CI, Br, I, or F, preferably CI, Br, or I), sulfate, and methylsulfate. Others can also be used, as this list is not exclusive.
The cationic nitrogen-containing moiety will be present generally as a substituent, on a fraction of the total monomer units of the cationic hair i s conditioning polymers. Thus, the cationic polymer 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 polymers are known in the art, and a variety can be found in the CTFA Cosmetic Ingredient Dictionary, 3rd edition, edited by Estrin, Zo Crosiey, and Haynes, (The Cosmetic, Toiletry, and Fragrance Association, Inc., Washington, D.C., 1982).
Suitable cationic polymers include, for example, copolymers of vinyl monomers having cationic amine or quaternary ammonium functionalities with water soluble spacer monomers such as acrylamide, methacrylamide, alkyl and 25 dialkyl acrylamides, alkyl and dialkyl methacrylamides, alkyl acrylate, alkyl methacrylate, vinyl caprolactone, and vinyl pyrrolidone. The alkyl and dialkyl substituted monomers preferably have C1 - C7 alkyl groups, more preferably C1 - C3 alkyl groups. Other suitable spacer monomers include vinyl esters, vinyl alcohol (made by hydrolysis of polyvinyl acetate), malefic anhydride, propylene ao glycol, and ethylene glycol.
The cationic amines can be primary, secondary, or tertiary amines, depending upon the particular species and the pH of the composition. In general, secondary and tertiary amines, especially tertiary amines, are preferred.
Amine-substituted vinyl monomers can be polymerized in the amine form, ss and then optionally can be converted to ammonium by a quatemization reaction.

Amines can also be similarly quaternized subsequent to formation of the polymer. For example, tertiary amine functionalities can be quaternized by reaction with a salt of the formula R'X wherein R' is a short chain alkyl, preferably a C1 - C7 alkyl, more preferably a C1 - C3 alkyl, and X is an anion which forms a s water soluble salt with the quaternized ammonium.
Suitable cationic amino and quaternary ammonium monomers include, for example, vinyl compounds substituted with dialkylaminoalkyl acrylate, dialkylaminoalkyl methacrylate, monoalkylaminoalkyl acrylate, monoalkylaminoalkyl methacrylate, trialkyl methacryloxyalkyl ammonium salt, io trialkyl acryloxyalkyl ammonium salt, dialiyl quaternary ammonium salts, and vinyl quaternary ammonium monomers having cyclic cationic nitrogen-containing rings such as pyridinium, imidazolium, and quaternized pyrrolidone, e.g., alkyl vinyl imidazolium, alkyl vinyl pyridinium, alkyl vinyl pyrrolidone salts. The alkyl portions of these monomers are preferably lower alkyls such as the C1 - C3 alkyls, more i s preferably C1 and C2 alkyls. Suitable amine-substituted vinyl monomers for use herein include dialkylaminoalkyl acrylate, dialkylaminoalkyl methacrylate, dialkylaminoalkyl acrylamide, and dialkylaminoalkyl methacrylamide, wherein the alkyl groups are preferably C1 - C7 hydrocarbyls, more preferably C1 - C3, alkyls.
2o The cationic polymers hereof can comprise mixtures of monomer units derived from amine- andlor quaternary ammonium-substituted monomer and/or compatible spacer monomers.
Suitable cationic hair conditioning polymers include, for example:
copolymers of 1-vinyl-2-pyrrolidone and 1-vinyl-3-methylimidazolium salt (e.g., is chloride salt) (referred to in the industry by the Cosmetic, Toiletry, and Fragrance Association, "CTFA", as Polyquatemium-16), such as those commercially available from BASF Wyandotte Corp. (Parsippany, NJ, USA) under the LUVIQUAT tradename (e.g., LUVIQUAT FC 370); copolymers of 1-vinyl-2-pyrrolidone and dimethylaminoethyl methacrylate (referred to in the industry by so CTFA as Polyquaternium-11 ) such as those commercially available from Gaf Corporation (Vllayne, NJ, USA) under the GAFQUAT tradename (e.g., GAFQUAT
755N); cationic diallyl quaternary ammonium-containing polymers, including, for example, dimethyldiallylammonium chloride homopolymer and copolymers of acrylamide and dimethyldiallylammonium chloride, referred to in the industry 35 (CTFA) as Polyquaternium 6 and Polyquaternium 7, respectively; and mineral WO 99/24004 pC'r'/US97/20735 acid salts of amino-alkyl esters of homo- and co-polymers of unsaturated carboxylic acids having from 3 to 5 carbon atoms, as described in U.S. Patent 4,009,256, incorporated herein by reference.
Other suitable cationic polymers are amphoteric terpolymers consisting of acrylic acid methacrylamidopropyl trimethyiammonium chloride and methyl acrylate, having a structure as shown below referred to in the industry (CTFA) as Polyquaternium 47. An example of a suitable commerical mateiral is MERQUAT
2001~ wherein the ratio of n:n':n" is 45:45:10 supplied by Calgon Corp.

r CH2 H CHI ~ H; CH
-O ~-O
=O
O- n NH n~ OCH3 Jn"
~H~)3 CH3-N~ CH3 i o CH3 Other cationic polymers that can be used include polysaccharide polymers, such as cationic cellulose derivatives and cationic starch derivatives.
Cationic polysaccharide polymer materials suitable for use herein include i s those of the formula:
A-O-(R-~+ R X-R
wherein: A is an anhydroglucose residual group, such as a starch or cellulose Zo anhydroglucose residual, R is an alkylene oxyalkyiene, polyoxyalkylene, or hydroxyalkylene group, or combination thereof, R1, R2, and R3 independently are alkyl, aryl, alkylaryl, arylalkyl, alkoxyalkyl, or alkoxyaryl groups, each group containing up to about 18 carbon atoms, and the total number of carbon atoms for each cationic moiety (i.e., the sum of carbon atoms in R1, R2 and R3) 25 preferably being about 20 or less, and X is an anionic counterion, as previously described.

Cationic cellulose is available from Amerchol Corp. (Edison, NJ, USA) in their Polymer JR~ and LR~ series of polymers, as salts of hydroxyethyl cellulose reacted with trimethyl ammonium substituted epoxide, referred to in the industry (CTFA) as Polyquaternium 10. Another type of cationic cellulose includes the polymeric quaternary ammonium salts of hydroxyethyl cellulose reacted with lauryl dimethyl ammonium-substituted epoxide, referred to in the industry (CTFA) as Polyquaternium 24. These materials are available from Amerchol Corp.
(Edison, NJ, USA) under the tradename Polymer LM-200~.
Other cationic polymers that can be used include cationic guar gum ~ o derivatives, such as guar hydroxypropyltrimonium chloride (commercially available from Celanese Corp. in their Jaguar R series). Other materials include quaternary nitrogen-containing cellulose ethers (e.g., as described in U.S.
Patent 3,962,418, incorporated herein by reference), and copolymers of etherified cellulose and starch (e.g., as described in U.S. Patent 3,958,581, incorporated 1 s herein by reference.) SILICONE COMPOUNDS
The present invention comprises by weight from about 0.01 % to about 20%, preferably from about 0.05% to about 10% of a silicone compound. The silicone compounds useful herein include volatile soluble or insoluble, or Zo nonvolatile soluble or insoluble silicone conditioning agents. By soluble what is meant is that the silicone compound is miscible with the carrier of the composition so as to form part of the same phase. By insoluble what is meant is that the silicone forms a separate, discontinuous phase from the carrier, such as in the form of an emulsion or a suspension of droplets of the silicone. The is silicone compounds herein may be made by any suitable method known in the art, including emulsion polymerization. The silicone compounds may further be incorporated in the present composition in the form of an emulsion, wherein the emulsion is made my mechanical mixing, or in the stage of synthesis through emulsion polymerization, with or without the aid of a surfactant selected from ao anionic surfactants, nonionic surfactants, cationic surfactants, and mixtures thereof.
The silicone compounds for use herein will preferably have a viscosity of from about 1,000 to about 2,000,000 centistokes at 25oC, more preferably from about 10,000 to about 1,800,000, and even more preferably from about 100,000 35 to about 1,500,000. The viscosity can be measured by means of a glass WO 99!24004 PCTNS97120735 capillary viscometer as set forth in Dow Corning Corporate Test Method CTM0004, July 20, 1970; which is incorporated by reference herein in its entirety.
Silicone compound of high molecular weight may be made by emulsion polymerization. Suitable silicone fluids include polyalkyl siloxanes, polyaryl s siloxanes, polyalkylaryl siloxanes, polyether siloxane copolymers, and mixtures thereof. Other nonvolatile silicone compounds having hair conditioning properties can also be used.
The silicone compounds herein also include polyalkyl or polyaryl siloxanes with the following structure (I) ~o R R R
A-Si-O-[-Si-~-]x-Si-A (I ) R R IZ
wherein R is alkyl or aryl, and x is an integer from about 7 to about 8,000.
"A"
represents groups which block the ends of the silicone chains. The alkyl or aryl ~ s groups substituted on the siloxane chain (R) or at the ends of the siloxane chains (A) can have any structure as long as the resulting silicone remains fluid at room temperature, is dispersible, is neither irritating, toxic nor otherwise harmful when applied to the hair, is compatible with the other components of the composition, is chemically stable under normal use and storage conditions, and is capable of Zo being deposited on and conditions the hair. Suitable A groups include hydroxy, methyl, methoxy, ethoxy, propoxy, and aryloxy. The two R groups on the silicon atom may represent 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 phenyimethyl. The preferred silicone Zs compounds are polydimethylsiioxane, polydiethylsiloxane, and polymethylphenylsiloxane. Polydimethylsiloxane, which is also known as dimethicone, is especially preferred. The polyalkylsiloxanes that can be used include, for example, polydimethylsiioxanes. These silicone compounds are available, for example, from the General Electric Company in their ViscasilR
and ao SF 96 series, and from Dow Corning in their Dow Corning 200 series.
Polyalkylaryl siloxane fluids can also be used and include, for example, polymethylphenyisiloxanes. 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 Fluid.

