GB2315770A - Conditioning shampoo compositions comprising polyalkoxylated polyalkyleneamine - Google Patents

Abstract

Disclosed are conditioning shampoo compositions comprising an alkoxylated polyalkyleneamine and one or more detersive surfactant; in further embodiments, air conditioning shampoo composition comprising by weight from about 0.01% to about 10% of alkoxylated polyalkyleneamine, from about 0.01% to about 20% of a cationic surfactant conditioning agent, from about 5% to about 50% of a detersive surfactant, and from about 20% to about 90% of water.

Description

CONDITIONING SHAMPOO COMPOSITIONS COMPRISING POLYALKOXYLATED POLYALKYLENEAMIN E Jeffrey J. Scheibel Hirotaka Uchiyama Junichi Yokogi Mikiko Nakata Takashi Sako TECHNICAL FIELD The present invention relates to conditioning shampoo compositions comprising polyalkoxylated polyalkyleneamine.

BACKGROUND Human hair becomes soiled due - to its contact with the surrounding environment and from the sebum secreted by the scalp. The soiling of hair causes it to have a dirty feel and an unattractive appearance. The soiling of the hair necessitates shampooing with frequent regularity.

Shampooing cleans the hair by removing excess soil and sebum.

However, shampooing can leave the hair in a wet, tangled, and generally unmanageable state. Once the hair dries, it is often left in a dry, rough, lusterless, or frizzy condition due to removal of the hair's natural oils and other natural conditioning and moisturizing components. The hair can further be left with increased levels of static upon drying, which can interfere with combing and result in a condition commonly referred to as "fly-away hair." A variety of approaches have been developed to alleviate these aftershampoo problems. These approaches range from post-shampoo application of hair conditioners such as leave-on and rinse-off products, to hair conditioning shampoos which attempt to both cleanse and condition the hair from a single product. Hair conditioners are typically applied in a separate step following shampooing. The hair conditioners are either rinsed-off or left-on, depending upon the type of product used. Hair conditioners, however, have the disadvantage of requiring a separate and inconvenient treatment step.

Conditioning shampoos are highly desirable products because they are convenient for consumers to use by providing cleansing and conditioning benefits to the hair in one step.

In order to provide hair conditioning benefits in a cleansing shampoo base, a wide variety of conditioning actives have been proposed. However, they have not been totally satisfactory for a variety of reasons.

One problem relates to compatibility between anionic detersive surfactants and the many conventional cationic conditioning agents. Whereas efforts have been made to minimize adverse interaction through the use of alternative surfactants, it remains highly desirable to utilize anionic surfactants to some extent because of its overall superior cleaning properties. On the other hand, some consumers desire mild or non-stimulating shampoo compositions which usually comprise other classes of surfactants in addition to said anionic surfactants. Thus, a conditioning agent which is compatible with a wide variety of detersive surfactants is desired.

Materials which can provide improved overall conditioning benefits while maintaining cleaning performance with the use of anionic detersive surfactants are silicone conditioning agents. However, conditioning shampoos comprising silicone conditioning agents have a tendency of leaving the hair feeling coated, heavy, or soiled after the hair is dried. Further, in order to provide a well dispersed, storage stable shampoo composition including silicone conditioning agents, a silicone suspending agent such as acyl derivatives or long chain amine oxide is required. The combination of silicone conditioning agents and its suspending agents often provide a formulation which is relatively viscous and milky in appearance. However, in view of the various consumer needs, shampoos of less viscosity or transparent appearance are also desired. It would be desirable to provide a conditioning shampoo composition that would provide improved overall conditioning benefits with or without silicone conditioning agents.

It is believed that excellent overall conditioning benefits of a conditioning shampoo is achieved by the balance of good deposition of the conditioning agent to the hair and good cleaning properties. Good deposition of the conditioning agent results in soft and smooth feel of the hair after drying, which also positively effects easy dry combing. Good cleaning properties result in absence of negatives such as hair feeling coated, heavy, or soiled.

GB Patent specification 1,524,966 discloses a clear, homogeneous shampoo composition which comprises a polyethylene imine polymer as cationic conditioner, amine base detergent, and zinc 2-pyridinethiol-1 -oxide.

In the present invention new classes of conditioning agents; polyalkoxylated polyalkyleneamines; have been developed which are water soluble and compatible with a wide variety of components commonly formulated in conditioning shampoos, particularly with detersive surfactants which provide good cleaning properties. Further, the polyalkoxylated polyalkyleneamines of the present invention provide improved overall conditioning benefits with or without silicone conditioning agents. Particularly, conditioning benefits such as; wet and dry hair conditioning benefits recognized by the consumer as soft and smooth feel of the hair and easy dry combing; and absence of coated, heavy, or soiled hair feel, are improved.

SUMMARY The present invention relates to conditioning shampoo compositions comprising a polyalkoxylated polyalkyleneamine, a detersive surfactant, and water.

In further embodiments, the present invention further relates to a conditioning shampoo composition comprising by weight, from about 0.01% to about 10% of polyalkoxylated polyalkyleneamine, from about 0.01% to about 20% of a cationic surfactant conditioning agent, from about 5% to about 50% of a detersive surfactant, and from about 20% to about 90% of water.

Such compositions satisfy the need for a conditioning shampoo composition with improved overall conditioning benefits with or without silicone conditioning agents, and/or a conditioning shampoo composition with good cleaning properties.

These and other objects and benefits as may be discussed or apparent may be obtained with the present invention, which is described below.

DETAILED DESCRIPTION All percentages herein are by weight of the compositions unless otherwise indicated. All ratios are weight ratios unless otherwise indicated. All percentages, ratios, and levels of ingredients referred to herein are based on the actual amount of the ingredient, and do not include solvents, fillers, or other materials with which the ingredient may be combined as commercially available products, unless otherwise indicated.

The invention hereof can comprise, consist of, or consist essentially of the essential elements described herein as well as any of the preferred or optional ingredients also described herein.

POLYALKOXYLATED POLYALKYLENEAMINE The polyalkoxylated polyalkyleneamine of the present invention can be described by the following formula:

wherein R1 and R2 are independently C2 to C6 alkylene; A is a polyalkoxy of the formula (R30)yH wherein R3 is a C2 to C4 alkylene and y is an integer from 1 to about 40; and x is an integer from 0 to 100. A is preferably a polyethoxy or polypropoxy, most preferably a polyethoxy, and y is preferably from about 5 to about 30, most preferably from about 10 to about 20. R1 and R2 are preferably independently C2 to C4, most preferably both are C2; and x is preferably from 1 to about 10, most preferably from 1 to about 5. These polyalkoxylated polyalkyleneamines are water soluble and compatible with any detersive surfactant including anionic detersive surfactants, and also provide excellent conditioning benefits to the hair. Without being bound by theory, at mdst wash pH's, it is believed that the nitrogen atoms of these compounds are partially protonated. The resulting positively charged centers (and remaining polar nitrogen atoms) are believed to aid in the adsorption of the compound onto the negatively charged layers of the hair. Such adsorption is believed to provide conditioning benefits similar to that obtained by cationic conditioning agents. It is also believed that, when the hydrophilic alkoxy units of the compound meet an abundant amount of water in the rinsing process, it loses its cohesive character so that excess polyalkoxylated polyalkyleneamine is removed from the hair, thus not leaving the hair feel coated, heavy, or soiled.

The pH of the present compositions generally will be about 2 to about 9, preferably about 5 to about 7.

Exemplary polyalkoxylated polyalkyleneamines are ethoxylated and propoxylated; ethylenediamine, propylenediamine, n-butylenediamine, pentamethylenediamine, hexamethylenediamine, diethylenetriamine, triethylenetetramine, and tetraethylenepentamine. A highly preferred compound is polyethoxylated tetraethylenepentamine as shown below wherein y is an integer of from about 10 to about 20:

These polyalkoxylated polyalkyleneamines can be synthesized by standard methods for alkoxylating amines. First, there is an initial step of condensing sufficient alkylene oxide to provide 2-hydroxyethyl groups at each reactive site (hydroxyalkylation). This initial step can be omitted by starting with a 2-hydroxyalkylamine such as triethanolamine or polyalkyleneamine. The appropriate amount of alkylene oxide is then condensed with these 2hydroxyalkyleneamines or polyalkyleneamines using an alkali metal such as sodium or potassium; hydride or hydroxide as the catalyst to provide the respective alkoxylated amines.

The polyalkoxylated polyalkyleneamine of the present invention is incorporated in conditioning shampoo compositions at a level of from about 0.01% to about 10%, preferably from about 0.1% to about 2%, most preferably from about 0.2% to about 1.5%.

DETERSIVE SURFACTANT The compositions of the present invention comprise a detersive surfactant selected from the group consisting of one or more anionic, non ionic, amphoteric, or zwitterionic surfactants, or mixtures thereof. The purpose of the detersive surfactant is to provide cleansing performance to the composition. The term detersive surfactant, as used herein, is intended to distinguish these surfactants from surfactants which are primarily emulsifying surfactants, i.e. surfactants which provide an emulsifying benefit and which have low cleansing performance.

