WO2000066081A1

WO2000066081A1 - Anti-dandruff and conditioning shampoos containing polyalkylene glycols and cationic polymers

Info

Publication number: WO2000066081A1
Application number: PCT/US2000/011829
Authority: WO
Inventors: David Scott Dunlop; Susan Marie Guskey; Vicente Eduardo Leyba; Douglas Allan Royce
Original assignee: The Procter & Gamble Company
Priority date: 1999-05-03
Filing date: 2000-05-02
Publication date: 2000-11-09
Also published as: CN100344276C; EP1175202B3; ES2225136T3; CA2370939C; AU759514B2; EP1175202B1; HK1044706A1; HK1044706B; CA2370939A1; EP1175202A1; DE60013804T3; CN1353601A; US6451300B1; DE60013804D1; ATE275939T1; AU4689100A; JP2002543105A; DE60013804T2; ES2225136T7

Abstract

Disclosed are shampoo compositions that provide a superior combination of anti-dandruff efficacy and conditioning, and a method of cleansing and conditioning the hair comprising applying to the hair and scalp an effective amount of said compositions. The anti-dandruff and conditioning shampoos comprise: (A) from about 5% to about 50%, by weight of the composition, of an anionic surfactant; (B) from about 0.01% to about 10%, by weight of the composition, of a non-volatile conditioning agent; (C) from about 0.1% to about 4%, by weight of the composition, of an anti-dandruff particulate; (D) from about 0.02% to about 5%, by weight of the composition, of at least one cationic polymer; (E) from 0.005% to about 1.5%, by weight of the composition, of a polyalkylene glycol corresponding to the formula: H(OCH2-CHR)n-OH, (i) wherein R is selected from the group consisting of hydrogen, methyl and mixtures thereof, (ii) wherein n is an integer having an average value from about 1,500 to about 120,000; and (F) water.

Description

ANTI-DANDRUFF 4ND CONDITIONING SHAMPOOS CONTAINING POLYALKYLENE GLYCOLS AND CATIONIC POLYMERS

TECHNICAL FIELD OF THE INVENTION The present invention relates to shampoo compositions which provide a supenor combination of anti-dandruff efficacy and conditioning These compositions contain anionic surfactants, conditioning agents, anti-dandruff particulates, catiomc polymers, polyalkylene glycols, and water

BACKGROUND OF THE INVENTION Shampoo compositions comprising vanous combmations of detersive surfactants and conditioning agents, especially sihcone conditioning agents, are known m the art and are commercially available Many of these compositions have been found to provide excellent hair cleansmg and conditioning performance For example, Pantene® Shampoo Plus Pro- Vitamin Conditioner-in-One formulas which contam anionic surfactants, a catiomc polymer and sihcone conditioning agents provide excellent cleaning, conditioning and hair feel benefits upon application to hair

Anti-dandruff shampoos are also well known in the art and are also commercially available Anti- dandruff shampoos typically incorporate an anti-dandruff active and detersive surfactants Among the preferred type of anti-dandruff agents are particulate, crystallme anti-dandruff agents, such as sulfur, selemum disulfide and heavy metal salts of pyndinethione Soluble anti-dandruff agents, such as ketoconazole, are also known in the art

Anti-dandruff shampoos which also provide conditioning benefits are likewise known in the art For example, U S Pat No 5,624,666 exemplifies and claims shampoo compositions which contam anionic surfactants, catiomc polymers and zmc pyndinethione as an anti-dandruff agent U S Pat No 5,624,666 teaches that conditioning agents such as sihcone fluids can optionally be incorporated into the compositions therein Head & Shoulders® -Dandruff Shampoo Plus Conditioner is an example of a marketed product which provides both anti-dandruff and conditionmg benefits upon application of the shampoo to hair

Nevertheless, some consumers desire a shampoo which provides a supenor combmation of anti- dandruff efficacy and conditionmg performance versus currently marketed products Such a supenor combmation of efficacy and conditioning can be difficult to achieve For example, it was previously believed that excellent anti-dandruff efficacy could be achieved by utilizing a coacervate to deposit anti-dandruff actives on the hair and scalp Unfortunately, the use of coacervates to deposit anti-dandruff actives on the hair or scalp can negatively affect conditioning, specifically clean hair feel In order to achieve good conditioning, the level of anti-dandruff agent could be reduced, resultmg in good conditionmg, but less than optimal anti-dandruff efficacy Applicants have now discovered, however, that, surprisingly, bioavailabi ty and coverage of the anti-dandruff active are much more predictive of efficacy than deposition of the active on the hair or scalp In fact, Applicants have found that, in some cases, even when an anti-dandruff active deposited very well on the hair and scalp acceptable anti-dandruff efficacy was not achieved Conversely, good anti-dandruff efficacy could be achieved in situations where the anti-dandruff active had good coverage and was highly bioavailable, but did not deposit superiorly to the hair or scalp Thus, in order for a shampoo composition to provide a superior combination of anti-dandruff efficacy and conditioning compared to known shampoo compositions, it must meet certam criteria with respect to bioavailability and coverage, but it does not necessarily have to have the ability to deposit the anti-dandruff active superiorly on the hair or scalp

It is an object of the present invention to provide shampoo compositions, which provide a supenor combmation of anti-dandruff efficacy and conditionmg It is also an object of the present mvention to provide a method for cleansmg and conditionmg the hair These, and other objects, will become readily apparent from the detailed description below

SUMMARY OF THE INVENTION

The present invention relates to shampoo compositions which provide a superior combmation of anti-dandruff efficacy and conditioning These shampoo compositions comprise (A) from about 5% to about 50%, by weight, of an anionic surfactant, (B) from about 0 01% to about 10%, by weight, of a nonvolatile conditionmg agent, (C) from about 0 1% to about 4%, by weight, of an anti-dandruff particulate, (D) from about 0 02% to about 5%, by weight of the composition, of at least one catiomc polymer, (E) from 0 005% to about 1 5%, by weight, of a polyalkylene glycol, and (F) water The polyalkylene glycol corresponds to the formula H(0-CH₂-CHR)_n-OH, wherem R is hydrogen, methyl or mixtures thereof, and n is an integer having an average value from about 1,500 to about 120,000

The present mvention further relates to a method for providmg anti-dandruff efficacy and conditionmg hair compπsmg applying to the hair and scalp an amount of the above-described composition which is effective to provide such benefits

DETAILED DESCRIPTION OF THE INVENTION

The shampoo compositions of the present mvention provide a supenor combmation of anti- dandruff efficacy and conditionmg Such anti-dandruff and conditionmg shampoo compositions of the present mvention can compnse, consist of, or consist essentially of the essential elements and limitations of the mvention descnbed herem, as well as any of the additional or optional ingredients, components or limitations described herem

Particularly, these compositions compnse anionic surfactants, conditionmg agents, anti-dandruff parti ulates, catiomc polymers, polyalkylene glycols and water Upon dilution, the amonic surfactants and catiomc polymers form a coacervate, and the type and level of polyalkylene glycol employed will influence the amount of anti-dandruff particulates that are bioavailable This is important for anti-dandruff efficacy and conditioning

The components, including those which may optionally be added, of the shampoo compositions of the present invention, as well as methods for preparation, and methods for use, are descnbed m detail below I. Components

The anti-dandruff and conditioning shampoo compositions of the present invention compnse an anionic surfactant, a conditionmg agent, an anti-dandruff particulate, at least one catiomc polymer, a polyalkylene glycol, and water Each of these ingredients is descπbed in detail below.

A. Anionic surfactant

The anti-dandruff and conditioning shampoo compositions of the present invention comprise from about 5% to about 50%, by weight of the composition, preferably from about 8% to about 30%, more preferably from about 10% to about 25%, most preferably from about 12% to about 18%, of an amomc detersive surfactant component suitable for application to the hair or skin. The amomc detersive surfactant is believed to provide cleaning and lather performance to the composition Additionally, the amomc detersive surfactant forms a coacervate, upon aqueous dilution, with the catiomc polymer component (described below) of the present invention This coacervate is believed to be important m providing the efficacy and conditioning benefits described herem.

The anionic detersive surfactant component can comprise an amomc detersive surfactant, a zwittenonic or an amphoteπc detersive surfactant havmg an attached moiety that is amomc at the pH of the composition, or a combmation thereof; preferably an amomc detersive surfactant. Such surfactants should be physically and chemically compatible with the essential components descnbed herein, and should not otherwise unduly impair product stability, aesthetics or performance. Examples of amomc detersive surfactants which may be suitably employed m the shampoo compositions herem mclude, but are not limited to: sulfates, sulfonates, sarcosinates and sarcosine denvatives. 1. Sulfates Preferred amomc detersive surfactants for use m the anti-dandruff and conditionmg shampoo compositions of the present mvention are the alkyl and alkyl ether sulfates. These surfactants have the respective formulae ROS0₃M and R(C₂H4θ)_xOS0₃M, wherem R is alkyl or alkenyl from about C₈ to about Cis, x is an integer havmg a value from 1 to 10, and M is a cation selected from the group consisting of electropositive covalently bonded moieties (e.g. ammonium), alkanolammes (e.g. tπethanolamine), monovalent metals (e.g. sodium or potassium), polyvalent metal cations (e.g. magnesium and calcium) and mixtures thereof The cation M should be selected such that the amomc detersive surfactant component is water soluble. Solubility of the surfactant will depend upon the particular amomc detersive surfactants and cations chosen.

Preferably, R is from about C₈ to about g, more preferably from about do to about C,₆, most preferably from about C_\2 to about C| , in both the alkyl and alkyl ether sulfates. The alkyl ether sulfates are typically made as condensation products of ethylene oxide and monohydπc alcohols from about C₈ to about C₂₄ The alcohols can be synthetic or they can be deπved from fats, e.g., coconut oil, palm kernel oil, and tallow. Lauryl alcohol and straight chain alcohols derived from coconut oil or palm kernel oil are preferred Such alcohols are reacted with from 0 to about 10, preferably from about 2 to about 5, most preferably about 3, moles of ethylene oxide The resulting mixture of molecular species will have, for example, an average of 3 moles of ethylene oxide per mole of alcohol, and is sulfated and neutralized

Non-limiting examples of alkyl ether sulfates which may be used in the shampoo compositions of the present invention include sodium and ammonium salts of coconut alkyl tπethylene glycol ether sulfate, tallow alkyl tπethylene glycol ether sulfate, and tallow alkyl hexaoxyethylene sulfate Preferred alkyl ether sulfates are those comprising a mixture of individual compounds, wherem the compounds in the mixture have an average alkyl chain length from about Cι₀ to about C,₆ and an average degree of ethoxylation of from about 1 to about 4 moles of ethylene oxide Specific examples of preferred alkyl sulfates include, but are not limited to, ammonium lauryl sulfate, ammonium cocoyl sulfate, potassium lauryl sulfate, potassium cocoyl sulfate, sodium lauryl sulfate, sodium cocoyl sulfate, monoethanolamine lauryl sulfate, monoethanolamine cocoyl sulfate, diethanolamine lauryl sulfate, tnethanolamine lauryl sulfate, tnethylamine lauryl sulfate, and mixtures thereof Especially preferred is ammonium lauryl sulfate Specific examples of preferred alkyl ether sulfates include, but are not limited to, ammonium laureth sulfate, potassium laureth sulfate, sodium laureth sulfate, monoethanolamine laureth sulfate, diethanolamine laureth sulfate, tnethanolamine laureth sulfate, tnethylamine laureth sulfate, and mixtures thereof Especially preferred is ammonium laureth sulfate

Still another class of sulfate surfactants suitable for use m the for use m the anti-dandruff and conditionmg shampoos of the present mvention are the sulfated glycendes, an example of which mcludes, but is not limited to, launc monoglycende sodium sulfate 2. Sulfonates

Also suitable for use m the anti-dandruff and conditionmg shampoos of the present mvention are those amomc detersive surfactants known as olefin sulfonates As used herein, the term "olefin sulfonates" refers to compounds which can be produced by the sulfonation of α-olefins by means of uncomplexed sulfur tπoxide, followed by neutralization of the acid reaction mixture m conditions such that any sulfones which have been formed m the reaction are hydrolyzed to give the corresponding hydroxy-alkanesulfonates The sulfur tnoxide can be liquid or gaseous, and is usually, but not necessaπly, diluted by inert diluents, for example by liquid S0₂, chlorinated hydrocarbons, and the like, when used m the liquid form, or by air, mtrogen, gaseous S0₂, and the like, when used in the gaseous form The α-olefins from which the olefin sulfonates are deπved are mono-olefins which are from about Cι₀ to about Q₄, preferably from about C,₂ to about C₁₆ Preferably, they are straight cham olefins In addition to the true alkene sulfonates and a proportion of hydroxy-alkanesulfonates, the olefin sulfonates can contain minor amounts of other matenals, such as alkene disulfonates dependmg upon the reaction conditions, proportion of reactants, the nature of the startmg olefins and l-mpunties m the olefin stock and side reactions during the sulfonation process A non-limiting example of such an α-olefin sulfonate mixture is described in U S Pat No 3,332,880, which description is incorporated herem by reference Another class of sulfonates suitable for use in the anti-dandruff and conditionmg shampoo compositions of the present invention are those anionic detersive surfactants known as β-alkyloxy alkane sulfonates These surfactants conform to the general Formula (I).

where R¹ is a straight chain alkyl group from about C₆ to about C₂₀, R² is a lower alkyl group from about C, to about d, preferably C,, and M is a water-soluble cation, as descπbed above.

Still other sulfonates suitable for use in the anti-dandruff and conditionmg shampoo compositions of the present mvention are those amomc detersive surfactants known as alkyl aryl sulfonates Non-limiting examples of alkyl aryl sulfonates include sodium tπdecyl benzene sulfonate, sodium dodecyl benzene sulfonate, and mixtures thereof.