Especially preferred, for enhancing the shine characteristics of hair, are highly arylated silicone compounds, such as highly phenylated polyethyl silicone having refractive index of about 1.46 or higher, especially about 1.52 or higher.
When these high refractive index silicone compounds are used, they should be s mixed with a spreading agent, such as a surfactant or a silicone resin, as described below to decrease the surface tension and enhance the film forming ability of the material.
The silicone compounds that can be used include, for example, a polypropylene oxide modified polydimethyisiloxane although ethylene oxide or ~ o mixtures of ethylene oxide and propylene oxide can also be used. The ethylene oxide and polypropylene oxide level should be sufficiently low so as not to interfere with the dispersibility characteristics of the silicone. These material are also known as dimethicone copolyols.
Other silicone compounds include amino substituted materials. Suitable i s alkylamino substituted silicone compounds include those represented by the following structure (II) ~H3 R
HO-[-~ i-O Jx-[-~ i-O-]y-H
C H3 (~ H2)a ( II ) NH
(~ Hob - -Zo wherein R is CHg or OH, x and y are integers which depend on the molecular weight, the average molecular weight being approximately between 5,000 and 10,000. This polymer is also known as "amodimethicone".
Suitable amino substituted silicone fluids include those represented by the formula (III) (R1 )aG3-a-Si-(-OSiG2)n-(-OSiGb(R1 )2-b)m-O-SiG3_a(R1 )a (III) in which G is chosen from the group consisting of hydrogen, phenyl, OH, C1-Cg alkyl and preferably methyl; a denotes 0 or an integer from 1 to 3, and preferably equals 0; b denotes 0 or 1 and preferably equals 1; the sum n+m is a number from 1 to 2,000 and preferably from 50 to 150, n being able to denote a number so from 0 to 1,999 and preferably from 49 to 149 and m being able to denote an integer from 1 to 2,000 and preferably from 1 to 10; R1 is a monovalent radical of formula CqH2qL in which q is an integer from 2 to 8 and L is chosen from the groups -N(R2)CH2-CH2-N(R2)2 -N(R2)2 -N(R2)3A--N(R2)CH2-CH2-NR2H2A-in which R2 is chosen from the group consisting of hydrogen, phenyl, benzyl, a saturated hydrocarbon radical, preferably an alkyl radical containing from 1 to 20 1 o carbon atoms, and A- denotes a halide ion.
An especially preferred amino substituted silicone corresponding to formula (III) is the polymer known as "trimethyisilylamodimethicone", of formula (IV):

(CH3)3~1-OL-'~1-p"_~n-y~i-O-]m- Si ~CH3)3 ( IV ) CH3 (~H~a NH
(~H~b In this formula n and m are selected depending on the exact molecular weight of the compound desired.
Other amino substituted silicone polymers which can be used are Zo represented by the formula (V):
R CH2-CHOH-CHZ N+(R )3Q

(R~3S~-OW-~~-O-)r-[-~;-p-)s-Si R3 V
( )3 ( ) where R3 denotes a monovalent hydrocarbon radical having from 1 to 18 carbon i5 atoms, preferably an alkyl or alkenyl radical such as methyl; R4 denotes a hydrocarbon radical, preferably a C1 - C1g alkylene radical or a C1 - Clg, and more preferably C1 - Cg, alkyleneoxy radical; Q- is a halide ion, preferably chloride; r denotes an average statistical value from 2 to 20, preferably from 2 to 8; s denotes an average statistical value from 20 to 200, and preferably from to 50. A preferred polymer of this class is available from Union Carbide under the name "UCAR SILICONE ALE 56."
References disclosing suitable nonvolatile dispersed silicone compounds s include U.S. Patent No. 2,826,551, to Geen; U.S. Patent No. 3,964,500, to Drakoff, issued June 22, 1976; U.S. Patent No. 4,364,837, to Pader; and British Patent No. 849,433, to Woolston, all of which are incorporated herein by reference in their entirety. Also incorporated herein by reference in its entirety is "Silicon Compounds" distributed by Petrarch Systems, Inc., 1984. This reference ~ o provides an extensive, though not exclusive, listing of suitable silicone compounds.
Another nonvolatile dispersed silicone that can be especially useful is a silicone gum. The term "silicone gum", as used herein, means a polyorganosiloxane material having a viscosity at 25°C of greater than or equal to ~ s 1,000,000 centistokes. It is recognized that the silicone gums described herein can also have some overlap with the above-disclosed silicone compounds. This overlap is not intended as a limitation on any of these materials. Silicone gums are described by Petrarch, and others including U.S. Patent No. 4,152,416, to Spitzer et al., issued May 1, 1979 and Noll, Walter, Chemistry and Technology of Zo Silicones, 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 in their entirety. The "silicone gums" will typically have a mass molecular weight in excess of about 200,000, generally between about 200,000 and about 25 1,000,000. Specific examples include polydimethylsiloxane, poly(dimethylsiloxane methylvinylsiloxane) copolymer, poly(dimethylsiloxane diphenylsiloxane methylvinylsiloxane) copolymer and mixtures thereof.
Also useful are silicone resins, which are highly crosslinked polymeric siioxane systems. The crosslinking is introduced through the incorporation of tri ao functional and tetra-functional silanes with mono-functional or di-functional, or both, silanes during manufacture of the silicone resin. As is well understood in the art, the degree of crosslinking that is required in order to result in a silicone resin will vary according to the specific silane units incorporated into the silicone resin. In general, silicone materials which have a sufficient level of trifunctional 3s 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 ratio of oxygen atoms to silicon atoms is indicative of the level of crosslinking in a particular silicone material. Silicone materials which have at least about 1.1 oxygen atoms per silicon atom will generally be silicone s resins herein. Preferably, the ratio of oxygenailicon atoms is at least about 1.2:1Ø Silanes used in the manufacture of silicone resins include monomethyl-, dimethyl-, trimethyl-, monophenyl-, Biphenyl-, methylphenyl-, monovinyl-, and methylvinylchlorosiianes, and tetrachlorosilane, with the methyl substituted silanes being most commonly utilized. Preferred resins are offered by General i o Electric as GE SS4230 and SS4267. Commercially available silicone resins will generally be supplied in a dissolved form in a low viscosity volatile or nonvolatile silicone fluid. The silicone resins for use herein should be supplied and incorporated into the present compositions in such dissolved form, as will be readily apparent to those skilled in the art. Without being bound by theory, it is ~ s believed that the silicone resins can enhance deposition of other silicone compounds on the hair and can enhance the glossiness of hair with high refractive index volumes.
Other useful silicone resins are silicone resin powders such as the material given the CTFA designation polymethylsilsequioxane, which is Zo commercially available as TospearITM from Toshiba Silicones.
The method of manufacturing these silicone compounds, can be found in Encyclopedia of Polymer Science and Engineering, Volume 15, Second Edition, pp 204-308, John Wiley 8~ Sons, Inc., 1989, which is incorporated herein by reference in its entirety.
25 Silicone materials and silicone resins in particular, can conveniently be identfied according to a shorthand nomenclature system well known to those skilled in the art as the "MDTQ" nomenclature. Under this system, the silicone is described according to the presence of various siloxane monomer units which make up the silicone. Briefly, the symbol M denotes the mono-functional unit so (CH3)3Si0).5; D denotes the drfunctional unit (CH3)2Si0; T denotes the trifunctional unit (CH3)Si01.5; and Q denotes the quadri- or tetra-functional unit Si02. 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, phenyl, amino, hydroxyl, etc.
35 The molar ratios of the various units, either in temls 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 and/or or M' in a s 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.
1 o 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.
Commercially available silicone compounds which are highly suitable herein include Dimethicone with tradename D-130, cetyl Dimethicone with i s tradename DC2502, stearyi Dimethicone with tradename DC2503, emulsified polydimethyl siloxanes with tradenames DC1664 and DC1784, and alkyl grafted copolymer silicone emulsion with tradename DC2-2845; all available from Dow Corning Corporation, and emulsion polymerized Dimethiconol available from Toshiba Silicone as described in GB application 2,303,857, incorporated herein Zo by reference.
AQUEOUS CARRIER
The compositions of the present invention comprise an aqueous carrier.
The level and species of the carrier are selected according to the compatibility with other components, and other desired characteristic of the product.
25 The carrier useful in the present invention include water and water solutions of lower alkyl alcohofs and polyhydric alcohols. The lower alkyl alcohol useful herein are monohydric alcohols having 1 to 6 carbons, more preferably ethanol and isopropanol. The polyhydric alcohols useful herein include propylene glycol, hexylene glycol, glycerin, and propane diol.
ao Preferably, the aqueous carrier is substantially water. Deionized water is preferably used. Water from natural sources including mineral cations can also be used, depending on the desired characteristic of the product.
Generally, the compositions of the present invention comprise from about 20%
to about 95%, preferably from about 30% to about 92%, and more preferably from as about 50% to about 90% water.