It is recognized that most surfactants have both detersive and emulsifying properties. It is not intended to exclude emulsifying surfactants from the present invention, provided the surfactant also possesses sufficient detersive properties to be useful herein.

The detersive surfactants will generally comprise from about 5% to about 50%, preferably from about 8% to about 30%, and more preferably from about 10% to about 25%, by weight of the composition.

Anionic Surfactants Anionic surfactants useful herein include alkyl and alkyl ether sulfates.

These materials have the respective formulae ROS03M and RO(C2H4O)xSO3M, wherein R is alkyl or alkenyl of from about 8 to about 30 carbon atoms, x is 1 to about 10, and M is hydrogen or a cation such as ammonium, alkanolammonium (e.g., triethanolammonium), a monovalent metal cation (e.g., sodium and potassium), or a polyvalent metal cation (e.g., magnesium and calcium). Preferably, M should be chosen such that the anionic surfactant component is water soluble. The anionic surfactant should be chosen such that the Kraffl temperature is about 15"C or less, preferably about 10"C or less, and more preferably about 0 C or less. It is also preferred that the anionic surfactant be soluble in the composition hereof.

Krafft temperature refers to the point at which solubility of an ionic surfactant becomes determined by crystal lattice energy and heat of hydration, and corresponds to a point at which solubility undergoes a sharp, discontinuous increase with increasing temperature. Each type of surfactant will have its own characteristic Krafft temperature. kraffl temperature for ionic surfactants is, in general, well known and understood in the art. See, for example, Myers, Drew, Surfactant Science and Technoloav, pp. 82-85, VCH Publishers, Inc. (New York, New York, USA), 1988 (ISBN 0-89573-399-0), which is incorporated by reference herein in its entirety.

In the alkyl and alkyl ether sulfates described above, preferably R has from about 12 to about 18 carbon atoms in both the alkyl and alkyl ether sulfates. The alkyl ether sulfates are typically made as condensation products of ethylene oxide and monohydric alcohols having from about 8 to about 24 carbon atoms. The alcohols can be derived from fats, e.g., coconut oil, palm oil, tallow, or the like, or the alcohols can be synthetic. Lauryl alcohol and straight chain alcohols derived from coconut oil and palm oil are preferred herein. Such alcohols are reacted with 1 to about 10, and especially about 3, molar proportions of ethylene oxide and the resulting mixture of molecular species having, for example, an average of 3 moles of ethylene oxide per mole of alcohol, is sulfated and neutralized.

Specific examples of alkyl ether sulfates which can be used in the present invention are sodium and ammonium salts of coconut alkyl triethylene glycol ether sulfate; tallow alkyl triethylene glycol ether sulfate, and tallow alkyl hexaoxyethylene sulfate. Highly preferred alkyl ether sulfates are those comprising a mixture of individual compounds, said mixture having an average alkyl chain length of from about 12 to about 16 carbon atoms and an average degree of ethoxylation of from 1 to about 4 moles of ethylene oxide. Such a mixture also comprises from 0% to about 20% by weight C12-13 compounds; from about 60% to about 100% by weight of C14-15-16 compounds, from 0% to about 20% by weight of C17-18-19 compounds; from about 3% to about 30% by weight of compounds having a degree of ethoxylation of 0; from about 45% to about 90% by weight of compounds having a degree of ethoxylation of from 1 to about 4; from about 10% to about 25% by weight of compounds having a degree of ethoxylation of from about 4 to about 8; and from about 0. % to about 15% by weight of compounds having a degree of ethoxylation greater than about 8.

Other suitable anionic surfactants are the water-soluble salts of organic, sulfuric acid reaction products of the general formula [R1-S03-M] where R1 is selected from the group consisting of a straight or branched chain, saturated aliphatic hydrocarbon radical having from about 8 to about 24, preferably about 10 to about 18, carbon atoms; and M is as previously described above in this section. Examples of such surfactants are the salts of an organic sulfuric acid reaction product of a hydrocarbon of the methane series, including iso-, neo-, and n-paraffins, having about 8 to about 24 carbon atoms, preferably about 12 to about 18 carbon atoms and a sulfonating agent, e.g., S03, H2S04, obtained according to known sulfonation methods, including bleaching and hydrolysis.

Preferred are alkali metal and ammonium sulfonated C10-18 n-paraffins.

Still other suitable anionic surfactants are the reaction products of fatty acids esterified with isethionic acid and neutralized with sodium hydroxide where, for example, the fatty acids are derived from coconut or palm oil; or sodium or potassium salts of fatty acid amides of methyl tauride in which the fatty acids, for example, are derived from coconut oil. Other similar anionic surfactants are described in U.S. Patents 2,486,921, 2,486,922, and 2,396,278, which are incorporated by reference herein in their entirety.

Other anionic surfactants suitable herein are the succinates, examples of which include disodium N-octadecylsulfosuccinate; disodium lauryl sulfosuccinate; diammonium lauryl sulfosuccinate; tetra sodium N-(1,2dicarboxyethyl)-N-octadecyl- sulfosuccinate; the diamyl ester of sodium sulfosuccinic acid; the dihexyl ester of sodium sulfosuccinic acid; and the dioctyl ester of sodium sulfosuccinic acid.

Other anionic surfactants suitable herein are those that are derived from amino acids. Nonlimiting examples of such surfactants include N-acyl-Lglutamate, N-acyl-N-methyl-alanate, N-acylsarcosinate, and their salts.

Still other useful surfactants are those that are derived from taurine, which is also known as 2-aminoethanesulfonic acid. An example of such an acid is Nacyl-N-methyl taurate.

Other suitable anionic surfactants include olefin sulfonates having about 10 to about 24 carbon atoms. The term "olefin sulfonates" is used herein to mean compounds which can be produced by the sulfonation of alpha-olefins by means of uncomplexed sulfur trioxide, followed by neutralization of the acid reaction mixture in conditions such that any sulfones which have been formed in the reaction are hydrolyzed to give the corresponding hydroxy-alkanesulfonates.

The sulfur trioxide can be liquid or gaseous, and is usually, but not necessarily, diluted by inert diluents, for example by liquid SO2, chlorinated hydrocarbons, etc., when used in the liquid form, or by air, nitrogen, gaseous S02, etc., when used in the gaseous form.

The alpha-olefins from which the olefin sulfonates are derived are monoolefins having about 12 to about 24 carbon atoms, preferably about 14 to about 16 carbon atoms. Preferably, they are straight chain olefins.

In addition to the true alkene sulfonates and a proportion of hydroxyalkanesulfonates, the olefin sulfonates can contain minor amounts of other materials, such as alkene disulfonates depending upon the reaction conditions, proportion of reactants, the nature of the starting olefins and impurities in the olefin stock and side reactions during the sulfonation process. A specific alphaolefin sulfonate mixture of the above type is described more fully in U.S. Patent 3,332,880, to Pflaumer and Kessler, issued July 25, 1967, which is incorporated by reference herein in its entirety.

Another class of anionic surfactants suitable for use in the present invention are the betaalkyloxy alkane sulfonates. These compounds have the following formula:

where R1 is a straight chain alkyl group having from about 6 to about 20 carbon atoms, R2 is a lower alkyl group having from about 1, preferred, to about 3 carbon atoms, and M is as hereinbefore described. Many other anionic surfactants suitable for use are described in McCutcheon's, Emulsifiers and Detergents, 1989 Annual, published by M. C. Publishing Co., and in U.S. Patent 3,929,678, which descriptions are incorporated herein by reference in their entirety. Preferred anionic surfactants for use include ammonium lauryl sulfate, ammonium laureth sulfate, triethylamine lauryl sulfate, triethylamine laureth sulfate, triethanolamine lauryl sulfate, triethanolamine laureth sulfate monoethanolamine lauryl sulfate, monoethanolamine laureth sulfate, diethanolamine lauryl sulfate, diethanolamine laureth sulfate, lauric monoglyceride sodium sulfate, sodium lauryl sulfate, sodium laureth sulfate, potassium lauryl sulfate, potassium laureth sulfate, sodium lauryl sarcosinate, sodium lauroyl sarcosinate, lauryl sarcosine, cocoyl sarcosine, ammonium cocoyl sulfate, ammonium lauroyl sulfate, sodium cocoyl sulfate, sodium lauroyl sulfate, potassium cocoyl sulfate, potassium lauryl sulfate, triethanolamine lauryl sulfate, triethanolamine lauryl sulfate, monoethanolamine cocoyl sulfate, monoethanolamine lauryl sulfate, sodium tridecyl benzene sulfonate, and sodium dodecyl benzene sulfonate, sodium N-lauroyl-L-glutamate, triethanol Nlauryoyl-L-glutamate, sodium N-lauroyl-N-methyl taurate, sodium N-lauroyl-Nmethyl-aminopropionate, and mixtures thereof.

