WO2000006094A1

WO2000006094A1 - Hair care composition comprising antioxidants

Info

Publication number: WO2000006094A1
Application number: PCT/US1998/015756
Authority: WO
Inventors: Ananthanarayan Venkateswaran; Minmin Tian; Junichi Yokogi
Original assignee: The Procter & Gamble Company
Priority date: 1998-07-29
Filing date: 1998-07-29
Publication date: 2000-02-10
Also published as: AU8670898A

Abstract

The present invention relates to a hair care composition comprising an organic antioxidant, an inorganic reducing agent selected from the group consisting of alkali metal sulfites, alkali metal bisulfites, alkali metal monopersulfates, alkali metal bisulfates, ammonium sulfites, ammonium bisulfites, ammonium persulfates, and mixtures thereof; a hair conditioning agent, and an aqueous carrier. The use of inorganic reducing agents substantially reduces malodor and/or discoloration of the hair care composition due to the oxidation of organic antioxidants over time.

Description

HAIR CARE COMPOSITION COMPRISING ANTIOXIDANTS

FIELD

The present invention relates to a hair care composition comprising hair conditioning agents and antioxidants.

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. Although shampooing cleans the hair, it can also 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 after-shampoo problems. These approaches range from post-shampoo application of hair conditioners such as leave-on and rinse-off products, to hair conditioning shampoos which attempt to both cleanse and condition the hair from a single product.

Hair care compositions, as described above, may contain organic antioxidants. Antioxidants, such as Vitamin E, may be intentionally added to hair care compositions for various reasons, including improving the health of hair. Antioxidants may also be used in hair care compositions to prevent oxidation of particular materials so that certain actives in the composition do not decompose or otherwise become oxidized. In addition, some antioxidants exist as part of a hair composition raw material, such as in perfume compositions. However, these materials may oxidize and decompose in the hair care composition over time. When these organic antioxidants become oxidized, they release unpleasant odor and/or discolor the composition to an undesirable color, which is very undesirable to consumers.

Based on the foregoing, there remains a desire to provide hair care compositions comprising antioxidants which provide good conditioning benefits while not generating undesirable odor or color under normal shelf conditions.

None of the existing art provides all of the advantages and benefits of the present invention.

SUMMARY

It has now been found that the use of particular inorganic reducing agents in such products substantially reduces the malodor and also substantially prevents product discoloration over time.

The present invention relates to a hair care composition comprising an organic antioxidant, an inorganic reducing agent selected from the group consisting of alkali metal sulfites, alkali metal bisulfites, alkali metal monopersulfates, alkali metal bisulfates, ammonium sulfites, ammonium bisulfites, ammonium persulfates, and mixtures thereof; a hair conditioning agent, and an aqueous carrier.

These and other features, aspects, and advantages of the present invention will become evident to those skilled in the art from a reading of the present disclosure.

DETAILED DESCRIPTION

While the specification concludes with claims which particularly point out and distinctly claim the invention, it is believed the present invention will be better understood from the following description. All cited references are incorporated herein by reference in their entireties.

Citation of any reference is not an admission regarding any determination as to its availability as prior art to the claimed invention.

Herein, "comprising" means that other steps and other ingredients which do not affect the end result can be added. This term encompasses the terms "consisting of and "consisting essentially of. All percentages, parts and ratios are based upon the total weight of the shampoo compositions of the present invention, unless otherwise specified. All such weights as they pertain to listed ingredients are based on the active level and, therefore, do not include carriers or by-products that may be included in commercially available materials. ORGANIC ANTIOXIDANT

The hair care compositions of the present invention contain an organic antioxidant. The organic antioxidant is preferably included in the composition at a level by weight of from about 0.001% to about 5%, preferably from about 0.005% to about 0.5%, more preferably from about 0.005% to about 0.1 %.

The organic antioxidant becomes oxidized in the hair care composition, especially over time. After oxidation takes place, the composition may have malodor and/or the product may become discolored. Examples of organic antioxidants useful in the present invention include tocopherols (e.g. Vitamin E), such as alpha, beta, gamma and delta-tocopherol, tocopherol acetate tocopherol sorbate, flavon derivatives, caffeic acid, gallic acid and its derivatives, sesamol, sesamolin gossypol, nordihydroguaialetinic acid, ascorbic acid, paramethoxyphenol, beta carotene, Malachite Green, adrenaline, and extracts of Rumex japonicus, Polygonaceae and its close families. Preferred organic antioxidants include butyl hydroxy toluene, butyl hydroxy anisole, tertiary butyl hydroquinone, hydroquinone, Vitamin E and its derivatives, Vitamin C and its derivatives, and mixtures thereof.

The organic antioxidant material may be present in the composition, or may be part of a raw material (e.g. by-product, impurity, etc.) used in the composition of the present invention. For example, some perfumes may contain some organic antioxidant materials as part of the perfume raw material. INORGANIC REDUCING AGENT

The compositions of the present invention contains an inorganic reducing agent selected from the group consisting of alkali metal sulfites, alkali metal bisulfites, alkali metal monopersulfates, alkali metal bisulfates, ammonium sulfites, ammonium bisulfites, ammonium persulfates, and mixtures thereof. The inorganic reducing agent is preferably included in the composition at a level by weight of from about 0.001% to about 2%, preferably from about 0.02% to about 0.5%, more preferably from about 0.02% to about 0.1%. Preferably, the molar ratio of inorganic reducing agent to organic antioxidant is from about 100:1 to about 1 :100, more preferably from about 10:1 to about 1 :10.

Preferably the inorganic reducing agent is selected from the group consisting of sodium sulfite, sodium bisulfite, sodium metabisulfite, potassium sulfite, potassium bisulfite, ammonium sulfite, ammonium bisulfite, and mixtures thereof.

HAIR CONDITIONING AGENT

The compositions of the present invention also contain a hair conditioning agent. The preferred hair conditioning agent is selected from the group consisting of silicone compounds, cationic polymers, fatty compounds, high molecular weight ester oils, cationic surfactants, amines, hydrocarbon oils, and mixtures thereof. The hair conditioning agent is preferably used at levels by weight of the composition of from about 0.01% to about 20%, more preferably from about 0.1 % to about 20%, still preferably from about 1% to about 15%. Silicone Compound Silicone compounds are useful as hair conditioning agents herein. The silicone compounds useful herein include volatile soluble or insoluble, or nonvolatile soluble or insoluble silicone conditioning agents. By soluble what is meant is that the silicone compound is miscible with the carrier of the composition so as to form part of the same phase. By insoluble what is meant is that the silicone forms a separate, discontinuous phase from the carrier, such as in the form of an emulsion or a suspension of droplets of the silicone. The silicone compounds herein may be made by any suitable method known in the art, including emulsion polymerization. The silicone compounds may further be incorporated in the present composition in the form of an emulsion, wherein the emulsion is made my mechanical mixing, or in the stage of synthesis through emulsion polymerization, with or without the aid of a surfactant selected from anionic surfactants, nonionic surfactants, cationic surfactants, and mixtures thereof.

The silicone compounds for use herein will preferably have a viscosity of from about 1 ,000 to about 2,000,000 centistokes at 25°C, 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. Silicone compound of high molecular weight may be made by emulsion polymerization. Suitable silicone fluids include polyalkyl siloxanes, polyaryl siloxanes, polyalkylaryl siloxanes, polyether siloxane copolymers, and mixtures thereof. Other nonvolatile silicone compounds having hair conditioning properties can also be used.

The silicone compounds herein also include polyalkyl or polyaryl siloxanes with the following structure (I)

wherein R¹²³ is alkyl or aryl, and x is an integer from about 7 to about 8,000. Z⁸ represents groups which block the ends of the silicone chains. The alkyl or aryl groups substituted on the siloxane chain (R¹²³) or at the ends of the siloxane chains Z⁸ 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 Z⁸ groups include hydroxy, methyl, methoxy, ethoxy, propoxy, and aryloxy. The two R¹²³ groups on the silicon atom may represent the same group or different groups. Preferably, the two R¹²³ groups represent the same group. Suitable R¹²³ groups include methyl, ethyl, propyl, phenyl, methylphenyl and phenylmethyl. The preferred silicone compounds are polydimethylsiloxane, polydiethylsiloxane, and polymethylphenylsiloxane. Polydimethylsiloxane, which is also known as dimethicone, is especially preferred. The polyalkylsiloxanes that can be used include, for example, polydimethylsiloxanes. These silicone compounds are available, for example, from the General Electric Company in their Viscasil® 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 silicone compounds, such as highly phenylated polyethyl silicone having refractive index of about 1.46 or higher, especially about 1.52 or higher. When these high refractive index silicone compounds are used, they should be mixed with a spreading agent, such as a surfactant or a silicone resin, as described below to decrease the surface tension and enhance the film forming ability of the material.