ADDITIONAL DETERSIVE SURFACTANT
The compositions of the present invention may further contain an additional detersive surfactant selected from the group consisting of secondary anionic surfactants, amphoteric surfactants, zwitterionic surfactants, nonionic s surfactants, and mixtures thereof. The level and species of the additional detersive surfactant are selected according to the compatibility with other components, and desired characteristic of the product.
In preferred embodiments, the additional detersive surfactant contains a secondary anionic surfactant, more preferably further contains an amphoteric ~ o surfactant. In a still preferred embodiment, the additional detersive surfactant is substantially free of alkyl sulfate surfactants.
The term detersive surfactant, as used herein, is intended to distinguish these surfactants from surfactants which are primarily emulsifying surfactants, i.e.
surfactants which provide an emulsifying benefit and which have low cleansing i s performance. It is recognized that most surfactants have both detersive and emulsifying properties. It is not intended to exclude emulsifying surfactants from the present invention, provided the surfactant also possesses sufficient detersive properties to be useful herein.
When present, the additional detersive surfactant is included at a level so 2o that the total of additional detersive surfactant and polyhydrophilic anionic surfactant are from about 5% to about 75%, preferabty from about 8% to about 50%, and more preferably from about 10% to about 30%, by weight of the composition.
Secondary Anionic Surfactants Zs Anionic surfactants useful herein include alkyl and alkyl ether sulfates.
These materials have the respective formulae ROS03M and RO(C2H40)xS03M, wherein R is alkyl or alkenyl of from about 8 to about 30 carbon atoms, x is 1 to about 10, and M is hydrogen or a cation such as ammonium, alkanolammonium (e.g., triethanolammonium), a monovalent metal 3o ration (e.g., sodium and potassium), or a polyvalent metal ration (e.g., magnesium and calcium). Preferably, M should be chosen such that the anionic surfactant component is water soluble. The anionic surfactant or surfactants should be chosen such that the Krafft temperature is about 15°C or less, preferably about 10°C or less, and more preferably about 0°C or less. It is also 35 preferred that the anionic surfactant be soluble in the composition hereof.

Krafft temperature refers to the point at which solubility of an ionic surfactant becomes determined by crystal lattice energy and heat of hydration, and corresponds to a point at which solubility undergoes a sharp, discontinuous increase with increasing temperature. Each type of surfactant will have its own characteristic Krafft temperature. Krafft temperature for ionic surfactants is, in general, well known and understood in the art. See, for example, Myers, Drew, Surfactant Science and Technology, pp. 82-85, VCH Publishers, Inc. (New York, New York, USA), 1988 (ISBN 0-89573-399-0), which is incorporated by reference herein in its entirety.
~o In the alkyl and alkyl ether sulfates described above, preferably R has from about 12 to about 18 carbon atoms in both the alkyl and alkyl ether sulfates.
The alkyl ether sulfates are typically made as condensation products of ethylene oxide and monohydric alcohols having from about 8 to about 24 carbon atoms.
The alcohols can be derived from fats, e.g., coconut oil, palm oil, tallow, or the ~ s like, or the alcohols can be synthetic. Lauryl alcohol and straight chain alcohols derived from coconut oil and palm oil are preferred herein. Such alcohols are reacted with 1 to about 10, and especially about 3, molar proportions of ethylene oxide and the resulting mixture of molecular species having, for example, an average of 3 moles of ethylene oxide per mole of alcohol, is sulfated and Zo neutralized.
Specific examples of alkyl ether sulfates which can be used in the present invention are sodium and ammonium salts of coconut alkyl triethylene glycol ether sulfate; tallow alkyl triethylene glycol ether sulfate, and tallow alkyl hexaoxyethylene sulfate. Highly preferred alkyl ether sulfates are those Zs 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 1 to about 4 moles of ethylene oxide. Such a mixture also comprises from 0% to about 20% by weight C12-13 compounds;
from about 60% to about 100% by weight of C14-15-16 compounds, from 0% to ao 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 compounds having a degree of ethoxylation of from 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 as weight of compounds having a degree of ethoxylation greater than about 8.

WO 99lZ4004 PCT/US97/20735 Other suitable anionic surfactants are the water-soluble salts of organic, sulfuric acid reaction products of the general formula [R1-S03-M] where R1 is selected from the group consisting of a straight or branched chain, saturated aliphatic hydrocarbon radical having from about 8 to about 24, preferably about s 10 to about 18, carbon atoms; and M is as previously described above in this section. Examples of such surfactants are the salts of an organic sulfuric acid reaction product of a hydrocarbon of the methane series, including iso-, neo-, and n-paraffins, having about 8 to about 24 carbon atoms, preferably about 12 to about 18 carbon atoms and a sulfonating agent, e.g., S03, H2S04, obtained i o according to known sulfonation methods, including bleaching and hydrolysis.
Preferred are alkali metal and ammonium sulfonated C10-1g n-paraffins.
Other anionic surfactants include olefin suffonates having about 10 to about 24 carbon atoms. The term "olefin sulfonates" is used herein to mean compounds which can be produced by the sulfonation of alpha-olefins by means ~ s of uncomplexed sulfur trioxide, followed by neutralization of the acid reaction mixture in conditions such that any sulfones which have been formed in the reaction are hydrolyzed to give the corresponding hydroxy-alkanesulfonates.
The sulfur trioxide can be liquid or gaseous, and is usually, but not necessarily, diluted by inert diluents, for example by liquid S02, chlorinated hydrocarbons, 2o etc., when used in the liquid form, or by air, nitrogen, gaseous S02, etc., when used in the gaseous form. The a-olefins from which the olefin sulfonates are derived are mono-olefins having about 12 to about 24 carbon atoms, preferably about 14 to about 16 carbon atoms. Preferably, they are straight chain olefins.
In addition to the true alkene sulfonates and a proportion of 25 hydroxy-alkanesulfonates, the olefin sulfonates can contain minor amounts of other materials, such as alkene disulfonates depending upon the reaction conditions, proportion of reactants, the nature of the starting olefins and impurities in the olefin stock and side reactions during the sulfonation process. A
specific a-olefin sulfonate mixture of the above type is described more fully in ao U.S. Patent 3,332,880, to Pflaumer and Kessler, issued July 25, 1967, which is incorporated by reference herein in its entirety.
Still other suitable anionic surfactants are the reaction products of fatty acids esterified with isethionic acid and neutralized with sodium hydroxide where, for example, the fatty acids are derived from coconut or palm oil; or sodium or 35 potassium salts of fatty acid amides of methyl tauride in which the fatty acids, for example, are derived from coconut oil. Other similar anionic surfactants are described in U.S. Patents 2,486,921, 2,486,922, and 2,396,278, which are incorporated by reference herein in their entirety.
Another class of anionic surfactants suitable for use in the shampoo s compositions are the ~i-alkyloxy alkane sulfonates. These compounds have the following formula:
ORZ H
R' S03 M
H H
where R1 is a straight chain alkyl group having from about 6 to about 20 carbon ~ o atoms, R2 is a lower alkyl group having from about 1, preferred, to about carbon atoms, and M is as hereinbefore described. Many other anionic surfactants suitable for use in the shampoo compositions are described in McCutcheon's, Emulsifiers and Detergents, 1989 Annual, published by M. C.
Publishing Co., and in U.S. Patent 3,929,678, which descriptions are ~ s incorporated herein by reference in their entirety.
Another class of suitable anionic surfactants are amino acid surfactants which are sufactants that have the basic chemical structure of an amino acid compound, i.e., that contains a structural component of one of the naturally-occurring amino acids.
2o Preferred anionic surtactants for use in the shampoo compositions include ammonium laureth sulfate, triethylamine laureth sulfate, triethanolamine laureth sulfate, monoethanolamine laureth sulfate, diethanolamine laureth sulfate, lauric monoglyceride sodium sulfate, sodium laureth sulfate, potassium laureth sulfate, sodium tridecyl benzene sulfonate, sodium dodecyl benzene sulfonate, N-2s cocoylalaninate, N-acyl-N-methyl-~3-alaninate, sodium laurylsarcosinate, cocoyl sarcosine, lauroyl taurate, lauroyl lactylate, N-acyl potassium glysine, lauroamphohydroxy propylsulfonate, cocoglyceride sulfate, lauroyl isethionate, fauroamphoacetate, and mixtures thereof.
Amphoteric Surfactants so Amphoteric surfactants useful herein include those called zwitterionic surfactants in the art. Amphoteric surfactants useful herein include the derivatives of aliphatic secondary and tertiary amines in which the aliphatic radical is straight or branched and one of the aliphatic substituents contains from WO 99/24004 pC~~g97/20735 about 8 to about 18 carbon atoms and one contains an anionic water solubilizing group, e.g., carboxy, sulfonate, sulfate, phosphate, or phosphonate.
Amphoteric surfactants for use herein include the derivatives of aliphatic quaternary ammonium, phosphonium, and sulfonium compounds, in which the s aliphatic radicals are straight or branched, 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+ _ Cg2 _ R4 _ Z _ where R2 contains an alkyl, alkenyl, or hydroxy alkyl radical of from about 8 to j s about 18 carbon atoms, from 0 to about 10 ethylene oxide moieties and from to about 1 glyceryl moiety; Y is selected from the group consisting of nitrogen, phosphorus, and sulfur atoms; R3 is an alkyl or monohydroxyalkyl group containing 1 to about 3 carbon atoms; X is 1 when Y is a sulfur atom, and 2 when Y is a nitrogen or phosphorus atom; R4 is an alkylene or hydroxyalkylene of from Zo 1 to about 4 carbon atoms and Z is a radical selected from the group consisting of carboxylate, sulfonate, sulfate, phosphonate, and phosphate groups.
Examples of amphoteric surfactants also include sultaines and amidosultaines. Suttaines, including amidosultaines, include for example, cocodimethylpropylsultaine, stearyldimethylpropylsultaine, lauryl-bis-{2 2s hydroxyethyl)propylsultaine and the like; and the amidosultaines such as cocamidodimethylpropylsultaine, stearylamidododimethylpropylsultaine, laurylamido-bis-(2-hydroxyethyl)propylsultaine, and the like. Preferred are amidohydroxysultaines such as the Cg-C1g hydrocarbytamidopropylhydroxy suitaines, especially Cg-C14 hydrocarbylamidopropylhydroxysultaines, e.g., so laurylamidopropylhydroxysultaine and cocamidopropylhydroxysuitaine. Other sultaines are described in U.S. Patent 3,950,417, which is incorporated herein by reference in its entirety.
Other suitable amphoteric surfactants are the aminoalkanoates of the formula RNH(CH2)nCOOM, the iminodialkanoates of the formula 35 RN[(CH2)mCOOMj2 and mixtures thereof; wherein n and m are numbers from 1 to about 4, R is Cg - C22 alkyl or alkenyl, and M is hydrogen, alkali metal, alkaline earth metal, ammonium or alkanolammonium.
Other suitable amphoteric surfactants include those represented by the formula R1CON - (CH2)n - N+ - CH2Z