Amphoteric and Zwitterionic Surfactants The shampoo compositions can comprise amphoteric and/or zwitterionic surfactants.

Amphoteric surfactants for use in the shampoo compositions include the derivatives of aliphatic secondary and tertiary amines in which the aliphatic radical is straight or branched and one of the aliphatic substituents contains from about 8 to about 18 carbon atoms and one contains an anionic water solubilizing group, e.g., carboxy, sulfonate, sulfate, phosphate, or phosphonate.

Zwitterionic surfactants for use in the shampoo compositions include the derivatives of aliphatic quaternary ammonium, phosphonium, and sulfonium compounds, in which the aliphatic radicals are straight or branched, and wherein one of the aliphatic substituents contains from about 8 to about 18 carbon atoms and one contains an anionic group, e.g., carboxy, sulfonate, sulfate, phosphate, or phosphonate. A general formula for these compounds is:

where R2 contains an alkyl, alkenyl, or hydroxy alkyl radical of from about 8 to about 18 carbon atoms, from 0 to about 10 ethylene oxide moieties and from 0 to about 1 glyceryl moiety; Y is selected from the group consisting of nitrogen, phosphorus, and sulfur atoms; R3 is an alkyl or monohydroxyalkyl group containing 1 to about 3 carbon atoms; X is 1 when Y is a sulfur atom, and 2 when Y is a nitrogen or phosphorus atom; R4 is an alkylene or hydroxyalkylene of from 1 to about 4 carbon atoms and Z is a radical selected from the group consisting of carboxylate, sulfonate, sulfate, phosphonate, and phosphate groups.

Examples of amphoteric and zwitterionic surfactants also include sultaines and amidosultaines. Sultaines, including amidosultaines, include for example, cocodimethylpropylsultaine, stearyldimethylpropylsultaine, lauryl-bis (2-hydroxyethyl) propylsultaine and the like; and the amidosultaines such as cocamidodimethylpropylsultaine, - stearylamidododimethylpropylsultaine, laurylamidobis-(2-hydroxyethyl) propylsultaine, and the like. Preferred are amidohydroxysultaines such as the C12-C18 hydrocarbyl amidopropyl hydroxysultaines, especially C12-C14 hydrocarbyl amido propyl hydroxysultaines, e.g., laurylamidopropyl hydroxysultaine and cocamidopropyl hydroxysultaine. Other sultaines are described in U.S. Patent 3,950,417, which is incorporated herein by reference in its entirety.

Other suitable amphoteric surfactants are the aminoalkanoates of the formula R-NH(CH2)nCOOM, the iminodialkanoates of the formula R N[(CH2)mCOOM]2 and mixtures thereof; wherein n and m are numbers from 1 to about 4, R is Cg - C22 alkyl or alkenyl, and M is hydrogen, alkali metal, alkaline earth metal, ammonium or alkanolammonium.

Examples of suitable aminoalkanoates include n-alkylamino-propionates and n-alkyliminodipropionates, specific examples of which include N-lauryl-betaamino propionic acid or salts thereof, and N-lauryl-beta-imino-dipropionic acid or salts thereof, and mixtures thereof.

Other suitable amphoteric surfactants include those represented by the formula:

wherein R1 is Cg-C22 alkyl or alkenyl, preferably C12-C16, R2 and R3 is independently selected from the group consisting of hydrogen, CH2C02M, CH2CH20H, CH2CH20CH2CH2COOM, or (CH2CH20)mH wherein m is an integer from 1 to about 25, and R4 is hydrogen, CH2CH20H, or CH2CH20CH2CH2COOM, Z is CO2M or CH2C02M, n is 2 or 3, preferably 2, M is hydrogen or a cation, such as alkali metal (e.g., lithium, sodium, potassium), alkaline earth metal (beryllium, magnesium, calcium, strontium, barium), or ammonium. This type of surfactant is sometimes classified as an imidazolinetype amphoteric surfactant, although it should be recognized that it does not necessarily have to be derived, directly or indirectly, through an imidazoline intermediate. Suitable materials of this type are marketed under the tradename MIRANOL and are understood to comprise a complex mixture of species, and can exist in protonated and non-protonated species depending upon pH with respect to species that can have a hydrogen at R2. All such variations and species are meant to be encompassed by the above formula.

Examples of surfactants of the above formula are monocarboxylates and dicarboxylates. Examples of these materials include cocoamphocarboxypropionate, cocbamphocarboxypropionic acid, cocoamphocarboxyglycinate (alternately referred to as cocoamphodiacetate), and cocoamphoacetate.

Commercial amphoteric surfactants include those sold under the trade names MIRANOL C2M CONC. N.P., MIRANOL C2M CONC. O.P., MIRANOL C2M SF, MIRANOL CM SPECIAL (Miranol, Inc.); ALKATERIC 2CIB (Alkaril Chemicals); AMPHOTERGE W-2 (Lonza, Inc.); MONATERIC CDX-38, MONATERIC CSH-32 (Mona Industries); REWOTERIC AM-2C (Rewo Chemical Group); and SCHERCOTERIC MS-2 (Scher Chemicals).

Betaine surfactants, i.e. zwitterionic surfactants, suitable for use in the shampoo compositions are those renresented bv the formula:

wherein: R1 is a member selected from the group consisting of

R2 is lower alkyl or hydroxyalkyl; R3 is lower alkyl or hydroxyalkyl; R4 is a member selected from the group consisting of hydrogen and lower alkyl; R5 is higher alkyl or alkenyl; Y is lower alkyl, preferably methyl; m is an integer from 2 to 7, preferably from 2 to 3; n is the integer 1 or 0; M is hydrogen or a cation, as previously described, such as an alkali metal, alkaline earth metal, or ammonium. The term "lower alkyl" or "hydroxyalkyl" means straight or branch chained, saturated, aliphatic hydrocarbon radicals and substituted hydrocarbon radicals having from one to about three carbon atoms such as, for example, methyl, ethyl, propyl, isopropyl, hydroxypropyl, hydroxyethyl, and the like. The term "higher alkyl or alkenyl" means straight or branch chained saturated (i.e., "higher alkyl") and unsaturated (i.e., "higher alkenyl") aliphatic hydrocarbon radicals having from about eight to about 20 carbon atoms such as, for example, lauryl, cetyl, stearyl, oleyl, and the like. It should be understood that the term "higher alkyl or alkenyl" includes mixtures of radicals which may contain one or more intermediate linkages such as ether or polyether linkages or non-functional substitutents such as hydroxyl or halogen radicals wherein the radical remains of hydrophobic character.

Examples of surfactant betaines of the above formula wherein n is zero which are useful herein include the alkylbetaines such as cocodimethylcarboxymethylbetaine, lauryldimethylcarboxymethylbetaine, lauryl dimethyl-alpha-carboxyethylbetaine, cetyldimethylcarboxymethylbetaine, laurylbis-(2-hydroxyethyl )carboxymethylbetaine, stearyl-bis-(2hydroxypropyl )carboxymethylbetaine, oleyldimethyl-gamma- carboxypropylbetaine, lauryl-bix-(2-hydroxypropyl)alpha-carboxyethylbetaine, etc. The sulfobetaines may be represented by cocodimethylsulfopropylbetaine, stearyldimethylsulfopropylbetaine, lauryl-bis-(2-hydroxyethyl)sulfopropylbetaine, and the like.

Specific examples of amido betaines and amidosulfo betaines useful in the shampoo compositions include the amidocarboxybetaines, such as cocamidodimethylcarboxymethylbetaine, laurylamidodimethylcarboxymethylbetaine, cetylamidod imethylcarboxymethylbetaine, laurylamido-bis-(2-hydroxyethyl )- carboxymethylbetaine, cocamido-bis-(2-hydroxyethyl )-carboxymethylbetaine, etc. The amido sulfobetaines may be represented by cocamidodimethylsulfopropylbetaine, stearylamidodimethylsulfopropylbetaine, laurylamido-bis-(2-hydroxyethyl )-sulfopropylbetaine, and the like.

Nonionic Surfactants The shampoo compostions of the present invention can comprise a nonionic surfactant. Nonionic surfactants include those compounds produced by condensation of alkylene oxide groups, hydrophilic in nature, with an organic hydrophobic compound, which may be aliphatic or alkyl aromatic in nature.

