WO1995016432A2 - Cosmetic cleansing composition with dual blooming perfume system - Google Patents

Abstract

The present invention provides a cleansing composition containing one or more detersive surfactants, at least one additional cosmetic or pharmaceutical agent useful for treating the hair or skin, a dual blooming perfume system, and an aqueous carrier. The dual blooming perfume system comprises a first, substantially nonconfined perfume component and a second, confined perfume component, having a different aroma than the first perfume component, which is confined, by a frangible encapsulation material, such that said second perfume component is capable of being released by means of application of mechanical force during normal use.

Description

COSMETIC CLEANSING COMPOSITION WITH DUAL BLOOMING PERFUME SYSTEM

Field of The Invention

This invention relates to a perfumed, multiple function cleansing composition containing a surfactant useful for cleansing the hair or skin a perfume system, and an additional cosmetic or pharmaceutical agent

Background of the Invention

Personal cleansing compositions for topical application to the hair or skin, e g shampoos, which also contain conditioning agents or other cosmetic or pharmaceutical agents are well known in the art The convenience of allowing the user to perform two, or more treatments in one step is highly appealing to those in the population who do not wish to either purchase more than one product when one product will achieve the same goals, or spend the additional time to perform the separate steps needed to apply more than one product Shampoos that also condition the hair have become especially popular in recent years Other "two-in-one" products include skin cleansing and conditioning products, and anti-dandruff shampoos

It is common practice in the art to add a perfume to topical hair and skin compositions which is appealing to the user, or which otherwise imparts an aroma intended to convey a particular message Whereas the use of such perfumes can be quite effective whatever overall perfume aroma is selected would not signal to the user the dichotomy of distinct function that are performed by multiple function personal cleansing compositions

Many of these products have been very effective at carrying out their dual functions However they have not indicated to the user that the product performs multiple functions, other than with respect to the end-benefits of the additional ingredient Such benefits may not be noticeable for a substantial period after use (e g as for certain anti- dandruff actives other pharmaceutical actives) or may not otherwise be easily noticeable during use Accordingly it would be desirable to provide multiple function personal cleansing compositions for treatment of the hair or skin which provides the user with a clear indication of the multiple functions it performs

Perfumes are ingredients that have commonly been added to personal cleansing compositions to impart aesthetically attractive aromas Perfurmes can be designed and selected to make a variety of impressions on the user However any particular perfume will typically convey only a single overall message, and would not clearly communicate the multiple functions of a multiple function cleansing product As described below, it is an object of this invention to provide a composition that clearly imparts to the user a first perfume aroma upon initial dispensing of the product and then in order to convey the multiple, distinct functions of the product, impart a second perfume aroma upon distribution of the compositions throughout the area of skin or hair that is treated

SUMMARY OF THE INVENTION

The present invention provides a cleansing composition containing one or more detersive surfactants, at least one additional cosmetic or pharmaceutical agent useful for treating the hair or skin, a dual blooming perfume system, and an aqueous carrier The dual blooming perfume system comprises a first, substantially nonconfined perfume component and a second, confined perfume component having a different aroma then the first perfume component which is confined, by a frangible encapsulation material, such that said second perfume component is capable of being released by means of application of mechanical force during normal use

More particularly, in a preferred embodiment, the present invention provides a cleansing composition comprising

(a) from about 5% to about 40%, by weight of a detersive surfactant or mixture thereof,

(b) an additional cosmetic or pharmaceutical agent for treating the hair or skin, preferably selected from the group consisting of conditioning agents styling agents, and anti-dandruff agents and mixtures thereof

(c) a perfume system comprising

(i) a substantially nonconfined first perfume component and (n) a confined second perfume component having a different aroma than the first perfume component wherein said second perfume component is encapsulated by frangible microcapsules (d) an aqueous carrier, wherein said cleansing composition is characterized by a first aroma prior to use corresponding to said first perfume component, and a second aroma resulting from the release of said second perfume component upon application of mechanical force during use to fracture said microcapsules

Unless otherwise indicated, all percentages are calculated by weight of the total composition, and all ratios are calculated on a weight basis Unless otherwise indicated, ingredients are based on the active level and, therefore do not include carriers or by-products that may be included in commercially available materials

The present invention may comprise, consist of, or consist essentially of the required elements as well as any of the various optional or preferred elements disclosed herein

DETAILED DESCRIPTION OF THE INVENTION

The essential as well as a variety of preferred and optional elements and ingredients of the present invention are described below Detersive Surfactant

The level of detersive surfactants in the cleansing compositions of the present invention must be sufficient to effectively cleanse the hair or skin The cleansing compositions of the present invention will generally comprise from about 5% to about 40%, preferably from about 7% to about 30%, more preferably from about 10% to about 25%, by weight, of detersive surfactants

A wide variety of types of detersive surfactants and mixtures thereof, can be used These include anionic surfactants nonionic surfactants, amphoteπc surfactants and mixtures thereof Numerous of these are described in the non-exclusive description below

Anionic Surfactants Sulfates

Preferred anionic surfactants include alkyl sulfates alkyl ethoxylated sulfates and mixtures thereof These materials can have the respective formulae (I) ROSO3M and (II) RO(C2H- θ)_xSθ3M wherein R is alkyl or alkenyl of from about 8 to about 30 carbon atoms x is 1 to 10, and M is H or a soluble salt-forming cation such as ammonium, alkanolamine, such tπethanolamine, monovalent metals, such as sodium and potassium, and polyvalent metal cations, such as magnesium and calcium As with other anionic detersive surfactants, the cation M, of the anionic surfactant should be chosen such that the anionic surfactant component is water-soluble Solubility will depend upon the particular anionic surfactants and cations chosen As an aid to determining appropriate mixtures of anionic surfactants, the anionic surfactants should be chosen such that the Krafft temperature of the surfactants chosen is about 15°C or less, preferably about 10°C or less, more preferably about 0°C or less It is also preferred that the anionic surfactant be soluble in the composition hereof

Preferably, R in the above formulas has from about 10 to about 18 carbon atoms The alkyl ethoxylated sulfates are typically made as condensation products of ethylene oxide and monohydπc alcohols having from about 8 to about 24 carbon atoms The alcohols can be derived from fats, e g , coconut oil, palm kernal oil, or tallow, or can be synthetic Such alcohols are preferably reacted with about 1 to about 10 more preferably from about 1 to about 4, most preferably from about 2 to about 3 5, molar proportions of ethylene oxide and the resulting mixture of molecular species having, for example, an average of 3 moles of ethylene oxide per mole of alcohol, is sulfated and neutralized

Specific examples of alkyl ether sulfates which may be used in the present invention are sodium and ammonium salts of coconut alkyl tπethylene glycol ether sulfate, tallow alkyl tπethylene glycol ether sulfate and tallow alkyl hexaoxyethylene sulfate Highly preferred alkyl ether sulfates are those comprising a mixture of individual compounds said mixture having an average alkyl chain length of from about 12 to about 16 carbon atoms and an average degree of ethoxylation of from about 1 to about 4 moles of ethylene oxide N-Acylamino Acid Surfactant

Another type of anionic surfactant encompasses the N-acyl ammo acid surfactants For purposes hereof, these include N-acyl hydrocarbyl acids and salts thereof such as those represented by Formula III as follows 0 R2

II I R1 - C - N— (R³)_π— COOM (III)

wherein R is a C8-C24 alkyl or alkenyl radical, preferably C10-C18 R² is -H, C1-C4 alkyl, phenyl, or -CH2COOM, preferably C1 -C4 alkyl, more preferably C1-C2 alkyl, R³ is -CR⁴2- or C1-C2 alkoxy, wherein each R⁴ independently is -H or C-j-Ce alkyl or alkylester, and n is from 1 to 4, preferably 1 or 2, and M is -H or a cation as previously defined preferably an alkali metal such as sodium or potassium

A wide variety of N-acyl acid surfactants and their synthesis are described in Anionic Surfactants, Part II, Surfactant Science Series, Vol VII, edited by Warner M Linfield, Marcel Dekker, Inc (New York and Basel), 1976, pp 581-617

Especially preferred are compounds of Formula III wherein R² is methyl and R³ is -CH2-, and n is 1 , which are known as the N-acyl sarcosinates, and acids thereof Specific examples include lauroyl sarcosinate, mynstoyl sarcosinate, cocoyl sarcosinate, and oleoyl sarcosinate, preferably in their sodium and potassium salt forms

The "alkyl" or "alkenyl" radicals may contain one or more intermediate linkages such as ether or polyether linkages or non¬ functional substituents such as hydroxyi or halogen radicals wherein the radical remains of hydrophobic character Sulfonates

Examplary anionic detersive surfactants also include aliphatic sulfonates such as represented by the water-soluble salts of the organic, sulfuric acid reaction products of the general formula (IV)

R-I -SO3-M (IV) wherein R-| is chosen from the group consisting of a straight or branched chain, saturated aliphatic hydrocarbon radical having from about 8 to about 24, preferably about 12 to about 18 carbon atoms and M is a cation, as previously described subject to the same limitations regarding polyvalent metal cations as previously discussed Important examples are the salts of an organic sulfuric acid reaction product of a hydrocarbon of the methane series, including iso- neo- and n- paraffins having about 8 to about 24 carbon atoms, preferably about 12 about 18 carbon atoms and a sulfonating agent, e g , SO3 H2SO4 oleum, obtained according to known sulfonation methods including bleaching and hydrolysis Preferred are alkali metal and ammonium sulfonated C-12- 18 paraffins (e g normal and secondary paraffins)

Other suitable anionic detersive surfactants further include olefin sulfonates having about 12 to about 24 carbon atoms The term "olefin sulfonates" is used herein to mean compounds which can be produced by the sulfonation of alpha-olefins by means of uncomplexed sulfur tπoxide, followed by neutralization of the acid reaction mixture in conditions such that any sulfones which have been formed in the reaction are hydrolyzed to give the corresponding hydroxy- alkanesulfonates The sulfur tπoxide can be liquid or gaseous and is usually, but not necessarily, diluted by inert diluents, for example, by liquid SO2, chlorinated hydrocarbons, etc , when used in the liquid form or by air, nitrogen, gaseous SO2, etc , when used in the gaseous form The alpha-olefins from which the olefin sulfonates are derived are mono-olefins having about 12 to about 24 carbon atoms, preferably about 14 to about 16 carbon atoms Preferably, they are straight chain olefins Other Anionic Surfactants

Additional examples of synthetic anionic detersive surfactants which come within the terms of the present invention are the reaction products of fatty acids esteπfied with isethionic acid and neutralized with sodium hydroxide where, for example, the fatty acids are derived from coconut oil, sodium or potassium salts of fatty acid amides of methyl tauπde in which the fatty acids, for example, are derived from coconut oil Other synthetic anionic detersive surfactants of this variety are set forth in U S Patents 2,486,921 , 2 486,922 and 2,396 278

Still other synthetic anionic detersive surfactants are in the class designated as succinates This class includes such surface active agents as disodium N-octadecylsulfosuccinate tetrasodium N-(1 ,.- dιcarboxyethyl)-N-octadecylsulfosuccιnate diamyl ester of sodium sulfosuccinic acid, dihexyl ester of sodium sulfosuccinic acid dioctyl esters of sodium sulfosuccinic acid

Many additional synthetic anionic surfactants are described in McCutcheon's Emulsifiers and Detergents, 1989 Annual, published by M C Publishing Co , which is incorporated herein by reference Also U S Patent 3,929,678, Laughhn et al , issued December 30 1975 discloses many other anionic as well as other surfactant types and is incorporated herein by reference