wherein R1 is Cg - C22 alkyl or alkenyl, preferably Cg - Clg, R2 and R3 is independently selected from the group consisting of hydrogen, -CH2C02M, -CH2CH20H, -CH2CH20CH2CH2COOM, or -(CH2CH20)mH wherein m is an ~ 5 integer from 1 to about 25, and R4 is hydrogen, -CH2CH20H, or CH2CH20CH2CH2COOM, Z is C02M or CH2C02M, n is 2 or 3, preferably 2, M
is hydrogen or a ration, such as alkali metal (e.g., lithium, sodium, potassium), alkaline earth metal (beryllium, magnesium, calcium, strontium, barium), or ammonium. This type of surfactant is sometimes classified as an imidazoline-2o type amphoteric surfactant, although it should be recognized that it does not necessarily have to be derived, directly or indirectly, through an imidazoline intermediate. Suitable materials of this type are marketed under the tradename MIRANOL and are understood to comprise a complex mixture of species, and can exist in protonated and non-protonated species depending upon pH with 2s respect to species that can have a hydrogen at R2. All such variations and species are meant to be encompassed by the above formula.
Examples of surfactants of the above formula are monocarboxylates and di-carboxylates. Examples of these materials include cocoamphocarboxypropionate, cocoamphocarboxypropionic acid, ao cocoamphocarboxyglycinate (alternately referred to as cocoamphodiacetate), and cocoamphoacetate.
Commercial amphoteric surfactants include those sold under the trade names MIRANOL C2M CONC. N.P., MIRANOL C2M CONC. O.P., MIRANOL
C2M SF, MIRANOL CM SPECIAL (Miranol, Inc.); ALKATERIC 2CIB (Alkaril s5 Chemicals); AMPHOTERGE W-2 (Lonza, Inc.); MONATERIC CDX-38, MONATERIC CSH-32 (Mona Industries); REWOTERIC AM-2C (Rewo Chemical Group); and SCHERCOTERIC MS-2 (Scher Chemicals).
Betaine surfactants, i.e. zwitterionic surfactants, suitable for use in the conditioning compositions are those represented by the formula:

R5- [C - N - (CH2 ) m~ n-N+- y- R1 wherein: R1 is a member selected from the group consisting of COOM and CH(OH)CH2S03M
R2 is lower alkyl or hydroxyalkyl; R3 is lower alkyl or hydroxyalkyl; R4 is a ~ 5 member selected from the group consisting of hydrogen and lower alkyl; R5 is higher alkyl or alkenyl; Y is lower alkyl, preferably methyl; m is an integer from 2 to 7, preferably from 2 to 3; n is the integer 1 or 0; M is hydrogen or a cation, as previously described, such as an alkali metal, alkaline earth metal, or ammonium.
The term "lower alkyl" or "hydroxyalkyl" means straight or branch chained, Zo saturated, aliphatic hydrocarbon radicals and substituted hydrocarbon radicals having from one to about three carbon atoms such as, for example, methyl, ethyl, propyl, isopropyl, hydroxypropyl, hydroxyethyl, and the like. The term "higher alkyl or alkenyl" means straight or branch chained saturated (i.e., "higher alkyl") and unsaturated (i.e., "higher alkenyl") aliphatic hydrocarbon radicals having from i5 about 8 to about 20 carbon atoms such as, for example, lauryl, cetyi, stearyl, oleyl, and the like. It should be understood that the term "higher alkyl or alkenyl"
includes mixtures of radicals which may contain one or more intermediate linkages such as ether or polyether linkages or non-functional substituents such as hydroxyl or halogen radicals wherein the radical remains of hydrophobic so character.
Examples of surfactant betaines of the above formula wherein n is zero which are useful herein include the alkylbetaines such as cocodimethylcarboxymethylbetaine, lauryldimethylcarboxymethylbetaine, iauryldimethyl-a.-carboxyethytbetaine, cetyldimethylcarboxymethylbetaine, lauryl-35 bis-(2-hydroxyethyl)-carboxymethylbetaine, stearyl-bis-(2-hydroxypropyl)carboxymethylbetaine, oleyidimethyl-y-carboxypropylbetaine, lauryl-bis-(2-hydroxypropyl)-a-carboxyethylbetaine, etc. The sulfobetaines may be represented by cocodimethylsulfopropylbetaine, stearyldimethylsulfopropylbetaine, lauryl-bis-{2-hydroxyethyl)-sulfopropylbetaine, s and the like.
Specific examples of amido betaines and amidosulfobetaines useful in the conditioning compositions include the amidocarboxybetaines, such as cocamidodimethylcarboxymethylbetaine, laurylamidodimethylcarboxymethylbetaine, ~ o cetylamidodimethylcarboxymethylbetaine, laurylamido-bis-(2-hydroxyethyl)-carboxymethylbetaine, cocamido-bis-(2-hydroxyethyl)-carboxymethylbetaine, etc.
The amidosulfobetaines may be represented by cocamidodimethylsulfopropylbetaine, stearylamidodimethylsulfopropylbetaine, laurylamido-bis-(2-hydroxyethyl)-sulfopropylbetaine, and the like.
i s Nonionic Surfactants The shampoo compositions of the present invention can comprise a nonionic surfactant. Nonionic surfactants include those compounds produced by condensation of alkylene oxide groups, hydrophilic in nature, with an organic hydrophobic compound, which may be aliphatic or alkyl aromatic in nature.
Zo Preferred noniimiting examples of nonionic surfactants for use in the shampoo compositions include the foNowing:
(1) polyethylene oxide condensates of alkyl phenols, e.g., the condensation 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 is 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;
(2) those derived from the condensation of ethylene oxide with the product resulting from the reaction of propylene oxide and ethylene diamine products;
30 (3) condensation products of aliphatic alcohols having from about 8 to about 18 carbon atoms, in either straight chain or branched chain configurations, with ethylene oxide, e.g., a coconut alcohol ethylene oxide condensate having from about 10 to about 30 moles of ethylene oxide per mole of coconut alcohol, the coconut alcohol fraction having from about 10 to about 14 carbon atoms;