The silicone compounds that can be used include, for example, a polypropylene oxide modified 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 silicone compounds include amino substituted materials. Suitable alkylamino substituted silicone compounds include those represented by the following structure (II)

wherein R¹²⁴ is H, CH₃ or OH, p¹, p², q¹ and q² are integers which depend on the molecular weight, the average molecular weight being approximately between 5,000 and 10,000. This polymer is also known as "amodimethicone".

Suitable amino substituted silicone fluids include those represented by the formula (III)

(R¹²⁵)_aG₃-_a-Si-(OSiG₂)_P3-(OSiG_b(R¹²⁵)₂._b)_p4-0-SiG₃._a(R¹²⁵)_a (III) in which G is chosen from the group consisting of hydrogen, phenyl, OH, C^C_β 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 p³+p⁴ is a number from 1 to 2,000 and preferably from 50 to 150, p³ being able to denote a number from 0 to 1 ,999 and preferably from 49 to 149 and p⁴ being able to denote an integer from 1 to 2,000 and preferably from 1 to 10; R¹²⁵ is a monovalent radical of formula C_q3H_2q3L in which q³ is an integer from 2 to 8 and L is chosen from the groups

— N(R^{1 6})CH₂— CH₂— N(R¹²⁶)₂

— N(R¹²⁶)₂ — N(R¹²⁶)₃X'

— N(R¹²⁶)CH₂— CH₂— NR¹²⁶H₂X' in which R¹²⁶ 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 X' denotes a halide ion.

An especially preferred amino substituted silicone corresponding to formula (III) is the polymer known as "trimethylsilylamodimethicone" wherein R¹²⁴ is CH₃.

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

where R¹²⁸ denotes a monovalent hydrocarbon radical having from 1 to 18 carbon atoms, preferably an alkyl or alkenyl radical such as methyl; R¹²⁹ denotes a hydrocarbon radical, preferably a C_rC₁₈ alkylene radical or a C^C^, and more preferably C_rC₈, alkyleneoxy radical; Q- is a halide ion, preferably chloride; p⁵ denotes an average statistical value from 2 to 20, preferably from 2 to 8; p⁶ denotes an average statistical value from 20 to 200, and preferably from 20 to 50. A preferred polymer of this class is available from Union Carbide under the name "UCAR SILICONE ALE 56." References disclosing suitable nonvolatile dispersed silicone compounds include U.S. Patent No. 2,826,551 , to Geen; U.S. Patent No. 3,964,500, to Drakoff, issued June 22, 1976; U.S. Patent No. 4,364,837, to Pader; and British Patent No. 849,433, to Woolston. "Silicon Compounds" distributed by Petrarch Systems, Inc., 1984, provides an extensive, though not exclusive, listing of suitable silicone compounds.

Another nonvolatile dispersed silicone that can be especially useful is a silicone gum. The term "silicone gum", as used herein, means a polyorganosiloxane material having a viscosity at 25°C of greater than or equal to 1 ,000,000 centistokes. It is recognized that the silicone gums described herein can also have some overlap with the above-disclosed silicone compounds. This overlap is not intended as a limitation on any of these materials. Silicone gums are described by Petrarch, and others including U.S. Patent No. 4,152,416, to Spitzer et al., issued May 1 , 1979 and Noll, Walter, Chemistry and Technology of 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. 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, polydimethylsiloxane diphenylsiloxane 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 tri- functional and tetra-functional silanes with mono-functional or di-functional, or both, silanes during manufacture of the silicone resin. As is well understood in the art, the degree of crosslinking that is required in order to result in a silicone resin will vary according to the specific silane units incorporated into the silicone resin. In general, silicone materials which have a sufficient level of trifunctional 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 methylvinylchlorosilanes, 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 silicone compounds on the hair and can enhance the glossiness of hair with high refractive index volumes.

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

The method of manufacturing these silicone compounds, can be found in Encyclopedia of Polymer Science and Engineering, Volume 15, Second Edition, pp. 204-308, John Wiley & Sons, Inc., 1989.

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 mono-functional unit (CH₃)₃SiO₀₅; D denotes the difunctional unit (CH₃)₂SiO; T denotes the trifunctional unit (CHaJSiU_{! 5}; and Q denotes the quadri- or tetra-functional unit Si02. Primes of the unit symbols, e.g., M', D', T, and Q' denote substituents other than methyl, and must be specifically defined for each occurrence. Typical alternate substituents include groups such as vinyl, phenyl, amino, hydroxyl, etc. 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.

Commercially available silicone compounds which are useful herein include Dimethicone with tradename D-130, cetyl Dimethicone with tradename DC2502, stearyl Dimethicone with tradename DC2503, emulsified polydimethyl siloxanes with tradenames DC1664 and DC1784, and alkyl grafted copolymer silicone emulsion with tradename DC2-2845; all available from Dow Corning Corporation, and emulsion polymerized Dimethiconol available from Toshiba Silicone as described in GB application 2,303,857. Cationic Polymer Cationic polymers are useful as hair conditioning agents herein. As used herein, the term "polymer" shall include materials whether made by polymerization of one type of monomer or made by two (i.e., copolymers) or more types of monomers.

Preferably, the cationic polymer is a water-soluble cationic polymer. By "water soluble" cationic polymer, what is meant is a polymer which is sufficiently soluble in water to form a substantially clear solution to the naked eye at a concentration of 0.1% in water (distilled or equivalent) at 25°C. The preferred polymer will be sufficiently soluble to form a substantially clear solution at 0.5% concentration, more preferably at 1.0% concentration. The cationic polymers hereof will generally have a weight average molecular weight which is at least about 5,000, typically at least about 10,000, and is less than about 10 million. Preferably, the molecular weight is from about 100,000 to about 2 million. The cationic polymers will generally have cationic nitrogen-containing moieties such as quaternary ammonium or cationic amino moieties, and mixtures thereof.

The cationic charge density is preferably at least about 0.1 meq/gram, more preferably at least about 1.5 meq/gram, even more preferably at least about 1.1 meq/gram, still more preferably at least about 1.2 meq/gram. Cationic charge density of the cationic polymer can be determined according to the Kjeldahl Method. Those skilled in the art will recognize that the charge density of amino-containing polymers may vary depending upon pH and the isoelectric point of the amino groups. The charge density should be within the above limits at the pH of intended use.

Any anionic counterions can be utilized for the cationic polymers so long as the water solubility criteria is met. Suitable counterions 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 pyrrolidone. The alkyl and dialkyl substituted monomers preferably have C, - C₇ alkyl groups, more preferably C, - 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 R¹¹⁸X wherein R¹¹⁸ is a short chain alkyl, preferably a C., - C₇ alkyl, more preferably a C, - C₃ alkyl, and X is a salt forming anion as defined above.

Suitable cationic amino and quaternary ammonium monomers include, for example, vinyl compounds substituted with dialkylaminoalkyl acrylate, dialkylaminoalkyl methacrylate, monoalkylaminoalkyl acrylate, monoalkylaminoalkyl methacrylate, trialkyl methacryloxyalkyl ammonium salt, trialkyl acryloxyalkyl ammonium salt, 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 C, - C₃ alkyls, more preferably C, 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, - C₇ hydrocarbyls, more preferably C, - C₃, alkyls. The cationic polymers hereof can comprise mixtures of monomer 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-vinyl-2-pyrrolidone and 1-vinyl-3-methylimidazolium salt (e.g., chloride salt) (referred to in the industry by the Cosmetic, Toiletry, and Fragrance Association, "CTFA", as Polyquatemium-16), such as those commercially available from BASF Wyandotte Corp. (Parsippany, NJ, USA) under the LUVIQUAT tradename (e.g., LUVIQUAT FC 370); copolymers of 1-vinyl-2- pyrrolidone and dimethylaminoethyl methacrylate (referred to in the industry by CTFA as Polyquaternium-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 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.