Amphoteπc Surfactants

Examples of amphoteπc surfactants which can be used in the compositions of the present invention are those which are broadly described as derivatives of aliphatic secondary and tertiary amines in which the aliphatic radical can be straight or branched chain and wherein one of the aliphatic substituents contains from about 8 to about 18 carbon atoms and one contains an anionic water solubilizing group, e g , carboxy, sulfonate, sulfate, phosphate, or phosphonate

The amphoteric surfactant hereof include the imidazolinium amphoteric surfactants such as thoses depicted by Formula V

R3

I R¹CON ( CH₂ ) _n N⁺ - CH₂Z V

I I

R⁴ R2 wherein R - is C8-C22 alkyl or alkenyl, preferably C12- 16. ^{R2 IS} hydrogen or CH₂CO₂M, R³ is CH₂CH₂OH or CH₂CH₂OCH₂CH COOM, R⁴ is hydrogen, CH₂CH₂OH, or CH2CH2OCH2CH2COOM. Z is CO2M or CH2CO2M, n is 2 or 3, preferably 2, M is hydrogen or a cation, such as alkali metal, alkaline earth metal, ammonium, or alkonol ammonium

Suitable materials of this type are marketed under the tradename MIRANOL and are understood to comprise a complex mixture of species, and can exist in protonated and non-protonated species depending upon pH with respect to species that can have a hydrogen at R² The imidazolinum amphoteric surfactant hereof can be derived via an imidazolinium intermediate However, it will be recognized by thosed in the art that it needn't necessarily be derived via an imidazolinium

Preferred amphoteric surfactants of Formula VII are monocarboxylates and dicarboxylates Examples of these materials include cocoamphocarboxypropionate, cocoamphocarboxypropionic acid, cocoamphocarboxyglycinate (alternately referred to as cocoamphodiacetate), and cocoamphoacetate Specific commercial products providing the imidazolinium derivative surfactants include those sold under the trade names MIRANOL C2M CONC N P , MIRANOL C2M CONC 0 P , MIRANOL C2M SF, MIRANOL CM SPECIAL (Miranol, Inc ), ALKATERIC 2CIP (Alkaπl Chemicals), AMPHOTERGE W-2 (Lonza, Inc ), MONATERIC CDX-38 MONATERIC CSH-32 (Mona Industries), REWOTERIC AM-2C (Rewo Chemical Group), and SCHEROTERIC MS-2 (Scher Chemicals)

Amphoteric surfactants also include aminoalkanoates of the formula (VI)

R-NH(CH₂)_nCOOM, (VI) and

iminodialkanoates of the formula (VII)

R-N[(CH₂)mCOOM]₂ (VII)

and mixtures thereof, wherein n and m are numbers from 1 to 4, R is δ" 22 alkyl ^or alkenyl, and M is hydrogen, alkali metal, alkaline earth metal, ammonium or alkanolammonium

Examples of such amphoteric surfactants include n- alkylaminopropionates and n-alkyhminodipropionates Such materials are sold under the tradeπame DERIPHAT by Henkel and MIRATAINE by Miranol, Inc Specific examples include N-lauryl-beta-amino propioπic acid or salts thereof, and N-lauryl-beta-imino-dipropionic acid or salts thereof

Suitable surfactants include those represented by the Formula (VIII)

0 R R₂

II I I

R5- C - N - (CH₂)_m N⁺-Y-Rι (VIII)

I

R3 n wherein

R-_| is a member selected from the group consisting of COOM and CH-CH2SO3M

OH R₂ is C-1-C3 alkyl or hydroxy (C-1-C3) alkyl, R3 is C1-C3 alkyl or hydroxy (C^Cs) alkyl, R4 is a member selected from the group consisting of hydrogen and C-| -

C₃ alkyl, R5 is C8-C20 alkyl or alkenyl, Y is C-1-C3 alkyl, m is an integer from 2 to 7, n is the integer 1 or 0,

M is hydrogen or a cation, such as an alkali metal or alkaline earth cation metal, ammonium, or alkanolamide

The term "alkyl" or "hydroxyalkyl" means straight or branch chained, saturated, aliphatic hydrocarbon radicals and substituted hydrocarbon radicals such as, for example, methyl, ethyl, propyl isopropyl, hydroxypropyl, hydroxyethyl, and the like

Nonionic Surfactants

Nonionic detersive surfactants which can be used include those broadly defined as compounds produced by the condensation of alkylene oxide groups (hydrophilic in nature) with an organic hydrophobic compound, which may be aliphatic or alkyl aromatic in nature Examples of preferred classes of nonionic detersive surfactants are

1 The polyethylene oxide condensates of alkyl phenols, e g , the condensation products of alkyl phenols having an alkyl group containing from about 6 to about 20 carbon atoms in either a straight chain or branched chain configuration, with ethylene exode the said ethylene oxide being present in amounts equal to from about 10 to about 60 moles of ethylene oxide per mole of alkyl phenol

2 Those derived from the condensation of ethylene oxide with the product resulting from the reaction of propylene oxide and ethylene diamine products

3 The condensation product of aliphatic alcohols having from about 8 to about 18 carbon atoms, in either straight chain or branched chain configuration, with ethylene oxide, e g , a coconut alcohol ethylene oxide condensate having from about 10 to about 30 moles of ethylene oxide per mole of coconut alcohol, the coconut alcohol fraction having from about 10 to about 14 carbon atoms 4 Long chain tertiary amine oxides corresponding to the following general formula

R-| R₂R3N → 0 wherein R^«| contains an alkyl, alkenyl or monohydroxy alkyl radical of from about 8 to about 18 carbon atoms, from 0 to about 10 ethylene oxide moieties, and from 0 to about 1 glyceryl moiety, and R2 and R3 contain from about 1 to about 3 carbon atoms and from 0 to about 1 hydroxy group e.g , methyl, ethyl, propyl, hydroxyethyl or hydroxypropyl radicals the arrow in the formula is a conventional representation of a semipolar bond

5 Long chain tertiary phosphine oxides corresponding to the following general formula

RR'R"P → 0 wherein R contains an alkyl, alkenyl or monohydroxyalkyl radical ranging from about 8 to about 18 carbon atoms in chain length from 0 to about 10 ethylene oxide moieties and from 0 to about 1 glyceryl moiety and R' and R" are each alkyl or monohydroxyalkyl groups containing from about 1 to about 3 carbon atoms

6 Long chain dialkyl sulfoxides containing one short chain alkyl or hydroxy alkyl radical of from about 1 to about 3 carbon atoms (usually methyl) and one long hydrophobic chain which include alkyl alkenyl, hydroxy alkyl, or keto alkyl radicals containing from about 8 to about 20 carbon atoms, from 0 to about 10 ethylene oxide moieties and from 0 to about 1 glyceryl moiety

7 Alkyl polysacchaπde (APS) surfactants such as the alkyl polyglycosides Such surfactants are described in U S Patent 4,565,647, Llenado, issued January 21 , 1986, incorporated herein by reference, which discloses APS surfactants having a hydrophobic group with about 6 to about 30 carbon atoms and polysacchaπde (e g polyglycoside) as the hydrophilic group Optionally there can be a polyalkylene-oxide group joining the hydrophobic and hydrophilic moieties The alkyl group (i e , the hydrophobic moiety) can be saturated or unsaturated branched or unbranched and unsubstituted or substituted (e g , with hydroxy or cyclic rings)

8 Polyethylene glycol (PEG) glyceryl fatty esters such as those of the formula R(0)OCH₂CH(OH)CH2(OCH2CH₂)_πOH wherein n is from about 5 to about 200, preferably from about 20 to about 100 and R is an aliphatic hydrocarbyl having from about 8 to about 20 carbon atoms

Cosmetic or Pharmaecutical Agent

The cleansing compositions of the present invention comprise an effective amount of an additional cosmetic or pharmaceutical agent, such as a conditioning agent, styling agent, or medicament, or combination thereof, in an amount sufficient to accomplish the intended purpose of such ingredient or ingredients The additional cosmetic agent, as used herein, does not encompass fragrances or perfumes, nor does it encompass detersive surfactants Conditioning Agents

The cleansing compositions of the present invention can contain any of a wide variety of conditioning agents safe and effective for conditioning the hair or skin from the present cleansing compositions These include silicones, cationic surfactants and polymers, hydrocarbon esters, and fatty alcohols Treatment of the skin in connection with the present invention shall encompass treatment of the scalp as well as other-areas of the body, such as the hands, face, arms, underarms, back, neck, legs, etc "Conditioning agents", as the term is used herein, is intended to encompass all varieties of hair and/or skin conditioning ingredients including humectants, emollients, and moisturizers Silicone Conditioning Agents

Conditioning agents useful for treatment of the skin or hair can include nonvolatile soluble or insoluble silicone conditioning agents By soluble what is meant is that the silicone conditioning agent is miscible with the aqueous carrier of the composition so as to form part of the same phase By insoluble what is meant is that the silicone from a separate phase from the aqueous carrier, preferably as in the form of an emulsion or a suspension of droplets of the silicone

The silicone hair conditioning agent will tipically be used in the shampoo compositions hereof at levels of from about 05% to about 10% by weight of the composition, preferably from about 0 1 % to about 6%, more preferably from about 0 5% to about 5% most preferably from about 0 5% to about 3%

Soluble silicones include silicone copolyols such as dimethicone copolyols, e g polyether siloxane-modified polymers such as polypropylene oxide, polyethylene oxide modified polydimethylsiloxane wherein the level of ethylene and/or propylene oxide sufficient to allow solubility in the composition

Suitable insoluble silicone fluids include polyalkyl siloxanes polyaryl siloxanes, polyalkylaryl siloxanes polyether siloxane copolymers, and mixtures thereof

The insoluble silicone hair conditioning agent for use herein will preferably have viscosity of from about 1.000 to about 2 000,000 centistokes at 25°C, more preferably from about 10,000 to about 1 ,800,000, even more preferably from about 100,000 to about 1 ,500,000 The viscosity can be measured by means of a glass capillary viscometer as set forth in Dow Corning Corporate Test Method CTM0004, July 20, 1970

Silicone fluids hereof include polyalkyl or polyaryl siloxanes with the following structure

R R R

I I I

1 1 1 Sι - O - Sι - 0 - Si - A

I I I

1 1 1 R R „ R

wherein R is alkyl or aryl, and x is an integer from about 7 to about 8 000 may be used "A" represents groups which block the ends of the silicone chains

The alkyl or aryl groups substituted on the siloxane chain (R) or at the ends of the siloxane chains (A) may have any structure as long as the resulting silicones remain fluid at room temperature are hydrophobic are neither irritating, toxic nor otherwise harmful when applied to the hair, are compatible with the other components of the composition, are chemically stable under normal use and storage conditions and are capable of being deposited on and of conditioning hair

Suitable A groups include methyl, methoxy ethoxy, propoxy and aryloxy The two R groups on the silicone atom may represent the same group or different groups Preferably, the two R groups represent the same group Suitable R groups include methyl ethyl propyl phenyl methylphenyl and phenylmethyl The preferred silicones are polydimethyl siloxane polydiethylsiloxane and polymethylphenylsiloxane Polydimethylsiloxane is especially preferred

The nonvolatile polyalkylsiloxane fluids that may be used include, for example, polydimethylsiloxanes These siloxanes are available, for example, from the General Electric Company in their ViscasilR and SF 96 series, and from Dow Corning in their Dow Corning 200 series

The polyalkylaryl siloxane fluids that may be used, also include, 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