(4) long chain tertiary amine oxides of the formula [ R1 R2R3N --> O J
where R1 contains an alkyl, alkenyl or monohydroxy alkyl radical of from about to about 18 carbon atoms, from 0 to about 10 ethylene oxide moieties, and from 0 to about 1 glyceryl moiety, and R2 and R3 contain from about 1 to about 3 s carbon atoms and from 0 to about 1 hydroxy group, e.g., methyl, ethyl, propyl, hydroxyethyl, or hydroxypropyl radicals;
(5) long chain tertiary phosphine oxides of the formula [RR'R"P ~ O]
where R contains an alkyl, alkenyi or monohydroxyalkyl radical ranging from about 8 to about 18 carbon atoms in chain length, from 0 to about 10 ethylene i o oxide moieties and from 0 to 1 glyceryl moieties and R' and R" are each alkyl or monohydroxyalkyl groups containing from about 1 to about 3 carbon atoms;
(6) long chain dialkyl sulfoxides containing one short chain alkyl or hydroxy alkyl radical of from 1 to about 3 carbon atoms (usually methyl) and one long hydrophobic chain which include alkyl, alkenyl, hydroxy alkyl, or keto alkyl i s radicals containing from about 8 to about 20 carbon atoms, from 0 to about ethylene oxide moieties and from 0 to 1 glyceryl moieties;
(7) alkyl polysaccharide (APS) surfactants (e.g. alkyl polyglycosides), examples of which are described in U.S. Patent 4,565,647, which is incorporated herein by reference in its entirety, and which discloses APS surfactants having a Zo hydrophobic group with about 6 to about 30 carbon atoms and a polysaccharide (e.g., polyglycoside) as the hydrophilic group; optionally, there can be a polyalkylene-oxide group joining the hydrophobic and hydrophilic moieties; and the alkyl group (i.e., the hydrophobic moiety) can be saturated or unsaturated, branched or unbranched, and unsubstituted or substituted (e.g., with hydroxy or is cyclic rings); a preferred material is alkyl polyglucoside which is commercially available from Henkel, ICI Americas, and Seppic; and (8) polyoxyethylene alkyl ethers such as those of the formula RO(CH2CH2)nH and polyethylene glycol (PEG) glyceryl fatty esters, such as those of the formula R(O)OCH2CH(OH)CH2(OCH2CH2)nOH, wherein n is from ao 1 to about 200, preferably from about 20 to about 100, and R is an alkyl having from about 8 to about 22 carbon atoms.
ANTIDANDRUFF AGENT
The present composition may further comprise a safe and effective amount of an antidandruff agent. When present, the antidandruff agent is typically used at a level from about 0.1 % to about 5%, preferably from about 0.3% to about 5% by weight of the composition.
Without being bound by theory, it is believed that the coacervate made by the polyhydrophilic anionic surfactants and cationic conditioning agents of the s present invention are also capable of trapping and effectively delivering the antidandruff agents herein to the hair surface.
Pyrithione salts are useful herein. Suitable pyrithione salts are heavy metal salts of 1-hydroxy-2-pyridinethione, the heavy metal salts being zinc, tin, cadmium, magnesium, aluminium, and zirconium. Preferred is zinc salt of 1-~o hydroxy-2-pyridinethione known in the art as zinc pyrithione, more preferably in a particle size of up to about 20 microns, still preferably from about 1 to about 10 microns. Commerically available pyrithione salts suitable herein include Zinc Pyrithione available from Olin.
Selenium sulfides are useful herein. Selenium sulfides herein include ~ s selenium disulfide, as well as SexSy in cyclic structure, wherein x and y are integers and x + y equals 8. Preferred selenium sulfides are those having a particle size of less than about 15 microns, more preferably less than about microns; wherein the particle size is measured by a laser light scatterring device such as Malvern 3600 instrument.
2o Sulfur and octopirox, its salts, and its derivatives are also useful herein.
Antidandruff agents as mentioned above can be used alone, or in combination with one another.
ADDITIONAL CONDITIONING AGENTS
The compositions of the present invention may further comprise from 2s about 0.05% to about 20%, preferably from about 0.1 % to about 10%, and more preferably from about 0.5% to about 10% of additional conditioning agents selected from the group consisting of high melting point compounds, oily compounds, and nonionic polymers.
High Melting Point Compound ao The compositions may comprise a high melting point compound having a melting point of at least about 25°C selected from the group consisting of fatty aicohols, fatty acids, fatty alcohol derivatives, fatty acid derivatives, hydrocarbons, steroids, and mixtures thereof. Without being bound by theory, it is believed that these high melting point compounds cover the hair surface and as reduce friction, thereby resulting in providing smooth feel on the hair and ease of WO 99/24004 PC'T/US97/20735 combing. It is understood by the artisan that the compounds disclosed in this section of the specification can in some instances fall into more than one classification, e.g., some fatty alcohol derivatives can also be classified as fatty acid derivatives. However, a given classification is not intended to be a limitation s on that particular compound, but is done so for convenience of classification and nomenclature. Further, it is understood by the artisan that, depending on the number and position of double bonds, and length and position of the branches, certain compounds having certain required carbon atoms may have a melting point of less than about 25°C. Such compounds of low melting point are not i o intended to be included in this section. Nonlimiting examples of the high melting point compounds are found in International Cosmetic Ingredient Dictionary, Fifth Edition, 1993, and CTFA Cosmetic Ingredient Handbook, Second Edition, 1992, both of which are incorporated by reference herein in their entirety.
The fatty aicohols useful herein are those having from about 14 to about ~ s 30 carbon atoms, preferably from about 16 to about 22 carbon atoms. These fatty alcohols can be straight or branched chain alcohols and can be saturated or unsaturated. Nonlimiting examples of fatty alcohols include, cetyl alcohol, stearyl alcohol, behenyl alcohol, and mixtures thereof.
The fatty acids useful herein are those having from about 10 to about 30 Zo carbon atoms, preferably from about 12 to about 22 carbon atoms, and more preferably from about 16 to about 22-carbon atoms. These fatty acids can be straight or branched chain acids and can be saturated or unsaturated. Also included are diacids, triacids, and other multiple acids which meet the requirements herein. Also included herein are salts of these fatty acids.
25 Nonlimiting examples of fatty acids include lauric acid, palmitic acid, stearic acid, behenic acid, sebacic acid, and mixtures thereof.
The fatty alcohol derivatives and fatty acid derivatives useful herein include alkyl ethers of fatty alcohols, alkoxylated fatty alcohols, alkyl ethers of alkoxylated fatty alcohols, esters of fatty alcohols, fatty acid esters of compounds so having esterifiable hydroxy groups, hydroxy-substitued fatty acids, and mixtures thereof. Nonlimiting examples of fatty alcohol derivatives and fatty acid derivatives include materials such as methyl stearyl ether; the ceteth series of compounds such as ceteth-1 through ceteth-45, which are ethylene glycol ethers of cetyl alcohol, wherein the numeric designation indicates the number of a5 ethylene glycol moieties present; the steareth series of compounds such as WO 99/24004 PC'T/US97/20735 steareth-1 through 10, which. are ethylene glycol ethers of steareth alcohol.
wherein the numeric designation indicates the number of ethylene glycol moieties present; ceteareth 1 through ceteareth-10, which are the ethylene glycol ethers of ceteareth alcohol, i.e. a mixture of fatty alcohols containing predominantly cetyl s and stearyl alcohol, wherein the numeric designation indicates the number of ethylene glycol moieties present; C1-Cgp alkyl ethers of the ceteth, steareth, and ceteareth compounds just described; pofyoxyethyiene ethers of behenyl alcohol;
ethyl stearate, cetyl stearate, cetyl palmitate, stearyl stearate, myristyl myristate, polyoxyethylene cetyl ether stearate, polyoxyethylene stearyl ether stearate, ~ o polyoxyethylene lauryl ether stearate, ethyleneglycol monostearate, polyoxyethylene monostearate, polyoxyethylene distearate, propyleneglycol monostearate, propyleneglycol distearate, trimethyioipropane distearate, sorbitan stearate, polyglyceryl stearate, glyceryl monostearate, glyceryl distearate, glyceryl tristearate, and mixtures thereof.
~ s Hydrocarbons useful herein include compounds having at least about 20 carbons.
Steroids useful herein include compounds such as cholesterol.
High melting point compounds of a single compound of high purity are preferred. Single compounds of pure fatty alcohols selected from the group of Zo pure cetyl alcohol, stearyi alcohol, and behenyl alcohol are highly preferred. By "pure" herein, what is meant is that the compound has a purity of at least about 90%, preferably at least about 95%. These single compounds of high purity provide good rinsability from the hair when the consumer rinses off the composition.
25 Commercially available high melting point compounds useful herein include: cetyl alchol, stearyl alcohol, and behenyl alcohol having tradenames KONOL series available from New Japan Chemical (Osaka, Japan), and NAA
series available from NOF (Tokyo, Japan); pure behenyl alcohol having tradename 1-DOCOSANOL available from WAKO (Osaka, Japan), various fatty ao acids having tradenames NEO-FAT available from Akzo (Chicago Illinois, USA), HYSTRENE available from Witco Corp. (Dublin Ohio, USA), and DERMA
available from Vevy (Genova, Italy); and cholesterol having tradename NIKKOL
AGUASOME LA available ftom Nikko.