Other suitable sulfonates for use in the anti-dandruff and conditionmg shampoos of the present invention are the water-soluble salts of orgamc, sulfunc acid reaction products conforming to the formula [ R'-S0₃-M ] where R¹ is a straight or branched cham, saturated, aliphatic hydrocarbon radical from about C_g to about C₂4, preferably about C,₀ to about C₁₈, and M is a cation descnbed above. Non-limiting examples of such anionic detersive surfactants are the salts of an organic sulfunc acid reaction product of a hydrocarbon of the methane senes, including iso-, neo-, and -^-paraffins, and a sulfonating agent, e.g., S0₃, H S0 , obtamed accordmg to known sulfonation methods The sulfonation methods may mclude bleaching and hydrolysis. The salts are preferably from about C₈ to about C₂₄; more preferably from about C₎₂ to about C|₈. Preferred are alkali metal and ammonium sulfonated C_I0 to d₈ ^-paraffins.

Still other suitable sulfonates for use m the anti-dandruff and conditionmg shampoo compositions of the present mvention are the reaction products of fatty acids, which are esteπfied with lsethionic acid, and then neutralized with sodium hydroxide. Preferred fatty acids are those denved from coconut oil or palm kernel oil. Also suitable are the sodium or potassium salts of fatty acid amides of methyl taunde m which the fatty acids are denved from coconut oil or palm kernel oil. Other similar amomc surfactants are described in U.S. Pat. No. 2,486,921 ; U.S. Pat No. 2,486,922; and U.S Pat. No. 2,396,278, which descπptions are incorporated herem by reference.

Other sulfonates suitable for use m the anti-dandruff and conditionmg shampoo compositions of the present mvention are the succinnates, examples of which mclude, but are not limited to, disodium N-octadecylsulfosuccinate, disodium lauryl sulfosuccinate, diammomum lauryl sulfosuccinate, tetrasodium N-(l,2-dιcarboxyethyl)-N-octadecylsulfosuccιnnate, diamyl ester of sodium sulfosuccinic acid, dihexyl ester of sodium sulfosuccinic acid, dioctyl esters of sodium sulfosuccinic acid, and mixtures thereof 3. Sarcosinates and sarcosine derivatives Also suitable for use in the anti-dandruff and conditioning shampoos of the present mv ention are those amomc detersive surfactants known as sarcosinates and sarcosine derivatives Sarcosinates are the derivatives of sarcosine and N-methyl glycine, acylated with a fatty acid chloride They conform to the general Formula (II)

O

II

R— C— N— CH, ^• C— O— O— X

CH,

wherein RCO- is a fatty acid radical and wherein X is either hydrogen (acid form) or a catiomc species, such as Na^÷ or TEA⁺ (salt form) Non-limiting examples of sarcosinates and sarcosme denvatives include sodium lauryl sarcosmate, lauryl sarcosme, cocoyl sarcosine, and mixtures thereof A preferred sarcosmate is sodium lauryl sarcosmate

B. Conditioning agent

The anti-dandruff and conditionmg shampoo compositions of the present mvention compnse from about 0 01% to about 10%, by weight of the composition, preferably from about 0 1% to about 8%, more preferably from about 0 1% to about 5%, most preferably from about 0 2% to about 3 5%, of a conditionmg agent suitable for application to the hair or skin It is believed that the conditionmg agent provides improved conditionmg benefits to the hair, particularly clean hair feel and wet rmse feel

The conditionmg agent compnses a water insoluble, water dispersible, non-volatile, liquid that forms emulsified, liquid particles or are solubilized by the surfactant micelles, m the amomc detersive surfactant component (described above) Suitable conditioning agents for use in the shampoo composition are those conditionmg agents characterized generally as si cones (e g sihcone oils, catiomc si cones, sihcone gums, high refractive sihcones, and sihcone resins), organic conditionmg oils (e g hydrocarbon oils, polyolefins, and fatty esters) or combmations thereof, or those conditionmg agents which otherwise form liquid, dispersed, particles m the aqueous surfactant matnx herem Such conditionmg agents should be physically and chemically compatible with the essential components of the composition, and should not otherwise unduly impair product stability, aesthetics or performance

The concentration of the conditionmg agent m the shampoo composition should be sufficient to provide the desired conditionmg benefits, and as will be apparent to one of ordinary skill m the art Such concentration can vary with the conditionmg agent, the conditioning performance desired, the average size of the conditionmg agent particles, the type and concentration of other components, and other like factors 1. Sihcones

The conditionmg agent of the anti-dandruff and conditioning shampoo compositions of the present invention is preferably an insoluble sihcone conditionmg agent The sihcone conditionmg agent particles may comprise volatile sihcone, non-volatile sihcone, or combmations thereof Preferred are non- volatile sihcone conditioning agents If volatile sihcones are present, it will typically be incidental to their use as a solvent or carrier for commercially available forms of non- volatile sihcone materials ingredients, such as sihcone gums and resins The sihcone conditioning agent particles may comprise a sihcone fluid conditioning agent and may also comprise other ingredients, such as a sihcone resm to improve sihcone fluid deposition efficiency or enhance glossiness of the hair (especially when high refractive mdex (e g above about 1 46) sihcone conditioning agents are used (e g highly phenylated sihcones)

The concentration of the sihcone conditioning agent typically ranges from about 0 01% to about 10%, by weight of the composition, preferably from about 0 1% to about 8%, more preferably from about 0 1% to about 5%, most preferably from about 0 2% to about 3% Non- limiting examples of suitable sihcone conditioning agents, and optional suspendmg agents for the sihcone, are descnbed m U S Reissue Pat No 34,584, U S Pat No 5, 104,646, and U S Pat No 5,106,609, which descπptions are incorporated herein by reference The sihcone conditioning agents for use in the anti-dandruff and conditionmg shampoo compositions of the present invention preferably have a viscosity, as measured at 25 °C, from about 20 to about 2,000,000 centistokes ("csk"), more preferably from about 1,000 to about 1,800,000 csk, even more preferably from about 50,000 to about 1,500,000 csk, most preferably from about 100,000 to about 1,500,000 csk

The dispersed, sihcone conditionmg agent particles typically have a number average particle diameter rangmg from about 0 Olμm to about 50μm For small particle application to hair, the number average particle diameters typically range from about 0 Olμm to about 4μm, preferably from about 0 Olμm to about 2μm, more preferably from about 0 Olμm to about 0 5μm For larger particle application to hair, the number average particle diameters typically range from about 4μm to about 50μm, preferably from about 6μm to about 30μm, more preferably from about 9μm to about 20μm, most preferably from about 12μm to about 18μm Conditionmg agents having an average particle size of less than about 5μm may deposit more efficiently on the hair It is believed that small size particles of conditioning agent are contamed within the coacervate that is formed between the amomc surfactant component (described above) and the catiomc polymer component (descπbed below), upon dilution of the shampoo

Background matenal on sihcones including sections discussmg sihcone fluids, gums, and resins, as well as manufacture of sihcones, are found m Encyclopedia of Polymer Science and Engineering, vol 15, 2d ed , pp 204-308, John Wiley & Sons, Inc (1989), incorporated herem by reference i. Silicone oils

Sihcone fluids mclude sihcone oils, which are flowable sihcone materials havmg a viscosity, as measured at 25°C, less than 1,000,000 csk, preferably from about 5 csk to about 1,000,000 csk, more preferably from about 10 csk to about 100,000 csk Suitable sihcone oils for use m the anti-dandruff and conditioning shampoo compositions of the present mvention include polyalkyl siloxanes, polyaryl siloxanes, polyalkylaryl siloxanes, polyether siloxane copolymers, and mixtures thereof Other msoluble, non- volatile sihcone fluids having hair conditionmg properties may also be used

Sihcone oils mclude polyalkyl or polyaryl siloxanes which conform to the following Formula (III)

wherein R is aliphatic, preferably alkyl or alkenyl, or aryl, R can be substituted or unsubstituted, and x is an integer from 1 to about 8,000 Suitable unsubstituted R groups for use in the anti-dandruff and conditioning shampoo compositions of the present invention mclude, but are not limited to alkoxy, aryloxy, alkaryl, arylalkyl, arylalkenyl, alkamino, and ether-substituted, hydroxyl-substituted, and halogen-substituted aliphatic and aryl groups Suitable R groups also mclude catiomc amines and quaternary ammonium groups The aliphatic or aryl groups substituted on the siloxane chain may have any structure so long as the resulting sihcones remain fluid at room temperature, are hydrophobic, are neither irritating, toxic nor otherwise harmful when applied to the hair, are compatible with the other components of the shampoo compositions, are chemically stable under normal use and storage conditions, are insoluble m the shampoo compositions herein, and are capable of being deposited on and conditionmg the hair The two R groups on the silicon atom of each monomeπc sihcone umt may represent the same or different groups Preferably, the two R groups represent the same group

Prefeπed alkyl and alkenyl substituents are C, to C₅ alkyls and alkenyls, more preferably from C, to C , most preferably from Ci to C₂ The aliphatic portions of other alkyl-, alkenyl-, or alkynyl-containing groups (such as alkoxy, alkaryl, and alkamino) can be straight or branched chains, and are preferably from C, to C₅, more preferably from Ci to C₄, even more preferably from Ci to C₃, most preferably from C, to C₂ As discussed above, the R substituents can also contam ammo functionalities (e g alkamino groups), which can be primary, secondary or tertiary amines or quaternary ammonium These mclude mono-, di- and tn- alkylamino and alkoxyamino groups, wherein the aliphatic portion cham length is preferably as descπbed above The R substituents may also be substituted with other groups, such as halogens (e g chlonde, fluonde, and bromide), halogenated aliphatic or aryl groups, hydroxy (e g hydroxy substituted aliphatic groups), and mixtures thereof Suitable halogenated R groups could include, for example, tn-halogenated (preferably tπ-fluoro) alkyl groups such as -R'CF₃, wherem R¹ is a Ci - C₃ alkyl An example of such a polysiloxane includes, but is not limited to, polymethyl 3,3,3-tπfluoropropylsιloxane

Suitable R groups for use in the anti-dandruff and conditionmg shampoo compositions of the present invention include, but are not limited to methyl, ethyl, propyl, phenyl, methylphenyl and phenylmethyl Specific non-limiting examples of prefened sihcones mclude polydimethyl siloxane, polydiethylsiloxane, and polymethylphenylsiloxane Polydimethylsiloxane is especially preferred Other suitable R groups mclude methyl, methoxy, ethoxy, propoxy, and aryloxy The three R groups on the end caps of the sihcone may represent the same or different groups Non-volatile polyalkylsiloxane fluids that may be used include, for example, low molecular weight polydimethylsiloxanes These siloxanes are available, for example, from the General Electric Company in their Viscasil R and SF 96 series, and from Dow Corning m their Dow Corning 200 series Polyalkylaryl siloxane fluids that may be used, also mclude. for example, polymethylphenylsiloxanes 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 Polyether siloxane copolymers that may be used mclude, for example, a polypropylene oxide modified polydimethylsiloxane (e g , Dow Corning DC-1248) although ethylene oxide or mixtures of ethylene oxide and propylene oxide may also be used The ethylene oxide and polypropylene oxide concentrations must be sufficiently low to prevent solubihty in water and the composition descπbed herein

Alkylamino substituted sihcones suitable for use m the anti-dandruff and conditionmg shampoo compositions of the present invention mclude, but are not limited to, those which conform to the following general Formula (IV)

wherem x and y are integers This polymer is also known as "amodimethicone " ii. Cationic silicones

Catiomc sihcone fluids suitable for use in the anti-dandruff and conditionmg shampoo compositions of the present mvention mclude, but are not limited to, those which conform to the general formula (V):

(R₁)_aG₃._a-Si-(-OSiG₂)_n-(-OSiG_b(R₁)₂ b)m-0-SiG₃._a(R₁)_a

wherem G is hydrogen, phenyl, hydroxy, or C C₈ alkyl, preferably methyl; a is 0 or an mteger havmg a value from 1 to 3, preferably 0; b is 0 or 1, preferably 1 ; n is a number from 0 to 1,999, preferably from 49 to 149; m is an mteger from 1 to 2,000, preferably from 1 to 10, the sum of n and m is a number from 1 to 2,000, preferably from 50 to 150; Rj is a monovalent radical conforming to the general formula CqH_2qL, wherein q is an mteger havmg a value from 2 to 8 and L is selected from the following groups

-N(R₂)CH₂-CH₂-N(R₂)₂ 10

-N(R₂)₂

-N(R₂)₃A^"

-N(R₂)CH₂-CH -NR₂H₂A^"

wherem R₂ is hydrogen, phenyl, benzyl, or a saturated hydrocarbon radical, preferably an alkyl radical from about C, to about C₂₀, and A is a halide ion.