Other suitable cationic polymers are amphoteric terpolymers consisting of acrylic acid methacrylamidopropyl trimethylammonium chloride and methyl acrylate, having a structure as shown below referred to in the industry (CTFA) as Polyquaternium 47. An example of a suitable commercial material is MERQUAT 2001® wherein the ratio of n6:n7:n8 is 45:45:10 supplied by Calgon Corp.

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

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

wherein: Z⁷ is an anhydroglucose residual group, such as a starch or cellulose anhydroglucose residual, R¹¹⁹ is an alkylene oxyalkylene, polyoxyalkylene, or hydroxyalkylene group, or combination thereof, R¹²⁰, R¹²¹, and R¹²² 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 R¹²⁰, R¹²¹ and R¹²²) preferably being about 20 or less, and X is as previously described.

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

Other cationic polymers that can be used include cationic guar gum derivatives, such as guar hydroxypropyltrimonium chloride commercially available from Celanese Corp. in their Jaguar R series. Other materials include quaternary nitrogen-containing cellulose ethers as described in U.S. Patent 3,962,418, and copolymers of etherified cellulose and starch as described in U.S. Patent 3,958,581.

Particularly useful cationic polymers herein include Polyquaternium-7, Polyquaternium-10, Polyquaternium-24, Polyquaternium-39, Polyquatemium-47, and mixtures thereof. Fatty Compound

Another preferred hair conditioning agent is a fatty compound. 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 nonionic surfactants and can alternatively be classified as such. However, a given classification is not intended 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 8 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, linaiool, oleyl alcohol, cis-4-t-butylcyclohexanol, myricyl 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 8 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; 2-ethylhexyl dodecyl ether; stearyl acetate; cetyl propionate; the ceteth series of compounds such as ceteth-1 through ceteth-45, which are ethylene glycol ethers of cetyl alcochol, wherein the numeric designation indicates the number of ethylene glycol moieties present; the steareth series of compounds such as steareth-1 through 10, which are ethylene glycol ethers of steareth alcohol, wherein the numeric designation indicates the number of ethylene glycol moieties present; ceteareth 1 through ceteareth-10, which are the ethylene glycol ethers of ceteareth alcohol, i.e. a mixture of fatty alcohols containing predominantly cetyl 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 alcohol, 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, steareth-4, 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 acid, glycerol monostearate, 12-hydroxy stearic acid, ethyl stearate, cetyl stearate, cetyl palmitate, polyoxyethylene cetyl ether stearate, polyoxyethylene stearyl ether stearate, polyoxyethylene lauryl ether stearate, ethyleneglycol monostearate, polyoxyethylene monostearate, polyoxyethylene distearate, propyleneglycol monostearate, propyleneglycol distearate, trimethylolpropane distearate, sorbitan stearate, polyglyceryl stearate, dimethyl sebacate, PEG-15 cocoate, PPG-15 stearate, glyceryl monostearate, glyceryl distearate, glyceryl tristearate, PEG-8 laurate, PPG-2 isostearate, PPG-9 laurate, and mixtures thereof.

Preferred fatty alcohol include those selected from the group consisting of C₆-C₃₀ saturated fatty alcohol, oleyl alcohol, elaidyl alcohol, recinoleyl alcohol, linoleyl alcohol, linolenyl alcohol, erucyl alcohol, and mixtures thereof. Even more preferred fatty alcohols include those selected from the group consisting of cetyl alcohol, stearyl alcohol, oleyl alcohol, and mixtures thereof. If fatty compounds are used, it is preferably included in the composition at a level by weight of from about 0.5% to about 20%, preferably from about 1% to about 10%, more preferably from about 2% to about 10%.

Steroids useful herein include compounds such as cholesterol. High Molecular Weight Ester Oil

High molecular weight ester oils are useful as hair conditioning agents herein. Preferred high molecular weight ester oils are selected from the group consisting of pentaerythritol ester oils, trimethylol ester oils, poly α-olefin oils, citrate ester oils, glyceryl ester oils, and mixtures thereof. The high molecular weight ester oils useful herein are those which are water-insoluble, and are in liquid form at 25°C. As used herein, the term "water-insoluble" means the compound is substantially not soluble in water at 25°C; when the compound is mixed with water at a concentration by weight of above 1.0%, preferably at above 0.5%, the compound is temporarily dispered to form an unstable colloid in water, then is quickly separated from water into two phases.

The high molecular weight ester oil herein provides moisturized feel, smooth feel, and manageability control to the hair when the hair is dried, yet not leave the hair feeling greasy. Thus, with the addition of the high molecular weight ester oil, obtained is a composition that can provide particularly suitable conditioning benefits both when the hair is wet and also after it has dried. The high molecular weight ester oil may be comprised at a level of preferably from about 0.2% to about 10%, more preferably from about 0.5% to about 5% by weight of the composition.

Pentaerythritol ester oils useful herein are those of the following formula having a molecular weight of at least 800:

wherein R¹, R², R³, and R⁴, independently, are branched, straight, saturated, or unsaturated alkyl, aryl, and alkylaryl groups having from 1 to about 30 carbons. Preferably, R\ R², R³, and R⁴, independently, are branched, straight, saturated, or unsaturated alkyl groups having from about 8 to about 22 carbons. More preferably, R¹, R², R³ and R⁴ are defined so that the molecular weight of the compound is from about 800 to about 1200.

Trimethylol ester oils useful herein are those of the following formula having a molecular weight of at least 800:

wherein R¹¹ is an alkyl group having from 1 to about 30 carbons, and R¹², R¹³, and R¹⁴, independently, are branched, straight, saturated, or unsaturated alkyl, aryl, and alkylaryl groups having from 1 to about 30 carbons. Preferably, R¹¹ is ethyl and R ², R¹³, and R¹⁴, independently, are branched, straight, saturated, or unsaturated alkyl groups having from 8 to about 22 carbons. More preferably, R¹¹, R¹², R ³ and R¹⁴ are defined so that the molecular weight of the compound is from about 800 to about 1200.

Poly α-olefin oils useful herein are those derived from 1-alkene monomers having from about 6 to about 16 carbons, preferably from about 6 to about 12 carbons atoms. Nonlimiting examples of 1-alkene monomers useful for preparing the poly α-olefin oils include 1-hexene, 1-octene, 1-decene, 1- dodecene, 1-tetradecene, 1-hexadecene, branched isomers such as 4-methyl-1- pentene, and mixtures thereof. Preferred 1-alkene monomers useful for preparing the poly α-olefin oils are 1-octene, 1-decene, 1-dodecene, 1- tetradecene, 1-hexadecene, and mixtures thereof. Poly α-olefin oils useful herein further have a viscosity of from about 1 to about 35,000 cst, a molecular weight of from about 200 to about 60,000, and a polydispersity of no more than about 3.

Poly α-olefin oils having a molecular weight of at least about 800 are useful herein. Such high molecular weight poly α-olefin oils are believed to provide long lasting moisturized feel to the hair. Poly α-olefin oils having a molecular weight of less than about 800 are useful herein. Such low molecular weight poly α-olefin oils are believed to provide a smooth, light, clean feel to the hair.

Citrate ester oils useful herein are those having a molecular weight of at least about 500 having the following formula:

wherein R²¹ is OH or CH₃COO, and R²², R²³, and R²⁴, independently, are branched, straight, saturated, or unsaturated alkyl, aryl, and alkylaryl groups having from 1 to about 30 carbons. Preferably, R²¹ is OH, and R²², R²³, and R²⁴, independently, are branched, straight, saturated, or unsaturated alkyl, aryl, and alkylaryl groups having from 8 to about 22 carbons. More preferably, R²¹, R²², R²³ and R²⁴ are defined so that the molecular weight of the compound is at least about 800.