WO 99/24004 PC'T/US97/20735 Oily Compound The compositions comprise an oily compound having a melting point of not more than about 25°C selected from the group consisting of a first oily compound, a second oily compound, and mixtures thereof. The oily compounds useful herein may be volatile or nonvolatile. Without being bound by theory, it is believed that, the oily compounds may penetrate the hair to modify the hydroxy bonds of the hair, thereby resulting in providing softness and flexibility to the hair.
The oily compound may comprise either the first oily compound or the second oily compound as described herein. Preferably, a mixture of the first oily i o compound and the second oily compound is used. The oily compounds of this section are to be distinguished from the high melting point compounds described above. Nonlimiting examples of the oily compounds are found in International Cosmetic Ingredient Dictionary, Fifth Edition, 1993, and CTFA Cosmetic Ingredient Handbook, Second Edition, 1992, both of which are incorporated by i s reference herein in their entirety.
First Oily Compound The fatty alcohols useful herein include those having from about 10 to about 30 carbon atoms, preferably from about 12 to about 22 carbon atoms, and more preferably from about 16 to about 22 carbon atoms. These fatty alcohols zo can be straight or branched chain alcohols and can be saturated or unsaturated alcohols, preferably unsaturated alcohols. Nonlimiting examples of these compounds include oleyl alcohol, palmitoleic alcohol, isostearyl alcohol, isocetyl alchol, undecanol, octyl dodecanol, octyl decanol, octyl alcohol, caprylic alcohol, decyl alcohol and lauryl alcohol.
25 The fatty acids useful herein include those having from about 10 to about 30 carbon atoms, preferably from about 12 to about 22 carbon atoms, and more preferably from about 16 to about 22 carbon atoms. These fatty acids can be straight or branched chain acids and can be saturated or unsaturated. Suitable fatty acids include, for example, oleic acid, linoleic acid, isostearic acid, linolenic so acid, ethyl linolenic acid, ethyl linolenic acid, arachidonic acid, and ricinolic acid.
The fatty acid derivatives and fatty alcohol derivatives are defined herein to include, for example, esters of fatty alcohols, alkoxylated fatty alcohols, alkyl ethers of fatty alcohols, alkyl ethers of alkoxylated fatty alcohols, and mixtures thereof. Nonlimiting examples of fatty acid derivatives and fatty alcohol 35 derivatives, include, for example, methyl linoleate, ethyl linoleate, isopropyl linoleate, isodecyl oleate, isopropyl oleate, ethyl oleate, octyldodecyl oleate, oleyl oleate, decyi oleate, butyl oleate, methyl oleate, octyldodecyl stearate, octyldodecyl isostearate, octyidodecyl isopalmitate, octyl isopelargonate, octyl pelargonate, hexyl isostearate, isopropyl isostearate, isodecyl isononanoate, s Oleth-2, pentaerythritol tetraoleate, pentaerythritol tetraisostearate, trimethylolpropane trioleate, and trimethylolpropane triisostearate.
Commercially available first oily compounds useful herein include: oleyl alcohol with tradename UNJECOL 90BHR available from New Japan Chemical, pentaerythritol tetraisostearate and trimethylolpropane triisostearate with ~ o tradenames KAKPTI and KAKTTI available from Kokyu Alcohol (Chiba, Japan), pentaerythritol tetraoleate having the same tradename as the compound name available from New Japan Chemical, trimethylolpropane trioleate with a tradename ENUJERUBU available from New Japan Chemical, various liquid esters with tradenames SCHERCEMOL series available from Scher, and hexyl ~ s isostearate with a tradename HiS and isopropryl isostearate having a tradename ZPIS available from Kokyu Alcohol.
Second Oily Compound The second oily compounds useful herein include straight chain, cyclic, and branched chain hydrocarbons which can be either saturated or unsaturated, Zo so tong as they have a melting point of not more than about 25°C. These hydrocarbons have from about 12 to about 40 carbon atoms, preferably from about 12 to about 30 carbon atoms, and preferably from about 12 to about 22 carbon atoms. Also encompassed herein are polymeric hydrocarbons of alkenyl monomers, such as polymers of C2_g aikenyl monomers. These polymers can is be straight or branched chain polymers. The straight chain polymers will typically be relatively short in length, having a total number of carbon atoms as described above. The branched chain polymers can have substantially higher chain lengths. The number average molecular weight of such materials can vary widely, but will typically be up to about 500, preferably from about 200 to about 30 400, and more preferably from about 300 to about 350. Also useful herein are the various grades of mineral oils. Mineral oils are liquid mixtures of hydrocarbons that are obtained from petroleum. Specific examples of suitable hydrocarbon materials include paraffin oil, mineral oil, dodecane, isododecane, hexadecane, isohexadecane, eicosene, isoeicosene, tridecane, tetradecane, 3s polybutene, polyisobutene, and mixtures thereof. Preferred for use herein are hydrocarbons selected from the group consisting of mineral oil, isododecane, isohexadecane, polybuterie, polyisobutene, and mixtures thereof.
Commercially available second oily compounds useful herein include isododecane, isohexadeance, and isoeicosene with tradenames PERMETHYL
99A, PERMETHYL 101A, and PERMETHYL 1082, available from Presperse (South Plainfield New Jersey, USA), a copolymer of isobutene and normal butene with tradenames INDOPOL H-100 available from Amoco Chemicals (Chicago Illinois, USA), mineral oil with tradename BENOL available from Witco, isoparaffin with tradename ISOPAR from Exxon Chemical Co. (Houston Texas, io USA), a-olefin oligomer with tradename PURESYN 6 from Mobil Chemical Co., and trimethylolpropane tricaprylate/tricaprate with tradename MOBIL ESTER P43 from Mobil Chemical Co.
Nonionic Polymer Nonionic polymers useful herein include cellulose derivatives, ~ s hydrophobically modfied cellulose derivatives, ethylene oxide polymers, and ethylene oxide/propylene oxide based polymers. Suitable nonionic polymers are cellulose derivatives including methylcellulose with tradename BENECEL, hydroxyethyl cellulose with tradename NATROSOL, hydroxypropyl cellulose with tradename KLUCEL, cetyl hydroxyethyl cellulose with tradename POLYSURF
Zo 67, all supplied by Herculus. Other suitable nonionic polymers are ethylene oxide and/or propylene oxide based polymers with tradenames CARBOWAX
PEGs, POLYOX WASRs, and UCON FLUIDS, all supplied by Amerchol.
Polvalkylene Glvcols These compounds are particularly useful for compositions which are 25 designed to impart a soft, moist feeling to the hair. When present, the polyalkylene glycol is typically used at a level from about 0.025% to about 1.5%, preferably from about 0.05% to about 1 %, and more preferably from about 0.1 to about 0.5% of the compositions.
The polyalkylene glycols are characterized by the general formula:
H (OCH2CH) n - OH
R

wherein R is selected from the group consisting of H, methyl, and mixtures thereof. When R is H, these materials are polymers of ethylene oxide, which are also known as polyethylene oxides, polyoxyethylenes, and polyethylene glycols.
When R is methyl, these materials are polymers of propylene oxide, which are 5 also known as polypropylene oxides, polyoxypropylenes, and polypropylene glycols. When R is methyl, it is also understood that various positional isomers of the resulting polymers can exist.
In the above structure, n has an average value of from about 1500 to about 25,000, preferably from about 2500 to about 20,000, and more preferably ~o from about 3500 to about 15,000.
Polyethylene glycol polymers useful herein are PEG-2M wherein R equals H and n has an average value of about 2,000 (PEG-2M is also known as Polyox WSR~ N-10, which is available from Union Carbide and as PEG-2,000); PEG-5M wherein R equals H and n has an average value of about 5,000 (PEG-5M is ~ 5 also known as Polyox WSR~ N-35 and Polyox WSR~ N-80, both available from Union Carbide and as PEG-5,000 and Polyethylene Glycol 300,000); PEG-7M
wherein R equals H and n has an average value of about 7,000 (PEG-7M is also known as Polyox WSR~ N-750 available from Union Carbide); PEG-9M wherein R equals H and n has an average value of about 9,000 (PEG 9-M is also known Zo as Poiyox WSR~ N-3333 available from Union Carbide); and PEG-14 M wherein R equals H and n has an average value of about 14,000 (PEG-14M is also known as Polyox WSR~ N-3000 available from Union Carbide).
Other useful polymers include the polypropylene glycols and mixed polyethylene/poiypropylene glycols.
2s ADDITIONAL COMPONENTS
The shampoo compositions of the present invention may include a variety of additional components, which may be selected by the artisan according to the desired characteristics of the final product. Additional component include, for example, polyvalent metal cations, suspending agents, ethoxytated glucose 3o derivatives, and other additional components.
Polyvalent Metal Cations Suitable polyvalent metal cations include divalent and trivalent metals, divalent metals being preferred. Exemplary metal cations include alkaline earth metals, such as magnesium, calcium, zinc, and copper, and trivalent metals such as as aluminum and iron. Preferred are calcium and magnesium.