Preferred nonlimiting examples of nonionic surfactants for use in the shampoo compositions include the following: (1) polyethylene oxide condensates of alkyl phenols, e.g., the condensation products of alkyl phenols having an alkyl group containing from about 6 to about 20 carbon atoms in either a straight chain or branched chain configuration, with ethylene oxide, the said ethylene oxide being present in amounts equal to from about 10 to about 60 moles of ethylene oxide per mole of alkyl phenol; (2) those derived from the condensation of ethylene oxide with the product resulting from the reaction of p;opylene oxide and ethylene diamine products; (3) condensation products of aliphatic alcohols having from about 8 to about 18 carbon atoms, in either straight chain or branched chain configurations, with ethylene oxide, e.g., a coconut alcohol ethylene oxide condensate having from about 10 to about 30 moles of ethylene oxide per mole of coconut alcohol1 the coconut alcohol fraction having from about 10 to about 14 carbon atoms; (4) long chain tertiary amine oxides of the formula [ R1R2R3N o 0 where R1 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 O to about (7) alkyl polysaccharide (APS) surfactants (e.g. alkyl polyglycosides), examples of which are described in U.S. Patent 4,565,647, which is incorporated herein by reference in its entirety, and which discloses APS surfactants having a hydrophobic group with about 6 to about 30 carbon atoms and a polysaccharide (e.g., polyglycoside) as the hydrophilic group; optionally, there can be a polyalkylene-oxide group joining the hydrophobic and hydrophilic moieties; and the alkyl group (i.e., the hydrophobic moiety) can be saturated or unsaturated, branched or unbranched, and unsubstituted or substituted (e.g., with hydroxy or cyclic rings); a preferred material is alkyl polyglucoside which is commercially available from Henkel, ICI Americas, and Seppic; and (8) polyoxyethylene alkyl ethers such as those of the formula RO(CH2CH2)nH and polyethylene glycol (PEG) glyceryl fatty esters, such as those of the formula R(O)OCH2CH(OH)CH2(OCH2CH2)nOH, wherein n is from 1 to about 200, preferably from about 20 to about 100, and R is an alkyl having from about 8 to about 22 carbon atoms.

CATION IT SURFACTANT The compositions of the present invention preferably further comprise from about 0.1% to about 20% by weight, preferably from about 0.25% to about 5%, more preferably from about 0.5% to about 2% of a cationic surfactant.

These cationic surfactants typically contain quaternary nitrogen moieties.

The cationic surfactant will preferably, though not necessarily, be insoluble in the compositions hereof.

Among the cationic surfactants useful herein are those corresponding to the general formula (I):

wherein R1, R27 R37 and R4 are independently selected from an aliphatic group of from 1 to about 22 carbon atoms or an aromatic, alkoxy, polyoxyalkylene, alkylamido, hydroxyalkyl, aryl or atkylaryl group having up to about 22 carbon atoms; and X is a salt-forming anion such as those selected from halogen, (e.g.

chloride, bromide), acetate, citrate, lactate, glycolate, phosphate, nitrate, sulfonate, sulfate, alkylsulfate, and alkyl sulfonate radicals. The aliphatic groups can contain, in addition to carbon and hydrogen atoms, ether linkages, and other groups such as amino groups. The longer chain aliphatic groups, e.g., those of about 12 carbons, or higher, can be saturated or unsaturated. Preferred is when R1, R2, R3, and R4 are independently selected from C1 to about C22 alkyl.

Nonlimiting examples of cationic surfactants useful in the present invention include the materials having the following CTFA designations: quaternium-8, quaternium-24, quaternium-26, quaternium-27, quaternium-30, quaternium-33, quaternium43, quaternium-52, quaternium-53, quaternium-56, quaterni um60, quaternium42, quaternium-70, quaternium-72, quaternium-75, quaternium-77, quaternium-78, quaternium-80, quaternium-81, quaternium-82, quaternium-83, quaternium-84, and mixtures thereof.

Also preferred are hydrophilically substituted cationic surfactants in which at least one of the substituents contain one or more aromatic, ether, ester, amido, or amino moieties present as substituents or as linkages in the radical chain, wherein at least one of the R1 - R4 radicals contain one or more hydrophilic moieties selected from alkoxy (preferably C1 - C3 alkoxy), polyoxyalkylene (preferably C1 - C3 polyoxyalkylene), alkylamido, hydroxyalkyl, alkylester, and combinations thereof. Preferably, the hydrophilically substituted cationic conditioning surfactant contains from 2 to about 10 nonionic hydrophile moieties located within the above stated ranges. Preferred hydrophiiically substituted cationic surfactants include those of the formula (II) through (VII) below:

wherein n is from 8-28, x+y is from 2 to about 40, Z1 is a short chain alkyl, preferably a C1 - C3 alkyl, more preferably methyl, or (CH2CH2O)zH wherein x+y+z is up to 60, and X is a salt forming anion as defined above;

wherein m is 1 to 5, one or more of R5, R6, and R7 are independently an C1 C30 alkyl, the remainder are CH2CH2OH, one or two of R8, R9, and R10 are independently an C1 - C30 alkyl, and remainder are CH2CH2OH, and X is a salt forming anion as mentioned above;

wherein z2 is an alkyl, preferably a C1 - C3 alkyl, more preferably methyl, and Z3 is a short chain hydroxyalkyl, preferably hydroxymethyl or hydroxyethyl, p and q independently are integers from 2 to 4, inclusive, preferably from 2 to 3, inclusive, more preferably 2, R11 and R12 , independently, are substituted or unsubstituted hydrocarbyls, preferably C12 - C20 alkyl or alkenyl, and X is a salt forming anion as defined above;

wherein R13 is a hydrocarbyl, preferably a C1 - C3 alkyl, more preferably methyl, Z4 and Z5 are, independently, short chain hydrocarbyls, preferably C2 C4 alkyl or alkenyl, more preferably ethyl, a is from 2 to about 40, preferably from about 7 to about 30, and X is a salt forming anion as defined above;

wherein R14 and R15 independently, are C13 alkyl, preferably methyl, Z6 is a C12 to C22 hydrocarbyl, alkyl carboxy or alkylamido, and A is a protein, preferably a collagen, keratin, milk protein, silk, soy protein, wheat protein, or hydrolyzed forms thereof; and X is a salt forming anion as defined above;

wherein b is 2 or 3, R16 and R177 independently are C1 - C3 hydrocarbyls preferably methyl, and X is a salt forming anion as defined above. Nonlimiting examples of hydrophilically substituted cationic surfactants useful in the present invention include the materials having the following CTFA designations: quaternium-16, quaternium-61, quaternium-71, quaternium-79 hydrolyzed collagen, quaternium-79 hydrolyzed keratin, quaternium-79 hydrolyzed milk protein, quaternium-79 hydrolyzed silk, quaternium-79 hydrolyzed soy protein, and quaternium-79 hydrolyzed wheat protein. Highly preferred compounds include commercially available materials; VARIQUAT K1215 and 638 from Witco Chemical, MACKPRO KLP, MACKPRO WLW, MACKPRO MLP, MACKPRO NSP, MACKPRO NLW, MACKPRO WWP, MACKPRO NLP, MACKPRO SLP from Mclntyre, ETHOQUAD 18/25, ETHOQUAD O/12PG, ETHOQUAD C125, ETHOQUAD S/25, and ETHODUOQUAD from Akzo, DEHYQUAT SP from Henkel, and ATLAS G265 from ICI Americas.

Salts of primary, secondary and tertiary fatty amines are also suitable cationic surfactants. The alkyl groups of such amines preferably have from about 12 to about 22 carbon atoms, and can be substituted or unsubstituted.

Such amines, useful herein, include stearamido propyl dimethyl amine, diethyl amino ethyl stearamide, dimethyl stearamine, dimethyl soyamine, soyamine, myristyi amine, tridecyl amine, ethyl stearylamine, N-tallowpropane diamine, ethoxylated (with 5 moles of ethylene oxide) stearylamine, dihydroxy ethyl stearylamine, and arachidylbehenylamine. Suitable amine salts include the halogen, acetate, phosphate, nitrate, citrate, lactate, and alkyl sulfate salts.

Such salts include stearylamine hydrochloride, soyamine chloride, stearylamine formate, N-tallowpropane diamine dichloride 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, which is incorporated by reference herein in its entirety.

The cationic surfactants for use herein may also include a plurality of ammonium quaternary moieties or amino moieties, or a mixture thereof.

OTHER CONDITIONING AGENTS Other conditioning agents known in the industry may be comprised in the present invention. Suitable conditioning agents include water soluble cationic polymers, fatty compounds, nonvolatile dispersed silicones, hydrocarbons, proteins, and mixtures thereof. These conditioning agents are comprised at a level of from about 0.01 % to about 20% of the conditioning shampoo composition of the present invention.

Water Soluble Cationic Polymers Water soluble cationic polymers are useful herein. By "water soluble" is meant 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, i.e. distilled or equivalent, at 250C. Preferably, the polymer will be sufficiently soluble to form a substantially clear solution at a 0.5% concentration, more preferably at a 1.0% concentration.

The water soluble cationic polymers hereof will generally have a weight average molecular weight which is at least about 5,000, typically at least about 10,000, and is less than about 10 million. Preferably, the molecular weight is from about 100,000 to about 2 million. The cationic polymers will generally have cationic nitrogen-containing moieties such as quaternary ammonium or cationic amino moieties, and mixtures thereof.