Glyceryl ester oils useful herein are those having a molecular weight of at least about 500 and having the following formula:

wherein R⁴¹, R⁴², and R⁴³, independently, are branched, straight, saturated, or unsaturated alkyl, aryl, and alkylaryl groups having from 1 to about 30 carbons. Preferably, R⁴¹, R⁴², and R⁴³, independently, are branched, straight, saturated, or unsaturated alkyl, aryl, and alkylaryl groups having from 8 to about 22 carbons. More preferably, R⁴¹, R⁴², and R⁴³ are defined so that the molecular weight of the compound is at least about 800.

Particularly preferable high molecular weight ester oils are pentaester oils and trimethylol ester oils. Particularly useful pentaerythritol ester oils and trimethylol ester oils herein include pentaerythritol tetraisostearate, pentaerythritol tetraoleate, trimethylolpropane triisostearate, trimethylolpropane trioleate, and mixtures thereof. Such compounds are available from Kokyo Alcohol with tradenames KAKPTI, KAKTTI, and Shin-nihon Rika with tradenames PTO, ENUJERUBU TP3SO.

Particularly useful poly α-olefin oils herein include polydecenes with tradename PURESYN 6 having a molecular weight of about 500 and PURESYN 100 having a molecular weight of over 3000 available from Mobil Chemical Co.

Particularly useful citrate ester oils herein include triisocetyl citrate with tradename CITMOL 316 available from Bernel, triisostearyl citrate with tradename PELEMOL TISC available from Phoenix, and trioctyldodecyl citrate with tradename CITMOL 320 available from Bernel.

Particularly useful glyceryl ester oils herein include thisostearin with tradename SUN ESPOL G-318 available from Taiyo Kagaku, triolein with tradename CITHROL GTO available from Croda Surfactants Ltd., trilinolein with tradename EFADERMA-F available from Vevy, or tradename EFA- GLYCERIDES from Brooks. Cationic Surfactant

Also preferred are cationic surfactants. The cationic surfactants useful herein are any known to the artisan, and is preferably included in the composition at a level by weight from about 0.01% to about 20%, more preferably from about 0.05% to about 10%.

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

101

R £ N±-R^«» x^"

_R104

(I) wherein at least one of R¹⁰¹, R¹⁰², R¹⁰³ and R¹⁰⁴ is selected from an aliphatic group of from 8 to 30 carbon atoms or an aromatic, alkoxy, polyoxyalkylene, alkylamido, hydroxyalkyl, aryl or alkylaryl group having up to about 22 carbon atoms, the remainder of R¹⁰¹, R¹⁰², R¹⁰³ and R¹⁰⁴ are independently selected from an aliphatic group of from 1 to about 22 carbon atoms or an aromatic, alkoxy, polyoxyalkylene, alkylamido, hydroxyalkyl, aryl or alkylaryl group having up to about 22 carbon atoms; and X is a salt-forming anion such as those selected from halogen, (e.g. chloride, bromide), acetate, citrate, lactate, 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 R ⁰¹, R¹⁰², R¹⁰³ and R¹⁰⁴ are independently selected from C, 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-14, quatemium-18, quaternium-18 methosulfate, quaternium-24, and mixtures thereof.

Among the cationic surfactants of general formula (I), preferred are those containing in the molecule at least one alkyl chain having at least 16 carbons. Nonlimiting examples of such preferred cationic surfactants include: behenyl trimethyl ammonium chloride available, for example, with tradename INCROQUAT TMC-80 from Croda and ECONOL TM22 from Sanyo Kasei; cetyl trimethyl ammonium chloride available, for example, with tradename CA-2350 from Nikko Chemicals, hydrogenated tallow alkyl trimethyl ammonium chloride, dialkyl (14-18) dimethyl ammonium chloride, ditallow alkyl dimethyl ammonium chloride, di hydrogenated tallow alkyl dimethyl ammonium chloride, distearyl dimethyl ammonium chloride, dicetyl dimethyl ammonium chloride, di(behenyl/arachidyl) dimethyl ammonium chloride, dibehenyl dimethyl ammonium chloride, stearyl dimethyl benzyl ammonium chloride, stearyl propyleneglycol phosphate dimethyl ammonium chloride, stearoyl amidopropyl dimethyl benzyl ammonium chloride, stearoyl amidopropyl dimethyl (myristylacetate) ammonium chloride, and N-(stearoyl colamino formyl methy) pyridinium chloride. Amine and Amidoamine Amines are also suitable as hair conditioning agents. Primary, secondary, and tertiary fatty amines are useful. Particularly useful are tertiary amido amines having an alkyl group of from about 12 to about 22 carbons. The compositions of the present invention may preferably comprise by weight from about 0.5% to about 5.0%, preferably from about 1.0 % to about 3.0%, more preferably from about 1.5% to about 2.5%, of an amidoamine or mixture of amidoamines. The preferred amidoamines hereof have the following general formula: R1 CONH (CH₂)_m N (R²)2 wherein R1 is a residue of C11 to C24 fatty acids, R2 is a C-| to C4 alkyl, and m is an integer from 1 to 4. Exemplary tertiary amido amines include: stearamidopropyldimethylamine, stearamidopropyldiethylamine, stearamidoethyldiethylamine, stearamidoethyldimethylamine, palmitamidopropyldimethylamine, palmitamidopropyldiethylamine, palmitamidoethyldiethylamine, palmitamidoethyldimethylamine, behenamidopropyldimethylamine, behenamidopropyldiethylamine, behenamidoethyldiethylamine, behenamidoethyldimethylamine, arachidamidopropyldimethylamine, arachidamidopropyldiethylamine, arachidamidoethyldiethylamine, arachidamidoethyldimethylamine, diethylaminoethylstearamide. Also useful are dimethylstearamine, dimethylsoyamine, soyamine, myristylamine, tridecylamine, ethylstearylamine, N-tallowpropane diamine, ethoxylated (with 5 moles of ethylene oxide) stearylamine, dihydroxyethylstearylamine, and arachidylbehenylamine. Useful amines in the present invention are disclosed in U.S. Patent 4,275,055, Nachtigal, et al. Hydrocarbon Oil Hydrocarbon oils are also suitable as hair conditioning agents. The hydrocarbon oils useful herein include straight chain, cyclic, and branched chain hydrocarbons which can be either saturated or unsaturated. Without being bound by theory, it is believed that, the hydrocarbon oils may penetrate into the hair to modify the hydroxy bonds of the hair, thereby resulting in providing softness and flexibility to the hair. Nonlimiting examples of the hydrocarbon oils are found in International Cosmetic Ingredient Dictionary, Fifth Edition, 1993, and CTFA Cosmetic Ingredient Handbook, Second Edition, 1992.

The present invention preferably contains by weight from about 0.01% to about 10%, more preferably from about 0.5% to about 10% of the hydrocarbon oil.

The hydrocarbon oils useful herein have from about 12 to about 40 carbon atoms, preferably from about 12 to about 30 carbon atoms, and preferably from about 12 to about 22 carbon atoms. Also encompassed herein are polymeric hydrocarbon oils of alkenyl monomers, such as polymers of C₂.₆ 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. 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 hydrocarbon oils 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 Preferred for use herein are hydrocarbon oils selected from the group consisting of mineral oil, poly α-olefin oils such as isododecane, isohexadecane, polybutene, polyisobutene, and mixtures thereof.

Commercially available hydrocarbon oils useful herein include isododecane, isohexadeance, and isoeicosene with tradenames PERMETHYL 99A, PERMETHYL 101 A, and PERMETHYL 1082, available from Presperse (South Plainfield New Jersey, USA), a copolymer of isobutene and normal butene with tradenames INDOPOL H-100 available from Amoco Chemicals (Chicago Illinois, USA), mineral oil with tradename BENOL available from Witco, and isoparaffin with tradename ISOPAR from Exxon Chemical Co. (Houston Texas, USA). AQUEOUS CARRIER

The compositions of the present invention contain an aqueous carrier. The level and species of the carrier are selected according to the compatibility with other components, and other desired characteristic of the product.

Carriers useful in the present invention include water and water solutions of lower alkyl alcohols and polyhydric alcohols. Lower alkyl alcohols useful herein are monohydric alcohols having 1 to 6 carbons, more preferably ethanol and isopropanol. The polyhydric alcohols useful herein include propylene glycol, hexylene glycol, glycerin, and propane diol.