Especially preferred, for enhancing the shine characteristics of hair, are highly arylated silicones, such as highly phenylated polyethyl silicone having refractive indices of about 1 46 or higher, especially about 1 52 or higher. When these high refractive index silicones are used, they should be mixed with a spreading agent, such as a surfactant or a silicone resin, as described below to decrease the surface tension and enhance the film forming ability of the material

The polyether siloxane copolymers that may be used include 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 level for insoluble silicones should be sufficiently low to prevent solubility in the composition hereof

Another silicone hair conditioning material that can be especially useful in the silicone conditioning agents is insoluble silicone gum The term "silicone gum", as used herein, means polyorganosiloxane materials having a viscosity at 25°C of greater than or equal to 1 000 000 centistokes Silicone gums are described by Petrarch and others including U S Patent 4 152,416 Spitzer et al issued May 1 , 1979 and Noll Walter, Chemistry and Technology of Silicones, New York Academic Press 1968 Also describing silicone gums are General Electric Silicone Rubber Product Data Sheets SE 30, SE 33 SE 54 and SE 76 All of these described references are incorporated herein by reference The "silicone gums" will typically have a mass molecular weight in excess of about 200,000, generally between about 200,000 and about 1 000,000 Specific examples include polydimethylsiloxane,

(polydimethylsiloxane) (methylvinylsiloxane) copolymer polydi¬ methylsiloxane) (diphenyl sιloxane)(methylvιnylsιloxane) copolymer and mixtures thereof

Preferably the silicone hair conditioning agent comprises a mixture of a polydimethylsiloxane gum, having a viscosity greater than about 1 ,000,000 centistokes and polydimethylsiloxane fluid having a viscosity of from about 10 centistokes to about 100,000 centistokes, wherein the ratio of gum to fluid is from about 30 70 to about 70 30, preferably from about 40 60 to about 60 40

References disclosing suitable silicone fluids include U S Patent 2,826,551 , Geen, U S Patent 3,964,500, Drakoff, issued June 22, 1976, U S Patent 4,364,837, Pader, and British Patent 849,433, Woolston All of these patents are incorporated herein by reference Also incorporated herein by reference is Silicon Compounds distributed by Petrarch Systems, Inc 1984 This reference provides an extensive (though not exclusive) listing of suitable silicone fluids Cationic Surfactants

Cationic surfactants useful in compositions of the present invention, contain ammo or quaternary ammonium moieties The cationic surfactant will preferably, though not necessarily, be insoluble in the compositions hereof Cationic surfactants among those useful herein are disclosed in the following documents all incorporated by reference herein M C Publishing Co , McCutcheon's, Detergents & Emulsifiers, (North American edition 1979), Schwartz, et al Surface Active Agents Their Chemistry and Technology New York Interscience Publishers, 1949, U S Patent 3,155,591 , Hilfer issued November 3 1964 U S Patent 3 929 678 Laughhn et al issued December 30 1975 U S Patent 3,959 461 Bailey et al , issued May 25, 1976 and U S Patent 4 387,090 Bolich, Jr issued June 7 1983

Among the quaternary ammonium-containing cationic surfactant materials useful herein are those of the general formula I Rl R₃

N X-

R₂ R wherein R1-R are independently an aliphatic group of from about 1 to about 30 carbon atoms (preferably from about 1 to about 22) or an aromatic, alkoxy, polyoxyalkylene alkylamido, hydroxyalkyi, aryl or alkylaryl group having from about 1 to about 30 carbon atoms (preferably from about 1 to about 22), and X is a salt-forming anion such as those selected from halogen, (e g chloride, bromide iodide) acetate, citrate, lactate, glycolate, phosphate nitrate, sulfate, and alkylsulfate radicals The aliphatic groups may contain, in addition to carbon and hydrogen atoms, either linkages, and other groups such as am o groups The longer chain aliphatic groups, eg , those of about 12 carbons, or higher, can be saturated or unsaturated Especially preferred are di-long chain (e g , di C12-C22. preferably C16- 18 aliphatic, preferably alkyl) di-short chain (e g , C1-C3 alkyl, preferably C1-C2 alkyl) ammonium salts,

Salts of primary, secondary and tertiary fatty amines are also suitable cationic surfactant materials The alkyl groups of such amines preferably have from about 12 to about 22 carbon atoms, and may be substituted or unsubstituted Such amines, useful herein, include stearamido propyl dimethyl amine, diethyl ammo ethyl stearamide dimethyl stearamine, dimethyl soyamine, soyamme, myπstyl amine tridecyl amine, ethyl stearylamine, N-tallowpropane diamme ethoxylated (5 moles E O ) stearylamine, dihydorxy ethyl stearylamine and arachidylbehenylamine Suitable amine salts include the halogen acetate, phosphate, nitrate, citrate, lactate, and alkyl sulfate salts Such salts include stearylamine hydrochloπde soyamine chloride stearylamine formate, N-taliowpropane diamine dichloπde and stearamidopropyl dimethylamine citrate Cationic amine surfactants included among those useful in the present invention are disclosed in U S Patent 4,275,055, Nachtigal, et al , issued June 23 1981 incorporated by reference herein

Cationic surfactants are preferably utilized at levels of from about 0 1 % to about 10%, more preferably from about 025% to about 5% most preferably from about 0 5% to about 2% by weight of the composition Preferred cationic conditioning agents for use in the present invention are quaternary ammonium or ammo compounds having at least one radical covalently bonded to nitrogen containing one or more hydrophilic moieties selected from alkoxy, polyoxyalkylene, alkylamido hydroxyalkyi, and alkylester moieties, and combinations thereof In such cationic surfactants R-1-R4 can be as defined above, and at least one of the R1 -R4 radicals contains one or more hydrophilic moieties selected from alkoxy (preferably C-1 -C3 alkoxy), polyoxyalkylene (preferably C1-C3 polyoxyalkylene) alkylamido, hydroxyalkyi alkylester, and combinations thereof Preferably, the cationic conditioning surfactant contains from 2 to about 10 nonionic hydrophile moieties located within the above stated ranges Each hydrophilic amido, alkoxy, hydroxyalkyi, alkylester, alkylamido or other unit is considered to be a distinct nonionic hydrophile moiety

Examples of such quaternary ammonium salts include polyoxyethylene (2) stearyl methyl ammonium chloride, methyl bis (hydrogenated tallowamidoethyl) 2-hydroxyethyl ammonium methyl sulfate, polyoxypropylene (9) diethyl methyl ammonium chloride, tnpolypxyethylene (total PEG=10) stearyl ammonium phosphate, bιs(N- hydroxyethyl -2-oleyl imidazolinium chloride) polyethylene glycol (12), and isododecylbenzyl tπethanolammonium chloride Cationic Polymer Conditioning Agent

The compositions of the present invention can also comprise one or more cationic polymer conditioning agents The cationic polymer conditioning agent will preferably be water soluble Cationic polymers are typically used in the same ranges as disclosed above for cationic surfactants

By a "water soluble" cationic organic polymer, what is meant is a polymer which is sufficiently soluble in water to form a substantially clear solution to the naked eye at a concentration of 0 1 % in water (distilled or equivalent) at 25°C Preferably, the polymer will be sufficiently soluble to form a substantially clear solution at 0 5% concentration, more preferably at 1 0% concentration

As used herein, the term "polymer" shall include materials whether made by polymerization of one type of monomer or made by two (i e copolymers) or more types of monomers The cationic polymers hereof will generally have a weight average molecular weight which is at least about 5,000, typically at least about 10,000, and is less than about 10 million Preferably, the molecular weight is from about 100,000 to about 2 million The cationic polymers will generally have cationic nitrogen-containing moieties such as quaternary ammonium or cationic ammo moieties, or a mixture thereof

The cationic charge density is preferably at least about 0 1 meq/gram, more preferab at least about 1 5 meq/gram, even more referably at least abut 1 . meq/gram, most preferably at least about 1 2 meq/gram Cationic charge density of the cationic polymer can be determined according to the Kjeldahl Method Those skilled in the art will recognize that the charge density of ammo-containing polymers may vary depending upon pH and the isoelectric point of the ammo groups The charge density should be within the above limits at the pH of intended use

Any anionic counteπons can be utilized for the cationic polymers so long as the water solubility criteria is met Suitable countenons include halides (e g , Cl, Br, I, or F, preferably Cl, Br, or I), sulfate, and methylsulfate Others can also be used, as this list is not exclusive

The cationic nitrogen-containing moiety will be present generally as a substituent, on a fraction of the total monomer units of the cationic hair conditioning polymers Thus, the cationic polymer can comprise copolymers, terpolymers, etc of quaternary ammonium or cationic amine-substituted monomer units and other non-cationic units referred to herein as spacer monomer units Such polymers are known in the art, and a variety can be found in the CTFA Cosmetic Ingredient Dictionary, 3rd edition, edited by Estrin, Crosley, and Haynes, (The Cosmetic, Toiletry, and Fragrance Association, Inc , Washington D C 1982)

Suitable cationic polymers include, for example, copolymers of vinyl monomers having cationic amine or quaternary ammonium functionalities with water soluble spacer monomers such as acrylamide methacrylamide, alkyl and dialkyl acrylamides, alkyl and dialkyl methacrylamides, alkyl acrylate, alkyl methacrylate vinyl caprolactone and vinyl pyrrohdone The alkyl and dialkyl substituted monomers preferably have C1-C7 alkyl groups, more preferably C1-C3 alkyl groups Other suitable spacer monomers include vinyl esters vinyl alcohol (made by hydrolysis of polyvinyl acetate) maleic anhydride propylene glycol, and ethylene glycol

The cationic amines can be primary, secondary, or tertiary amines, depending upon the particular species and the pH of the shampoo In general, secondary and tertiary amines, especially tertiary amines, are preferred

Amine-substituted vinyl monomers can be polymerized in the amine form, and then optionally can be converted to ammonium by a quaternizatioπ reaction Amines can also be similarly quaternized subsequent to formation of the polymer For example, tertiary amine functionalities can be quaternized by reaction with a salt of the formula R'X wherein R' is a short chain alkyl, preferably a C-1 -C7 alkyl, more preferably a C-1 -C3 alkyl, and X is an anion which forms a water soluble salt with the quaternized ammonium

Suitable cationic am o and quaternary ammonium monomers include, for example, vinyl compounds substituted with dialkylaminoalkyl acrylate, dialkylaminoalkyl methacrylate, monoalkylaminoalkyl acrylate, monoalkylaminoalkyl methacrylate, tπalkyl methacryloxyalkyl ammonium salt, tnalkyl acryloxyalkyl ammonium salt, diallyl quaternary ammonium salts, and vinyl quaternary ammonium monomers having cyclic cationic nitrogen-containing rings such as pyπdinium, imidazolium, and quaternized pyrro done, e g , alkyl vinyl imidazolium alkyl vinyl pyπdinium, alkyl vinyl pyrrohdone salts The alkyl portions of these monomers are preferably lower alkyls such as the C-1 -C3 alkyls more preferably Cj and C₂ alkyls Suitable amine-substituted vinyl monomers for use herein include dialkylaminoalkyl acrylate dialkylaminoalkyl methacrylate, dialkylaminoalkyl acrylamide, and dialkylaminoalkyl methacrylamide, wherein the alkyl groups are preferably C-1 -C7 hydrocarbyls more preferably C1 -C3, alkyls

The cationic polymers hereof can comprise mixtures of monorrer units derived from amine- and/or quaternary ammonium-substituted monomer and/or compatible spacer monomers