The cationic charge density is preferably at least about 0.1 meq/gram, more preferably at least about 0.2 meq/gram, and preferably less than about 3.0 meqlgram, more preferably less than about 2.75 meq/gram.

The cationic charge density of the cationic polymer can be determined according to the Kjeldahl Method, which is well-known to those skilled in the art.

Those skilled in the art will recognize that the charge density of aminocontaining polymers can vary depending upon pH and the isoelectric point of the amino groups. The charge density should be within the above limits at the pH of intended use.

Any anionic counterions can be utilized for the water soluble cationic polymers so long as the water solubility criteria is met. Suitable counterions include halides (e.g., Cl, Br, I, or F, preferably Cl, Br, or 1), 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 water soluble cationic polymer can comprise copolymers, terpolymers, etc. of quaternary ammonium or cationic aminesubstituted 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 International Cosmetic Ingredient Dicitonary, Fifth Edition, 1993, which is incorporated by reference herein in its entirety.

Suitable water soluble 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 pyrrolidone. The alkyl and dialkyl substituted monomers preferably have C1-C7 alkyl groups, more preferably C1 - C3 alkyl groups. Other suitable spacer monomers include vinyl esters, vinyl alcohol (made by hydrolysis of polyvinyl acetate), 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 composition. 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 quaternization reaction.

Amines can also be similarly quaternized subsequent to formation of the polymer. For example, tertiary amine functionalities can be quaternized by reaction with a salt of the formula R'X wherein R' is a short chain alkyl, preferably a C1-C7 alkyl, more preferably a C1-C3 alkyl, and X is an anion which forms a water soluble salt with the quaternized ammonium.

Suitable cationic amino and quaternary ammonium monomers include, for example, vinyl compounds substituted with dialkylaminoalkyl acrylate, dialkylaminoalkyl methacrylate, monoalkylaminoalkyl acrylate, monoalkylaminoalkyl methacrylate, trialkyl methacryloxyalkyl ammonium salts, trialkyl acryloxyalkyl ammonium salts, diallyl quaternary ammonium salts, and vinyl quaternary ammonium monomers having cyclic cationic nitrogen-containing rings such as pyridinium, imidazolium, and quaternized pyrrolidone, e.g., alkyl vinyl imidazolium, alkyl vinyl pyridinium, alkyl vinyl pyrrolidone salts. The alkyl portions of these monomers are preferably lower alkyls such as the C1-C3 alkyls, more preferably C1 and C2 alkyls. Suitable amine-substituted vinyl monomers for use herein include dialkylaminoalkyl acrylate, dialkylaminoalkyl methacrylate, dialkylaminoalkyl acrylamide, and dialkylaminoalkyl methacrylamide, wherein the alkyl groups are preferably C1-C7 alkyl and more preferably C1-C3, alkyl.

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

Suitable water soluble cationic polymers include, for example: copolymers of 1-vinyl-2-pyrrolidone and 1-vinyl-3-methylimidazolium salt (e.g., chloride salt), referred to in the industry by the CTFA designation as polyquaternium-16, which is commercially available from BASF Corporation under the LUVIQUAT tradename (e.g., LUVIQUAT FC 370); copolymers of 1-vinyl-2-pyrrolidone and dimethylaminoethyl methacrylate, referred to as polyquaternium-1 1, which is 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 by the CTFA designations polyquaternium-6 and polyquaternium-7, respectively; and mineral acid salts of amino-alkyl esters of homo- and co-polymers of unsaturated carboxylic acids having from 3 to 5 carbon atoms, as described in U.S. Patent 4,009,256, incorporated herein by reference.

Other water soluble cationic polymers that can be used include polysaccharide polymers, such as cationic cellulose derivatives and cationic starch derivatives. Cationic polysaccharide polymer materials suitable for use herein include those of the formula:

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, R1, R2, and R3 independently are alkyl, aryl, alkylaryl, arylalkyl, alkoxyalkyl, or alkoxyaryl groups, each group containing up to about 18 carbon atoms, and the total number of carbon atoms for each cationic moiety (i.e., the sum of carbon atoms in R1, R2 and R3) preferably being about 20 or less, and X is an anionic counterion, e.g., halide, sulfate, nitrate, and the like.

Cationic cellulose is available from Amerchol Corp. (Edison, NJ, USA) in their Polymer JRC, LR8 and SR(E) series of polymers, as salts of hydroxyethyl cellulose reacted with trimethyl ammonium substituted epoxide, referred to by the CTFA designation polyquaternium-10. Another type of cationic cellulose includes the polymeric quaternary ammonium salts of hydroxyethyl cellulose reacted with lauryl dimethyl ammonium-substituted epoxide, referred to by the CTFA as polyquaternium-24, and which is available from Amerchol Corp.

(Edison, NJ, USA) under the tradename Polymer LM-200.

Other water soluble cationic polymers that can be used include cationic guar gum derivatives, such as guar hydroxypropyltrimonium chloride (commercially available from Celanese Corp. in their Jaguar R series). Other materials include quaternary nitrogen-containing cellulose ethers (e.g., as described in U.S. Patent 3,962,418, which is incorporated by reference herein in its entirety), and copolymers of etherified cellulose and starch (e.g., as described in U.S. Patent 3,958,581, which is incorporated herein by reference in its entirety).

Preferred for use herein are watersoluble cationic polymers selected from the group consisting of polyquaternium-7, polyquaternium-10, polyquaternium11, and mixtures thereof.

Fattv ComPounds Fatty compounds including fatty alcohols, fatty acids, fatty alcohol derivatives, fatty acid derivatives, and mixtures thereof are preferred conditioning agents. It is recognized that the compounds disclosed in this section of the specification can in some instances fall into more than one classification, e.g., some fatty alcohol derivatives can also be classified as fatty acid derivatives. Also, it is recognized that some of these compounds can have properties as non ionic surfactants and can alternatively be classified as such.

However, a given classification is not intendend to be a limitation on that particular compound, but is done so for convenience of classification and nomenclature. Nonlimiting examples of the fatty alcohols, fatty acids, fatty alcohol derivatives, and fatty acid derivatives are found in International Cosmetic Ingredient Dictionary, Fifth Edition, 1993, and CTFA Cosmetic Ingredient Handbook, Second Edition, 1992, both of which are incorporated by reference herein in their entirety.

The fatty alcohols useful herein are those having from about 10 to about 30 carbon atoms, preferably from about 12 to about 22 carbon atoms, and more preferably from about 16 to about 22 carbon atoms. These fatty alcohols can be straight or branched chain alcohols and can be saturated or unsaturated.

Nonlimiting examples of fatty alcohols include decyl alcohol, undecyl alcohol, dodecyl, myristyl, cetyl alcohol, stearyl alcohol, isostearyl alcohol, isocetyl alcohol, behenyl alcohol, linalool, oleyl alcohol, cholesterol, cis4-tbutylcyclohexanol, myricy alcohol and mixtures thereof. Especially preferred fatty alcohols are those selected from the group consisting of cetyl alcohol; stearyl alcohol, isostearyl alcohol, oleyl alcohol, and mixtures thereof.

The fatty acids useful herein are those having from about 10 to about 30 carbon atoms, preferably from about 12 to about 22 carbon atoms, and more preferably from about 16 to about 22 carbon atoms. These fatty acids can be straight or branched chain acids and can be saturated or unsaturated. Also included are diacids, triacids, and other multiple acids which meet the carbon number requirement herein. Also included herein are salts of these fatty acids.

Nonlimiting examples of fatty acids include lauric acid, palmitic acid, stearic acid, behenic acid, arichidonic acid, oleic acid, isostearic acid, sebacic acid, and mixtures thereof. Especially preferred for use herein are the fatty acids selected from the group consisting of palmitic acid, stearic acid, and mixtures thereof.

The fatty alcohol derivatives are defined herein to include alkyl ethers of fatty alcohols, alkoxylated fatty alcohols, alkyl ethers of alkoxylated fatty alcohols, esters of fatty alcohols and mixtures thereof. Nonlimiting examples of fatty alcohol derivatives include materials such as methyl stearyl ether; 2ethylhexyl dodecyl ether; stearyl acetate; cetyl propionate; the ceteth series of compounds such as ceteth-1 through ceteth45, which are ethylene glycol ethers of cetyl alcohol, wherein the numeric designation indicates the number of ethylene glycol moieties present; the steareth series of compounds such as steareth-1 through 100, which are ethylene glycol ethers of steareth alcohol, wherein the numeric designation indicates the number of ethylene glycol moieties present; ceteareth 1 through ceteareth-50, which are the ethylene glycol ethers of ceteareth alcohol, i.e. a mixture of fatty alcohols containing predominantly cetyl and stearyl alcohol, wherein the numeric designation indicates the number of ethylene glycol moieties present; C1-C30 alkyl ethers of the ceteth, steareth, and ceteareth compounds just described; polyoxyethylene ethers of branched alcohols such as octyldodecyl alochol, dodecylpentadecyl alcohol, hexyldecyl alcohol, and isostearyl alcohol; polyoxyethylene ethers of behenyl alcohol; PPG ethers such as PPG-9-steareth-3, PPG-11 stearyl ether, PPG-8-ceteth-1, and PPG-10 cetyl ether; and mixtures of all of the foregoing compounds. Preferred for use herein are steareth-2, steareth4, ceteth-2, and mixtures thereof.