Preferably, the aqueous carrier is substantially water. Deionized water is preferably used. Water from natural sources including mineral cations can also be used, depending on the desired characteristic of the product. Generally, the compositions of the present invention comprise from about 20% to about 95%, preferably from about 30% to about 92%, and more preferably from about 50% to about 90% water.

ADDITIONAL COMPONENTS The hair care compositions of the present invention may include a variety of additional components, which may be selected by the artisan according to the desired characteristics of the final product. DETERSIVE SURFACTANTS

The compositions of the present invention may further contain a detersive surfactant selected from the group consisting of anionic surfactants, amphoteric surfactants, nonionic surfactants, and mixtures thereof. The level and species of the additional detersive surfactant are selected according to the compatibility with other components, and desired characteristic of the product.

In preferred embodiments, the additional detersive surfactant contains an anionic surfactant, more preferably further contains an amphoteric surfactant. Herein, "detersive surfactant" 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 surfactant is included at a level so that the total of detersive surfactant is from about 5% to about 75%, preferably from about 8% to about 50%, and more preferably from about 10% to about 30%, by weight of the composition.

Anionic Surfactants

Anionic surfactants useful herein include alkyl and alkyl ether sulfates. These materials have the respective formulae R⁵¹OS0₃M and R⁵¹0(C₂H₄0)_xS0₃M, wherein R⁵¹ 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 so that the anionic surfactant component is water soluble. The anionic surfactant or surfactants should be chosen such that the Krafft temperature is about 15°C or less, preferably about 10°C or less, and more preferably about 0°C or less. It is also preferred that the anionic surfactant be soluble in the composition hereof.

Krafft temperature refers to the point at which solubility of an ionic surfactant becomes determined by crystal lattice energy and heat of hydration, and corresponds to a point at which solubility undergoes a sharp, discontinuous increase with increasing temperature. Each type of surfactant will have its own characteristic Krafft temperature. Krafft temperature for ionic surfactants is, in general, well known and understood in the art. See, for example, Myers, Drew, Surfactant Science and Technology, pp. 82-85, VCH Publishers, Inc. (New York, New York, USA), 1988 (ISBN 0-89573-399-0). In the alkyl and alkyl ether sulfates described above, preferably R⁵¹ 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 C₁₄.₁₆ compounds, from 0% to about 20% by weight of C₁₇.₁₉ compounds; from about 3% to about 30% by weight of compounds having a degree of ethoxylation of 0; from about 45% to about 90% by weight of compounds having a degree of ethoxylation of from 1 to about 4; from about 10% to about 25% by weight of compounds having a degree of ethoxylation of from about 4 to about 8; and from about 0.1% to about 15% by 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 R⁵²-S0₃-M where R⁵² 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.

Other anionic surfactants include olefin sulfonates having about 10 to about 24 carbon atoms. Herein, "olefin sulfonates" means compounds which can be produced by the sulfonation of alpha-olefins by means of uncompiexed sulfur trioxide, followed by neutralization of the acid reaction mixture in conditions such that any sulfones which have been formed in the reaction are hydrolyzed to give the corresponding hydroxy-alkanesulfonates. The sulfur trioxide can be liquid or gaseous, and is usually, but not necessarily, diluted by inert diluents, for example by liquid S0₂, chlorinated hydrocarbons, etc., when used in the liquid form, or by air, nitrogen, gaseous S0₂, etc., when used in the gaseous form. The α-olefins from which the olefin sulfonates are derived are mono-olefins having about 12 to about 24 carbon atoms, preferably about 14 to about 16 carbon atoms. Preferably, they are straight chain olefins. In addition to the true alkene sulfonates and a proportion of hydroxy-alkanesulfonates, the olefin sulfonates can contain minor amounts of other materials, such as alkene disulfonates depending upon the reaction conditions, proportion of reactants, the nature of the starting olefins and impurities in the olefin stock and side reactions during the sulfonation process. A specific α-olefin 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.

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.

Another class of anionic surfactants suitable for use in the shampoo compositions are the β-alkyloxy alkane sulfonates. These compounds have the following formula:

where R⁵³ is a straight chain alkyl group having from about 6 to about 20 carbon atoms, R⁵⁴ is a lower alkyl group having from about 1 , preferred, to about 3 carbon atoms, and M is as previously described in this section. Many other anionic surfactants suitable for use in the shampoo compositions are described in McCutcheon's, Emulsifiers and Detergents, 1989 Annual, published by M. C. Publishing Co., and in U.S. Patent 3,929,678.

Another class of suitable anionic surfactants are amino acid surfactants which are surfactants that have the basic chemical structure of an amino acid compound, i.e., that contains a structural component of one of the naturally- occurring amino acids.

Also useful herein are N-acyl-L-glutamates such as N-cocoyl-L-glutamate and, N-lauroyl-L-glutamate, sodium lauryl aminodiacetic acid, laurimino diproprionate, and N-lauryl-β-imino-dipropionate, N-acyl-L-aspartate, polyoxyethylene laurylsuifosuccinate, disodium N-octadecylsulfosuccinate; disodium lauryl sulfosuccinate; diammonium lauryl sulfosuccinate; tetra sodium N-(1 ,2-dicarboxyethyl)-N-octadecylsulfosuccinate; the diamyl ester of sodium sulfosuccinic acid; the dihexyl ester of sodium sulfosuccinic acid; and the dioctyl ester of sodium sulfosuccinic acid, and 2-cocoalkyl N-carboxyethyl N- carboxyethoxyethyl imidazolinium betaine.

Other suitable anionic surfactants include those of the following formula (I) and (II):

H0₂CH₂C-N-CH₂CH₂N(CH₂COOH)₂ C=0

R⁵⁵

(I) wherein R⁵⁵ is an alkyl of 12 to 18 carbons; and

wherein R⁵⁶ is a straight or branched alkyl or alkenyl of 5 to 21 carbons; and M¹ and M², independently, are hydrogen, alkaline metal, alkaline earth metal, ammonium, alkyl or alkenyl ammonium of 1 to 22 carbons, alkyl or alkenyl substituted pyridinium of 1 to 18 carbons, or basic amino acids. Suitable examples of formula (I) include acid salts of N-acyl-N,N'-ethylenediaminetriacetic acid, such as sodium, triethanolamine and ammonium salts of lauroyl-N,N'- ethylenediaminetriacetic acid, myristoyl-N.N'-ethylenediaminetriacetic acid, cocoyl-N,N'-ethylenediaminetriacetic acid, and oleoyl-N,N'- ethylenediaminetriacetic acid. Suitable examples of formula (II) include acid and salt forms of N-hexanoyl-N-carboxyethyl-β-alanine, N-octanoyl-N-carboxyethyl-β- alanine, N-decanoyl-N-carboxyethyl-β-alanine, N-lauroyl-N-carboxyethyl-β- alanine, N-tetradecanoyl-N-hydroxyethyl-β-alanine, N-hexadecanoyl-N- carboxyethyl-β-alanine, N-isostearoyl-N-carboxyethyl-β-alanine, and N-oleoyl-N- carboxyethyl-β-alanine.

Preferred anionic surfactants for use in the shampoo compositions include ammonium lauryl sulfate, ammonium laureth sulfate, triethylamine laureth sulfate, triethanolamine laureth sulfate, monoethanolamine laureth sulfate, diethanolamine laureth sulfate, lauric monoglyceride sodium sulfate, sodium laureth sulfate, potassium laureth sulfate, sodium tridecyl benzene sulfonate, sodium dodecyl benzene sulfonate, N-cocoylalaninate, N-acyl-N-methyl-β- alaninate, sodium laurylsarcosinate, cocoyl sarcosine, lauroyl taurate, lauroyl lactylate, N-cocoyl-L-glutamate, N-acyl potassium glysine, lauroamphohydroxy propylsulfonate, cocoglyceride sulfate, lauroyl isethionate, lauroamphoacetate, and mixtures thereof. Amphoteric Surfactants

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

Amphoteric surfactants for use herein include the derivatives of aliphatic quaternary ammonium, phosphonium, and sulfonium compounds, in which the 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 R⁵⁷ 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; R⁵⁸ 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; R⁵⁹ 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 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, laurylamido-bis-(2-hydroxyethyl)propylsultaine, and the like. Preferred are amidohydroxysultaines such as the C₈-C₁₈ hydrocarbylamidopropylhydroxy sultaines, especially C₈-C₁₄ hydrocarbylamidopropylhydroxysultaines, e.g., laurylamidopropylhydroxysultaine and cocamidopropylhydroxysultaine. Other sultaines useful herein are described in U.S. Patent 3,950,417.