Suitable cationic hair conditioning polymers include for example copolymers of 1-vιnyl-2-pyrrolιdone and 1 -vιnyl-3-methylιmιdazolιum salt (e g , chloride salt) (referred to in the industry by the Cosmetic Toiletry and Fragrance Association "CTFA", as Polyquaternιum-16) such as those commercially available from BASF Wyandotte Corp (Parsippany, NJ, USA) under the LUVIQUAT tradename (e g LUVIQUAT FC 370) copolymers of 1-vιnyl-2-pyrrolιdone and dimethylaminoethyl methacrylate (referred to in the industry by CTFA as Polyquaternιum-11 ) such as those commercially available from Gaf Corporation (Wayne, NJ, USA) under the GAFQUAT tradename (e g , GAFQUAT 755N), cationic diallyl quaternary ammonium-containing polymers, including, for example, dimethyldiallylammonium chloride homopolymer and copolymers of acrylamide and dimethyldiallylammonium chloride, referred to in the industry (CTFA) as Polyquatemium 6 and Polyquatemium 7, respectively, and mineral acid salts of ammo-alkyl esters of homo- and co-polymers of unsaturated carboxylic acids having from 3 to 5 carbon atoms, as described in U S Patent 4,009,256, incorporated herein by reference

Other cationic polymers that can be used include polysacchande polymers, such as cationic cellulose derivatives and cationic starch derivatives

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

Ri I

A- 0 ( - R-N^{+ ~} R₃X- ) I R2

wherein A is an anhydroglucose residual group, such as a starch or cellulose anhydroglucose residual, R is an alkylene oxyalkylene, polyoxyalkylene, or hydroxyalkylene group, or combination thereof, R-| , R2, and R3 independently are alkyl, aryl, alkylaryl, arylalkyl, alkoxyalkyl, or alkoxyaryl groups, each group containing up to about 18 carbon atoms, and the total number of carbon atoms for each cationic moiety (i e ,the sum of carbon atoms in R-^ , R2, and R3) preferably being about 20 or less, and X is an anionic countenon as previously described

Cationic cellulose is available from Amerchol Corp (Edison, NJ USA) in their Polymer JR^R and LR^R series of polymers as salts of hydroxyethyl cellulose reacted with tnmethyl ammonium substituted epoxide referred to in the industry (CTFA) as Polyquatemium 10 Another type of cationic cellulose includes the polymeric quaternary ammonium salts of hydroxyethyl cellulose reacted with lauryl dimethyl ammonium-substituted opoxide, referred to in the industry (CTFA) as Polyquatemium 24 These materials are available from Amerchol Corp (Edison, NJ, USA) under the tradename Polymer LM-200

Other cationic polymers that can be used include cationic guar gum derivatives such as guar hydroxypropyltπmonium chloride (commercially available from Celanese Corp in their JaguarR series) Other materials include quaternary nitrogen-containing cellulose ethers (e g , as described in U S Patent 3,962,418, incorporated by reference herein), and copolymers of ethenfied cellulose and starch (e g , as described in U S Patent 3,958,581 , incorporated by reference herein)

As discussed above, the cationic polymer hereof is water soluble This does not mean, however, that it must be soluble in the shampoo composition Preferably however, the cationic polymer is either soluble in the shampoo composition, or in a complex coacervate phase in the shampoo composition formed by the cationic polymer and anionic material Complex coacervates of the cationic polymer can be formed with anionic surfactants or with anionic polymers that can optionally be added to the compositions hereof (e g , sodium polystyrene sulfonate) Hydrocarbon. Ester and Alcohol Conditioning Agents

The conditioning agents hereof include fatty alcohols, and fluids selected from the group consisting of hydrocarbon fluids and fatty esters Such conditioning agents are typically used at a level of from about 0 1 % to about 10%, by weight of the composition, preferably from about 0 1 % to about 5%, more preferably from about 0 5% to about 2% The fatty esters hereof are characterized by having at least 10 carbon atoms and include esters with hydrocarbyl chains derived from fatty acids or alcohols, e g mono-esters, polyhydπc alcohol esters and di- aπd tπ-carboxylic acid esters The hydrocarbyl radicals of the fatty esters hereof can also include or have covalently bonded thereto other compatible functionalities, such as amides and alkoxy moieties (e g ethoxy or ether linkages, etc )

Hydrocarbon fluids include oils such as cyclic hydrocarbons straight chain aliphatic hydrocarbons (saturated or unsaturated), and branched chain aliphatic hydrocarbons (saturated or unsaturated), and mistures thereof Straight chain hydrocarbon oils will preferably contain from about 12 to about 19 carbon atoms, although it is not necessarily meant to limit the hydrocarbons to this range Branched chain hydrocarbon oils can and typically may contain higher numbers of carbon atoms Also encompassed herein are polymeric hydrocarbons of alkenyl monomers, such as C2-C_β alkenyl monomers These polymers can be straight or branched chain polymers The straight chain polymers will typically be relatively short in length, having a total number of carbon atoms as described above for straight chain hydrocarbons in general The branched chain polymers can have substantially higher chain length The number average molecular weight of such materials can vary widely, but will typically be up to about 500, preferably from about 200 to about 400, more preferably from about 300 to about 350 Specific examples of suitable materials include paraffin oil, mineral oil, saturated and unsaturated dodecane, saturated and unsaturated tridecane, saturated and unsaturated tetradecane, saturated and unsaturated pentadecane, saturated and unsaturated hexadecane, and mixtures thereof Branched-cham isomers of these compounds, as well as of higher chain length hydrocarbons, can also be used Exemplary branched-cham isomers are highly branched saturated or unsaturated alkanes, such as the permethyl-substituted isomers, e g , the permethyl-substituted isomers of hexadecane and eiocosane, such as 2, 2, 4, 4, 6, 6, 8, 8-dιmethyl-10- methylundecane and 2, 2, 4, 4, 6, 6-dιmethyl-8-methylnonane, sold by Permethyl Corporation Polymeric organic materials are also useful conditioning agents A preferred organic polymer is polybutene such as the copolymer of isobutylene and butene A commercially available material of this type if L-14 polybutene from Amoco Chemical Co (Chicago, Illinois, U S A ) Other polymeric conditioners can include polyisoprene, polybutadiene, and other hydrocarbon polymers of C4 to C12 straight and branched chain mono- and di- unsaturated aliphatic monomers, and derivatives thereof Monocarboxy c acid esters hereof include esters of alcohols and/or acids of the formula R'COOR wherein alkyl or alkenyl radicals and the sum of carbon atoms in R' and R is at least 10, preferably at least 20

Fatty esters include, for example, alkyl and alkenyl esters of fatty acids having aliphatic chains with from about 10 to about 22 carbon atoms, and alkyl and alkenyl fatty alcohol carboxylic acid esters having an alkyl and/or alkenyl alcohol-derived aliphatic chain with about 10 to about 22 carbon atoms, and combinations thereof Examples include isopropyl isostearate, hexyl laurate, isohexyl laurate, isohexyl palmitate, isopropyl palmitate, decyl oleate, isodecyl oleate, hexadecyl stearate, decyl stearate, isopropyl isostearate, dihexyldecyl adipate, lauryl lactate, myristyl lactate, cetyl lactate, oleyl stearate, oleyl oleate, oleyl myπstate, lauryl acetate, cetyl propionate, and oleyl adipate

The mono-carboxylic acid ester however need not necessarily contain at least one chain with at least 10 carbon atoms, so long as the total number of aliphatic chain carbon atoms is at least 10 Examples include dnsopropyl adipate, dusohexyl adipate, and dnsopropyl sebacate

Di- and tn-alkyl and alkenyl esters of carboxylic acids can also be used These include, for example, esters of C4-C8 dicarboxylic acids such as C-1 -C22 esters (preferably C-| -C6) of succ ic acid, glutanc acid, adipic acid, hexanoic acid, heptanoic acid, and octanoic acid Specific example include isocetyl stearyol stearate, dnsopropyl adipate and tristearyl citrate

Polyhydπc alcohol esters include alkylene glycol esters, for example ethylene glycol mono and di-fatty acid esters, diethyleπe 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 are satisfactory polyhydπc alcohol esters for use herein Glycerides include mono-, dι-, and tri-glycerides More specifically, included are the mono-, dι-, and tπ-estres of glycerol and long chain carboxylic acids, such as C-1 -C22 carboxylic 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 tπolein and tristeann glyceryl dilaurate Preferred glycerides are dι-, and tri-glycerides Especially preferred are triglycerides

Fatty alcohols useful for conditioning agents include both saturated and unsaturated nonvolatile C8-C22 alcohols

By nonvolatile what is meant is they have a boiling point at 1 0 atmospheres of at least about 260°C, preferably at least about 275°C, more preferably at least about 300°C

Suitable fatty alcohols include unsaturated monohydπc straight chain fatty alcohols, saturated branched chain fatty alcohols, saturated straight chain monohydπc fatty alcohols and mixtures thereof The unsaturated straight chain fatty alcohols will typically have about one degree of unsaturation Di- and tn- unsaturated alkenyl chains may be present at low levels, preferably less than about 5% by total weight of the unsaturated straight chain fatty alcohol more preferably less than about 2%, most preferably less than about 1 %

Preferably, the unsaturated straight chain fatty alcohols will have an aliphatic chain size of from C12-C22 more preferably from C14-C20. most preferably from C-|6-C-| 8 Exemplary alcohols of this type include oleyl alcohol, palmitoleic alcohol

The branched chain alcohols will typically have aliphatic chain sizes of from C12-C22. preferably from C14-C 20 ^more preferably C-J 6- C-| 8 Exemplary branched chain alcohols for use herein include isostearyl alcohol octyl dodecanol, and octyl decanol

Examples of saturated C8-C22 straight chain alcohols include octyl alcohol, caprylic alcohol, decyl alcohol, lauryl alcohol, coconut fatty alcohol, cetyl alcohol, stearyl alcohol, benzyl alcohol, etc

Suitable polyhydroxy alcohols include glycerol, butylene glycol hexyleπe glycol, sorbitol, hexanetnol, propylene glycol and polyethylene glycols

Other conditioning agents include panthenol 24 Adhesive Polymers

Adhesive polymers can be useful as cosmetic agents as hair setting agents and skin film forming agents, generally at a level of from about 0 01 % to about 15%, preferably from about 0 1 % to about 10%, more preferably from about 0 2% to about 8%, by weight of the composition

Exemplary adhesive polymers include polyvinylpyrro done (PVP), particularly poly N-vmyl pyrrohdone, copolymers of PVP and methylmetharylate, copolymers of PVP and vinyl acetate (VA), and polyvinyl alcohol (PVA)

Exemplary adhesive polymers also include copolymers of VA and crotonic acid, copolymers of methylvinylether and maleic hemiesters (e g maleic ethyl ester and maleic butyl ester), hydroxypropyl cellulose hydroxypropyl guar gum, polystyrene sulfonate salts, polyacry c polymers such as polymers and copolymers of acrylic acid and methacryhc acid, co- and ter- polymers of acrylic acid and/or methacyhc acid with acrylamide and/or vinyl pyrrohdone such as terpolymers of vinyl pyrrolidone/methyl methacrylate/methacryhc, terpolymers of vinyl pyrrolidone/ethylmethacrylate/methacryhc acid, terpolymers of t-butyl acrylamide/ethyl acrylate/acry c acid, and terpolymers of VA/crotonic acid/vinyl neodecanoate

Other examples of adhesive polymers are crotonic acid and a vinyl ester of an alpha-branched saturated aliphatic monocarboxyhc acid such as vinyl neodecanoate, and copolymers of methyl vinyl ether and maleic anhydride (e g molar ratio about 1 1 ) wherein such copolymers are 50% estenfied with a saturated aliphatic alcohol containing from 1 to 4 carbon atoms such as ethanol or butanol, and acrylic copolymers and terpolymers containing acrylic acid or methacryhc acid as the anionic radical-containing moiety such as copolymers with, butyl acrylate, ethyl methacrylate, etc