The polyvalent metal cation can be added as an inorganic salt, organic salt, or as a hydroxide. The polyvalent metal cation may also be added as a salt with anionic surfactants as mentioned above.
Preferably, the polyvalent metal cation is introduced as an inorganic salt or organic salt. Inorganic salts include chloride, bromide, iodine, nitrate, or sulfate, more preferably chloride or sulfate. Organic salts include L-glutamate, lactate, malate, succinate, acetate, fumarate, L-glutamic acid hydrochloride, and tartarate.
It will be clear to those skilled in the art that, if polyvalent salts of the i o anionic surfactant is used as the mode of introducing the polyvalent metal cations into the compositions hereof, only a fraction of the anionic surfactant may be of polyvalent form, the remainder of the anionic surfactant being necessarily added in monovalent form.
Hardness of the conditioning shampoo compositions can be measured by i s standard methods in the art, such as by ethylene diamine tetraacetic acid (EDTA) titration. In the event that the composition contains dyes or other color materials that interfere with the ability of EDTA titration to yield a perceptible color change, hardness should be determined from the composition in the absence of the interfering dye or color.
Zo Suspending Agents A preferred additional component is a suspending agent, particularly for compositions comprising silicone compounds of high viscosity and/or large particle size. When present, the suspending agent is in dispersed form in the compositions. The suspending agent will generally comprise from about 0.1 % to 2s about 10%, and more typically from about 0.3% to about 5.0%, by weight, of the composition.
Preferred suspending agents include acyl derivatives such as ethylene glycol stearates, both mono and distearate, long chain amine oxides such as alkyl (C16-C22) dimethyl amine oxides, e.g., stearyl dimethyl amine oxide, and 3o mixtures thereof. When used in the shampoo compositions, these preferred suspending agents are present in the composition in crystalline form. These suspending agents are described in U.S. Patent 4,741,855.
Other suitable suspending agents include alkanol amides of fatty acids, preferably having from about 16 to about 22 carbon atoms, more preferably 3s about 16 to 18 carbon atoms, preferred examples of which include stearic monoethanolamide, cocomonoethanolamide, stearic diethanolamide, stearic monoisopropanolamide and stearic monoethanolamide stearate.
Other suitable suspending agents include N,N-dihydrocarbyl amido benzoic acid and soluble salts thereof (e.g., Na and K salts), particularly N,N-di(hydrogenated) C16, C1g and tallow amido benzoic acid species of this family, which are commercially available from Stepan Company (Northfield, Illinois, USA).
Other suitable suspending agents include xanthan gum. The use of xanthan gum as a suspending agent in silicone containing shampoo ~o compositions is described, for example, in U.S. Patent 4,788,006, which is incorporated herein by reference in its entirety. Combinations of long chain acyl derivatives and xanthan gum may also be used as a suspending agent in the shampoo compositions. Such combinations are described in U.S. Patent 4,704,272, which is incorporated herein by reference in its entirety.
i s Other suitable suspending agents include carboxyvinyl polymers.
Preferred among these polymers are the copolymers of acrylic acid crosslinked with polyallylsucrose as described in U.S. Patent 2,798,053, which is incorporated herein by reference in its entirety. Examples of these polymers include the carbomers, which are hompoiymers of acrylic acid crosslinked with an Zo allyl ether of pentaerythritol, an allyl ether of sucrose, or an ally) ether of propylene. Neutralizers may be required, for example, amino methyl propanol, triethanol amine, or sodium hydroxide.
Other suitable suspending agents can be used in the compositions, including those that can impart a gel-like viscosity to the composition, such as is water soluble or colloidally water soluble polymers like cellulose ethers such as hydroxyethyl cellulose, hydroxymethyl cellulose, hydroxypropyl cellulose, and materials such as guar gum, polyvinyl alcohol, polyvinyl pyrroiidone, hydroxypropyl guar gum, starch and starch derivatives.
Ethoxylated Glucose Derivatives 3o A preferred additional component is an ethoxylated glucose derivative, particularly for increasing the viscosity of compositions, and for the phase stability of compositions at high and low temperatures. When present, the ethoxylated glucose derivative is included at a level of from about 0.1 % to about 10%, and more typically from about 0.3% to about 5.0%, by weight, of the 3s composition.

Suitable ethoxylated glucose derivatives include methyl gluceth 10, methyl gluceth 20, PEG-120 methylglucose dioleate, PPG-10 methylglycose ether, and PPG-20 methylglycose ether. Commercially available material highly suitable herein include methyl gluceth 10 with tradename GLUCAM E-10, PEG-120 s methylglucose dioleatewith tradename Glucamate DOE-120, PPG-10 methylglucose ether with tradename GLUCAM P-10, and PPG-20 methylglucose ether with tradename GLUCAM P-20, all available from Amerchol.
Other Additional Components A wide variety of other additional ingredients can be formulated into the i o present compositions. These include: other conditioning agents such as hydrolyzed collagen with tradename Peptein 2000 available from Hormel, vitamin E with tradename Emix-d available from Eisai, panthenol available from Roche, panthenyl ethyl ether available from Roche, hydrolysed keratin, proteins, plant extracts, and nutrients; emulsifying surfactants for dispersing water insoluble ~ s components in the carrier; hair-fixative polymers such as amphoteric fixative polymers, cationic fixative polymers, anionic fixative polymers, nonionic fixative polymers, and silicone grafted copolymers; optical brighteners such as polystyrylstilbenes, triazinstilbenes, hydroxycoumarins, aminocoumarins, triazoles, pyrazolines, oxazoles, pyrenes, porphyrins, and imidazoles;
Zo preservatives such as benzyl alcohol, methyl paraben, propyl paraben and imidazolidinyl urea; pH adjusting agents, 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 FDIC or DS~C dyes; hair oxidizing (bleaching) agents, such as 25 hydrogen peroxide, perborate and persulfate salts; hair reducing agents such as the thioglycolates; perfumes; and sequestering agents, such as disodium ethylenediarnine tetra-acetate; ultraviolet and infrared screening and absorbing agents such as octyl salicylate. Such optional ingredients generally are used individually at levels from about 0.01 % to about 10.0%, preferably from about ao 0.05% to about 5.0% by weight of the composition.
EXAMPLES
The following examples further describe and demonstrate embodiments within the scope of the present invention. The examples are 35 given solely for the purpose of illustration and are not to be construed as PC'T/US97/Z0735 limitations of the present invention, as many variations thereof are possible without departing from the spirit and scope of the invention. Ingredients are identified by chemical or CTFA name, or otherwise defined below.
Ex.1 Ex.2 Ex.3 Ex.4 Ex.S Ex.6 N-cocoyl-L-glutamate *1 4 0 0 0 8 18 Disodium Lauryl Sulfosuccinate0 5 0 0 0 0 *2 N-acyl-L- Aspartate *3 0 0 5 0 0 0 Sodium Lauryl Aminodiacetic 0 0 0 5 0 0 acid *4 Cocamidopropylbetaine *5 4 5 5 5 0 t Ammonium Laureth-3 Sulfate 10 10 10 10 10 0 ~

Behenyl trimethylamonium chloride*60.5 0.25 0.5 0.5 0.5 0.5 ' Pofyquaterium-10 *8 0.5 0.5 0.5 0.5 1.0 2.0 Silicone Emulsion 1 *11 2.0 0 0 0 0 0 Silicone Emulsion 2 *12 0 0 2.0 0 0 0 Dimethicone *13 0 3.0 0 0 0 0 Silicone Emulsion *14 0 0 0 0 0 2.0 Alkyl Silicone *15 0 0 0 0 2.0 0 Alkyl Silicone Emulsion *16 0 0 0 2.0 0 0 Cetyl Alcohol 0.5 0 0 0 1.0 0 Cocamide MEA 1.5 1. 1.5 1.5 1.5 3.0 Ethylene Glycol Distearate 1.5 3.0 1.5 1.5 0 6.0 Perfume solution 0.5 0.5 0.5 0.5 0.5 0.5 DMDM Hydantoim 0.37 0.37 0.37 0.37 0.37 0.37 PEG120 Methyl Glucose Dioleate0.5 0 0 1.0 1.5 3.0 *17 ~IMgCl2 0.5 0 0 0 0 0 MgSO 0 0.5 0 0 0 0 Deionized Water ---q.s.
to 100%
-Ex. Ex. Ex. Ex. Ex. Ex.12 7 8 9 10 11 '~