An especially preferred catiomc sihcone corresponding to formula (V) is the polymer known as "tπmethylsilylamodimethicone", which is shown below in formula (VI):

m

Other sihcone catiomc polymers which may be used in the anti-dandruff and conditionmg shampoo compositions of the present invention are represented by the general formula (VII):

wherem R³ is a monovalent hydrocarbon radical from d to C,₈, preferably an alkyl or alkenyl radical, such as methyl; R, is a hydrocarbon radical, preferably a C, to C_[8 alkylene radical or a C₁₀ to C₁₈ alkyleneoxy radical, more preferably a C, to Cg alkyleneoxy radical; Q is a halide ion, preferably chloπde; r is an average statistical value from 2 to 20, preferably from 2 to 8; s is an average statistical value from 20 to 200, preferably from 20 to 50. A preferred polymer of this class is known as UCARE SILICONE ALE 56™, available from Umon Carbide. 11

iii. Silicone gums

Other sihcone fluids suitable for use in the anti-dandruff and conditioning shampoo compositions of the present invention are the insoluble sihcone gums These gums are polyorganosiloxane mateπals having a viscosity, as measured at 25°C, of greater than or equal to 1,000,000 csk. Sihcone gums are described in U S. Pat. No 4,152,416, Noll and Walter, Chemistry and Technology of Sihcones, New York Academic Press (1968); and in General Electric Sihcone Rubber Product Data Sheets SE 30, SE 33, SE 54 and SE 76, all of which are incorporated herem by reference. The sihcone gums will typically have a weight average molecular weight in excess of about 200,000, preferably from about 200,000 to about 1,000,000 Specific non-limiting examples of sihcone gums for use in the anti-dandruff and conditiomng shampoo compositions of the present invention include polydimethylsiloxane, (polydimethylsiloxane) (methylvinyl- siloxane) copolymer, poly(dιmethylsιloxane) (diphenyl sιloxane)(methylvιnylsιloxane) copolymer and mixtures thereof iv. High refractive index silicones

Other non- volatile, insoluble sihcone fluid conditionmg agents that are suitable for use m the anti- dandruff and conditiomng shampoo compositions of the present mvention are those known as "high refractive index sihcones," havmg a refractive mdex of at least about 1.46, preferably at least about 1.48, more preferably at least about 1 52, most preferably at least about 1.55 The refractive mdex of the polysiloxane fluid will generally be less than about 1.70, typically less than about 1.60. In this context, polysiloxane "fluid" includes oils as well as gums. The high refractive index polysiloxane fluid mcludes those represented by general Formula (III) above, as well as cyclic polysiloxanes such as those represented by Formula (VIII) below:

wherem R is as defined above, and n is a number from about 3 to about 7, preferably from about 3 to about 5.

The high refractive index polysiloxane fluids contain an amount of aryl-containing R substituents sufficient to mcrease the refractive mdex to the desired level, which is descnbed above. Additionally, R and n must be selected so that the material is non-volatile Aryl-containing substituents mclude those which contam ahcychc and heterocychc five and six member aryl rings and those which contain fused five or six member rings The aryl rings themselves can be substituted or unsubstituted. Substituents mclude aliphatic substituents, and may also include alkoxy substituents, acyl substituents, ketones, halogens (e.g., Cl and Br), amines, and the like. Examples of aryl-contaimng groups mclude, but are not limited to, substituted and unsubstituted arenes, such as phenyl, and phenyl derivatives, such as phenyls with C_rC- alkyl or alkenyl substituents Specific non-limiting examples include allylphen l, methyl phenyl and ethyl phenyl, vinyl phenyls (e g styrenyl), and phenyl alkynes (e g phenyl C₂-C₄ alkynes) Heterocychc aryl groups include, but are not limited to, substituents derived from furan, lmidazole, pyrrole, pyπdine, and the like Examples of fused aryl ring substituents include, but are not limited to, napthalene, coumaπn, and purine

Generally, the high refractive index polysiloxane fluids will have a degree of aryl-containing substituents of at least about 15%, preferably at least about 20%, more preferably at least about 25%, even more preferably at least about 35%, most preferably at least about 50% Typically, the degree of aryl substitution will be less than about 90%, more generally less than about 85%, preferably from about 55% to about 80%

The high refractive mdex polysiloxane fluids are also characteπzed by relatively high surface tensions as a result of their aryl substitution Generally, the polysiloxane fluids will have a surface tension of at least about 24 dynes/cm², typically at least about 27 dynes/cm^" Surface tension, for purposes hereof, is measured by a de Nouy rmg tensiometer accordmg to Dow Corning Corporate Test Method CTM 0461 (23 November, 1971) Changes m surface tension can be measured accordmg to the above test method or accordmg to ASTM Method D 1331

Preferred high refractive index polysiloxane fluids have a combmation of phenyl or phenyl derivative substituents (most preferably phenyl), with alkyl substituents, preferably C_rC₄ alkyl (most preferably methyl), hydroxy, or C C₄ alkylamino (especially -R'NHR²NH2 wherem each R¹ and R² mdependently is a C C₃ alkyl, alkenyl, and/or alkoxy) High refractive mdex polysiloxanes are available from Dow Coming, Huls Amenca, and General Electnc

When high refractive mdex sihcones are used in the anti-dandruff and conditiomng shampoo compositions of the present mvention, they are preferably used m solution with a spreadmg agent, such as a sihcone resin or a surfactant, to reduce the surface tension by a sufficient amount to enhance spreading and thereby enhance the glossmess (subsequent to drymg) of hair treated with the compositions Generally, an amount of the spreadmg agent is used that is sufficient to reduce the surface tension of the high refractive mdex polysiloxane fluid by at least about 5%, preferably at least about 10%, more preferably at least about 15%o, even more preferably at least about 20%, most preferably at least about 25% Reductions m surface tension of the polysiloxane fluid/spreading agent mixture may improve shine of the hair Also, the spreadmg agent will preferably reduce the surface tension by at least about 2 dynes/cm', preferably at least about 3 dynes/cm², even more preferably at least about 4 dynes/cm², most preferably at least about 5 dynes/cm² 13

The surface tension of the mixture of the polysiloxane fluid and the spreading agent, at the proportions present in the final product, is preferably less than or equal to about 30 dynes/cm², more preferably less than or equal to about 28 dynes/cm^", most preferably less than or equal to about 25 dynes/cm^: Typically, the surface tension will be m the range from about 15 dynes/cm² to about 30 dynes/cm², more typically from about 18 dynes/cm^" to about 28 dynes/cirT, and most generally from about 20 dynes/cm² to about 25 dynes/cm²

The weight ratio of the highly arylated polysiloxane fluid to the spreadmg agent will, m general, be from about 1000 1 to about 1 1, preferably from about 100 1 to about 2 1, more preferably from about 50 1 to about 2 1, most preferably from about 25 1 to about 2 1 When fluoπnated surfactants are used, particularly high polysiloxane fluid to spreadmg agent ratios may be effective due to the efficiency of these surfactants Thus, it is contemplated that ratios significantly above 1000 1 may be used

Sihcone fluids suitable for use in the anti-dandruff and conditionmg shampoo compositions of the present mvention are disclosed m U S Pat No 2,826,551, U S Pat No 3,964,500, U S Pat No 4,364,837, British Pat No 849,433, and Silicon Compounds, Petrarch Systems, Inc (1984), all of which are incorporated herem by reference v. Silicone resins

Sihcone resms may be included m the sihcone conditiomng agent of the anti-dandruff and conditionmg shampoo compositions of the present mvention These resms are highly cross-linked polymenc siloxane systems The cross-linking is introduced through the incorporation of tπfunctional and tetrafunctional silanes with mono-functional or difunctional, or both, silanes durmg manufacture of the sihcone resm As is apparent to one of ordinary skill m the art, the degree of cross-linkmg that is required m order to result in a sihcone resm will vary accordmg to the specific silane units incorporated mto the sihcone resm Generally, sihcone matenals which have a sufficient level of tπfunctional and tetrafunctional siloxane monomer units (and hence, a sufficient level of cross-linking) such that they dry down to a rigid, or hard, film are considered to be sihcone resins The ratio of oxygen atoms to silicon atoms is indicative of the level of cross-linking in a particular sihcone matenal Sihcone resins suitable for use in the anti-dandruff and conditionmg shampoo compositions of the present mvention generally have at least about 1 1 oxygen atoms per silicon atom Preferably, the ratio of oxygen to silicon atoms is at least about 1 2 1 0 Silanes used m the manufacture of sihcone resms mclude, but are not limited to monomethyl-, dimethyl-, tπmethyl-, monophenyl-, diphenyl-, methylphenyl-, monovmyl-, and methylvmyl-chlorosilanes, and tetra- chlorosilane, with the methyl-substituted silanes bemg most commonly utilized Preferred resms are available from General Electnc as GE SS4230 and GE SS4267 Commercially available si cone resms are generally supplied in a dissolved form m a low viscosity volatile or non-volatile sihcone fluid The sihcone resms for use herem should be supplied and incorporated mto the present compositions m such dissolved form, as will be readily apparent to one of ordinary skill in the art

Sihcone mateπals and sihcone resms in particular, can convemently be identified accordmg to a shorthand nomenclature system known to those of ordinary skill m the art as "MDTQ" nomenclature Under 14

this system, the sihcone is descπbed according to presence of various siloxane monomer units which make up the sihcone. Briefly, the symbol M denotes the monofunctional unit (CH₃)₃SιO₀ s; D denotes the difunctional unit (CH₃)₂SιO; T denotes the tπfunctional unit (CH₃)SιOι ₅, and Q denotes the quadra- or tetra-fϊinctional unit Sι0₂. 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, but are not limited to, groups such as vinyl, phenyls, amines, hydroxyls, and the like The molar ratios of the various units, either in terms of subscripts to the symbols indicating the total number of each type of umt m the sihcone (or an average thereof) or as specifically indicated ratios combination with molecular weight complete the descnption of the sihcone material under the MDTQ system. Higher relative molar amounts of T, Q, T' and/or Q' to D, D', M and/or M' in a sihcone resm indicates higher levels of cross- linking. As discussed above, however, the overall level of cross-linking can also be indicated by the oxygen to silicon ratio

Prefeπed sihcone resms for use m the anti-dandruff and conditionmg shampoo compositions of the present invention include, but are not limited to MQ, MT, MTQ, MDT and MDTQ resins. Methyl is a preferred sihcone substituent Especially prefeπed sihcone resins are MQ resms, wherem the M Q ratio is from about 0.5: 1.0 to about 1.5: 1 0 and the average molecular weight of the sihcone resm is from about 1000 to about 10,000.

The weight ratio of the non-volatile sihcone fluid, havmg refractive mdex below 1 46, to the sihcone resm component, when used, is preferably from about 4: 1 to about 400: 1, more preferably from about 9.1 to about 200 1, most preferably from about 19: 1 to about 100 1, particularly when the sihcone fluid component is a polydimethylsiloxane fluid or a mixture of polydimethylsiloxane fluid and polydimethylsiloxane gum as descπbed above Insofar as the sihcone resm forms a part of the same phase in the compositions hereof as the sihcone fluid, i.e. the conditionmg active, the sum of the fluid and resin should be mcluded m determining the level of sihcone conditionmg agent m the composition. 2. Organic conditioning oils

The conditionmg component of the anti-dandruff and conditiomng shampoo compositions of the present mvention may also compnse from about 0.05% to about 3%, by weight of the composition, preferably from about 0.08% to about 1.5%, more preferably from about 0.1% to about 1%, of at least one organic conditiomng oil as the conditionmg agent, either alone or m combination with other conditionmg agents, such as the sihcones (described above).

It is believed that these orgamc conditiomng oils provide the shampoo composition with improved conditionmg performance when used in combmation with the essential components of the composition, and m particular when used m combmation with catiomc polymers (descπbed below). The conditiomng oils may add shine and luster to the hair. Additionally, they may enhance dry combing and dry hair feel Most or all of these organic conditionmg oils are believed to be solubilized m the surfactant micelles of the shampoo composition It is also believed that this solubilization into the surfactant micelles contπbutes to the improved hair conditionmg performance of the shampoo compositions herein The organic conditioning oils suitable for use as the conditioning agent herein are preferably low viscosity, water insoluble, liquids selected from the hydrocarbon oils, polyolefins, fatty esters, and mixtures thereof The viscosity, as measured at 40°C, of such organic conditioning oils is preferably from about 1 centipoise to about 200 centipoise, more preferably from about 1 centipoise to about 100 centipoise, most preferably from about 2 centipoise to about 50 centipoise. i. Hydrocarbon oils

Suitable orgamc conditionmg oils for use as conditioning agents in the anti-dandruff and conditioning shampoo compositions of the present mvention mclude, but are not limited to, hydrocarbon oils having at least about 10 carbon atoms, such as cyclic hydrocarbons, straight cham aliphatic hydrocarbons (saturated or unsaturated), and branched cham aliphatic hydrocarbons (saturated or unsaturated), including polymers and mixtures thereof. Straight cham hydrocarbon oils preferably are from about C,₂ to about C,₉. Branched chain hydrocarbon oils, mcludmg hydrocarbon polymers, typically will contain more than 19 carbon atoms.