Polymeric adhesive polymers also include amphoteric polymers One class of amphoteric polymers that can be used are acrylic resins with both cationic and carboxylic groups Examples include terpolymers of octyl and acrylamide/acryhc acid/butylammoethyi methacrylate copolymers of acrylic acid/betaine methacrylate, and copolymers of octylacrylamide/acrylates Silicone grafted adhesive copolymers can also be used These polymers typically comprise an organic backbone, especially a carbon backbone such as a vinyl polymeric backbone, and a polydimethylsiloxane macromer having a weight average molecular weight of at least about 500, preferably from about 1 ,000 to about 100,000, more preferably from about 2,000 to about 50,000 more preferably about 5,000 to about 20,000, is grafted to the backbone Organic backbones contemplated include those that are derived from polymeπzable, ethy nically unsaturated monomers These include vinyl monomers, and other condensation monomers (e g , those that polymerize to form polyamides and polyesters) and ring-opening monomers (e g , ethyl oxazohne and caprolactone) Silicone grafted copolymers can be made by copolymeπzation of non-silicone-containmg monomers with silicone-containmg polymeπzable monomers

The preferred polymeπzable silicone-containmg monomer (C monomer) can be exemplified by the general formula

X(Y)πSι(R)3-mZ_m wherein X is a vinyl group copolymeπzable with the A and B monomers,

Y is a divalent linking group, R is a hydrogen, hydroxyl, lower alkyl (e g

C-1-C4), aryl, alkaryl, alkoxy, or alkylammo, Z is a monovalent siloxane polymeric moiety having a number average molecular weight of at least about 500, is essentially unreactive under copolymeπzation conditions, and is pendant from the vinyl polymeric backbone described above n is

0 or 1 , and m is an integer from 1 to 3

Examples of useful polymers and how they are made are described in detain in U.S Patent 4,693,935 Mazurek issued September 15, 1987, U S Patent 4,728,571 , Clemens at al , issued March 1 1988, both of which are incorporated herein by reference

Suitable polymers are also disclosed in EPO Application 90307528 1 , published as EPO Application 0 408 311 A2 on January 11 , 1991 , Hayama, et al , U S Patent 5,061 ,481 issued October 20 1991 Suzuki et al , U S Patent 5,106,609, Bohch et al , issued April 21 1992, U S Patent 5,100,658, Bohch et al , issued March 31 , 1992 U S Patent 5,100,657, Ansher-Jackson et al , issued March 31 , 1992 U S Patent 5,104,646 Bohch et al issued April 14, 1992, and U S Serial No 08/104 232 Bo ch et al filed August 10 1993 all of which are incorporated by reference herein Examples of these polymers are copolymers comprising t-butyl acrylate and/or t-butyl methacrylate with vinyl monomers having polydimethylsiloxane macromers covalently attached thereto Pharmaceutical Agents

The compositions of the present invention can comprise a safe and effective amount of a pharmaceutical agent The phrase "safe and effective amount", as used herein, means an amount of an active high enough to significantly or positively modify the condition to be treated, but low enough to avoid serious side effects (at a reasonable benefit/risk ratio), within the scope of sound medical judgement A safe and effective amount of the pharmaceutical active will vary with the specific active, the ability of the composition to penetrate the active through the skin, the amount of composition to be applied the particular condition being treated, the age and physical condition of the patient being treated, the severity of the condition, the duration of the treatment, the nature of concurrent therapy, and like factors

The pharmaceutical agents generally comprise from about 0 1 % to about 20% by weight of the compositions when used, more typically from about 0 1 % to about 10%, and most typically from about 0 1 % to about 5% Mixtures of pharmaceutical agents may also be used

Nonlimiting examples of pharmaceutical agents can include the following

Useful pharmaceutical agents in the compositions of the present invention include anti-acne drugs Anti-acne drugs include the keratolytics such as salicylic acid, sulfur, lactic acid, glycohc, pyruvic acid, urea, resorcmol, and N-acetylcysteine, retinoids such as retmoic acid and its derivatives (e g , cis and trans) antibiotics and antimicrobials such as benzoyl peroxide, octopirox, erythromycin zinc, tetracychn, tπclosan azelaic acid and its derivatives, phenoxy ethanol and phenoxy proponol, ethylacetate, chndamycin and meclocyc ne sebostats such as flavmoids, alpha and beta hydroxy acids, and bile salts such as scymnol sulfate and its derivatives deoxycholate and cholate

Useful pharmacetuical agents in the compositions of the present invention include non-steroidal anti-inflammatory drugs (NSAIDS) The NSAIDS can be selected from the following categories propionic acid derivatives acetic acid derivatives fenamic acid derivatives biphenylcarboxyhc acid derivatives, and oxicams All of these NSAIDS are fully described in the U S Patent 4,985,459 to Sunshine et al , issued January 15, 1991 , incorporated by reference herein Most preferred are the propionic NSAIDS including but not limited to aspirin, acetaminophen, ibuprofen, naproxen, benoxaprofen, flurbiprofen, fenoprofen, fenbufen, ketoprofen, mdoprofen, pirprofen, carprofen, oxaprozm, pranoprofen, miroprofen, tioxaprofen, suprofen, almmoprofen, tiaprofenic acid, fluprofen and bucloxic acid Also useful are the steroidal anti-inflammatory drugs including hydrocortisone and

Useful pharmaceutical agents in the compositions of the present invention include antipruritic drugs Antipruπtic drugs preferred for inclusion in compositions of the present invention include pharmaceu- tically-acceptable salts of methdilizme and trimeprazine

Useful pharmaceutical agents in the compositions of the present invention include include anesthetic drugs Anesthetic drugs preferred for inclusion in compositions of the present invention include pharmaceutically-acceptable salts of docaine, bupivacaine, chlorprocame, dibucaine, etidocaine, mepivacaine, tetracaine, dyclonme, hexylcame, procame, cocaine, ketamme, pramoxine and phenol

Useful pharmaceutical agents in the compositions of the present invention include antimicrobial drugs (antibacterial, antifungal, antiprotozoal and antiviral drugs) Antimicrobial drugs preferred for inclusion in compositions of the present invention include pharmaceu¬ tically-acceptable salts of β-lactam drugs, qumolone drugs, ciprofloxacin, norfloxacin, tetracychne, erythromycin, amikacin, tπclosan, doxycyc ne, capreomycm, chlorhexidine, chlortetracychne, oxytetracychne, chndamycin, ethambutol, metronidazole, pentamidine ^""•ntamicin, kanamycm, hneomycin methacychne, metheπamine minocychne, neomycin netilmicm, paromomycm streptomycin tobramycin miconazole and amanfadme Antimicrobial drugs preferred for inclusion in compositions of the present invention include tetracychne hydrochlonde, erythromycin estolate erythromycin stearate (salt) amikacin sulfate. doxycychne hydrochlonde capreomycm sulfate chlorhexidine gluconate chlorhexidine hydrochlonde chlortetracychne hydrochlonde, oxytetracychne hydrochlonde chndamycin hydrochlonde ethambutol hydrochlonde metronidazole hydrochlonde, pentamidine hydrochlonde, gentamicm sulfate, kanamycin sulfate hneomycin hydrochlonde, methacychne hydrochlonde, metheπamme hippurate methenamme mandelate, minocychne hydrochlonde, neomycm sulfate, netilmicin sulfate, paromomycm sulfate, streptomycin sulfate, tobramycin sulfate, miconazole hydrochlonde amanfadme hydrochlonde, amanfadme sulfate, tnclosan, octopirox, parachlorometa xylenol, nystatm, tolnaftate and clotπmazole

Also useful herein as pharmaceutical agents are sunscreenmg agents A wide variety of sunscreenmg agents are described in U S Patent No 5,087,445, to Haffey et al , issued February 1 1 , 1992 U S Patent No 5,073,372, to Turner et al , issued December 17, 1991 U S Patent No 5,073,371 , to Turner et al issued December 17, 1991 , and Segarin, et al , at Chapter VIII, pages 189 et seq of Cosmetics Science and Technology, all of which are incorporated herein by reference in their entirety

Preferred among the sunscreens are those selected from the group consisting of 2-ethylhexyl p-methoxycmnamate, 2-ethylhexyl N,N- dimethyl-p-aminobenzoate, p-ammobeπzoic acid, 2- phenylbenzιmιdazole-5-sulfoπιc acid octocrylene, oxybenzone homomenthyl sa cylate, octyl sahcylate, 4,4'-methoxy-t- butyldibenzoylmethane, 4-ιsopropyl dibenzoylmethane, 3-benzyhdene camphor, 3-(4-methylbenzylιdene) camphor, titanium dioxide zinc oxide, silica, iron oxide, and mixtures thereof

Still other useful sunscreens are those disclosed in U S Patent No 4,937,370, to Sabatel , issued June 26, 1990, and U S Patent No 4.999,186, to Sabatelh et al , issued March 12 1991 , these two references are incorporated by reference herein in their entirety The sunscreenmg agents disclosed therein have, in a single molecule, two distinct chromophore moieties which exhibit different ultra-violet radiation absorption spectra One of the chromophore moieties absorbs predominantly in the UVB radiation range and the other absorbs strong¬ ly in the UVA radiation range These sunscreenmg agents provide higher efficacy, broader UV absorption lower skin penetration and longer lasting efficacy relative to conventional sunscreens Especially preferred examples of these sunscreens include those selected from the group consisting of 4-N N-(2-ethylhexyl)methylamιnobenzoιc acid ester of 2 4-dιhydroxybenzophenone, 4-N N-(2- ethylhexyl)methylamιnobenzoιc acid ester with 4- hydroxydibenzoylmethaπe 4-N,N- (2-ethylhexyl)methylamιnobenzoιc acid ester of 2-hydroxy-4-(2-hydroxyethoxy)benzophenone 4-N,N-(2- ethylhexyl)-methylamιnobenzoιc acid ester of 4-(2-hydroxyeth- oxy)dιbenzoylmethane, and mixtures thereof

Generally, the sunscreens can comprise from about 0 5% to about 20% of the compositions useful herein Exact amounts will vary depending upon the sunscreen chosen and the desired Sun Protection Factor (SPF) SPF is a commonly used measure of photoprotection of a sunscreen against erythema See Federal Register, Vol 43, No 166, pp 38206-38269, August 25, 1978, which is incorporated herein by reference in its entirety

Also useful in the present invention as cosmetic agents are sunless tanning agents including dihydroxyacetone, glyceraldehyde, indoles and their derivatives, and the like These sunless tanning agents may also be used in combination with the sunscreen agents

— Other useful cosmetic agents include skin bleaching (or lightening) agents including but not limited to hydroqumone, ascorbic acid, kojic acid and sodium metabisulfite

Other useful pharmaceutical agents which are especially useful for hair care compositions include anti-dandruff actives such as zinc pynthione, octopirox, selenium disulfide, sulfur, coal tar, salicylic acid,