Other suitable amphoteric surfactants are the aminoalkanoates of the formula R⁶⁰NH(CH₂)_nCOO-, the iminodialkanoates of the formula R⁶⁰N[(CH₂)_mCOO"]₂ and mixtures thereof; wherein n and m are numbers from 1 to about 4, R⁶⁰ is C₈-C₂₂ alkyl or alkenyl. Other suitable amphoteric surfactants include those represented by the formula :

wherein R⁶¹ is C₈-C₂₂ alkyl or alkenyl, preferably C₈-C₁₆, R⁶² and R⁶³ is independently selected from the group consisting of hydrogen, -CH₂C0₂", CH₂CH₂OH, -CH₂CH₂OCH₂CH₂COO-, or -(CH₂CH₂0)_mH wherein m is an integer from 1 to about 25, and R⁶⁴ is hydrogen, -CH₂CH₂OH, or -CH₂CH₂OCH₂CH₂COO-, Z' is C0₂" or CH₂C0₂-, y is 2 or 3, preferably 2. This type of surfactant is sometimes classified as an imidazoline-type amphoteric surfactant, although it should be recognized that it does not necessarily have to be derived, directly or indirectly, through an imidazoline intermediate. Suitable materials of this type are marketed under the tradename MIRANOL and are understood to comprise a complex mixture of species, and can exist in protonated and non-protonated species depending upon pH with respect to species that can have a hydrogen at R⁶². All such variations and species are meant to be encompassed by the above formula.

Examples of surfactants of the above formula are monocarboxylates and di-carboxylates. Examples of these materials include cocoamphocarboxypropionate, cocoamphocarboxypropionic acid, 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 conditioning compositions are those represented by the formula:

wherein: R⁶⁵ is a member selected from the group consisting of COO" and CH(OH)CH₂S0₃-; R⁶⁶ is lower alkyl or hydroxyalkyl; R⁶⁷ is lower alkyl or hydroxyalkyl; R⁶⁸ is a member selected from the group consisting of hydrogen and lower alkyl; R⁶⁹ is higher alkyl or alkenyl; Y' is lower alkyl, preferably methyl; x¹ is an integer from 2 to 7, preferably from 2 to 3; y¹ is the integer 1 or 0. 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 8 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 substituents 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, lauryldimethyl-α-carboxyethylbetaine, cetyldimethylcarboxymethylbetaine, lauryl- bis-(2-hydroxyethyl)-carboxymethylbetaine, stearyl-bis-(2- hydroxypropyi)carboxymethylbetaine, oleyldimethyl-γ-carboxypropylbetaine, lauryl-bis-(2-hydroxypropyl)-α-carboxyethylbetaine, etc. The sulfobetaines may be represented by cocodimethylsulfopropylbetaine, stearyldimethylsulfopropylbetaine, lauryl-bis-(2-hydroxyethyl)-sulfopropylbetaine, and the like.

Specific examples of amido betaines and amidosulfobetaines useful in the conditioning compositions include the amidocarboxybetaines, such as cocamidodimethylcarboxymethylbetaine, laurylamidodimethylcarboxymethylbetaine, cetylamidodimethylcarboxymethylbetaine, laurylamido-bis-(2-hydroxyethyl)- carboxymethylbetaine, cocamido-bis-(2-hydroxyethyl)-carboxymethylbetaine, etc. The amidosulfobetaines may be represented by cocamidodimethylsulfopropylbetaine, stearylamidodimethylsulfopropylbetaine, laurylamido-bis-(2-hydroxyethyl)-sulfopropylbetaine, and the like. Nonionic Surfactant

Nonionic surfactants useful herein 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 propylene 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 alcohol, the coconut alcohol fraction having from about 10 to about 14 carbon atoms;

(4) long chain tertiary amine oxides of the formula [R⁷⁰R⁷¹R⁷²N → O] where R⁷⁰ 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 R⁷¹ and R⁷² 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;

(5) long chain tertiary phosphine oxides of the formula [R⁷³R⁷⁴R⁷⁵P → O] where R⁷³ 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 1 glyceryl moieties and R⁷⁴ and R⁷⁵ are each alkyl or monohydroxyalkyl groups containing from about 1 to about 3 carbon atoms;

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

(7) alkyl polysaccharide (APS) surfactants (e.g. alkyl polyglycosides), examples of which are described in U.S. Patent 4,565,647, which 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 R⁷⁶0(CH₂CH₂)_x2H and polyethylene glycol (PEG) glyceryl fatty esters, such as those of the formula R⁷⁶(0)OCH₂CH(OH)CH₂(OCH₂CH₂)_x2OH, wherein x2 is from

1 to about 200, preferably from about 20 to about 100, and R⁷⁶ is an alkyl having from about 8 to about 22 carbon atoms. STABILIZING AGENT

The compositions of the present invention may further contain a stabilizing agent. Specifically, the stabilizing agents are believed to prevent coagulation, flocculation, creaming, coalescence, and phase separation of a material, such as silicone.

The stabilizing agents are preferably comprised at a level of from about 0.01 % to about 10%, more preferably from about 0.1% to about 5% by weight of the composition. Crystalline Stabilizing Agent Crystalline stabilizing agents are useful stabilizing agents herein, if used.

The crystalline stabilizing agents herein are those which have a melting point of at least 40°C, and are preferably present the composition in crystalline form. In a particularly preferred embodiment, the crystalline stabilizing agent is in the form of a needle shape crystal having an average chord length of about 0.1 to about 200 microns.

Preferred suspending agents include acyl derivatives such as ethylene glycol stearates, both mono and distearate such as stearyl dimethyl amine oxide, and mixtures thereof. When used in the hair care compositions, these preferred suspending agents are present in the composition in crystalline form. These suspending agents are described in U.S. Patent 4,741 ,855. Commercially available acyl derivatives suitable herein include ethylene glycol distearate with tradenames Elfacos RGDS available from Akzo, Lexemul EGDS available from Inolex, and Nikkol Estepearl 10, Nikkol PEARL-1222 available from Nikko, ethylene glycol monostearate with tradenames EGMS-70 available from Nikko, Kemester 5220 available from Witco, Mackester EGMS from Mclntyre, and ethylene glycol monopalmitate with tradename Lanol P available from Seppic.

Useful herein are 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, cocomonoethanolamide, stearic diethanolamide, stearic monoisopropanolamide and stearic monoethanolamide stearate.

Useful herein are 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). Mica

Micas are useful stabilizing agents herein, if used. Particles of titanium dioxide coated mica are preferred. In general, smaller particles give the composition a pearly appearance, whereas particles having a larger diameter will result in a glittery appearance. The particles may vary in size from about 0.5μm to about 150μm in diameter. Smaller-sized particles are preferred.

Suitable micas are sold under the tradenames TIMIRON (Merck) or FLAMENCO (Mearl). The micas are preferably present at level of about 1% to about 10% in the present compositions. Polymeric Stabilizing Agent

Polymeric stabilizing agents suitable herein, if used, include xanthan gum. The use of xanthan gum as a suspending agent 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 stabilizing agents. Such combinations are described in U.S. Patent 4,704,272, which is incorporated herein by reference in its entirety.

Polymeric stabilizing agents useful herein 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 pentaerythritol, an allyl ether of sucrose, or an allyl ether of propylene. Neutralizers may be required, for example, amino methyl propanol, triethanol amine, or sodium hydroxide. Polymeric stabilizing agents useful herein include cellulose derivatives, hydrophobically modified cellulose derivatives, ethylene oxide polymers, and ethylene oxide/propylene oxide based polymers. Suitable polymers are cellulose derivatives including methyicellulose with tradename BENECEL, hydroxyethyl cellulose with tradename NATROSOL, hydroxypropyl cellulose with tradename KLUCEL, cetyl hydroxyethyl cellulose with tradename POLYSURF 67, all supplied by Herculus. Other suitable polymers are ethylene oxide and/or propylene oxide based polymers with tradenames CARBOWAX PEGs, POLYOX WASRs, and UCON FLUIDS, all supplied by Amerchol. Polymeric stabilizing agents useful herein include polyalkylene glycols. These compounds are particularly useful for compositions which are designed to impart a soft, moist feeling to the hair.