Specific non-limiting examples of these hydrocarbon oils mclude paraffin oil, mineral oil, saturated and unsaturated dodecane, saturated and unsaturated tndecane, saturated and unsaturated tetradecane, saturated and unsaturated pentadecane, saturated and unsaturated hexadecane, polybutene, polydecene, and mixtures thereof Branched-chain isomers of these compounds, as well as of higher chain length hydrocarbons, can also be used, examples of which include highly branched, saturated or unsaturated, alkanes such as the permethyl-substituted isomers, e.g., the permethyl-substituted isomers of hexadecane and eicosane, such as 2, 2, 4, 4, 6, 6, 8, 8-dimethyl-10-methylundecane and 2, 2, 4, 4, 6, 6-dιmethyl-8- methylnonane, available from Permethyl Corporation Hydrocarbon polymers such as polybutene and polydecene. A preferred hydrocarbon polymer is polybutene, such as the copolymer of isobutylene and butene. A commercially available mateπal of this type is L-14 polybutene from Amoco Chemical Corporation ii. Polyolefins

Orgamc conditiomng oils for use m the anti-dandruff and conditiomng shampoo compositions of the present mvention can also mclude liquid polyolefins, more preferably liquid poly-α-olefins, most preferably hydrogenated liquid poly-α-olefins. Polyolefins for use herem are prepared by polymerization of C to about Ci₄ olefemc monomers, preferably from about C₆ to about Cι₂ Non-limiting examples of olefemc monomers for use m preparing the polyolefin liquids herein mclude ethylene, propylene, 1 -butene, 1-pentene, 1-hexene, 1-octene, 1-decene, 1-dodecene, 1-tetradecene, branched cham isomers such as 4-methyl- 1-pentene, and mixtures thereof. Also suitable for preparmg the polyolefin liquids are olefin-containing refinery feedstocks or effluents. Preferred hydrogenated α-olefin monomers mclude, but are not limited to- 1-hexene to 1-hexadecenes, 1-octene to 1-tetradecene, and mixtures thereof. iii. Fatty Esters 16

Other suitable organic conditioning oils for use as the conditioning agent in the anti-dandruff and conditioning shampoo compositions of the present invention include, but are not limited to, fatty esters havmg at least 10 carbon atoms These fatty esters include esters with hydrocarbyl chams derived from fatty acids or alcohols (e g mono-esters, polyhydπc alcohol esters, and di- and tn-carboxyhc acid esters) The hydrocarbyl radicals of the fatty esters hereof may include or have covalently bonded thereto other compatible functionalities, such as amides and alkoxy moieties (e g , ethoxy or ether linkages, etc )

Suitable for use in the anti-dandruff and conditiomng shampoo compositions of the present mvention are alkyl and alkenyl esters of fatty acids having from about C₍₀ to about C₂₂ aliphatic chains, and alkyl and alkenyl fatty alcohol carboxyhc acid esters havmg a C₁₀ to about C₂ alkyl and/or alkenyl alcohol- derived aliphatic chain, and mixtures thereof Specific examples of prefeπed fatty esters mclude, but are not limited to isopropyl isostearate, hexyl laurate, isohexyl laurate, isohexyl palmitate, isopropyl palmitate, decyl oleate, isodecyl oleate, hexadecyl stearate, decyl stearate, isopropyl isostearate, dihexyldecyl adipate, lauryl lactate, myπstyl lactate, cetyl lactate, oleyl stearate, oleyl oleate, oleyl myπstate, lauryl acetate, cetyl propionate, and oleyl adipate Other fatty esters suitable for use m the anti-dandruff and conditionmg shampoo compositions of the present mvention are mono-carboxyhc acid esters of the general formula R'COOR, wherem R' and R are alkyl or alkenyl radicals, and the sum of carbon atoms m R' and R is at least 10, preferably at least 20 The mono-carboxyhc acid ester need not necessanly contam at least one cham with at least 10 carbon atoms, rather the total number of aliphatic chain carbon atoms must be least 10 Specific non-limiting examples of mono-carboxyhc acid esters include isopropyl myπstate, glycol stearate, and isopropyl laurate

Still other fatty esters suitable for use m the anti-dandruff and conditiomng shampoo compositions of the present invention are di- and tn-alkyl and alkenyl esters of carboxyhc acids, such as esters of C₄ to Cg dicarboxy c acids (e g Ci to C₂₂ esters, preferably C, to C₆, of succinic acid, glutanc acid, adipic acid, hexanoic acid, heptanoic acid, and octanoic acid) Specific non-limiting examples of di- and tn- alkyl and alkenyl esters of carboxyhc acids mclude isocetyl stearyol stearate, diisopropyl adipate, and tnstearyl citrate

Other fatty esters suitable for use m the anti-dandruff and conditiomng shampoo compositions of the present mvention are those known as polyhydπc alcohol esters Such polyhydnc alcohol esters mclude alkylene glycol esters, such as ethylene glycol mono and di-fatty acid esters, diethylene glycol mono- and di- fatty acid esters, polyethylene glycol mono- and di-fatty acid esters, propylene glycol mono- and di-fatty acid esters, polypropylene glycol monooleate, polypropylene glycol 2000 monostearate, ethoxylated propylene glycol monostearate, glyceryl mono- and di-fatty acid esters, polyglycerol poly-fatty acid esters, ethoxylated glyceryl monostearate, 1,3-butylene glycol monostearate, 1,3-butylene glycol distearate, polyoxyethylene polyol fatty acid ester, sorbitan fatty acid esters, and polyoxyethylene sorbitan fatty acid esters

Still other fatty esters suitable for use in the anti-dandruff and conditiomng shampoo compositions of the present invention are glycendes, including, but not limited to, mono-, di-, and tπ-glycendes, 17

preferably di- and tπ-glyceπdes, most preferably tπglyceπdes For use in the shampoo compositions descπbed herein, the glycendes are preferably the mono-, di-, and tπ-esters of glycerol and long chain carboxyhc acids, such as C,₀ to C₂₂ carboxyhc acids. A variety of these types of materials can be obtained from vegetable and animal fats and oils, such as castor oil, safflower oil, cottonseed oil, corn oil, olive oil, cod liver oil, almond oil, avocado oil, palm oil, sesame oil, lanolin and soybean oil Synthetic oils include, but are not limited to, tπolein and tπsteaπn glyceryl dilaurate

Other fatty esters suitable for use in the anti-dandruff and conditioning shampoo compositions of the present invention are water msoluble synthetic fatty esters. Some prefeπed synthetic esters conform to the general Formula (IX):

wherein R¹ is a C₇ to C₉ alkyl, alkenyl, hydroxyalkyl or hydroxyalkenyl group, preferably a saturated alkyl group, more preferably a saturated, linear, alkyl group; n is a positive mteger havmg a value from 2 to 4, preferably 3; and Y is an alkyl, alkenyl, hydroxy or carboxy substituted alkyl or alkenyl, havmg from about 2 to about 20 carbon atoms, preferably from about 3 to about 14 carbon atoms. Other prefeπed synthetic esters conform to the general Formula (X).

wherem R² is a C₈ to C₁₀ alkyl, alkenyl, hydroxyalkyl or hydroxyalkenyl group; preferably a saturated alkyl group, more preferably a saturated, lmear, alkyl group; n and Y are as defined above m Formula (X).

It is believed that the prefeπed synthetic esters provide improved wet hair feel when used m combination with the essential components of the shampoo compositions of the present mvention, particularly when used m combmation with the catiomc polymer component (descπbed below). These synthetic esters improve wet hair feel by reducmg the slimy or excessively conditioned feel of wet hair that has been conditioned by a catiomc polymer.

Specific non-limiting examples of suitable synthetic fatty esters for use m the anti-dandruff and conditiomng shampoo compositions of the present invention mclude: P-43 (Cg-C,₀ tπester of trunethylolpropane), MCP-684 (tetraester of 3,3 diethanol-1,5 pentadiol), MCP 121 (C₈-C₁₀ diester of adipic acid), all of which are available from Mobil Chemical Company.

3. Other conditioning agents 18

Also suitable for use in the compositions herein are the conditioning agents descπbed by the Procter & Gamble Company in U S Pat Nos 5.674,478, and 5,750,122, both of which are incorporated herein in their entirety by reference. Also suitable for use herein are those conditionmg agents descπbed in U S. Pat Nos 4,529,586 (Clairol), 4,507,280 (Clairol), 4,663.158 (Clairol), 4, 197,865 (L'Oreal), 4,217, 914 (L'Oreal), 4,381,919 (L'Oreal), and 4,422, 853 (L'Oreal), all of which descriptions are incorporated herein by reference.

Some other prefeπed sihcone conditiomng agents for use in the compositions of the present mvention include: Abil^® S 201 (dimethicone/sodium PG-propyldimethicone thiosulfate copolymer), available from Goldschmidt; DC Q2-8220 (tπmethylsilyl amodimethicone) available from Dow Corning; DC 949 (amodimethicone, cetnmomum chloride, and Trιdeceth-12), available from Dow Corning; DC 749 (cyclomethicone and tπmethylsiloxysihcate), available from Dow Coming, DC2502 (cetyl dimethicone), available from Dow Corning, BC97/004 and BC 99/088 (ammo functionahzed sihcone microemulsions), available from Basildon Chemicals; GE SME253 and SM21 15-D2_and SM2658 and SF1708 (ammo functionalized sihcone microemulsions), available from General Electric; sihconized meadowfoam seed oil, available from Croda; and those sihcone conditiomng agents descnbed by GAF Corp. in U.S. Pat. No 4,834,767 (quatemized ammo lactam), by Biosil Technologies m U.S. Pat. No. 5,854,319 (reactive sihcone emulsions containing ammo acids), and by Dow Corning in U.S. Pat. No. 4,898,585 (polysiloxanes), all of which descriptions are incorporated herem by reference.

C. Anti-dandruff particulate

The anti-dandruff and conditio ng shampoo compositions of the present mvention compnse from about 0.1%) to about 4%, by weight of the composition, preferably from about 0 1% to about 3%, most preferably from about 0.3% to about 2%, of an anti-dandruff particulate suitable for application to the hair or skin. The anti-dandruff particulate provides the shampoo compositions with anti-microbial activity. Suitable, non-limiting examples of anti-dandruff particulates mclude- pyndinethione salts, selemum sulfide, particulate sulfur, and mixtures thereof Prefeπed are pyndinethione salts. Such anti-dandruff particulate should be physically and chemically compatible with the essential components of the composition, and should not otherwise unduly impair product stability, aesthetics or performance. 1. Pyridinethione salts Pyndinethione anti-dandruff particulates, especially l-hydroxy-2-pyndmethιone salts, are highly prefeπed particulate anti-dandruff agents for use m the anti-dandruff and conditionmg shampoo compositions of the present mvention. The concentration of pyndinethione anti-dandruff particulate typically ranges from about 0.1 % to about 4%, by weight of the composition, preferably from about 0.1 % to about 3%, most preferably from about 0.3% to about 2%. Prefeπed pyndinethione salts mclude those formed from heavy metals such as zmc, tm, cadmium, magnesium, aluminum and zircomum, preferably zmc, more preferably the zmc salt of l-hydroxy-2 -pyndinethione (known as "zmc pyπdmethione" or "ZPT"), most preferably l-hydroxy-2-pyndιnethιone salts platelet particle form, wherem the particles 19

have an average size of up to about 20μ, preferably up to about 5μ, most preferably up to about 2.5μ Salts formed from other cations, such as sodium, may also be suitable Pyndinethione anti-dandruff agents are described, for example, in U S. Pat. No. 2,809,971, U S. Pat. No. 3.236,733, U S Pat. No 3,753,196; U S Pat. No 3,761,418, U S. Pat No 4,345,080, U S Pat. No. 4,323,683, U S Pat No 4,379,753; and U.S Pat. No 4,470,982, all of which are incorporated herein by reference. It is contemplated that when ZPT is used as the anti-dandruff particulate m the shampoo compositions herein, that the growth or re-growth of hair may be stimulated or regulated, or both, or that hair loss may be reduced or inhibited, or that hair may appear thicker or fuller.

2. Selenium sulfide Selemum sulfide is a particulate anti-dandruff agent suitable for use in the anti-dandruff and conditioning shampoo compositions of the present invention, effective concentrations of which range from about 0 1% to about 4%, by weight of the composition, preferably from about 0 3% to about 2.5%, more preferably from about 0.5% to about 1.5%. Selemum sulfide is generally regarded as a compound havmg one mole of selenium and two moles of sulfur, although it may also be a cyclic structure that conforms to the general formula Se_xS_y, wherein x + y = 8. Average particle diameters for the selemum sulfide are typically less than 15μm, as measured by forward laser light scattering device (e.g. Malvern 3600 instrument), preferably less than 10 μm. Selemum sulfide compounds are descnbed, for example, m U.S. Pat. No 2,694,668; U.S. Pat No. 3,152,046, U.S. Pat No. 4,089,945, and U S. Pat. No. 4,885, 107, all of which descriptions are incorporated herem by reference. 3. Sulfur

Sulfur may also be used as the particulate anti-dandruff agent m the anti-dandruff and conditionmg shampoo compositions of the present invention. Effective concentrations of the particulate sulfur are typically from about 1% to about 4%, by weight of the composition, preferably from about 2% to about 4%

D. Cationic polymer

The anti-dandruff and conditionmg shampoo compositions of the present mvention compnse from about 0.02% to about 5%, by weight of the composition, preferably from about 0.05% to about 3%, more preferably from about 0.1% to about 2%, most preferably from about 0.5% to about 1%, of at least one orgamc, catiomc deposition and conditionmg polymer suitable for application to the hair or skin. The catiomc polymers are believed to provide mcreased anti-dandruff efficacy and mcreased conditiomng to the shampoo compositions described herem. Such catiomc polymers should be physically and chemically compatible with the essential components descπbed herein, and should not otherwise unduly impair product stability, aesthetics or performance.