Dual Blooming Perfume System

The compositions of the present invention comprise a first perfume component which is substantially nonconfined By substantially nonconfined what is meant is that the perfume is incorporated in the composition in a form such that it is able to volatilize upon exposure of the composition to the atmosphere without the application of external mechanical force In other words when the composition is stored in a closed container, and the container is then opened to dispense the product the substantially nonconfined perfume is able to impart its aroma to a user under normal usage conditions Preferably, but not necessarily, the substantially nonconfined perfume component is incorporated into the composition without any form of encapsulation or other restrictions upon release to the atmosphere The present compositions also contain a second perfume component, which is encapsulated by a frangible microcapsules made from an encapsulation material The second perfume component must be characterized by a different aroma than the first perfume component The user of a composition of the present invention will first be exposed to the first perfume component while in the act of dispensing it for eventual use Upon application of the composition to the hair or skin with application of mechanical force, such as by rubbing or distributing the composition throughout the hair or onto an area of skin with ones hands and fingers, the frangible microcapsules of the second perfume component rupture, or fracture, thereby releasing the second perfume component to the atmosphere During the application of mechanical force, the composition is spread throughout the area to be treated Release of the second perfume component consequently coincides with the distribution of the additional cosmetic or pharmaceutical agent over the intended area of treatment It is also contemplated to utilize additional encapsulated perfume components of additional, aromatic characters

By frangible encapsulation material what is meant is that the encapsulation material is capable of rupturing, fracturing, to release the enclosed perfume by application of mechanical force during use of the composition, such as when application rubbing or massaging the composition onto or into the skin or hair The encapsulation should have sufficient integrity such that merely pouring the composition or otherwise dispensing it from its container does not cause a sufficient amount of the second perfume cpmponent to be released to cause a change in aroma

The type and amount of the second perfume component that should be used should be such that upon release during use, there is a change in the overall aroma of the cleansing composition By a change in aroma what is meant is a user of ordinary olfactory acuity c.n perceive that the aromatic character of the composition not merely the intensity of the aroma has changed A sufficient base size of users in accordance with good statistical practice should be utilized to provide statistically significant results Changes in aroma can also be determined by an expert perfumer who is duly recognized as such within the perfume industry Expert perfumers would include, for example, perfumers who are members (excluding merely honorary members) of The American Society of Perfumers or other perfume societies having substantially equivalent membership requirements

Typically, the present compositions will comprise from about 0 01 % to about 3% by weight of the composition, more typically from about 0 05% to about 2%, most typically from about 0 1 % to about 1 %, of each perfume component The level of the second perfume component includes microcapsule materials that are present

The perfume components hereof can each contain one or more perfume ingredients By perfume ingredient what is meant is any safe, odofenous material which exudes a pleasant or otherwise desired aroma at ambient temperatures

The perfume components hereof are, in general, liquids at ambient temperature and are characterized by a flash point of from about 10°C to about 120°C, more typically from about 35°C to about 95° C (as determined according to ASTM D-56 (c c ) - Standard Test Method for Flash Point by Tag Closed Tester)

The perfume ingredients are typically incorporated into the perfume components in liquid form, but can also be solids (such as the various camphoraceous perfumes known in the art) which are solubi zed form in other ingredients of the perfume component

In addition to the perfume ingredients, the perfume components hereof can also include additional ingredients such as diluents, solvents for solid perfume ingredients, and fixatives, etc Diluents may or may not have their own aroma and, to the extent that they do, they are categorized for purposes of this invention as perfume ingredients Exemplary diluents and solvents include alcohols (e g ethyl alcohol, benzyl alcohol, dipropyleπe glycol, etc ), and liquid hydrocarbon and hydrocarbon esters (e g benzyl benzoate and other hydrocarbons and esters described above) Fixatives are ingredients which prolong the lasting quality of the perfume upon use and can do so by modifying the overall volatility of the perfume component Some fixatives can function as perfume ingredients whereas other do not To the extent that a particular ingredient performs both functions, it shall be considered a perfume ingredient for purposes of this invention Exemplary fixatives include musk perfume ingredients described below A wide variety of perfume ingredients are described in S Arctander, Perfume Flavors and Chemicals, Vols I and II , Aurthor Montclair, NJ, the Merck Index, 8th Edition Merck & Co , Inc Rahway NJ, and Secondmi, Handbook of Perfumes and Flavors, Chemical Publishing Co , Inc , New York, NY, 1990 (ISBN) 0-8206-0334-1 )

The typical perfume component will comprise a plurality of individual ingredients, although it can consist essentially of a single perfume ingredient It is well within the scope of the perfumer of ordinary skill in the art changing ingredients in the perfume component and/or modifying the relative levels of perfume ingredients

Various types of chemical compounds are commonly known for perfumery uses including phenolic compounds, essential oils, aldehydes, ketones, polycychc compounds, esters, and alcohols Many perfume ingredients contain a combination of functional groups and can be categorized under two or more of the above classes

From the standpoint of the perfumer, it is convenient to consider the perfume ingredients in terms of the type of aroma it imparts rather than 4he particular chemical class or classes it may fall within The perfume components herein can be formulated to provide a variety of odor categories a nonexclusive list includes woody, sweet, citrus floral, fruity, animal, spice, green, musk, balsamic, chemical, and mint A variety of exemplary perfume ingredients are described below for several of the commonly used ordor categories, long with their representative (but not necessarily exclusive) chemical categories

Woody perfume ingredients include cedarwood oil (essential oil) guaicwood oil (essential oil), gamma lonone (ketone) sandalwood oil (essential oil), and methyl cedrylone (ketone)

Sweet perfume ingredients include coumaπn (ketone), vanillin (4 hydroxy-3methoxy benzaldehyde) (aldehyde), ethyl maltol (Alcohol) phenyl acetaldehyde (aldehyde), hehotropin (aldehyde) acetopheπone (ketone), and dihydrocoumarin (ketone)

Citrus perfume ingredients include orange oil (essential oil) lemon oil (essential oil), citral (aldehyde), beta methyl naphthyl ketone (ketone) terpmyl acetate (ester) nonyl aldehyde (aldehyde), terpineol (alcohol), and dihydromyrcenol (alcohol)

Floral perfume ingredients include a variety of floral subcategoπes, such as rose lavender, jasmin, and muguet Rose perfume ingredients include geraπyl acetate (ester), geraniol (alcohol) citronelyl acetate (ester), phenyl ethyl alcohol (alcohol) alpha damascone (ketone), beta damascone (ketone), geranium oil (essential oil), and natural rose oil (essential oil) Lavender perfume ingredients include dihydro terpmyl acetate (ester), ethyl hexyl ketone (ketone) lavandin (essential oil), lavender (essential oil), tetra hydro Imalool (alcohol), Imalool (alcohol), and linalyl acetate (ester) Jasmin perfume ingredients include benzyl acetate (ester), butyl cmnamic aldehyde (aldehyde), methyl benzoate (ester), natural jasmin oil (essential oil), methyl dihydro jasmonate (ester) Muguet perfume ingredients include cycalmen aldehyde (aldehyde), benzyl salycilate (ester) hydroxycitronellol (alcohol), citronellyl oxyacetaldehyde (aldehyde), and hydroxy aldehyde (aldehyde)

Fruity perfume ingredients include ethyl-2-methyl butyrate (ester), allyl cyclohexane propionate (ester) amyl acetate (ester), ethyl acetate (ester), gamma decalactone (ketone), octalactone (ketone), undecalactone (aldehyde), ethyl aceto acetate (ester), benzaldehyde (aldehyde)

Animal perfume ingredients include methyl phenyl acetate (ester), mdol (2,3, benzpyrrole) (phenolic), creosol (phenolic), iso butyl quinohn (phenolic), and androstenol (phenolic)

Spice perfume ingredients include anisic aldehyde (aldehyde) anise (essential oil), clove oil (essential oil) eugenol (phenolic), iso eugenol (phenolic), thymol (phenolic), anethol (phenolic), cmnamic alcohol (alcohol), and cmnamic aldehyde (aldehyde)

Green perfume ingredients include beta gamma hexenol (alcohol), brom styrol (alcohol), dimethyl benzyl carbmol (alcohol) methyl heptme carbonate (ester), cιs-3-hexenyl acetate (ester) and galbanum oil (essential oil)

Musk perfume ingredients often also function as fixatives Examples of musk include glaxohde (phenol), cyclopeπtadecanohde (phenol), musk ketone (ketone), ambrettohde (phenol) tonahd (phenol) and ethylene brassylate (ester)

Balsamic perfume ingredients include fir balsam (essential oil peru balsam (essential oil) and benzoin resmoid (essential oil) Chemical perfume ingredients include benzyl alcohol (alcohol) diproplene glycol (alcohol) ethanol (alcohol) and benzyl benzoate (ester)

Mint perfume ingredients include laevo carvone (ketone) menthol (alcohol), methyl sahcylate (ester), peppermint oil (essential oil), spearmint oil (essential oil), eucalyptus (essential oil) anisyl acetate (ester), methyl chavicol (alcohol) Encapsulation

As an essential aspect of the present invention, the second confined perfume component is encapsulated by a frangible microcapsules

The microcapsules should be insoluble in water and be of sufficient integrity to remain intact during processing, packaging shipment, and normal storage The encapsulation material should be sufficiently frangible such that it ruptures, or fractures, upon application of mechanical force during use (e g , as when lathering the hair or scalp or otherwise rubbing the composition onto or into the skin or hair with hands or fingers), a sufficient portion of the microcapsules rupture to release the second perfume component and change the aroma of the composition

The size of the microcapsules is not critical so long as the requirements of the invention as stated herein are met In general, the capsules will have an average diameter of from about 5 microns to about 1000 microns, more generally from 10 microns to about 300 mcirons

The microcapsuled second perfume component thus comprise a liquid core of the second perfume component and a water insoluble shell of the encapsulation material (i e , microcapsules) containing the liquid core

The shell material surrounding the perfume core to form the microcapsule can be any suitable film forming material which is impervious to the materials in the liquid core and to the materials which may come in contact with the outer surface of the microcapsule shell The microcapsule shell wall can be composed of a wide variety of polymeric materials including polyurethane, polyamide polyester polysacchande silicone resins epoxy resins polyvmyl alcohol and proteins such as gelatin casein, and serum albumen Many of these types of polymeric microcapsule shell materials are further described and exemplified in Ida et al, U S Patent 3,870,542, issued March 1 1 , 1975, U S Patent 3,516 941 , Matson, issued June 23, 1970 and U S Patent 3,755,190, Hart et al , issued August 28, 1973, the disclosures of which is incorporated herein by reference

Exemplary materials for the microcapsule shell wall include the animoplast polymers comprising the reactive products of urea and aldehyde, e g formaldehyde Such materials are those which are capable of acid condition polymerization from a water-soluble prepolymer state Such prepolymers can be made by reacting urea and formaldehyde in a formaldehyde, urea molar ratio of from about 1.2 1 to 2 6 1 Thiourea, cyanuramide, guaπidme, N-alkyl ureas, phenols, sulfonamides, anilines and amines can be included in small amounts as modifiers for the urea Polymers formed from such prepolymer materials under acid conditions are water-insoluble and can provide the requisite capsule frangible characteristics as described more fully hereinafter.