N-cocoyl-L-glutamate *1 4 10 10 5 10 5 Disodium Lauryl Sulfosuccinate0 5 0 0 0 0 *2 N-acyl-L- Aspartate *3 0 0 5 0 0 0 Sodium Lauryl Aminodiacetic 0 0 0 5 0 0 acid *4 Cocamidopropylbetaine *5 4 5 10 5 10 0 Cocoamidohydroxysultaine *18 0 0 0 0 0 5 Ammonium Laureth-3 Sulfate 10 0 0 10 0 10 Behenyl trimethylamonium chloride*61.0 0 0.5 0 0.5 0.5 Dihydrogenated Tallowamidoethyl0 0 0 1.0 0 0 Hydroxyethylmonium Methosuffate *7 Polyquaterium-10 *8 0.25 0.5 1.0 0.5 1.0 2.0 Polyquaterium-24 *9 0.25 0 0 0 0 0 Polyquaterium-47 *10 0 0.5 0 0 0 0 Silicone Emulsion 1 *11 2.0 0 0 2.0 0 0 Silicone Emulsion 2 *12 0 0 2.0 0 2.0 0 Dimethicone *13 0 3.0 0 0 0 2.0 Cocamide MEA 1.5 1.5 1.5 3.0 5.0 3.0 Ethylene Glycol Distearate 1.5 3.0 1.5 1.5 0 3.0 Perfume solution 0.5 0.5 0.5 0.5 0.5 0.5 DMDM Hydantoim 0.37 0.37 0.37 0.37 0.37 0.37 PEG120 Methyl Glucose Dioleate0 0 0 0 1.5 0 *17 Methyl Gluceth-20 *18 0.5 0 0 1.0 0 0 MgCi 0.5 0 0 0 0 0 IMgSO 0 0 0.5 0 0 0.5 Deionized Water -q.s.
to 100%
---Ex. Ex. Ex. Ex.

N-cocoyl-L-glutamate *1 4 4 10 5 Disodium Lauryl Sulfosuccinate0 0 0 0 *2 N-acyl-L- Aspartate *3 0 0 5 0 Sodium Lauryl Aminodiacetic 0 0 0 5 acid *4 Cocamidopropylbetaine *5 4 5 10 5 Cocoamidohydroxysultaine *18 0 0 0 0 Ammonium Laureth-3 Sulfate 10 0 0 10 Behenyl trimethylamonium chloride*60.5 0.5 0.5 0 Polyquaterium-10 *8 0.5 0.5 1.0 0.5 Silicone Emulsion 1 *11 2.0 0 2.0 2.0 Dimethicone *13 0 3.0 0 0 Zinc Pyrithion*23 0 0 1.0 1.0 Cocamide MEA 1.5 1.5 1.5 3.0 Ethylene Glycol Distearate 1.5 1.5 1.5 1.5 PEG120 Methyl Glucose Dioleate0 0 0 0.5 *17 Methyl Gluceth-20 *18 0.5 0 0 0 Hydrolyzed Collagen x19 0.01 0 0 0 Vitamine E *20 0 0.01 0 0.01 Panthenol *21 0 0.0250 0.025 Panthenyl Ethyl Ether *22 0 0.0250 0.025 Perf~ ume solution 0.5 0.5 0.5 0.5 DMDM Hydantoim 0.37 0.37 0.37 0.37 MgSO 0 0 0.5 0 Deionized Water --q.s.
to 100%

Definitions *1 Amisoft CT-12S obtained from Ajinomoto.
s *2 Emcol 4400-1 obtained from I/V~tco *3 Asparak obtained from Mitsubishi *4 Nissan Anon LA obtained from Nippon Oil and Fat *5 Tego Betaine F obtained from TH Goldschmidt *6 Econol TM22 obtained from Sanyo Kasei ~ o *7 Varisoft 110 obtained from Witco *8 UCare Polymer LR400 obtained from Amerchol *9 Quatrisoft Polymer LM-200 obtained from Amerchol *10 Merquat 2001 obtained from Calgon *11 Emulsion of 1,OO,OOOcp Dimethiconol with particle size of approximately s 200nm obtained from Toshiba Silicone *12 Emulsion of 500,OOOcp Dimethiconol with particle size of approximately 200nm obtained from Toshiba Silicone *13 40(gum)/60(fluid) weight ratio blend of SE-76 dimethicone gum obtained from General Electric Silicone ~ o *14 Emulsion of 60,OOOcsk polydimethyl siloxane with particle size of approximately 300nm obtained as DC1664 from Dow Coming *15 Silicone alkyl grafted coplymer DC2502 obtained from Dow Coming *16 Alkyl grafted coplymer silicone emulsion DC2-2845 from Dow Corning , *17 GLUCAMATE DOE-'120 obtained from Amerchol i s *18 GLUCAM E-20 obtained from Amerchol *19 Peptein 2000 obtained from Hormel *20 Emix-d obtained from Eisai *21 available from Roche *22 available from Roche 20 *23 available from Olin Method of Preparation The shampoo compositions of Examples 1 through 16 as shown above can be prepared by any conventional method well known in the art. Suitable is methods are described below.
Polymers and surfactants are dispersed in water to form a homogenous mixture. To this mixture are added the other ingredients except for silicone emulsion (if present), perfume, and salt; the obtained mixture is agitated. If a silicone blend is present, the silicone emulsion is made with the silicone blend, a ao small amount of detersive surfactant, and a portion of water. The obtained mixture is then passed through a heat exchanger to cool, and the silicone emulsion, perfume, and salt are added. The obtained compositions are poured into bottles to make hair shampoo compositions. Alternatively, water and surfactants and any other solids that need to be melted can be mixed together at ss elevated temperature, e.g., above about 70°C, to speed the mixing into shampoo. Additional ingredients can be added either to this hot premix or after cooling the premix. The ingredients are mixed thoroughly at the elevated temperature and then pumped through a high shear mill and then through a heat exchanger to cool them to ambient temperature. If present in the composition, s silicone emulsified at room temperature in concentrated surfactant is added to the cooled mix.
Examples 1 through 16 have many advantages. For example, improved squeakyl hair feel, softness, smoothness and combing ease during rinsing and after rinsing as well as overall dry conditioning benefits.
i o It is understood that the examples and embodiments described herein are for illustrative purposes only and that various modifications or changes in light thereof will be suggested to one skilled in the art without departing from its spirit and scope.

Claims

WHAT IS CLAIMED IS:

1. A conditioning shampoo composition comprising by weight:
(a) from about 0.05% to about 50% of a polyhydrophilic anionic surfactant;
(b) from about 0.05% to about 20% of a cationic conditioning agent selected from the group consisting of cationic surfactants, cationic polymers, and mixtures thereof;
(c) from about 0.01 % to about 20% of a silicone compound; and (d) an aqueous carrier.

2. The conditioning shampoo composition according to Claim 1 wherein the polyhydrophilic anionic surfactant comprises at least one carboxy group in the molecule.

3. The conditioning shampoo composition according to Claim 1 further comprising an additional detersive surfactant.

4. The conditioning shampoo composition according to Claim 3 wherein the additional detersive surfactant comprises a secondary anionic surfactant and an amphoteric surfactant, wherein the total of the polyhydrophilic anionic surfactant and the additional detersive surfactant are from about 5% to about 75% by weight of the composition.

5. The conditioning shampoo composition according to Claim 4 wherein the composition is substantially free of alkyl sulfate surfactants.

6. The conditioning shampoo composition according to Claim 1 wherein the cationic surfactant contains in the molecule at least one alkyl chain having at least 16 carbons.

7. The conditioning shampoo composition according to Claim 1 wherein the cationic polymer is selected from Polyquaternium 10, Polyquaternium 24, and mixtures thereof.

45~

8. The conditioning shampoo composition according to Claim 1 wherein the silicone compound is a dimethicone having a viscosity of from about 100,000 centistokes to about 1,500,000 centistokes.

9. The conditioning shampoo composition according to Claim 1 wherein the silicone compound is an emulsion polymerized silicone polymer wherein the silicone polymer is dispersed as a particle having an average size of not more than about 450 nm.

10. The conditioning shampoo composition according to Claim 9 wherein the emulsion polymerized silicone polymer is selected from the group consisting of a dimethiconol having a molecular weight of at least 100,000, an amodimethicone having a molecular weight of at least 10,000, and mixtures thereof.

11. The conditioning shampoo composition according to Claim 10 wherein the silicone emulsion comprises the silicone polymer dispersed as a particle having an average size of from about 150nm to about 250nm.

12. The conditioning shampoo composition according to Claim 1 further comprising by weight from about 0.1 % to about 5% of an antidandruff agent.

13. The conditioning shampoo composition according to any of the preceding claims further comprising by weight from about 0.05% to about 20% of an additional conditioning agent selected from the group consisting of high melting point compounds, oily compounds, nonionic polymers, and mixtures thereof.