1. Characteristics of the cationic polymers The cationic polymers useful m the present mvention must be selected and must be present at a level such that the cationic polymers are soluble m the shampoo composition, and which are preferably soluble m 20

a complex coacervate phase in the shampoo composition, upon dilution Such coacervate is described in detail below Also, physical properties of the cationic polymers and suitable counteπons are detailed

i. Coacervate formed from cationic polymer A coacervate is formed, upon dilution of the shampoo composition, between the catiomc polymer and the amomc detersive surfactant component (described above) of the present invention It is believed that the catiomc moiety of the polymer binds with the amomc moiety of the surfactant to form an insoluble complex that precipitates, upon dilution (the coacervate) Complex coacervates of the cationic polymer can also be formed with other optional amomc components of the shampoo composition (descπbed below) Coacervate formation is dependent upon a vanety of criteπa, such as molecular weight, component concentration, and ratio of interactmg ionic components, ionic strength (including modification of ionic strength, for example, by addition of salts), charge density of the catiomc and amomc components, pH, and temperature Coacervate systems and the effect of these parameters have been described, for example, in J Caelles, et al , "Amomc and Catiomc Compounds in Mixed Systems", Cosmetics & Toiletries, vol 106, (April 1991), pp 49-54, C J van Oss, "Coacervation, Complex-Coacervation and Flocculation", J Dispersion Science and Tech , vol 9 (5,6), (1988-89), pp 561-73, and m D J Burgess, "Practical Analysis of Complex Coacervate Systems", J of Colloid and Interface Science, vol 140, no 1, (November 1990), pp 227-38, all of which descnptions are incorporated herem by reference The shampoo compositions descπbed herein, typically have a ratio of amomc detersive surfactant component to catiomc polymer component from about 25 0 02 to about 1 5, preferably from about 20 0 1 to about 12 1

Coacervates are believed to provide conditionmg benefits, especially conditionmg benefits duπng product use when the hair is wet, by helpmg to deposit conditioning agents onto the hair and scalp Coacervates are also known m the art to aid deposition of other types of particulates This is thought to occur by concentrating particulates within coacervate boundanes upon dilution It has also been found that the charactenstics of polymer m such compositions can affect the bioavailabihty/coverage of anti-dandruff particulates, such characteπstics include cationic guar polymer molecular weight and charge density Guars with lower molecular weight are prefeπed, guars with lower charge density are prefeπed Guars with lower molecular weight and lower charge density are highly prefeπed It is believed that these select guars impart modified physical properties (l e rheology) to the coacervates formed

Techniques for analysis of formation of complex coacervates are known in the art For example, microscopic analyses of the shampoo compositions, at any chosen stage of dilution, can be utilized to identify whether a coacervate phase has formed Such coacervate phase will be identifiable as an additional emulsified phase m the composition The use of dyes can aid in distinguishing the coacervate phase from other insoluble phases dispersed m the shampoo composition ii. Physical properties of the cationic polymer 21

The average molecular weight of canonic conditioning polymers suitable for use herein is typically from about 5,000 to about 10,000 000, preferably from about 100,000 to about 2,000,000, more preferably from about 200,000 to about 1,500,000, more preferably from about 250,000 to about 850,000, more preferably from about 350.000 to about 850,000, most preferably from about 350,000 to about 500,000 The polymers have a catiomc charge density typically from about 0 2 meq/g to about 7 meq/g, as measured at the pH of intended use of the shampoo composition, preferably from about 0 4meq/gm to about 5 meq/g, more preferably from about 0 6meq/g to about 2 meq g, more preferably from about 0 5 meq/g to about 0 1 meq/g, more preferably from about 0 5 meq/g to about 0 9 meq/g The pH of intended use of the shampoo composition typically ranges from about pH 3 to about pH 9, preferably from about pH 4 to about pH 7

iii. Counterions used in forming cationic polvmer

Any amomc counterions may be use m association with the catiomc polymers so long as the cationic polymers remain soluble m water, in the shampoo composition, or in a coacervate phase of the shampoo composition, and so long as the counterions are physically and chemically compatible with the essential components of the shampoo composition or do not otherwise unduly impair product performance, stability or aesthetics Non-limiting examples of such counteπons mclude hahdes (e g , chlonde, fluonde, bromide, iodide), sulfate, methylsulfate, and mixtures thereof 2. Types cationic polymers Examples of catiomc polymers which may be suitably employed in the shampoo compositions herein include, but are not limited to catiomc polysacchandes (e g catiomc cellulose deπvatives and catiomc guars), copolymers of vinyl monomers, vmyl pyrro done copolymers, catiomc modified protems, and certam polymeric quaternary salts Such catiomc polymers are descπbed m detail below i. Cationic polvsaccharides Prefeπed catiomc polymers for use m the anti-dandruff and conditiomng shampoo compositions of the present mvention are those known as catiomc polysacchandes Catiomc polysacchandes are those polymers based on C₅ to C₆ sugars and deπvatives which have been made catiomc by engrafting of catiomc moieties on the polysacchande backbone, and mclude homopolymers, copolymers, terpolymers, and so forth, of quaternary ammonium or catiomc amine-substituted monomer units, optionally in combmation with non- catiomc monomers The polysacchandes may be composed of one type of sugar or of more than one type The catiomc amines can be primary, secondary, or tertiary amines (preferably secondary or tertiary), dependmg upon the particular species and the selected pH of the shampoo composition The monomers may be in straight chain or branched cham geometric aπangements All of the monomer units may have cationic mtrogen-contaimng moieties attached thereto, preferably some of the monomer units do not have such moieties attached Non-limiting examples of catiomc polysacchandes are descnbed m the CTFA Cosmetic Ingredient Dictionary, 3d ed , edited by Estnn, Crosley, and Haynes, (The Cosmetic, Toiletry, and Fragrance Association, Inc , Washington, D C ( 1982), which description is incorporated herem by reference W

22

Cationic polysacchaπde polymers include the following cationic celluloses and hydroxyethylcelluloses cationic starches and hydroxyalkyl starches, catiomc polymers based on the galactomannan copolymer known as guar gum obtained from the endosperm of the guar bean, catiomc polymers based on arabinose vegetable gums, cationic polymers derived from xylose polymers (such as those found in wood, straw, cottonseed hulls, and corn cobs), catiomc polymers derived from fricose polymers (such as those found as a component of cell walls in seaweed), catiomc polymers derived from fructose polymers (such as Inulin, which is found in certam plants), catiomc polymers based on acid-containing sugars (such as galacturonic acid and glucouromc acid), cationic polymers based on amine sugars (such as galactosarmne and glucosamme), cationic polymers based on 5 and 6 member ring polyalcohols, catiomc polymers based on galactose monomers (such as those found in plant gums and mucilates), and cationic polymers based on mannose monomers (such as those found m plants, yeasts, and red algae) Prefeπed are cationic celluloses and hydroxyethylcelluloses, catiomc starches and hydroxyalkyl starches, catiomc polymers based on guar gum, and mixtures thereof a. Cationic cellulose derivatives Suitable polysacchaπde cationic polymers for use in the anti-dandruff and conditionmg shampoo compositions of the present invention are the catiomc cellulose deπvatives and catiomc starch denvatives Such catiomc polymers include those which conform to the general Formula (XI)

wherein A is an anhydroglucose residual group (e g a starch or cellulose anhydroglucose residual), R is an alkylene oxyalkylene, polyoxyalkylene, or hydroxyalkylene group, or combmation thereof, R¹, R², and R³ are mdependently 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 m R¹, R², and R³) preferably being about 20 or less, and X is an amomc counteπon as described above

Prefeπed catiomc cellulose polymers mclude, but are not limited to, those polymers available from Amerchol Corporation, in their Polymer JR and LR seπes of polymers, as salts of hydroxyethyl cellulose reacted with tπmethyl ammonium substituted epoxide, known in the industry (CTFA) as Polyquatermum 10 (e g JR 30M®, available from Amerchol Corporation) Prefeπed Polyquatermum 10 polymers for use herein, typically have a charge density from about 0 3 meq/g to about 3 meq/g and a molecular weight from about 200,000 to about 1,500,00 Another non-limiting of a prefeπed type of catiomc cellulose mcludes the polymeric quaternary ammonium salt of hydroxyethyl cellulose reacted with lauryl dimethyl ammonium- 23

substituted epoxide, known in the industry (CTFA) as Polyquatermum 24, (e g Polymer LM 200&, available from Amerchol Corporation)

Also suitable for use herein are those quaternary nitrogen-containing cellulose copolymers of hydroxyethylcellulose reacted with diallyldimethyl ammomum chloride, known in the industry (CTFA) as Polyquatermum 4 (e g Celquat® H- 100, available from National Starch Corporation) Quaternary nitrogen- containing cellulose ethers suitable for use herein are described in U S Pat No 3,962,418, and still other copolymers of etheπfied cellulose and starch suitable for use herein are described in U S Pat No 3,958,581, both of which descriptions are incorporated herein by reference b. Cationic guars Other suitable polysacchaπde cationic polymers for use m the anti-dandruff and conditionmg shampoo compositions of the present invention are catiomc guar polymers Guars are catiomcally substituted galactomannan (guar) gum derivatives The molecular weight of such derivatives ranges typically from about 50,000 to about 2,500,000, preferably from about 50,000 to about 1,000,000, more preferably from about 50,000 to about 700,000 Guar gum for use m preparing these guar gum derivatives is typically obtamed as a naturally occurring material from the seeds of the guar plant The guar molecule itself is a straight chain mannan branched at regular intervals with single membered galactose units on alternative mannose units The mannose units are linked to each other by means of β (1-4) glycosidic linkages The galactose branching arises by way of an (1-6) linkage Catiomc denvatives of the guar gums are obtained by reaction between the hydroxyl groups of the polygalactomannan and reactive quatemary ammomum compounds The degree of substitution of the catiomc groups onto the guar structure must be sufficient to provide the requisite catiomc charge density descπbed above

Suitable quaternary ammonium compounds for use in forming the catiomc guar polymers include those conforming to the general Formula (XII)

R1

I

R4— N— R2

I

R3

wherein where R¹, R² and R³ are methyl or ethyl groups, R is either an epoxyalkyl group of the general Formula (XIII)

H,C- -CH— R5—

\ / 24

or R⁴ is a halohydπn group of the general Formula (XIV)

X-CH₂-CH-R5 —

I

OH

wherein R⁵ is a Ci to C₃ alkylene, X is chlorine or bromine, and Z is an anion such as Cl", Br", I" or HS0₄"

Catiomc guar polymers (cationic derivatives of guar gum) formed from the reagents described above are represented by the general Formula (XV)

-

wherein R is guar gum Preferably, the catiomc guar polymer is guar hydroxypropyltnmethylammomum chlonde, which can be more specifically represented by the general Formula (XVI)

R— 0-CH₂-CH-CH₂N⁺(CH₃)₃Cr OH

Specific non-limiting examples of catiomc guar polymers which conform to Formula XVI include Jaguar® C 13S, havmg a catiomc charge density of 0 8meq/g (available from Rhodia Company) and Jaguar® C 17, havmg a cationic charge density of 1 6meq/g (available from Rhodia Company) Other suitable catiomc guar polymers mclude hydroxypropylated catiomc guar deπvatives Still other suitable catiomc polymers mclude copolymers of etheπfied guar, some examples of which are descnbed m U S Pat No 3,958,581, which descnphon is incorporated herein by reference ii. Copolymers of vinyl monomers Other suitable catiomc polymers for use in the anti-dandruff and conditionmg shampoo composmons of the present mvention are copolymers of vmyl monomers, havmg catiomc protonated amine or quaternary ammomum functionalities, reacted with water soluble monomers Non-limiting examples of such monomers mclude acrylamide, methacrylamide, alkyl and dialkyl acrylamides, alkyl and dialkyl methacrylamides, alkyl acrylate, alkyl methacrylate, vinyl caprolactone , vinyl pyπohdone, and mixtures thereof The alkyl and dialkyl substituted monomers preferably have from Ci to C₇ alkyl groups, more preferably from C, to C₃ alkyl groups Other suitable monomers include vmyl esters, vmyl alcohol (made by hydrolysis of poly- vinyl acetate), maleic anhydride, propylene glycol, ethylene glycol, and mixtures thereof O 0 /

25

Suitable cationic protonated ammo and quaternary ammonium monomers, for inclusion in the catiomc polymers of the shampoo composition herein, include vinyl compounds substituted with dialkyl- aminoalkyl acrylate, dialkylaminoalkyl methacrylate, monoalkylaminoalkyl acrylate, monoalkylammoalkyl methacrylate, tπalkyl methacryloxyalkyl ammonium salt, tπalkyl acryloxyalkyl ammomum salt, diallyl quaternary ammonium salts, and vinyl quaternary ammonium monomers having cyclic catiomc nitrogen- containing rings such as pyπdinium, lmidazohum, and quatemized pyrrohdones, such as alkyl vmyl imidazo um, alkyl vmyl pyndimum, and alkyl vinyl pyπohdone salts The alkyl portions of these monomers are preferably lower alkyls such as the Ci - C₃ alkyls

Suitable amine-substituted vinyl monomers for use herem include, dialkylaminoalkyl acrylamide, and dialkylaminoalkyl methacrylamide, wherein the alkyl groups are preferably C, to C₇ hydrocarbyls, more preferably C, to C₃ alkyls iii. Vinyl pyrrolidone copohmers

Other suitable catiomc polymers for use in the anti-dandruff and conditionmg shampoo compositions of the present invention include copolymers of l-vιnyl-2-pyrrolιdone and 1 -vιnyl-3-methylιmιdazolιum salt (e g , chloride salt), known in the industry (CTFA) as Polyquatermum 16 (e g Luviquat® FC 370, available from BASF Wyandotte Corporation), copolymers of 1 -vmyl-2-ρyπohdone and dimethylaminoethyl methacrylate, known m the industry (CTFA) as Polyquatermum 11 (e g Gafquat® 755N, available from ISP Corporation), cationic diallyl quaternary ammonium-containing polymers, mcludmg, for example, dimethyldiallylammonium chlonde homopolymer, known m the mdustry (CTFA) as Polyquatermum 6, copolymers of acrylarmde and dunethyldiallylammomum chlonde, known m the industry (CTFA) as Polyquatermum 7, and mineral acid salts of amino-alkyl esters of homopolymers and copolymers of unsaturated C₃ to C₅ carboxyhc acids, such as those described in U S Pat No 4,009,256, which descπption is incorporated herem by reference iv. Cationic modified proteins and polymeric quaternary salts Still other catiomc polymers for use in the anti-dandruff and conditionmg shampoo compositions of the present mvention are cationic modified protems, such as lauryldimonium hydroxypropyl collagen (e g Croquat® L, available from Croda Corporation), or cocodimonium hydroxypropyl hydrolized hair keratm (e g Croquat® HH, available from Croda Corporation) Other catiomc polymers mclude the polymeric quaternary salt prepared the reaction of adipic acid and dimethylaminopropylamine, reacted with dichloroethyl ether, known m the mdustry (CTFA) as Polyquatermum 2 (e g Mirapol® AD-1, available from Rhodia), and the polymeπc quatemary salt prepared by the reaction of azelaic acid and dimethylaminopropylether, known m the mdustry (CTFA) as Polyquatermum 18 (e g Mirapol® AZ-1, available from Rhodia Corporation) v. Other cationic polymers Yet other cationic polymers suitable for use herein are the Arquad^® seπes of quaternary ammonium salts, available from Akzo Nobel Other prefeπed catiomc polymers for use herein mclude Polymer KG30M (polyquatermum 10 and quatemized cellulose), Incroquat^® behenyl tπmomum methosulfate 26