The fatty acid derivatives are defined herein to include fatty acid esters of the fatty alcohols as defined above in this section, fatty acid esters of the fatty alcohol derivatives as defined above in this section when such fatty alcohol derivatives have an esterifiable hydroxyl group, fatty acid esters of alcohols other than the fatty alcohols and the fatty alcohol derivatives described above in this section, hydroxy-substitued fatty acids, and mixtures thereof. Nonlimiting examples of fatty acid derivatives inlcude ricinoleic acid7 glycerol monostearate, 12-hydroxy stearic acid, ethyl stearate, cetyl stearate, cetyl palmitate, polyoxyethylene cetyl ether stearate, polyoxyethylene stearyl ether stearate, polyoxyethylene lauryl ether stearate, ehtyleneglycol monostearate, polyoxyethylene monostearate, polyoxyethylene distearate, propyleneglycol monostearate, propyleneglycol distearate, trimethyl olpropane distearate, sorbitan stearate, polyglyceryl stearate, dimethyl sebacate, PEG-1 5 cocoate, PPG-15 stearate, glyceryl monostearate, glyceryl distearate, glyceryl tristearate, PEG-8 laurate, PPG-2 isostearate, PPG-9 laurate, and mixtures thereof.

Preferred for use herein are glycerol monostearate, 12-hydroxy stearic acid, and mixtures thereof.

Nonvolatile Dispersed Silicones Other conditioning agents useful herein include nonvolatile, dispersed silicones. By nonvolatile is meant that the silicones exhibit very low or no significant vapor pressure at ambient conditions, e.g., 1 atmosphere at 25"C.

The nonvolatile dispersed silicone conditioning agent preferably has a boiling point at ambient pressure of about 250"C or higher, preferably of about 260"C, and more preferably of about 275"C. By dispersed is meant that the silicones form a separate, discontinuous phase from the aqueous carrier such as in the form of an emulsion or a suspension of droplets. The droplets have an average particle diameter from about 0.1 microns to about 25 microns, preferably from about 5 microns to about 20 microns.

The nonvolatile dispersed silicones for use herein will preferably have a viscosity of from about 1,000 to about 2,000,000 centistokes at 250C, more preferably from about 10,000 to about 1,800,000, and 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, which is incorporated by reference herein in its entirety. Suitable silicone fluids include polyalkyl siloxanes, polyaryl siloxanes, polyalkylaryl siloxanes, polyether siloxane copolymers, and mixtures thereof.

Other nonvolatile silicones having hair conditioning properties can also be used.

The nonvolatile dispsersed silicones herein also include polyalkyl or polyaryl siloxanes with the following structure:

wherein R is alkyl or aryl, and x is an integer from about 7 to about 8,000. "A" represents groups which block the ends of the silicone chains. The alkyl or aryl groups substituted on the siloxane chain (R) or at the ends of the siloxane chains (A) can have any structure as long-as the resulting silicone remains fluid at room temperature, is dispersible, is neither irritating, toxic nor otherwise harmful when applied to the hair, is compatible with the other components of the composition, is chemically stable under normal use and storage conditions, and is capable of being deposited on and conditions the hair. Suitable A groups include hydroxy, methyl, methoxy, ethoxy, propoxy, and aryloxy. The two R groups on the silicon atom may represent the same group or different groups.

Preferably, the two R groups represent the same group. Suitable R groups include methyl, ethyl, propyl, phenyl, methylphenyl and phenylmethyl. The preferred silicones are polydimethyl siloxane, polydiethylsiloxane, and polymethylphenylsiloxane. Polydimethylsiloxane, which is also known as dimethicone, is especially preferred. The polyalkylsiloxanes that can be used include, for example, polydimethylsiloxanes. These silicones 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.

Polyalkylaryl siloxane fluids can also be used and 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 nonvolatile dispersed silicones that can be used include, for example, a polypropylene oxide modified polydimethylsiloxane although ethylene oxide or mixtures of ethylene oxide and propylene oxide can also be used. The ethylene oxide and polypropylene oxide level should be sufficiently low so as not to interfere with the dispersibility characteristics of the silicone. These material are also known as dimethicone copolyols.

Other nonvolatile dispersed silicones include amino substituted materials.

Suitable alkylamino substituted silicones include those represented by the following structure (II)

wherein x and y are integers which depend on the molecular weight, the average molecular weight being approximately between 5,000 and 10,000. This polymer is also known as "amodimethicone".

Suitable cationic silicone fluids include those represented by the formula (Ill) (R1 )aG3-a-Si-(-OSiG2)n-(-OSiGb(R1 )2-b)m-O-SiG3~a(R1 )a in which G is chosen from the group consisting of hydrogen, phenyl, OH, C1-Cg alkyl and preferably methyl; a denotes 0 or an integer from 1 to 3, and preferably equals 0; b denotes 0 or 1 and preferably equals 1; the sum n+m is a number from 1 to 2,000 and preferably from 50 to 150, n being able to denote a number from 0 to 1,999 and preferably from 49 to 149 and m being able to denote an integer from 1 to 2,000 and preferably from 1 to 10; R1 is a monovalent radical of formula CqH2qL in which q is an integer from 2 to 8 and L is chosen from the groups -N(R2)CH2-CH2-N(R2)2 -N(R2)2 -N(R2)3A -N(R2)CH2-CH2-NR2H2A in which R2 is chosen from the group consisting of hydrogen, phenyl, benzyl a saturated hydrocarbon radical, preferably an alkyl radical containing from 1 to 20 carbon atoms, and A- denotes a halide ion.

An especially preferred cationic silicone corresponding to formula (III) is the polymer known as "trimethylsilylamodimethicone", of formula (IV):

In this formula n and m are selected depending on the exact molecular weight of the compound desired.

Other silicone cationic polymers which can be used are represented by the formula (V):

where R3 denotes a monovalent hydrocarbon radical having from 1 to 18 carbon atoms, preferably an alkyl or alkenyl radical such as methyl; R4 denotes a hydrocarbon radical, preferably a C1-C18 alkylene radical or a C Compounds" distributed by Petrarch Systems, Inc., 1984. This reference provides an extensive, though not exclusive, listing of suitable silicones.

Another nonvolatile dispersed silicone that can be especially useful is a silicone gum. The term "silicone gum", as used herein, means a polyorganosiloxane material having a viscosity at 25"C of greater than or equal to 1,000,000 centistokes. It is recognized that the silicone gums described herein can also have some overlap with the above-disclosed silicones. This overlap is not intended as a limitation on any of these materials. Silicone gums are described by Petrarch, Id., and others including U.S. Patent No. 4,152,416, to Spitzer et al., issued May 1, 1979 and Noll, Walter, Chemistry and Technology of Silicones, New York: Academic Press 1968. Also describing silicone gums are General Electric Silicone Rubber Product Data Sheets SE 30, SE 33, SE 54 and SE 76. All of these described references are incorporated herein by reference in their entirety. The "silicone gums" will typically have a mass molecular weight in excess of about 200,000, generally between about 200,000 and about 1,000,000. Specific examples include polydimethylsiloxane, (polydimethylsiloxane) (methylvinylsiloxane) copolymer, poly(dimethylsiloxane) (diphenyl siloxane)(methylvinylsiloxane) copolymer and mixtures thereof.

Also useful are silicone resins, which are highly crosslinked polymeric siloxane systems. The crosslinking is introduced through the incorporation of trifunctional and tetrafunctional silanes with monofunctional or difunctional, or both, silanes during manufacture of the silicone resin. As is well understood in the art, the degree of crosslinking that is required in order to result in a silicone resin will vary according to the specific silane units incorporated into the silicone resin. In general, silicone materials which have a sufficient level of trifunctional and tetrafunctional siloxane monomer units, and hence, a sufficient level of crosslinking, such that they dry down to a rigid, or hard, film are considered to be silicone resins. The ratio of oxygen atoms to silicon atoms is indicative of the level of crosslinking in a particular silicone material. Silicone materials which have at least about 1.1 oxygen atoms per silicon atom will generally be silicone resins herein. Preferably, the ratio of oxygen:silicon atoms is at least about 1.2:1.0. Silanes used in the manufacture of silicone resins include monomethyl-, dimethyl-, trimethyl-, monophenyl-, diphenyl-, methylphenyl-, monovinyl-, and methylvinyl-chlorosilanes, and tetrachlorosilane, with the methyl-substituted silanes being most commonly utilized. Preferred resins are offered by General Electric as GE SS4230 and SS4267. Commercially available silicone resins will generally be supplied in a dissolved form in a low viscosity volatile or nonvolatile silicone fluid. The silicone resins for use herein should be supplied and incorporated into the present compositions in such dissolved form, as will be readily apparent to those skilled in the art. Without being bound by theory, it is believed that the silicone resins can enhance deposition of other silicones on the hair and can enhance the glossiness of hair with high refractive index volumes.