The polyalkylene glycols are characterized by the general formula:

wherein R²⁰¹ is selected from the group consisting of H, methyl, and mixtures thereof. When R²⁰ is H, these materials are polymers of ethylene oxide, which are also known as polyethylene oxides, polyoxyethylenes, and polyethylene glycols. When R²⁰¹ is methyl, these materials are polymers of propylene oxide, which are also known as polypropylene oxides, polyoxypropylenes, and polypropylene glycols. When R²⁰¹ is methyl, it is also understood that various positional isomers of the resulting polymers can exist.

In the above structure, x3 has an average value of from about 1500 to about 25,000, preferably from about 2500 to about 20,000, and more preferably from about 3500 to about 15,000.

Polyethylene glycol polymers useful herein are PEG-2M wherein R²⁰ equals H and n has an average value of about 2,000 (PEG-2M is also known as Polyox WSR® N-10, which is available from Union Carbide and as PEG-2,000); PEG-5M wherein R²⁰¹ equals H and x3 has an average value of about 5,000 (PEG-5M is also known as Polyox WSR® N-35 and Polyox WSR® N-80, both available from Union Carbide and as PEG-5,000 and Polyethylene Glycol 300,000); PEG-7M wherein R²⁰¹ equals H and x3 has an average value of about 7,000 (PEG-7M is also known as Polyox WSR® N-750 available from Union Carbide); PEG-9M wherein R²⁰¹ equals H and x3 has an average value of about 9,000 (PEG 9-M is also known as Polyox WSR® N-3333 available from Union Carbide); and PEG-14 M wherein R²⁰¹ equals H and x3 has an average value of about 14,000 (PEG-14M is also known as Polyox WSR® N-3000 available from Union Carbide).

Other useful polymeric stabilizing agents include the polypropylene glycols and mixed polyethylene/polypropylene glycols, guar gum, polyvinyl alcohol, polyvinyl pyrrolidone, polyacryl amide (commercially available as SEPIGEL 305, Seppic), hydroxypropyl guar gum, starch and starch derivatives. ACID The compositions may preferably contain by weight from about 0.05% to about 2.0%, preferably from about 0.2% to about 1.5%, and more preferably from about 0.3% to about 1.0% of an acid or mixture of acids.

The acids can be any acid used by those skilled in the art, including organic acids and inorganic acids. Preferred acids useful in the present invention include L-glutamic acid, lactic acid, citric acid, hydrochloric acid, maleic acid, succinic acid, acetic acid, fumaric acid, l-glutamic acid hydrochloride, tartaric acid, and mixtures thereof; more preferably L-glutamic acid, lactic acid, citric acid, hydrochloric acid, and mixtures thereof. Preferably if used, the mole ratio of amidoamines to acids is from about 1 :0.3 to about 1 :2, more preferably from about 1 :0.4 to about 1 :1. POLYVALENT METAL CATION

Suitable polyvalent metal cations include divalent and trivalent metals, divalent metals being preferred. Exemplary metal cations include alkaline earth metals, such as magnesium, calcium, zinc, and copper, and trivalent metals such as aluminum and iron. Preferred are calcium and magnesium.

The polyvalent metal cation can be added as an inorganic salt, organic salt, or as a hydroxide. The polyvalent metal cation may also be added as a salt with anionic surfactants as mentioned above. Preferably, the polyvalent metal cation is introduced as an inorganic salt or organic salt. Inorganic salts include chloride, bromide, iodine, nitrate, or sulfate, more preferably chloride or sulfate. Organic salts include L-glutamate, lactate, malate, succinate, acetate, fumarate, L-glutamic acid hydrochloride, and tartarate. It will be clear to those skilled in the art that, if polyvalent salts of the anionic surfactant are used as the mode of introducing the polyvalent metal cations into the compositions hereof, only a fraction of the anionic surfactant may be of polyvalent form, the remainder of the anionic surfactant being necessarily added in monovalent form. ETHOXYLATED GLUCOSE DERIVATIVES

A preferred additional component is an ethoxylated glucose derivative, particularly for increasing the viscosity of compositions, and for the phase stability of compositions at high and low temperatures. When present, the ethoxylated glucose derivative is included at a level of from about 0.1 % to about 10%, and more typically from about 0.3% to about 5.0%, by weight, of the composition.

Suitable ethoxylated glucose derivatives include methyl gluceth 10, methyl gluceth 20, PEG-120 methylglucose dioleate, PPG-10 methylgiycose ether, and PPG-20 methylgiycose ether. Commercially available material highly suitable herein include methyl gluceth 10 with tradename GLUCAM E-10, PEG-120 methylglucose dioleatewith tradename Glucamate DOE-120, PPG-10 methylglucose ether with tradename GLUCAM P-10, and PPG-20 methylglucose ether with tradename GLUCAM P-20, all available from Amerchol. OTHER ADDITIONAL COMPONENTS A wide variety of other additional components can be formulated into the present compositions. These include: other hair conditioning agents such as hydrolyzed collagen with tradename Peptein 2000 available from Hormel, panthenol available from Roche, panthenyl ethyl ether available from Roche, hydrolysed keratin, proteins, plant extracts, and nutrients; emulsifying surfactants for dispersing water insoluble components in the carrier; hair-fixative polymers such as amphoteric fixative polymers, cationic fixative polymers, anionic fixative polymers, nonionic fixative polymers, and silicone grafted copolymers; optical brighteners such as polystyrylstilbenes, triazinstilbenes, hydroxycoumarins, aminocoumarins, triazoles, pyrazolines, oxazoles, pyrenes, porphyrins, and imidazoles; preservatives such as benzyl alcohol, methyl paraben, propyl paraben and imidazolidinyl urea; zinc pyrithione, pH adjusting agents, such as citric acid, sodium citrate, succinic acid, phosphoric acid, sodium hydroxide, sodium carbonate; salts, in general, such as potassium acetate and sodium chloride; coloring agents, such as any of the FD&C or D&C dyes; hair oxidizing (bleaching) agents, such as hydrogen peroxide, and perborate salts; and sequestering agents, such as disodium ethylenediamine tetra-acetate; ultraviolet and infrared screening and absorbing agents such as octyl salicylate.

Perfumes may also be used as an additional component. Some perfumes may contain some organic antioxidant materials as part of the perfume raw material.

Such other additional components generally are used individually at levels from about 0.01% to about 10.0%, preferably from about 0.05% to about 5.0% by weight of the composition. EXAMPLES

The following examples further describe and demonstrate embodiments within the scope of the present invention. The examples are 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.

The compositions of the present invention are suitable for conditioning and/or cleaning the hair, and are also useful for making products in the form of a homogeneous single phase emulsion. The products substantially do not have malodor and the finished composition is not substantially discolored, nor become discolored over time.

EXAMPLES 1-6

Definitions of Components

^*1 N-cocoyl-L-glutamate: Amisoft CT-12S available from Ajinomoto. ^*2 Disodium Lauryl Sulfosuccinate : Emcol 4400-1 available from Witco ^*3 Cocamidopropylbetaine : Tego Betaine F available from TH Goldschmidt ^*4 Ethyleneglycol Distearate: Ethyleneglycol Distearate available from TH

Goldschmidt ^*5 Hydroxyethyl Cellulose: Available from Aqualon. ^*6 Polyoxyethylene (2000): WSR N-10 obtained Amerchol. ^*7 Silicone emulsion: Emulsion of 1 ,00,000cp Dimethiconol with particle size of approximately 200nm available from Toshiba Silicone

^*8 Silicone emulsion: Emulsion of 300,000csk polydimethyl siloxane with particle size of approximately 300nm available from Dow Corning ^*9 Dimethicone: 40(gum)/60(fluid) weight ratio blend of SE-76 dimethicone gum available from General Electric Silicone ^*10 Alkyl silicone: Silicone alkyl grafted copolymer DC2502 available from Dow

Corning ^*11 Alkyl silicone emulsion: Alkyl grafted copolymer silicone emulsion DC2-2845 from Dow Corning ^*12 Zinc Pyrithione : available from Olin ^*13 Panthenol : available from Roche

^*14 Panthenyl Ethyl Ether : available from Roche

^*15 Vitamin E and/or derivatives of Vitamin E (example, Emix-d available from

Eisai)

^*16 Vitamin C and/or derivatives of Vitamin C Method of Preparation

Examples 1 through 6 are hair care compositions of the present invention which are particularly useful for cleaning as well as conditioning the hair. The products do not have malodor and the finished composition is not substantially discolored, nor become discolored over time.