(cetearyl alcohol and behentπmonium methosulfate), available from Croda, Merquat^® 5 (quaternary ammonium resin), av ailable from Calgon; Gafquat series 440 (cationic quatemized copolymers), available from ISP, Akypoquat* 131, available from Kao; Salcare^ SC 60 (quaternary ammonium resm), or Salcare^® SC95 or SC96 (catiomc liquid dispersion thickeners), all available from Ciba; and Meadowquat^® HG (PEG- 2-dιmeadowfoamamιdo-ethylmonιum methosulfate), available from Fanning E. Polvalkylene glvcol

The anti-dandruff and conditiomng shampoo compositions of the present invention comprise from about 0.005% to about 1.5%, by weight of the composition preferably from about 0.025% to about 0.1%, more preferably from about 0.05% to about 1%, more preferably from about 0.1 % to about 0 5%, most preferably from about 0 1% to about 0.3%, of selected polyalkylene glycols suitable for application to the hair or skin The select polyalkylene glycols are believed to provide enhanced lather performance, improved shampoo spreadabihty, and importantly, mcreased anti-dandruff particulate efficacy to the compositions described herein. Such polyalkylene glycols should be physically and chemically compatible with the essential components described herein, and should not otherwise unduly impair product stability, aesthetics, or performance

It has been found that these polyalkylene glycols, when added to the shampoo compositions described herein, enhance lather performance by delivering a richer, denser lather which coπelates with consumer perception of hair conditiomng performance. It has also been found that, m those embodiments which contam sihcone conditionmg agents, the selected polyalkylene glycols can reduce the concentration of amomc detersive surfactant necessary to provide hair cleanmg. In such reduced-surfactant compositions, hair cleansing and conditionmg performance remains good, while overall lather performance is enhanced. Polyethylene glycols, for example, are known for use in improving lather performance in cleansing compositions, as descnbed m U S. Pat. No. 5,837,661 , which descπption is incorporated herem by reference It has also been found that these selected polyalkylene glycols, when added to a sihcone-contaming shampoo composition, enhance spreadabihty of the shampoo compositions in hair Enhanced spreading of the shampoo composition durmg application also provides consumers with a perception of enhanced conditionmg performance. This performance is especially surpπsmg from these selected polyalkylene glycols which are known thickening agents, and as thickening agents would be expected to impair rather than enhance spreadabihty of the shampoo compositions mto hair

The polyalkylene glycols suitable for use m the shampoo compositions herein are characterized by the general Formula (XVII)

H(OCH₂CH)_n— OH R 27

wherein R is hydrogen, methyl, or mixtures thereof, preferably hydrogen, and n is an integer having an average value from about 1,500 to about 120,000, preferably from about 1,500 to about 50,000, more preferably from about 2,500 to about 25,000, and most preferably from about 3,500 to about 15,000 When R is hydrogen, these materials are polymers of ethylene oxide, which are also known as polyethylene glycols When R is methyl, these mateπals are polymers of propylene oxide, which are also known as polypropylene glycols When R is methyl, it is also understood that various positional isomers of the resulting polymers can exist Prefeπed for use herein are polyethylene glycols, polypropylene glycols, and mixtures thereof.

Specific non-limiting examples of polyethylene glycol polymers for use in the anti-dandruff and conditioning shampoo compositions of the present invention include: PEG 2M, wherem R is hydrogen and n has an average value of about 2,000 (e.g. Polyox WSR® N-10, available from Union Carbide); PEG 5M, wherem R is hydrogen and n has an average value of about 5,000 (e g. Polyox WSR® N-35 and Polyox WSR® N-80, both available from Union Carbide); PEG 7M, wherem R is hydrogen and n has an average value of about 7.000 (e.g. Polyox WSR® N-750, available from Union Carbide); PEG 9M, wherem R is hydrogen and n has an average value of about 9,000 (e g. Polyox WSR® N-3333, available from Union Carbide), PEG 14 M, wherem R is hydrogen and n has an average value of about 14,000 (e g Polyox WSR® N-3000, available from Umon Carbide); PEG 23M, wherem R is hydrogen and n has an average value of about 23,000 (e.g. Polyox WSR® N-12k, available from Umon Carbide); PEG 90M, wherem R is hydrogen and n has an average value of about 90,000 (e.g. Polyox WSR® 301, available from Umon Carbide); and PEG 100M, wherein R is hydrogen and n has an average value of about 100,000 (e g Carbowax PEG 4600™, available from Umon Carbide) Prefeπed polyethylene glycols include PEG 7M, PEG 14M, PEG 25M, PEG 90M, and mixtures thereof

F. Water The anti-dandruff and conditiomng shampoo compositions of the present invention compnse from about 20% to about 94.75%, by weight of the composition, preferably from about 50% to about 94.75%, more preferably from about 60% to about 85%, of water.

II. Optional Components The anti-dandruff and conditiomng shampoo compositions of the present mvention may, m some embodiments, further compnse additional optional components known or otherwise effective for use m hair care or personal care products. Additional surfactants, suspendmg agents, hair growth regulating agents, and other optional components are descnbed m detail below.

A. Other surfactants

The anti-dandruff and conditiomng shampoo compositions of the present invention may, in some embodiments, further compnse from about 0.5% to about 25%, by weight of the composition, preferably 28

from about 1% to about 20%, most preferably from about 1% to about 10%, of a surfactant other than the amomc surfactants described above, suitable for application to the hair or skin Such optional other surfactants should be chemically and physically compatible with the essential components of the shampoo composition, and should not otherwise unduly impair product performance, aesthetics or stability Suitable other surfactants include, but are not limited to amphoteπc, zwitteπonic, catiomc, noniomc and mixtures thereof

Amphoteπc detersive surfactants suitable for use herein include, but are not limited to, those surfactants broadly described as denvatives of aliphatic secondary and tertiary amines in which the aliphatic radical can be straight or branched cham and wherein one of the aliphatic substituents contams from about 8 to about 18 carbon atoms and one contains an amomc water solubilizmg group such as carboxy, sulfonate, sulfate, phosphate, or phosphonate

Zwitteπonic detersive surfactants suitable for use herein include, but are not limited to, those surfactants broadly descπbed as deπvatives of aliphatic quaternary ammonium, phosphonium, and sulfonium compounds, in which the aliphatic radicals can be straight or branched cham, and wherem one of the aliphatic substituents contams from about 8 to about 18 carbon atoms and one contams an amomc group such as carboxy, sulfonate, sulfate, phosphate or phosphonate Prefeπed zwittenonic detersive surfactants are the betames

Cationic detersive surfactants suitable for use herein mclude, but are not limited to, surfactants containing quaternary nitrogen moieties Examples of suitable catiomc surfactants are those coπespondmg to the general Formula (XVIII)

wherein R-., R₂, R₃, and R are mdependently selected from a C, to C₂₂ aliphatic group or an aromatic, alkoxy, polyoxyalkylene, alkylarmdo, hydroxyalkyl, aryl or alkylaryl group havmg up to about 22 carbon atoms, preferably C, to C₂₂ alkyl, and X is a salt-forming amon, such as those selected from halogen (e g chloride, bromide), acetate, citrate, lactate, glycolate, phosphate nitrate, sulfate, and alkylsulfate radicals The aliphatic groups can contam, m addition to carbon and hydrogen atoms, ether linkages, and other groups, such as ammo groups The longer cham (e g C₎₂ and higher) aliphatic groups can be saturated or unsaturated

Prefeπed cationic detersive surfactants are those contaming two long alkyl chains and two short alkyl chains or those containing one long alkyl chain and three short alkyl chams Such long alkyl chains are preferably from C,₂ to C₂₂, more preferably from C,₆ to C₂₂ Such short alkyl chains are preferably from Ci to C₃, more preferably from C, to C₂ 29

Noniomc detersive surfactants suitable for use herein include, but are not limited to, those compounds produced by condensation of alkylene oxide groups (hydrophi c in nature) with an organic hydrophobic compound, which may be aliphatic or alkyl aromatic in nature

Non-limiting examples of other amphoteπc, zwitteπonic, cationic and noniomc detersive surfactants suitable for use in the anti-dandruff and conditiomng shampoo composition of the present invention are descπbed in McCutcheon's, Emulsifiers and Detergents, (1989), published by M C Pub. Co., and m U.S Pat. No. 2,438,091 ; U S Pat. No. 2,528,378, U.S. Pat. No. 2,658,072; U S. Pat. No 3,155,591, U.S. Pat. No. 3,929,678; U.S. Pat. No 3,959,461 , U.S. Pat. No 4,387,090; U S. Pat. No 5,104,646, U S Pat. No 5,106,609; and U.S Pat. No. 5,837,661, all of which descriptions are incorporated herem by reference

B. Suspending agent

The anti-dandruff and conditiomng shampoo compositions of the present mvention may, in some embodiments, compnse from about 0 1% to about 10%, by weight of the composition, preferably from about 0.3%) to about 5%, more preferably from about 0.3% to about 2.5%), of a suspendmg agent suitable for application to the hair or skin. It is believed that the suspendmg agent suspends water-insoluble, dispersed matenals m the shampoo compositions Such suspendmg agent should be physically and chemically compatible with the essential components of the composition, and should not otherwise unduly impair product stability, aesthetics or performance Examples of suspendmg agents which may be suitably employed in the shampoo compositions herem mclude, but are not limited to: acyl derivatives, long cham amine oxides, xanthan gum, and mixtures thereof. These and other suitable suspendmg agents are descnbed m further detail below

1. Acyl derivatives and long chain amine oxides

Acyl denvative suspendmg agents mclude, but are not limited to: glyceryl esters, long chain hydrocarbyls, long cham esters of long cham fatty acids, long cham esters of long cham alkanol amides. Another suitable suspendmg agent group mcludes the long chain amine oxides Acyl denvative and long cham amine oxide suspendmg agents are descπbed in U.S. Pat. No. 4,741,855, which descπption is incorporated herem by reference.

Prefeπed acyl derivative suspendmg agents for use herem are glyceryl esters, which mclude C|₆ to C₂₂ ethylene glycol esters of fatty acids. More prefeπed are the ethylene glycol stearates, both mono- and di-stearate, most prefeπed is ethylene glycol di-stearate containing less than about 7% of the mono-stearate.

Also suitable for use m the shampoo compositions herein are long cham (i.e Cg to C₂₂) hydrocarbyls, which include NN-dihydrocarbyl amido benzoic acid and soluble salts thereof (e.g , Na, K), particularly NN-dι-(hydrogenated) Cι₆, Cι₈ and tallow amido benzoic acid species of this family, available from Stepan Company Non-limiting examples of long cham esters of long chain fatty acids mclude. stearyl stearate and cetyl palmitate Non-limiting examples of long chain esters of long chain alkanol amides include: stearamide diethanolamide distearate and stearamide monoethanolamide stearate Non-limiting 30

examples of suitable long chain amine oxides for use as suspending agents herein include the alkyl (Cι₆-C₂₂) dimethyl amine oxides (e g stearyl dimethyl amine oxide)

2. Xanthan gum

Also suitable as a suspending agent herein is xanthan gum. The concentration of xanthan gum will typically range from about 0 1% to about 3%, by weight of the composition, preferably from about 0 4% to about 1 2% The use of xanthan gum as a suspending agent in sihcone containing shampoo compositions is described, for example, m U S. Pat. No 4,788,006, which description is incorporated herein by reference Combmations of long chain acyl derivatives and xanthan gum may also be used as a suspendmg agent in the shampoo compositions, as is descπbed in U S. Pat. No. 4,704,272, which descnption is incorporated herem by reference.

3. Other suspending agents

Still other suitable suspendmg agents for use m the anti-dandruff and conditioning shampoo compositions of the present invention include carboxyvinyl polymers. Prefeπed among these polymers are the copolymers of acrylic acid crosslinked with polyallylsucrose, as descnbed m U.S. Pat. No. 2,798,053, which descnption is incorporated herein by reference. Examples of these polymers mclude Carbopol 934, 940, 941, and 956, available from B. F. Goodπch Company

Other suitable suspending agents for use herem mclude primary amines having a fatty alkyl moiety havmg at least about 16 carbon atoms (e.g palmitamine, and stearamine), and secondary amines havmg two fatty alkyl moieties each havmg at least about 12 carbon atoms (e.g. dipalmitoylamine, and di- (hydrogenated tallow)-amιne). Also suitable are dι-(hydrogenated tallow)-phthahc acid amide, and cross- linked maleic anhydride-methyl vmyl ether copolymer

Still other suitable suspendmg agents may be used m the shampoo compositions, mcludmg those that can impart a gel-like viscosity to the composition, such as water soluble or colloidally water soluble polymers like cellulose ethers (e.g., methylcellulose, hydroxybutyl methylcellulose, hydroxypropylcellulose, hydroxypropyl methylcellulose, hydroxyethyl ethylcellulose and hydroxyethylcellulose), guar gum, polyvinyl alcohol, polyvinyl pyπohdone, hydroxypropyl guar gum, starch and starch denvatives, and other thickeners, viscosity modifiers, gelling agents, and mixtures thereof. A prefeπed viscosity modifier useful as a suspendmg agent is tπhydroxysteaπn, (e.g. Thixin R™, available from Rheox Company).