Other useful silicone resins are silicone resin powders such as the material given the CTFA designation polymethylsilsequioxane, which is commercially available as TospearlTM from Toshiba Silicones.

Background material on silicones, including sections discussing silicone fluids, gums, and resins, as well as the manufacture of silicones, can be found in Encyclopedia of Polymer Science and Engineering, Volume 15, Second Edition pp 204-308, John Wiley & Sons, Inc., 1989, which is incorporated herein by reference in its entirety.

Silicone materials and silicone resins in particular, can conveniently be identified according to a shorthand nomenclature system well known to those skilled in the art as the "MDTQ" nomenclature. Under this system, the silicone is described according to the presence of various siloxane monomer units which make up the silicone. Briefly, the symbol M denotes the monofunctional unit (CH3)3SiO) 5; D denotes the difunctional unit (CH3)2SiO; T denotes the trifunctional unit (CH3)SiO1.5; and Q denotes the quadri- or tetra-functional unit SiO2. Primes of the unit symbols, e.g., M', D', T', and Q' denote substituents other than methyl1 and must be specifically defined for each occurrence. Typical alternate substituents include groups such as vinyl, phenyl, amino, hydroxyl, etc.

The molar ratios of the various units, either in terms of subscripts to the symbols indicating the total number of each type of unit in the silicone, or an average thereof, or as specifically indicated ratios in combination with molecular weight, complete the description of the silicone material under the MDTQ system.

Higher relative molar amounts of T, Q, T' and/or Q' to D, D', M and/or or M' in a silicone resin is indicative of higher levels of crosslinking. As discussed before, however, the overall level of crosslinking can also be indicated by the oxygen to silicon ratio.

The silicone resins for use herein which are preferred are MQ, MT, MTQ, MQ and MDTQ resins. Thus, the preferred silicone substituent is methyl. Especially preferred are MQ resins wherein the M:Q ratio is from about 0.5:1.0 to about 1.5:1.0 and the average molecular weight of the resin is from about 1000 to about 10,000.

Hydrocarbons Hydrocarbons are useful herein as conditioning agents. Useful hydrocarbons include straight chain, cyclic, and branched chain hydrocarbons which can be either saturated or unsaturated. The hydrocarbons preferably will have from about 12 to about 40 carbon atoms, more preferably from about 12 to about 30 carbon atoms, and most preferably from about 12 to about 22 carbon atoms. Also encompassed herein are polymeric hydrocarbons of alkenyl monomers, such as polymers of C2-C6 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 in this paragraph. The branched chain polymers can have substantially higher chain lengths. The number average molecular weight of such materials can vary widely, but will typically be up to about 500, preferably from about 200 to about 400, and more preferably from about 300 to about 350.

Also useful herein are the various grades of mineral oils. Mineral oils are liquid mixtures of hydrocarbons that are obtained from petroleum. Specific examples of suitable hydrocarbon materials include paraffin oil, mineral oil, dodecane, isododecane, hexadecane, isohexadecane, eicosene, isoeicosene, tridecane, tetradecane, polybutene, polyisobutene, and mixtures thereof. Isododecane, isohexadeance, and isoeicosene are commercially available as Permethyl 99A, Permethyl 101A, and Permethyl 1082, from Presperse, South Plainfield, NJ. A copolymer of isobutene and normal butene is commercially available as Indopol H100 from Amoco Chemicals. Preferred for use herein are hydrocarbon conditioning agents selected from the group consisting of mineral oil, isododecane, isohexadecane, polybutene, polyisobutene, and mixtures thereof.

OTHER COMPONENTS The compositions herein can contain a variety of other optional components suitable for rendering such compositions more cosmetically or aesthetically acceptable or to provide them with additional usage benefits. Such optional components are well-known to those skilled in the art. Optional components generally are used individually at levels from about 0.01% to about 5.0%, preferably from about 0.05% to about 3.0% by weight of the composition.

A preferred optional component of the present invention is a polyalkylene glycol. The polyalkylene glycols are characterized by the general formula:

wherein R is selected from the group consisting of H, methyl, and mixtures thereof. When R is H, these materials are polymers of ethylene oxide, which are also known as polyethylene oxides, polyoxyethylenes, and polyethylene glycols.

When R is methyl, these materials are polymers of propylene oxide, which are also known as polypropylene oxides, poiyoxypropylenes, and polypropylene glycols. When R is methyl, it is also understood that various positional isomers of the resulting polymers can exist.

In the above structure, n has an average value of from about 1500 to about 25,000, preferably from about 2500 to abput 20,000, and more preferably from about 3500 to about 15,000.

Polyethylene glycol polymers useful herein are PEG-2M wherein R equals H and n has an average value of about 2,000 (PEG-2M is also known as Polyox WSRE N-10, which is available from Union Carbide and as PEG-2,000); PEG 5M wherein R equals H and n has an average value of about 5,000 (PEG-SM is also known as Polyox WSRX N-35 and Polyox WSRB N-80, both available from Union Carbide and as PEG-5,000 and Polyethylene Glycol 300,000); PEG-7M wherein R equals H and n has an average value of about 7,000 (PEG-7M is also known as Polyox WSRB N-750 available from Union Carbide); PEG-9M wherein R equals H and n has an average value of about 9,000 (PEG 9-M is also known as Polyox WSRB N-3333 available from Union Carbide); and PEG-14 M wherein R equals H and n has an average value of about 14,000 (PEG-14M is also known as Polyox WSRS) N-3000 available from Union Carbide). Other useful polymers include the polypropylene glycols and mixed polyethylene/polypropylene glycols.

Another optional component is a suspending agent, which is highly preferred for suspending the silicone hair conditioning agent, when present in dispersed form, in the compositions of the present invention. The suspending agent will generally comprise from about 0.1% to about 10%, and more typically from about 0.3% to about 5.0%, by weight, of the composition. Preferred suspending agents include acyl derivatives, long chain amine oxides, and mixtures thereof. When used in the compositions, these preferred suspending agents are present in crystalline form. These suspending agents are described in U.S. Patent 4,741,855, which is incorporated herein by reference in its entirety. These preferred suspending agents include ethylene glycol esters of fatty acids preferably having from about 16 to about 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 suitable 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 examples of which include stearic monoethanolamide, stearic diethanolamide, stearic monoisopropanolamide and stearic monoethanolamide stearate. Other long chain acyl derivatives include long chain esters of long chain fatty acids (e.g., stearyl stearate, cetyl palmitate, etc.); glyceryl esters (e.g., glyceryl distearate) and long chain esters of long chain alkanol amides (e.g., stearamide-diethanolamide distearate, stearamide monoethanolamide stearate). Long chain acyl derivatives, 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. For example, it is contemplated that suspending agents with long chain hydrocarbyls having Cg-C22 chains may be used.

Other long chain acyl derivatives suitable for use as suspending agents include N,N-dihydrocarbyl amido benzoic acid and soluble salts thereof (e.g., Na and K salts), particularly N,N-di(hydrogenated) C16, C18 and tallow amido benzoic acid species of this family, which are commercially available from Stepan Company (Northfield, Illinois, USA).

Examples of suitable long chain amine oxides for use as suspending agents include alkyl (C16-C22) dimethyl amine oxides, e.g., stearyl dimethyl amine oxide.

Other suitable suspending agents include xanthan gum. The use of xanthan gum as a suspending agent in silicone containing shampoo compositions is described, for example, in U.S. Patent 4,788,006, which is incorporated herein by reference in its entirety. Combinations of long chain acyl derivatives and xanthan gum may also be used as a suspending agent in the shampoo compositions. Such combinations are described in U.S. Patent 4,704,272, which is incorporated herein by reference in its entirety.

Other suitable suspending agents include carboxyvinyl polymers.

Preferred among these polymers are the copolymers of acrylic acid crosslinked with polyallylsucrose as described in U.S. Patent 2,798,053, which is incorporated herein by reference in its entirety. Examples of these polymers include the carbomers, which are hompolymers of acrylic acid crosslinked with an allyl ether of pentaerythrotol, an allyl ether of sucrose, or an allyl ether of propylene. Preferred carboxyvinyl polymers have a molecular weight of at least about 750,000; more preferred are carboxyvinyl polymers having a molecular weight of at least about 1,250,000; most preferred are carboxyvinyl polymers having a molecular weight of at least about 3,000,000.