Microcapsules having the liquid cores and polymer shell walls as described above can be prepared by any conventional process which produces capsules of the requisite size, frangihty and water-insolubility Generally, such methods as coacervation and interfacial polymerization can be employed in known manners to produce microcapsules of the desired characteristics Such methods are described in Ida et al U S Patent 3 870,542, issued Marcy 1 1 , 1975, Powell et al , U S Patent 3,415,758, issued December 10, 1968, and Anthony, U S Patent 3.041 ,288, issued June 26, 1962 All of these patents are incorporated herein by reference

Microcapsules made from urea-formaldehyde shell materials can be made by an interfacial polymerization process described more fully in Matson, U S Patent 3,516,941 , issued June 23, 1970, incorporated herein by reference By that process an aqueous solution of a urea- formaldehyde precondensate (methylol urea) is formed containing from about 3% to 30% by weight of the precondensate Water-insoluble liquid core material (i e , perfume) is dispersed throughout this solution in the form of microscopically-sized discret droplets While maintaining solution temperature between 20°C and 90°C acid is then added to catalyze polymerization of the dissolved urea-aldehyde precondensate

SUBSTrTUTE SHEET (RULE 26) If the solution is rapidly agitated during this polymerization step shells of water-insoluble urea-formaldehyde polymer form around and encapsulate the dispersed droplets of liquid core materials

Preferred microcapsules are made by complex coacervation utilizing hydrophilic colloids, such as gelatin casein zein, serum albumin, algmate (such as sodium algmate), carrageenan agar polyvmylmethylether maleic anhydride copolymer, pectins, carboxymethylcellulose, hexametapolyphosphate, and gum arable, among others that may be known or useful in the art Methods for making microcapsules of hpophihc materials such as perfumes, are well known in the art Specific examples are disclosed in U S patent

2.800.457, Green and Schleicher, issued July 23, 1957, U S Patent

2.800.458, Green, issued July 23, 1957, and U S Patent 3,041 ,289, Katchen et al , issued June 26, 1962, all of which are incorporated herein by reference

A variety of encapsulation techniques are also described by P B Deasy, Microencapsulation and Related Drug Processes, Dekker, NY, NY 1986 by A Kondo, Microencapsulation Processing and Technology, Dekker, Ny, NY, 1979, and by Curt Thies, Applied Advanced Microencapsulation By Complex Coacervation, Thies Technology Inc , St Louis, MO, USA, 1993

In general, complex coacervation microencapsulation can be carried out by dissolving in aqueous solution at elevated temperature a film forming polyelectrolyte hydrocolloid, dispersing the perfume in the solution and dissolving a polyion of opposite ionic character in the solution The hydrocolloid is typically amphoteric or cationic Preferred are proteins, especially Type A gelatin Type A gelatin refers to gelatin processed by acid-treatment Type A gelatin is generally amphoteric and becomes cationic as pH is reduced below the isoelectric point Suitable polyanions for use include water soluble phosphates (e g sodium or potassium hexametapolyphosphate), gum arable carageenan, carboxymethyl cellulose, and algmate (Alternately Type B gelatin can be used Type B gelatin refers to gelatin processed by alkali-treatment ) The pH is adjusted until formation of complex coacervates occurs, and the mixture is cooled to facilitate deposition of the coacervate on the droplets of perfume and gelation of the coacervate material A crosslinking agent is then added to impart water insolubility to the coacervate material Suitable crosslinking agents include low molecular weight aldehydes such as glutaraldehyde and formaldehyde, and polyhydroxyl compounds such as tannic acid and resorcinol

Microcapsules formed from simple coacervates can be similaπly made, utilizing film forming hydrocolloids and simple, monomeπc salts of opposite ionic character in place of the polymeric salts typically used to make complex coacervates Suitable salts would include sodium and potassium sulfates, and sodium and potassium ph sphates and sodium and potassium chlorides

These microcapsules will preferably have a percentage of total wall weight based upon the overall weight of the microcapsule of from about 3% to about 40%, more preferably from about 10% to about 25% The thickness of the wall can be varied by those skilled in the art to achieve the desired degree of frangibi ty, which will of course depend on the size of the perfume droplet and the specific type of encapsulation material Also, trie amount of crosslinking agent for hydrocolloid coacervates can be varied to adjust frangibihty of the microcapsule by those of ordinary skill in the art Typically, from about 0 005 grams to about 7 grams of crosslinking agent solution will be used per gram of hydrocolloid material For gelatin hydrocolloids, the preferred amount of crosshnker (preferably aldehyde crosshnkers such as glutaraldehyde) will be from about 0 025 grams to about 0 5 grams, more preferably from about 0 05 grams to about 0 4 grams, per gram of hydrocolloid material Aqueous Carrier

The compositions of the present invention will comprise an aqueous carrier for the detersive surfactant, cosmetic or pharmaceutical agent, and the dual blooming perfume system An essential component of the aqueous carrier is water, which will typically be present at a level of from about 40% to about 94 8%, by weight of the composition preferably from about 50% to about 90% more preferably from about 60% to about 85% Thickening/Suspending Agent

The compositions hereof can additionally comprise a thickening agent or suspending agent or a mixture thereof as an optional ingredient Thickening and suspending agents are particularly useful for increasing viscosity of the composition and/or physically stabilizing insoluble materials in the compositions to reduce or eliminate the need to redistribute such ingredients prior to use by shaking or stirring

Suspending and thickening agents when used are typically present at a level of from about 0 01 % to about 15%, more typically from about 0 01 % to about 10%, generally from about 0 01 % to about 5%, by weight

Preferred suspending agents are those that form a crystalline network in the composition Exemplary crystalline suspending agents are acyl derivatives and amine oxides, especially acyl derivatives, expecially those which can be solubihzed in a premix solution and then be recrystalhzed upon cooling These materials will comprise long chain (e g , C8-C22 preferably C14-C22, more preferably C15-C22) aliphatic groups, i e , long chain acyl derivative materials and long chain amine oxides, as well as mixtures of such materials Included are ethylene glycol long chain esters, alkanol amides of long chain fatty acids, long chain esters of long chain fatty acids, glyceryl long chain esters, long chain esters of long chain alkanolamides, and long chain alkyl dimethyl amine oxides, and mixtures thereof

Examples of crystalline suspending agents are described in U S Patent 4,741 ,855, Grote and Russell, issued May 3, 1988, incorporated herein by reference Suitable suspending agents for use herein include ethylene glycol esters of fatty acids preferably having from about 14 to about 22 carbon atoms, more preferably 16-22 carbon atoms More preferred are the ethylene glycol stearates, both mono and distearate but particularly the distearate containing less than about 7% of the mono stearate Other suspending agents include alkanol amides of fatty acids, preferably having from about 16 to about 22 carbon atoms more preferably about 16 to 18 carbon atoms Preferred alkanol amides are steaπc monoethanolamide, stearic diethanolamide steaπc monoisopropanolamide and stearic monoethanolamide stearate Ot er long chain acyl derivatives include long chain esters of long chain fatty acids (e g , stearyl stearate cetyl palmitate), glyceryl esters (e g glyceryl distearate) and long chain esters of long chain alkanol amides (e g , stearamide diethanolamide distearate, stearamide monoethanolamide stearate) Ethylene glycol esters of long chain carboxylic acids long chain amine oxides, and alkanol amides of long chain carboxylic acids, in addition to the preferred materials listed above, may be used as suspending agents

Suspending agents also include long chain amine oxides such as alkyl (C-15-C22) dimethyl amine oxides, e g , stearyl dimethyl amine oxide If the compositions contain an amine oxide or a long chain acyl derivative which is a surfactant, the suspending function could also be provided by such amine oxide or acyl derivative, provided at least a portion of them are present in crystalline form, and additional suspending agent may not be needed

Other long chain acyl derivatives that can be used include N,N-dιhydrocarbyl (C12-C22. preferably C16-C18) amido benzoic acid and soluble salts thereof (e g , Na and K salts), particularly N,N-dι(C-| 6- C^<| 8, and hydrogenated tallow) amido benzoic acid species of this family, which are commercially available from Stepan Company (Northfield, Illinois, USA)

The crystalline suspending agent serves to assist in suspending the particulate antidandruff agent, or other particulate matter or emulsions of insoluble fluids, in the shampoo compositions hereof, and may give pearlescence to the product

The crystalline suspending agent can be incorporated into the shampoos hereof by solubihzing it into a solution containing water and the anionic sulfate surfactant at a temperature above the melting point of the suspending agent The suspending agent is then recrystalhzed typically by cooling the solution to a temperature sufficient to induce crystallization

In general, the level of optional suspending agent and other viscosity modifiers should preferably be as low as possible to achieve the benefit for which the material is added

Optional suspending agents that can be used include polymeric thickeners, such as carboxyvinyl polymers Preferred carboxyvmyl polymers are copolymers of acrylic acid crosshnked with polyallylsucrose as described in U S Patent 2,798 053, Brown issued July 2, 1957, incorporated herein by reference These polymers are provided by B F Goodrich Company as, for example, Carbopol 934 940, 941 , and 956

A carboxyvmyl polymer is an interpolymer of a monomeπc mixture comprising a monomeπc olefmically unsaturated carboxylic acid and

SUBSΓΠTJTE SHEET (RULE 26) from about 0 01 % to about 10% by weight of the total monomers of a polyether of a polyhydnc alcohol, which polyhydnc alcohol conatms at least four carbon atoms to which are attached at least three hydroxyl groups, the polyether containing more than one alkenyl group per molecule Other monoolefinic monomenc materials may be present in the monomenc mixture if desired, even in predominant proportion Carboxyvmyl polymers are substantially insoluble in liquid, volatile organic hydrocarbons and are dimensionally stable on exposure to air

Preferred polyhydnc alcohols used to produce carboxyvmyl polymers include polyols selected from the class consisting of ohgosaccharides, reduced derivatives thereof in which the carbonyl group is converted to an alcohol group, and pentaerythntol, more preferred are ohgosaccharides, most preferred is sucrose It is preferred that the hydroxyl groups of the polyol which are modified be ethe fied with allyl groups, the polyol having at least two ally) ether groups per polyol molecule When the polyol is sucrose, it is preferred that the sucrose have at least about five allyl ether groups per sucrose molecule It is preferred that the polyether of the polyol comprise from about 0.01 % to about 4% of the total monomers, more preferably from about 0.02% to about 2.5%

Preferred monomenc olefinically unsaturated carboxylic acids for use in producing carboxyvmyl polymers used herein include monomenc, polymeπzable, alpha-beta monoolefmically unsaturated lower aliphatic carboxylic acids; more preferred are monomenc monoolefinic acrylic acids of the structure

CH₂ = C — COOH

where R is a substituent selected from the group consisting of hydrogen and lower alkyl groups, most preferred is acrylic acid

Preferred carboxyvmyl polymers used in formulations of the present invention have a molecular weight of at least about 750 000 more preferred are carboxyvmyl polymers having a molecular weight of at least about 1 ,250,000, most preferred are carboxyvmyl polymers having a molecular weight of at least about 3,000 000 Other materials can also be used as optional suspension agents include 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., hydroxyethyl cellulose), guar gum, polyvinyl alcohol, polyvinyl pyrrohdone, hydroxypropyl guar gum, starch and starch derivatives, and other thickeners, viscosity modifiers, gelling agents, etc. Mixtures of these materials can also be used.

Another type of suspending agent that can be used is xanthan gum. Shampoo compositions utilizing xanthan gum as a suspending agent for the silicone hair conditioning component are described in U.S. Patent 4,788,006, Bolich and Williams, issued November 29, 1988, incorporated herein by reference. Xanthan gum is biosynthetic gum material that is commercially available. It is a heteropolysacchahde with a molecular weight of greater than 1 million. It is believed to contain D-glucose, D-mannose and D-giucuronate in the molar ratio of 2.8:2.0:2.0. The polysacchande is partially acetylated with 4.7% acetyl. This information and other is found in Whistler, Roy L. Editor Industrial Gums - Polysaccharides and Their Derivatives New York: Academic Press, 1973. Kelco, a Division of Merck & Co., Inc. offers xanthan gum as KeltrolR.