C. Hair Growth Regulating Agents

The compositions herein may also optionally comprise, in addition to zmc pynthione, other hair growth regulatmg agents. Such agents can be chosen from a wide vanety of molecules which can function m different ways to enhance the hair growth effects of a compound of the present mvention. These optional agents, when present, are typically employed m the compositions herein at a level rangmg from about 0.001%) to about 15%, preferably from about 0.1% to about 10%, most preferably from about 0.5% to about 5% by weight of the composition 31

As used herein, the term "hair growth regulating" is meant to include stimulating hair growth and'or hair thickenmg, preventing, reducing, aπesting and/or retarding the loss of hair and/or the thinning of hair, increasing the rate of hair growth; inducing the formation of a greater number of hair strands, increasing the diameter of the hair strand, lengthening the hair strand; changing the hair follicle from vellus to terminal, converting follicles from telogen to anagen phase (thereby increasing the overall ratio of anagen phase follicles relative to telogen phase follicles); treating alopecias; and any combination thereof

Vasodilators such as potassium channel agonists including, for example, minoxidil and minoxidil derivatives such as ammexil and such as those described m U.S. Patent 3,382,247, U.S. Patent 5,756,092, issued May 26, 1998, U.S. Patent 5,772,990, issued June 30, 1998, U.S. Patent 5,760,043, issued June 2, 1998, U.S. Patent 328,914, issued July 12, 1994, U.S. Patent 5,466,694, issued November 14, 1995, 5,438,058, issued August 1, 1995, and U S. Patent 4,973,474, issued November 27, 1990, (all of which are herem incorporated by reference), and cromakalin and diazoxide can be used as optional hair growth regulating agents in the compositions herein.

One suitable class of optional activity enhancer for use herem are anti-androgens Examples of suitable anti-androgens may mclude, but are not limited 5-α-reductase inhibitors such as finesteπde and those described in U.S. Patent 5,516,779, issued May 14, 1996 (herein incorporated by reference) and m Nnane et al, Cancer Research 58. "Effects of Some Novel Inhibitors of C17,20-Lyase and 5ct-Reductase in Vitro and in Vivo and Then: Potential Role m the Treatment of Prostate Cancer., as well as cyproterone acetate, azelaic acid and its derivatives and those compounds descnbed in U S. Patent 5,480,913, issued January 2, 1996, flutamide, and those described in U.S Patents 5,411,981, issued May 2, 1995, U.S Patent 5,565,467, issued October 15, 1996 and U S Patent 4,910,226, issued March 20, 1990, all of which are herem incorporated by reference.

Another suitable class of optional hair growth regulating agents are lmmunosuppressants such as 1 ) cyclosponn and cyclospoπn analogs mcludmg those descnbed m U.S Provisional Patent Application No 60/122,925, Fulmer et al., "Method of Treatmg Hair Loss Using Non-Immunosuppressive Compounds", filed March 5, 1999, herem incorporated by reference, and 2) FK506 analogs such as those descnbed in U.S Provisional Patent Application No. 60/102,449, Mclver et al., "Heterocychc 2-Substιtuted Ketoaπudes", filed September 30, 1998, U.S Provisional Patent Application No 60/102,448, Mclver et al., "2-Subshtuted Ketoamides", filed September 30, 1998, U.S Provisional Patent Application No. 60/102,539, Mclver et al., "2-Substιtuted Heterocychc Sulfonamides", filed September 30, 1998, U.S. Provisional Patent Application No. 60/102,458, Tiesman et al., "Method of Treatmg Hair Loss Usmg Ketoamides", filed September 30, 1998, and U.S. Provisional Patent Application No. 60/102,437, Mclver et al , "Method of Treatmg Hair Loss Usmg Sulfonamides", filed September 30, 1998, all of which are herem incorporated by reference Another suitable class of optional hair growth regulatmg agents are antimicrobials such as selemum sulfide, ketoconazole, tnclocarbon, tπclosan, zmc pyπthione, ltraconazole, asiatic acid, hinokitiol, 32

mipirocm and those described in EPA 0,680,745 (herein incorporated by reference), c nacycin hydrochlonde, benzoyl peroxide, benzyl peroxide and minocyc n

Anti-mflammatoπes can also be incorporated into the compositions herein as an optional activity enhancer. Examples of suitable anti-inflammatoπes may mclude glucocorticoids such as hydrocortisone, mometasone furoate and prednisolone, nonsteroidal anti-inflammatories including cyclooxygenase or hpoxygenase inhibitors such as those described in U S Patent 5,756,092, and benzydamine, salicylic acid, and those compounds described in EPA 0,770,399, published May 2, 1997, WO 94/06434, published March 31, 1994 and FR 2,268,523, published November 21, 1975, all of which are herem incorporated by reference Another suitable class of optional hair growth regulating agents are thyroid hormones and deπvatives and analogs thereof. Examples of suitable thyroid hormones for use herein may include tπiodothyπonine Examples of thyroid hormone analogs which may be suitable for use herem include those descπbed m U S. Provisional Patent Application No. 60/136,996, Zhang et al., "Method of Treatmg Han- Loss", filed June 1, 1999, U.S. Provisional Patent Application No 60/137,024, Zhang et al, "Method of Treatmg Hair Loss Using Biphenyl Compounds", filed June 1, 1999, U S. Provisional Patent Application No. 60/137,022, Zhang et al, "Method of Treatmg Hair Loss Usmg Carboxyl Deπvatives", filed June 1, 1999, U.S Provisional Patent Application No. 60/137,023, Zhang et al., "Method of Treatmg Hair Loss Usmg Sulfonyl Thyromimetic Compounds", filed June 1, 1999, U.S. Provisional Patent Application No. 60/137,052, Youngquist et al , "Biaryl Compounds", filed June 1, 1999, U.S Provisional Patent Application No. 60/137,063, Youngquist et al., "Sulfur-Bndged Compounds", filed June 1, 1999, and U.S. Provisional Patent Application No. 60/136,958, Youngquist et al., "Substituted Biaryl Ether Compounds", filed June 1, 1999

Prostaglandin agonists or antagonists can also be used as optional hair growth regulatmg agents in the compositions herein. Examples of suitable prostaglandins agomsts or antagomsts mclude latanoprost and those descnbed m WO 98/33497, Johnstone, published August 6, 1998, WO 95/11003, Stjemschantz, published Apnl 27, 1995, JP 97-100091, and Ueno, JP 96-134242, Nakamura.

Another class of optional hair growth regulating agents for use herem are retmoids. Suitable retinoids may mclude isotretinoin, acitretin, tazarotene,

Non-limiting examples of penetration enhancers which may be used as optional hair growth regulatmg agents herein mclude, for example, 2-methyl propan-2-ol, propan-2-ol, ethyl-2- hydroxypropanoate, hexan-2,5-dιol, POE(2) ethyl ether, dι(2-hydroxypropyl) ether, pentan-2,4-dιol, acetone, POE(2) methyl ether, 2-hydroxypropιomc acid, 2-hydroxyoctanoιc acid, propan-J-ol, 1,4-dιoxane, tetrahydrofuran, butan-l,4-dιol, propylene glycol dipelargonate, polyoxypropylene 15 stearyl ether, octyl alcohol, POE ester of oleyl alcohol, oleyl alcohol, lauryl alcohol, dioctyl adipate, dicapryl adipate, di- isopropyl adipate, di-isopropyl sebacate, dibutyl sebacate, diethyl sebacate, dimethyl sebacate, dioctyl sebacate, dibutyl suberate, dioctyl azelate, dibenzyl sebacate, dibutyl phthalate, dibutyl azelate, ethyl myπstate, dimethyl azelate, butyl myπstate, dibutyl succmate, didecyl phthalate, decyl oleate, ethyl 33

caproate, ethyl sa cylate, wo-propyl palmitate, ethyl laurate, 2-ethyl-hexyl pelargonate,

isostearate, butyl laurate, benzyl benzoate, butyl benzoate, hexyl laurate, ethyl caprate, ethyl caprylate, butyl stearate, benzyl sahcylate, 2-hydroxypropanoιc acid, 2-hyroxyoctanoιc acid, methylsulfoxide, NN-dimethyl acetamide, NN-dimethyl formamide, 2-pyπohdone, l-methyl-2-pyπohdone, 5-methyl-2-pyrrohdone, 1,5- dιmethyl-2-pyπohdone, l-ethyl-2-pyπohdone, phosphine oxides, sugar esters, tetrahydrofurfural alcohol, urea, diethyl-m-toluamide,, l-dodecylazacyloheptan-2-one and those descπbed in U.S Patent 5,015,470, issued May 14, 1991 and U S Patent 5,496,827, issued July 15, 1994 (both of which are herein incorporated in its entirety by reference)

Other classes of optional hair growth regulatmg agents for use herein include flavinoids, ascomycm derivatives and analogs, histamine antagomsts such as diphenhydramine hydrochlonde, other tnterpenes such as oleanohc acid and urso c acid and those descπbed m U.S. Patent 5,529,769, JP 10017431, WO 95/35103, U.S. Patent 5,468,888, JP 09067253, WO 92/09262, JP 62093215, U.S. Patent 5,631,282, U.S Patent 5,679,705, JP 08193094, saponins such as those descπbed in EP 0,558,509 to Bonte et al, published September 8, 1993 and WO 97/01346 to Bonte et al, published January 16, 1997 (both of which are herem incorporated by reference in their entirety), proeoglycanase or glycosaminoglycanase inhibitors such as those described m U.S. Patents 5,015,470, issued May 14, 1991, U.S. Patent 5,300,284, issued Apnl 5, 1994 and U S. Patent 5,185,325, issued February 9, 1993 (all of which are herem incorporated in their entirety by reference) estrogen agomsts and antagomsts, pseudoteπns, cytokine and growth factor promotors, analogs or inhibitors such as lnterleukinl inhibitors, ιnterleukιn-6 inhibitors, ιnterleukιn-10 promotors, and tumor necrosis factor inhibitors, vitamins such as vitamm D analogs and parathyroid hormone antagonists, Vitamin B 12 analogs and panthenol, mterfuron agomsts and antagomsts, hydroxyacids such as those described in U.S. Patent 5,550,158, benzophenones and hydantom anticonvulsants such as phenytoin.

Other hair growth agents are descnbed m detail m, for example, JP 09-157,139 to Tsuji et al, published June 17, 1997; EP 0277455 Al to Mu-abeau, published August 10, 1988, WO 97/05887 to Cabo Soler et al, pubhshed February 20, 1997; WO 92/16186 to Bonte et al, published March 13, 1992; JP 62- 93215 to Okazaki et al, published Apnl 28, 1987; U.S. Patent 4,987,150 to Kurono et al, issued January 22, 1991 , JP 290811 to Ohba et al, published October 15, 1992; JP 05-286,835 to Tanaka et al, published November 2, 1993, FR 2,723,313 to Greff, published August 2, 1994, U. S. Patent 5,015,470 to Gibson, issued May 14, 1991, U S. Patent 5,559,092, issued September 24, 1996, U.S. patent 5,536,751, issued July 16, 1996, U S. Patent 5,714,515, issued February 3, 1998, EPA 0,319,991, published June 14, 1989, EPA 0,357,630, published October 6, 1988, EPA 0,573,253, published December 8, 1993, JP 61-260010, published November 18, 1986, U.S. Patent 5,772,990, issued June 30, 1998, U.S. Patent 5,053, 410, issued October 1, 1991, and U.S. Patent 4,761,401, issued August 2, 1988, all of which are herem incorporated by reference.

Some prefeπed hair growth regulatmg agents for use herem are zmc salts of carboxyhc acids, saponins, tnterpenes, oleanohc acid, ursohc acid, betuhnic acid, betulonic acid, crataego c acid, celastrol, 34

asiatic acid, inhibitors of 5-α-reductase. progesterone, 1 ,4-methyl-4-azasteroιds, 17-β-NN- dιethylcarbamoyl-4-methyl-4-aza-5-α-androstan-3-one, androgen receptor antagomsts, cyproterone acetate, minoxidil. azelaic acid and derivatives thereof, cyclospoπn, tπiodothyromne, diazoxide, potassium channel openers, cromakahn, phenytom, ketoconazole, finesteπde, dutastende, coal tar, zinc gluconate, glucocortisoids, macrohdes, aminexil, and mixtures thereof

D. Other Optional Ingredients

The anti-dandruff and conditioning shampoo compositions of the present invention may, in some embodiments, further comprise additional optional components known or otherwise effective for use in hair care or personal care products. The concentration of such optional ingredients generally ranges from zero to about 25%, more typically from about 0.05% to about 25%, even more typically from about 0.1 % to about 15%, by weight of the composition Such optional components should also be physically and chemically compatible with the essential components described herein, and should not otherwise unduly impair product stability, aesthetics or performance. Non limiting examples of optional components for use m the shampoo composition mclude antistatic agents, foam boosters, soluble anti-dandruff agents, viscosity adjustmg agents and thickeners, pH adjusting agents (e.g. sodium citrate, citnc acid, succinic acid, phosphoπc acid, sodium hydroxide, and sodium carbonate), preservatives (e.g. DMDM hydantom), anti-microbial agents (e.g. tπclosan or tnclocarbon), dyes, orgamc solvents or diluents, pearlescent aids, perfumes, fatty alcohols, protems, skin active agents, sunscreens, vitamins, and pediculocides

Optional anti-static agents such as water-msoluble catiomc surfactants may be used, typically m concentrations ranging from about 0.1 % to about 5%, by weight of the composition. Such anti-static agents should not unduly interfere with the ui-use performance and end-benefits of the shampoo composition; particularly, the anti-static agent should not interfere with the amomc surfactant. A specific non-limiting example of a suitable anti-static agents is tπcetyl methyl ammomum chlonde.

Optional foam boosters for use in the shampoo compositions descnbed herem mclude fatty ester (e g. C₈-C₂₂) mono- and di (C_rC₅, especially C C₃) alkanol amides. Specific non-limiting examples of such foam boosters mclude coconut monoethanolamide, coconut diethanolamide, and mixtures thereof.