Other suitable suspending 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 such as hydroxyethyl cellulose, and materials such as guar gum, polyvinyl alcohol, polyvinyl pyrrolidone, hydroxypropyl guar gum, starch and starch derivatives, and other thickeners, viscosity modifiers, gelling agents, etc. Mixtures of these materials can also be used.

A wide variety of additional optional components can be formulated into the present composition. These include: hair-hold polymers; additional thickening agents; viscosity modifiers such as methanolamides of long chain fatty acids such as cocomonoethanol amide; crystalline suspending agents; pearlescent aids such as ethylene glycol distearate; preservatives such as benzyl alcohol, benzoic acid, methyl paraben, propyl paraben and imidazolidinyl urea, iodopropynyl butyl carbamate, methylisothiazol inone, methychloroisothiazolinone, polyvinyl alcohol, ethyl alcohol; salts and electrolytes such as sodium chloride, potassium chloride, sodium sulfate, and ammonium xylene sulfonate; pH adjusting agents, such as citric acid, sodium citrate, succinic acid, phosphoric acid, sodium hydroxide, sodium carbonate; fragrances and colorings to modify the aesthetic appeal of the composition such as any of the FD & C or D & C dyes; hair oxidizing (bleaching) agents, such as hydrogen peroxide, perborate and persulfate salts; hair reducing agents, such as thioglycolates; hair coloring agents; sequestering agents, such as disodium ethylenediamine tetra-acetate; and polymer plasticizing agents, such as glycerin, disobutyl adipate, and butyl stearate; sunscreening agents; humectants such as glycerin and other polyhydric alcohols; moisturizers such as hydrolysed collagen and hydrolysed keratin; antidandruff agents such as zinc pyrithione; sunscreening agents, antioxidants; antiinflammatory agents; pediculicids; steroids; topical anesthetics; and scalp sensates such as menthol.

In addition to the required components, the compositions herein can also contain a wide variety of additional components. Nonlimiting examples of these additional components are disclosed in International Cosmetic Ingredient Dictionary, Fifth Edition, 1993, and CTFA Cosmetic Ingredient Handbook, Second Edition, 1992, both of which are incorporated by reference herein in their entirety.

EXAMPLES The following examples further describe and demonstrate embodiments within the scope of the present invention. The examples are given solely for the purpose of illustration and are not to be construed as limitations of the present invention, as many variations thereof are possible without departing from the spirit and scope of the invention. . Ingredients are identified by chemical or CTFA name, or otherwise defined below.

Method of Preparation The conditioning shampoo compositions of the present invention can be prepared by using conventional mixing and formulating techniques. The conditioning shampoo compositions illustrated hereinafter are prepared in the following manner.

The compositions of the present invention, in general, can be made by mixing the materials together at elevated temperature, e.g., about 750C. The nonvolatile dispersed silicones such as Dimethicone is first mixed before being mixed with the other ingredients. The complete mixture is then mixed thoroughly at the elevated temperature and is then pumped through a high shear mill and then through a heat exchanger to cool it to ambient temperature, until the desired silicone particle size is achieved. Alternatively, the nonvolatile dispersed silicones can be mixed with anionic surfactant and fatty compounds such as cetyl and stearyl alcohols, at elevated temperature, to form a premix.

The premix can then be added to and mixed with the remaining materials of the composition, pumped through a high shear mill, and cooled.

The composition illustrated, all of which are embodiments of the present invention, are useful for both cleansing and conditioning the hair from a single product. All percentages are based on weight.

Example Number Ingredient I 11 Ill IV V Ammonium Laureth-3 Sulfate 12.0 12.0 12.0 12.0 12.0 Ammonium Lauryl Sulfate 4.0 4.0 4.0 4.0 4.0 Polyquaternium-1 0 0 0 0 0.4 0.4 Mineral Oil 0 0 0 0.4 0.4 Dimethicone 1.25 1.25 1.25 2.0 2.0 Cetyl Alcohol 0.42 0.42 0.42 0.34 0.34 Stearyl Alcohol 0.18 0.18 0.18 0.14 0.14 Polyethoxylated tetraethylenepentamine 1 1 1 1 1 Variquat K1215*2 0 - 0 0 1 0 Mackpro KLP*3 0 0 1 0 1 Cocamide MEA 0.9 0.9 0.9 0.7 0.7 Ethylene Glycol Distearate 2.0 - 2.0 2.0 1.6 1.6 Fragrance 0.5 0.5 0.5 0.5 0.5 DMDM Hydantoin 0.20 0.20 0.20 0.20 0.20 Water ---------- q. s. to 100% -------- Example Number Ingredient VI VII VIII IV Ammonium Laureth-3 Sulfate 13.5 13.5 13.5 12.0 Ammonium Lauryl Sulfate 4.5 4.5 4.5 4.0 Polyquaternium-10 0.45 0.45 0.45 0 Mineral Oil 0.45 0.45 0.45 0 Dimethicone 2.25 2.25 2.25 0 Cetyl Alcohol 0.38 0.38 0.38 0.42 Stearyl Alcohol 0.16 0.16 0.16 0.18 Polyethoxylated tetraethylenepentamine 1 1 1 1 Stearyltrimethylammonium chloride 1 0 0 0 Ethoquad C/25*4 0 1 0 0 Ethoquad S/25*5 0 0 1 0 Variquat K1215*2 0 1 0 0 Cocamide MEA 0.8 0.8 0.8 0.8 Ethylene Glycol Distearate 1.8 1.8 1.8 1.5 Fragrance 0.5 0.5 0.5 0.65 DMDM Hydantoin 0.20 0.20 0.20 0.2 Water ---------- q. s. to 100% ---------- *1 Polyethoxylated tetraethylenepentamine

wherein y is an integer from about 10 to about 20 *2 Variquat K1215 supplied by Witco Chemical

wherein R is coconut radical and x+y=15 *3 MackproKLP supplied by Mclntyre Quaternium-79 hydrolyzed keratin *4 Ethoquad C/25 supplied by AKZO Cocoalkylmethyl [ethoxylated (15)] chloride *5 Ethoquad S/25 supplied by AKZO Stearylmethyl [ethoxylated (15)] chloride All publications, patent applications, and issued patents mentioned hereinabove are hereby incorporated in their entirety by reference.

What is claimed is:

Claims (10)

1. A hair conditioning shampoo composition comprising: (a) a polyalkoxylated polyalkyleneamine of the following formula:

wherein R1 and R2 are independently C2 to C6 alkylene; A is a polyalkoxy of the formula (R3O)yH wherein R3 is a C2 to C4 alkylene and y is an integer from 1 to about 40; and x is an integer from 0 to about 100; and the polyalkoxy moieties constitute more than about 50% by molecular weight of the entire molecule; and (b) a detersive surfactant.

2. The hair conditioning shampoo composition according to Claim 1 wherein R1 and R2 are independently C2 to C4 alkylene; A is polyethyoxy or polypropoxy, and y is an integer from about 5 to about 30; and x is an integer from 1 to about 10.

3. The hair conditioning shampoo composition according to Claim 2 wherein R1 and R2 are ethylene, A is polyethoxy and x is an integer from 1 to about 5; and the polyalkoxy moieties constitute more than about 80% by molecular weight of the entire molecule.

4. A hair conditioning shampoo composition comprising by weight: (a) from about 0.01% to about 10% of an polyalkoxylated polyalkyleneamine of the following formula:

wherein R1 and R2 are independently C2 to C6 alkylene; A is a polyalkoxy of the formula (R30)yH wherein R3 is a C2 to C4 alkylene and y is an integer from 1 to about 40; and x is an integer from 1 to about 100; and the polyalkoxy moieties constitute more than about 50% by molecular weight of the entire molecule; and (b) from about 0.01% to about 20% of a cationic surfactant conditioning agent; (c) from about 5% to about 50% of a detersive surfactant; and (d) from about 20% to about 90% of water.

5. The hair conditioning shampoo composition according to Claim 4 wherein R1 and R2 are independently C2 to C4 alkylene; A is polyethyoxy or polypropoxy, and y is an integer from about 5 to about 30; and x is an integer from 1 to about 10.

6. The hair conditioning shampoo composition according to Claim 5 wherein R1 and R2 are ethylene, A is polyethoxy and x is an integer from 1 to about 5; and the polyalkoxy moieties constitute more than about 80% by molecular weight of the entire molecule.

7. The hair conditioning shampoo composition according to Claim 4 wherein the cationic surfactant is substantially a hydrophilically substituted cationic surfactant.

8. The hair conditioning shampoo composition according to Claim 6 wherein the cationic surfactant is substantially a hydrophilically substituted cationic surfactant.

9. The hair conditioning shampoo composition according to Claim 4 wherein the detersive surfactant is substantially an anionic surfactant.

10. The hair conditioning shampoo composition according to Claim 8 wherein the detersive surfactant is substantially an anionic surfactant.