The hair care compositions of Examples 1 through 6 as shown above can be prepared by any conventional method well known in the art. A suitable method is described below.

Detersive surfactants, and if present, cationic polymers and high melting point compounds, are melted and dispersed in water to form a homogenous premix at elevated temperature, e.g., above about 70°C. If a silicone compound is present, a silicone emulsion is made comprising the silicone compound, a small amount of detersive surfactant, and a portion of water. The remaining components can be added either to the premix, or at the last stage of the process. The premix and, if present, the remaining components, are mixed thoroughly at the elevated temperature and then pumped through a high shear mill and then through a heat exchanger to cool them to ambient temperature. Perfume, and if present, inorganic salts, organic antioxidant, inorganic reducing agents, and the silicone emulsion are added to this obtained cooled mixture. The remaining components can alternatively be added at this stage.

EXAMPLES 7-12 Examples 7 through 12 are hair care compositions of the present invention which are particularly useful for rinse-off products and leave-on products, and are particularly useful for making products in the form of emulsion, cream, gel, spray, or mousse.

Definitions of Components

^*1 Cetyl Alcohol: Konol series obtained by Shin-Ninon Rika.

*2 Stearyl Alcohol: Konol series obtained by Shin-Ninon Rika.

^*3 Oleyl Alcohol : Obtained by New Japan Chemical ^*4 Stearamidopropyl Dimethylamine: Amidoamine MPS obtained by Nikko.

^*5 ^-Glutamic Acid: ^-Glutamic acid (cosmetic grade) obtained by Ajinomoto.

^*6 Stearamidopropyl betaine: Rikabion A-700 available from Shin-Ninon Rika.

*7 Hydroxyethyl Cellulose: Available from Aqualon.

^*8 Polyoxyethyleneglycol: WSR N-10 obtained by Amerchol ^*9 Silicone Blend: SE76 obtained by G.E.

^*10 Vitamin E and/or derivatives of Vitamin E (example, Emix-d available from

Eisai)

^*11 Vitamin C and/or derivatives of Vitamin C

^*12 Panthenol: Available from Roche. ^*13 Panthenyl Ethyl Ether: Available from Roche.

^*14 Citric Acid: Anhydrous Citric acid obtained by Haarman & Reimer.

Method of Preparation

Examples 7 through 12 are hair care compositions of the present invention which are particularly useful for cleaning as well as conditioning the hair. The products do not have malodor and the finished composition is not substantially discolored, nor become discolored over time. The hair care compositions of Examples 7 through 12 as shown above can be prepared by any conventional method well known in the art. A suitable method is described below.

The compositions of Examples 7 through 12 as shown above are prepared as follows: If included in the composition, polymeric materials such as hydroxyethyl cellulose, and polyoxyethyleneglycol are dispersed in water at room temperature to make a polymer solution. High melting point compounds, emulsifying agents, and the polymer solution, if present, are mixed and heated up to about 70°C. The inorganic reducing agent is added to the heated mixture. The mixture thus obtained is cooled down to about 45°C to 55°C, and the remaining components, including the organic antioxidant, are added with agitation, and further cooled down to about 30°C.

A triblender and/or mill can be used in each step, if necessary to disperse the materials. In another process, the inorganic reducing agent may be added to the mixture after the mixture has been cooled down to about 45°C to 55°C. In this case, the mixture should be mixed after the addition of the inorganic reducing agent to homogenize the mixture.

The embodiments disclosed and represented by the previous examples have many advantages. For example, they can provide softness and ease of combing when the hair is wet, as well as provide long lasting moisturized feel, smooth feel, and manageability control to the hair when the hair is dried, yet not leave the hair feeling greasy. In addition, the compositions are substantially free of malodor. The compositions are substantially not discolored and do not become discolored upon storage over time.

It is understood that the examples and embodiments described herein are for illustrative purposes only and that various modifications or changes in light thereof will be suggested to one skilled in the art without departing from its spirit and scope.

Claims

WHAT IS CLAIMED IS:

1. A hair care composition comprising:

(a) an organic antioxidant;

(b) an inorganic reducing agent selected from the group consisting of alkali metal sulfites, alkali metal bisulfites, alkali metal monopersulfates, alkali metal bisulfates, ammonium sulfites, ammonium bisulfites, ammonium persulfates, and mixtures thereof;

(c) a hair conditioning agent; and

(d) an aqueous carrier.

2. The composition of Claim 1 , wherein the organic antioxidant is selected from the group consisting of butyl hydroxy toluene, butyl hydroxy anisole, tertiary butyl hydroquinone, hydroquinone, Vitamin E and its derivatives, Vitamin C and its derivatives, and mixtures thereof.

3. The composition of Claim 1 , wherein the inorganic reducing agent is selected from the group consisting of sodium sulfite, sodium bisulfite, sodium metabisulfite, potassium sulfite, potassium bisulfite, ammonium sulfite, ammonium bisulfite, and mixtures thereof.

4. The composition of Claim 1 , wherein the hair conditioning agent is selected from the group consisting of silicone compounds, cationic polymers, fatty compounds, high molecular weight ester oils, cationic surfactants, amines, hydrocarbon oils, and mixtures thereof.

5. The composition of Claim 1 , wherein the composition further comprises a detersive surfactant selected from the group consisting of anionic surfactants, amphoteric surfactants, nonionic surfactants, and mixtures thereof.

6. The composition of Claim 5, wherein the hair conditioning agent is selected from the group consisting of silicone compounds, cationic polymers, fatty compounds, high molecular weight ester oils, cationic surfactants, amines, hydrocarbon oils, and mixtures thereof.

7. A hair care composition comprising by weight:

(a) from about 0.001% to about 5% of an organic antioxidant;

(b) from about 0.001% to about 2% of an inorganic reducing agent selected from the group consisting of alkali metal sulfites, alkali metal bisulfites, alkali metal monopersulfates, alkali metal bisulfates, ammonium sulfites, ammonium bisulfites, ammonium persulfates, and mixtures thereof;

(c) from about 0.01% to about 20% of a hair conditioning agent selected from the group consisting of silicone compounds, cationic polymers, fatty compounds, high molecular weight ester oils, cationic surfactants, amines, hydrocarbon oils, and mixtures thereof; and

(d) an aqueous carrier.

8. The composition of Claim 7, wherein the organic antioxidant is selected from the group consisting of butyl hydroxy toluene, butyl hydroxy anisole, tertiary butyl hydroquinone, hydroquinone, Vitamin E and its derivatives, Vitamin C and its derivatives, and mixtures thereof.

9. The composition of Claim 7, wherein the fatty compound is selected from the group consisting of C₆-C₃₀ saturated fatty alcohol, oleyl alcohol, elaidyl alcohol, recinoleyl alcohol, linoleyl alcohol, linolenyl alcohol, erucyl alcohol, and mixtures thereof.

10. The composition of Claim 7, wherein the composition further comprises by weight:

(a) from about 0.5% to about 5.0% of an amidoamine or mixture of amidoamines having the following general formula; R¹ CONH (CH₂)m N (R²)2 wherein R1 is a residue of Ci 1 to C24 fatty acids, R² is a C-| to C4 alkyl, and m is an integer from 1 to 4; and

(b) from about 0.05% to about 2.0% by weight, of an acid or mixture of acids; wherein the composition has a pH of from about 4 to about 6.5.