Optional anti-dandruff agents may be used m addition to the particulate anti-dandruff actives of the present mvention, typically m concentrations rangmg from about 0.1 % to about 4%>, by weight of the composition, preferably from about 0.2% to about 2%. Such optional anti-dandruff agents mclude soluble anti-dandruff agents, specific non-limiting examples of which mclude: piroctone olamine, ketoconazol, and mixtures thereof.

Optional viscosity modifiers and thickeners may used, typically m amounts effective for the anti- dandruff and conditiomng shampoo compositions of the present invention to generally have an overall viscosity from about 1,000 csk to about 20,000 csk, preferably from about 3,000 csk to about 10,000 csk 35

Specific non-limiting examples of such viscosity modifiers and thickeners include, sodium chloride, sodium sulfate, and mixtures thereof

III. Methods of Manufacture The anti-dandruff and conditiomng shampoo compositions of the present invention may be prepared by any known or otherwise effective technique, suitable for providing a shampoo composition provided that the resulting composition provides the excellent hair feel benefits described herein Methods for preparmg the anti-dandruff and conditiomng shampoos of the present mvention mclude conventional formulation and mixing techniques. A method such as that described m U.S. Pat. No. 5,837,661, which descnption is incorporated herein by reference, could be employed, wherem the anti-dandruff particulate of the present invention would typically be added m the same step as the sihcone premix is added m the '661 descnption.

IV. Methods of Use The anti-dandruff and conditionmg shampoo compositions of the present mvention are used m a conventional manner for cleansing and conditionmg the hair or skin. They are particularly used m a conventional manner for treatmg the condition commonly known as dandruff. An effective amount of the composition for cleansmg and conditionmg the hair or skin is applied to hair, or other region of the body, that has preferably been wetted, generally with water, and then the composition is rmsed off. Effective amounts typically range from about lg to about 50g, preferably from about lg to about 20g. Application to the hair typically mcludes working the composition through the hair such that most or all of the hair is contacted with the composition.

This method for providmg anti-dandruff efficacy and conditiomng hair compnses the steps of: (a) wetting the hair with water, (b) applying an effective amount of the shampoo composition to the hair, and (c) nnsmg the shampoo composition from the hair usmg water These steps may be repeated as many times as desired to achieve the cleansmg, conditiomng, and anti-dandruff benefits sought.

It is also contemplated that when the anti-dandruff particulate employed is zmc pyπthione, and/or if other optional hair growth regulatmg agents are employed, the shampoo compositions of the present mvention, may, provide for the regulation of growth of the hair. The method of regularly usmg such shampoo compositions compnses steps a, b, and c (above).

EXAMPLES

The following are non-limiting examples of the anti-dandruff and conditionmg shampoo compositions of the present mvention. The examples are given solely for the purpose of illustration and are not to be construed as limitations of the present mvention, as many vaπations thereof are possible without departing from the spirit artd scope of the mvention, which would be recognized by one of ordinary skill in 36

the art In the examples, all concentrations are listed as weight percent, unless otherwise specified As used herein, "minors" refers to those optional components such as preservatives, viscosity modifiers, pH modifiers, fragrances, foam boosters, and the like. As is apparent to one of ordinary skill in the art, the selection of these minors will vary depending on the physical and chemical characteristics of the paπicular ingredients selected to make the present invention as described herem

A suitable method for preparing the anti-dandruff and conditiomng shampoo compositions described in Examples I - XV (below) follows About one-third to all of the ammonium laureth sulfate (added as 25wt% solution) is added to a jacketed mix tank and heated to about 60°C to about 80°C with slow agitation to form a surfactant solution. Cocamide MEA and fatty alcohols, (where applicable), are added to the tank and allowed to disperse. Salts (e.g. sodium chloride) and pH modifiers (e.g. citπc acid, sodium citrate) are added to the tank and allowed to disperse. Ethylene glycol distearate ("EGDS") is added to the mixing vessel and allowed to melt. After the EGDS is melted and dispersed, preservative is added to the surfactant solution. The resultmg mixture is cooled to about 25°C to about 40°C and collected m a finishing tank. As a result of this coolmg step, the EGDS crystallizes to form a crystallme network m the product. The remainder of the ammomum laureth sulfate and other components, mcludmg the sihcone and anti-dandruff particulate, are added to the finishing tank with agitation to ensure a homogeneous mixture Catiomc polymer is dispersed m water as an about 0.1 % to about 10% aqueous solution and then added to the final mix. Once all components have been added, additional viscosity and pH modifiers may be added, as needed, to the mixture to adjust product viscosity and pH to the extent desired.

Example Number I II III IV V

Ammonium Laureth Sulfate 12 12 1 1 10 12

Ammonium Lauryl Sulfate 8 8 7 6 6

Guar Hydro xypropyltπmo mum Chloride¹ 0.4 0.4 0.25 0..6 0.6

PEG 23M² — — — — 0.1

PEG 90M³ 0.1 0.05 0.025 0.01 —

Zmc Pyπthione⁴ 1 1 1 1 1

1-decene homopolymer⁵ 0.2 0.3 0.3 0.5 0.4

Tπmethylpropane Capyl Caprylate⁶ 0.2 0.1 0.1 0.0 0.1

Dimethicone⁷ 1.0 2.0 0.8 0.5 1.25

Ethylene Glycol Distearate 1.0 2.0 1.5 2.0 1.5

Cocamide MEA 0.6 0.8 0.6 0.8 1.0

Cetyl Alcohol 0.9 0.9 0.9 0.9 1.0

Water and minors αuanl -ltv sufficient -

1. Guar having a molecular weight of about 200,000, and having a charge density of about 0.71 meq/g, available from Aqualon.

2. Polyox WSR N- 12k, available from Union Carbide.

3. Polyox WSR 301 , available from Union Carbide

4. ZPT having an average particle size of about 2 5μm, available from Arch/Olin

5. Puresyn 6, available from Mobil

6. Mobil P43, available from Mobil

7. Visasil 330,000 csk, available from General Electπc Sihcones.

Example Number VI VII VIII IX X

Ammonium Laureth Sulfate 12 12 10 10 12

Ammonium Lauryl Sulfate 8 6 6 5 6

Polyquatermum- 10¹ — — 0.25 0.25 0.1

Guar Hydroxypropyltrimonium Chloride² — 0.25 — — —

Guar Hydroxypropyltrimonium Chloride³ 0.5 — 0.25 0.35 0.4

PEG 7M⁴ 0.1 — 0.1 0.1 0.2

PEG 90M⁵ ... 0.1 — — —

Zinc Pyπthione⁶ 1 1 1 1 1

1 -decene homopolymer 0.2 0.4 0.4 0.5 0.5

Tπmethylpropane Capyl Caprylate⁸ 0.1 — 0.1 0.2 —

Dimethicone⁹ 0.55 1.15 1.35 3.25 3.35

Ethylene Glycol Distearate 1.5 1.0 1.5 2.0 2.0

Cocamide MEA 0.6 1.1 0.8 1.1 1.3

Cetyl Alcohol 0.9 0.6 0.9 1.0 1.0

Water and minors αuantitv ^r sufficient

1. UCARE Polymer LR400, available from Amerchol.

2. Jaguar C 17, available from Rhodia.

3. Guar having a molecular weight of about 200,000, and having a charge density of about 0 71 meq/g, available from Aqualon.

4. Polyox WSR N-750, available from Union Carbide

5. Polyox WSR 301, available from Union Carbide

6. ZPT having an average particle size of about 2.5 μm, available from Arch Olin

7. Puresyn 6, available from Mobil

8. Mobil P43, available from Mobil

9. Visasil 330,000 csk, available from General Electπc Sihcones

Example Number XI XII XIII XIV XV

Ammonium Laureth Sulfate 10 11 12 13 12

Ammomum Lauryl Sulfate 6 7 7 5 5

Polyquatermum- 10 0.15 — — — —

Guar Hydroxypropyltrimonium Chloride² — — 0.1 — —

Guar Hydroxypropyltrimonium Chlonde³ — 0.4 — 0.1 —

Guar Hydroxypropyltrimonium Chloride⁴ — — — — 0.5

Guar Hydroxypropyltnmomum Chloride⁵ 0.25 — — — —

PEG 90M⁶ 0.025 0.1 0.15 0.15 0.2

Zinc Pyπthione⁷ 1 1 1 1 1

1 -decene homopolymer⁸ 0.6 0.2 0.4 — 0.1

Tnmethylpropane Capyl Caprylate⁹ — — 0.3 0.2 0.1

Dimethicone¹⁰ 1.35 1.45 0.75 1.1 0.85

Ethylene Glycol Distearate 1.0 1.2 1.5 2.0 2.0

Cocamide MEA 0.6 1.0 0.6 0.6 1.1

Cetyl Alcohol 0.9 1.0 0.6 0.6 1.1

Water and minors αuanl :ιtv sufficient —

1. UCARE Polymer R400, available from Amerchol

2. Jaguar C 17, available from Rhodia

3. Jaguar C 14S, available from Rhodia

4. Guar having a molecular weight of about 900,000, and having a charge density of about 0 71 meq/g, available from Aqualon

5. Guar having a molecular weight of about 200,000, and having a charge density of about 0.71 meq/g, available from Aqualon

6. Polyox WSR 301, available from Union Carbide.

7. ZPT having an average particle size of about 2.5μm, available from Arch Olin

8. Puresyn 6, available from Mobil.

9. Mobil P43, available from Mobil

10. Visasil 330,000 csk, available from General Electπc Sihcones.

Claims

40

WHAT IS CLAIMED:

1. A shampoo composition characterised in that it compπses a) from 5% to 50%, by weight of the composition, of an anionic surfactant; b) from 0 01%> to 10%, by weight of the composition, of a non- volatile conditiomng agent; c) from 0.1 % to 4%, by weight of the composition, of an anti-dandruff particulate; d) from 0.02% to 5%, by weight of the composition, of at least one cationic polymer; e) from 0.005% to 1.5%, by weight of the composition, of a polyalkylene glycol coπespondmg to the formula-

H(OCH₂CH)_n— OH R ι) wherem R is selected from the group consisting of hydrogen, methyl and mixtures thereof, n) wherem n is an mteger havmg an average value from 1,500 to 120,000; and f) water.

2. A shampoo composition accordmg to any Claim 1, wherem said at least one catiomc polymer component is selected from the group consisting of: guar deπvatives, preferably guar hydroxypropyltnmomum chlonde; cellulose derivatives, preferably polyquatermum- 10; and mixtures thereof.

3. A shampoo composition accordmg to any precedmg claim, characteπsed in that it compnses from 0.1 % to 1%, by weight of the composition, of said at least one catiomc polymer

4. A shampoo composition accordmg to any precedmg claim, wherem said guar deπvatives have a molecular weight from 50,000 to 700,000, and a charge density from 0.05 meq/g to 0.9 meq/g; and said cellulose denvatives have a molecular weight from 200,000 to 1,500,000, preferably from 350,000 to 500,000, and a charge density from 0.2 meq/g to 0.6 meq/g.

5. A shampoo composition accordmg to any precedmg claim, wherem said non- volatile conditiomng agent compπses dispersed, sihcone.

6. A shampoo composition accordmg to any precedmg claim, wherem said polyalkylene glycol has an average value of n from 1,500 to 50,000, preferably from 3,500 to 15,000 A shampoo composition according to any preceding claim, wherein said anti-dandruff particulate is a zmc salt of 1 -hydroxy-2-pyπdιnethιone, and preferably wherem said zinc salt of l-hydroxy-2- pyπdinethione is in platelet particle form

A shampoo composition according to any precedmg claim, wherem said composition further comprises from 0 1% to 10%), by weight of the composition, of a suspending agent, and preferably wherein said suspending agent is ethylene glycol distearate

A shampoo composition characteπsed m that it compπses a) from 10%) to 25%>, by weight of the composition, of an amomc surfactant, b) from 0 01%) to 10%), by weight of the composition, of an msoluble, non- volatile sihcone conditiomng agent, c) from 0 3% to 2%, by weight of the composition, of a zmc salt of l-hydroxy-2-pyπdmethιone, d) from 0 1% to 0 1%), by weight of the composition, of at least one catiomc polymer selected from the group consisting of guar denvatives, cellulose denvatives, and mixtures thereof, e) from 0 025%) to 1 5%, by weight of the composition, of a polyalkylene glycol coπespondmg to the formula

H(OCH₂CH)_n— OH R

i) wherem R is selected from the group consistmg of hydrogen, methyl and mixtures thereof, n) wherem n is an mteger havmg an average value from 3,500 to 15,000, and f) water

A method for providmg anti-dandruff efficacy and conditionmg hair charactensed m that it compπses a) wetting said nan- with water, b) applying to said hair an effective amount of a shampoo composition accordmg to any precedmg claim, and c) nnsmg said shampoo composition from said hair usmg water

A shampoo composition accordmg to any precedmg claim, further characteπsed m that it compπses from 0 001% to 15%) of a hair growth regulatmg agent selected from the group consistmg of zmc salts of carboxyhc acids, saponins, tnterpenes, oleanohc acid, ursohc acid, betulinic acid, betulonic acid, crataegohc acid, celastrol, asiatic acid, inhibitors of 5- -reductase, progesterone, l,4-methyl-4- azasteroids, 17-β-NN-dιethylcarbamoyl-4-methyl-4-aza-5-α-androstan-3-one, androgen receptor antagonists, cyproterone acetate, minoxidil, azelaic acid and derivatives thereof, cyclospoπn, tπiodothyronme, diazoxide, potassium channel openers, cromakalin, phenytoin, ketoconazole, fmestende, dutastende, coal tar, zinc gluconate, glucocortisoids, macrohdes, armnexil, and mixtures thereof.

12. A method for regulating the growth of the hair characterised in that it comprises- a) wetting said hair with water; b) applymg to said hair an effective amount, of a shampoo composition accordmg to any precedmg claim; c) nnsmg said shampoo composition from said hair usmg water