Crosslinked polymers suitable for use herein as thickening agents are generally described in U.S. Patent 5,100,660, to Hawe et al., issued March 31 , 1992; U.S. Patent 4,849,484, to Heard, issued July 18, 1989; U.S. Patent 4,835,206, to Farrar et al., issued May 30, 1989; U.S. Patent 4,628,078 to Glover et al. issued December 9, 1986; U.S. Patent 4,599,379 to Flesher et al. issued July 8, 1986; and EP 228,868, to Farrar et al., published July 15, 1987; all of which are incorporated by reference herein in their entirety.

Crosslinked polymers for use herein can also be characterized by the general formula: (A)_m(B)_n(C)_p wherein (A) is a dialkylaminoalkyl acrylate monomer or its quaternary ammonium or acid addition salt, (B) is a dialkylaminoalkyl methacrylate monomer or its quaternary ammonium or acid addition salt, (C) is a nonionic monomer that is poiymerizable with (A) or (B) having a carbon-carbon double bond, m is an integer of 0 or greater, n is an integer of 0 or greater, either m or n, or both, must be 1 or greater, and p is an integer of 0 or greater.

SUBSTfTUTE SHEET (RULE 26) The (C) monomer can be selected from any of the commonly used monomers Nonhmiting examples of these monomers include ethylene, propylene, butylene, isobutylene, eicosene, maleic anhydride, acrylamide, methacrylamide, maleic acid, acroiem, cyclohexene, ethyl vinyl ether, and methyl vinyl ether In the polymers of the present invention, (C) is preferably acrylamide The alkyl portions of the (A) and (B) monomers are short chain length alkyls such as Ci-Cs, preferably C1 -C5, more preferably C1 -C3, most preferably C-1-C2 When quaternized, the polymers are preferably quartemized with short chain alkyls, l e , C-- -C8, preferably C1 -C5, more preferably C1 -C3, most preferably C1 -C2

These (A)_m(B)_n(C)p polymers also contain a crosslinking agent, which is typically a material containing two or more unsaturated functional groups The crosslinking agent is reacted with the monomer units of the polymer and is incorporated into the polymer, forming covalent bonds between two or more individual polymer chains or between two or more sections of the same polymer chain Nonhmiting examples of suitable crosslinking agents include those selected from the group consisting of methylenebisacrylamides, diacrylates, dimethacrylates, di-vinyl aryl (e g di-vmyl phenyl ring) compounds, polyaldenyl polyethers of polyhydnc alcohols, allyl acrylates vinyloxyalkylacrylates, and polyfunctional vinyhdenes Specific examples of crosslinking agents useful herein include those selected from the group consisting of methylenebisacrylamide, ethylene glycol propylene glycol, butylene glycol, dι-(meth)acrylate, dι-(meth)acrylamιde, cyanomethylacrylate, vmyloxyethylacrylate, vinyloxyethylmethacrylate, allyl pentaerythntol, tπmethylolpropane diallylether, allyl sucrose, butadiene, isoprene, 1 ,4 di-ethylene benzene, divmyl naphthalene, ethyl vinyl ether, methyl vinyl ether, and allyl acrylate Other crosshnkers include formaldehyde and glyoxal Preferred for use herein as a crosslinking agent is methylenebisacrylamide

Widely varying amounts of the crosslinking agent can be employed depending upon the properties desired in the final polymer e g viscosifymg effect The crosslinking agent will typically comprise from about 1 ppm to about 10 000 ppm, preferably from about 5 ppm to about 750 ppm, more preferably from about 25 ppm to about 500 ppm

SUBSTTTUTE SHEET (RULE 26) even more preferably from about 100 ppm to about 500 ppm, and most preferably from about 250 ppm to about about 500 ppm of the total weight of the polymer on a weight/weight basis.

The intrinsic viscosity of the crosslinked polymer, measured in one molar sodium chloride solution at 25° C, is generally above 6, preferably from about 8 to 14. The molecular weight (weight average) of the crosslinked polymers hereof is high, and is believed to typically be between about 1 million and about 30 million. The specific molecular weight is not critical and lower or higher weight average molecular weights can be used as long as the polymer retains its intended viscosifying effects in water or other aqueous carrier of the compositions hereof. Preferably, a 1.0% solution of the poly ^** in deionized water will have a viscosity at 25°C of at least about 2 30 cP, preferably at least about 30,000 cP, when measured at 20 RPM by a Brookfield RVT (Brookfield Engineering Laboratories, Inc. Stoughton, MA, USA).

Polymers useful herein include those conforming to the general structure (A)_m(B)_n(C)p wherein m is zero, (B) is methyl quaternized dimethylaminoethyl methacrylate, the ratio of (B):(C) is about 45:55 to about 55:45, and the crosslinking agent is methylenebisacrylamide. An example of such a cationic polymer is one that is commercially available as a mineral oil dispersion (which can also include various dispersing aids such as PPG-1 trideceth-6) under the trademark Salcare^R SC92 from Allied CTFA designation, "Polyquatemium 32 (and) Mineral Oil".

Other polymers useful herein, are those not containing acrylamide or other C monomer, that is, p is zero. In these polymers the (A) and (B) monomer components are as described above. An especially preferred group of these polymers is one in which m is also zero. In this instance the polymer is essentially a homopolymer of dialkylaminoalkyl methacrylate monomer or its quaternary ammonium or acid addition salt. These diaklylaminoalkyl methacrylate copolymers and homopolymers also contain a crosslinking agent as described above.

Another hor. opolymer useful herein is one conforming to the general structure (A)_m(B)_n(C)_p wherein m is zero, (B) is methyl quaternized dimethylaminoethyl methacrylate, p is zero, and tne crosslinking agent is methylenebisacrylamide. An example of such a homopolymer is commercially available as a mineral oil dispersion also containing PPG-1 trideceth-6 as a dispersing aid, from Allied Colloids Ltd, (Norfolk, VA) under the trademark Salcare^R SC95 This product has been designated by the Cosmetics, Toiletries, and Fragrance Association (CTFA) as "Polyquatemium 37 (and) Mineral Oil (and) PPG-1 Trιdeceth-6" Optional Ingredients

A variety of other optional, nonexclusive ingredients are described below

Such optional ingredients include, for example, preservatives such as benzyl alcohol, methyl paraben, propyl paraben and imidazo dinyl urea, foam boosters, including quatemery polymeric foam boosters such as Polyquatemium 10, and C10-C22 fatty ester, C1-C5 alkanol amides, block polymers of ethylene oxide and propylene oxide such as Pluroπic F88 offered by BASF Wyandotte, viscosity adjustors such as sodium chloride, sodium sulfate and ammonium xylene sulfonate, propylene glycol, polyvinyl alcohol, ethyl alcohol pH adjusting agents such as citric acid, succmic acid, phosphoric acid, sodium hydroxide, sodium carbonate, mono- and di- sodium phophase, dyes, etc These optional ingredients are typically used at levels of from about 0 01% to about 10% of the composition This list of optional ingredients is not meant to be exclusive, and other optional components can be utilized

METHOD OF USE

The present compositions are used in a conventional manner for cleaning hair or skin An effective amount of the composition typically from about 1 g to about 20 g of the composition, for cleaning hair or other region of the body, is applied and manipulated with the hands or fingers to distribute the composition throughout the intended area of treatment The area of treatment may be pre-wetted with water, if desired The composition is then applied and mechanically rubbed into or onto the hair or skin, and then optionally (and preferably) rinsed off e g with water

The following examples are intended to exemplify the present invention, the scope of which is defined by the claims which follow

Example 1

Encapsulated microcapsules of a perfume component are prepared as follows 45 At about 50°C, 150ml of deionized water and 1 1 grams of gelatin (Type A, 275 Bloom) are added to a 1000ml beaker. With agitation, 95ml of an oil-phase perfume component is added. Agitation is continued until oil phase droplet size is from about 50 to about 100 microns. Next, 20ml of a 5% aqueous solution of sodium hexametapolyphosphate and 117ml of deionized water are added to the beaker at about 50°C. The pH of the contents of the beaker is then lowered to 5.30 by the addition of glacial acetic acid. The pH is then further lowered by the further addition of glacial acetic acid until free coacervate is present or until then coacervate walls are formed, typically about pH 4.30. The beaker contents are then allowed to cool to room temperature by a water bath, and the further cooled by an ice water bath to about 5°C to about 10°C. Next, the coacervate microcapsules are crosslinked by the addition of 2.75ml of a 49% glutaraldehyde/aqueous solution for about eight hours or more. The crosslinked microcapsules are then drained of the aqueous phase and well-rinsed with water.

Example II This example exemplifies a cleansing/conditioning shampoo formulation of the present invention. Component Weight%

Ammonium Lauryl Sulfate 13.5 Ammonium Laureth (3) Sulfate 4.0 Coconut Monoethanol Amide 1.0 Ethylene Glycol Distearate 1.5 Xanthan Gum 0.5 Tricetylmonium Chloride 0.6 Polydimethylsiloxane (PDMS) 3.0

40% PDMS gum (G.E. SE76, General Electric Co., Silicone Products Div., Waterford, NY, USA)

60% Cyciomethicone (about 350 centistokes at 25°C) Cetyl Alcohol 0.4 Stearyl Alcohol 0.2 Methylchloroisthiazoline (and) 0.03

Methylisothiazolinone (Kathon CG, Rohm & Haas Co , Inc

Philadelphia, PA, USA) Ammonium Xylene Sulfonate* up to 1 0

Sodium Chloride* up to 1 0

Sodium Citrate (38% solution)* up to 1 0

Citric Acid Solution (50% concentration)* up to 1 0

Perfume Component 1 0 5

Perfume Component 2 (encapsulated) 04

Water and minors q s to 100%

* Levels varied to viscosity of about 3500 centipoise (Wells-Brookfield viscometer, 10 rpm at about 27°C, No 52 cone, model RVTD-CP) Perfume Component 1 can be equivalent to that used in any commercially available shampoo composition, such as that used in Pert Pius™ conditioning shampoo (Procter & Gamble, Cincinnati, OH, USA) Perfume Component 2 is prepared as described in Example 1 , using a perfume formulation similar to any commercially available hair conditioning rinse formulation, such as that used in Ivory™ conditioning rinse (Procter & Gamble)

Alternately to the polydimethylsiloxane, or in addition to it, any of the polymeric adhesive agents, other conditioning agents, or pharmaceutical agents disclosed above can be included in the composition

Claims

What is Claimed is

1 A cleansing composition useful for topical application to the skin or hair, comprising (a) from 5% to 40%, by weight of a detersive surfactant or mixture thereof, (b) an additional cosmetic or pharmaceutical agent for treating the hair or skin; and (c) an aqueous carrier, characterized in that is further contains a perfume system comprising

(i) a substantially nonconfined, first perfume component, and (ii) a confined second perfume component having a different aroma than the first perfume component, wherein said second perfume component is encapsulated by frangible microcapsules, wherein said cleansing composition is characterized by a first aroma prior to use corresponding to said first perfume component, and a second aroma resulting from the release of said second perfume component upon application of mechanical force during use to fracture said microcapsules

2 A cleansing composition as in Claim 1 , wherein said composition comprises a conditioning agent, a styling agent, or an anti-dandruff agent, or a mixture thereof.

3 A cleansing composition as in Claim 1 or 2, wherein said composition comprises a conditioning agent selected from the group consisting of silicone conditioning agents, cationic surfactants, cationic polymers, and hydrocarbon, ester, and alcohol conditioning agents, and mixtures thereof

4. A cleansing composition as in Claim 1 , 2 or 3, wherein said frangible microcapsules comprise a crosslinked gelatin coacervate

5. A cleansing composition as in Claim 4, wherein said microcapsules comprise a crosslinked, complex coacervate of a Type A gelatin