US005641480A United States Patent [19] [11] Patent Number: 5,641,480 Vermeer [45] Date of Patent: Jun. 24, 1997

[54] HAIR CARE COMPOSITIONS COMPRISING A New Family of Liquid Crystals: N-Substituted Aldona HETEROATOM CONTAINING ALKYL mides, Mol. Cryst. Liq. Cryst. 1986, vol. 135, pp. 93-110. ALDONAMIDE COMPOUNDS Molecular Packing and Hydrogen Bonding in the Crystal Structures of the N-(n-AlkyD-D-gluconarnide and the [75] Inventor: Robert Vermeer, Nutley, NJ. 1-Deoxy-(N-methyl-alkanamido)-D-glucitol Mesogens, Mol. Cryst. Liq. Cryst. 1990, vol. 185, PP - 209-213. [73] Assignee: Lever Brothers Company, Division of Conopco, Inc., New York, N.Y. Molecular Crystals and Liquid Crystals, vol. 198 (1991). Amphiphilic Properties of Synthetic Glycolipids Based on Amide Linkages, Zabel et al., Chemistry and Physics of [21] Appl. No.: 352,309 Lipids, 39 (1986) 313-327. [22] Filed: Dec. 8, 1994 Liquid-crystalline Behaviour in the N-alkyl Gluconamides and Other Related Carbohydrates, Pfanhemuller, Liquid [51] Int. (:1.6 ...... A61K 7/07; A61K 7/075 Crystals, 1986, vol. 1, vol. 1, No. 4, 357-370. [52] US. Cl...... 424/7024; 424/701 Amphiphilic Properties of Synthetic Glycolipids Based in [58] Field of Search ...... 424/701, 70.13, Amide Linkages, Makromol, Chem. 189, 2433-2442 424/7017, 70.24 (1988). [56] References Cited Molecular and Crystal Structures of N-(n-Heptyl)-and N-(n-DeCyD-D-GlycOnamide. Fahrnow et al., Carbohy U.S. PATENT DOCUMENTS drate Research 176 (1988) 165-174).

2,662,073 12/1953 Mehltretter et a1...... 536/172 Supramolecular Assemblies of Diacetylenic Aldonarnids, 2,721,211 10/1955 Frankel et al., J. Am. Chem. Soc., 1991, 113, 7436-7437. 2,752,334 6/1956 A New Class of Model Glycolipids; Synthesis, Character 2,776,951 1/1957 ization, and Interaction with Lectins, Williams et al., 2,785,152 3/1957 Archives of Biochemistry and Biophysics, vol. 195, No. 1, 3,766,267 l0/1973 Jun., pp. 145-151, 1979. 3,855,290 12/1974 3,990,991 11/1976 Synthesis of a New Class of Model Glycolipids, Williams et 4,038,294 7/1977 a1. —Carbohydrate Research, 67 (1978) C1-C3. 4,190,429 2/1980 Technical Notes, Scholnick et al, pp. 471-473. 4,342,706 8/1982 4,529,588 7/l985 Compositions Comprising Nonionic Glycolipid Surfactants, 4,534,964 8/1985 Filed as US. Ser. No. 816,419. 4,618,675 10/1986 Light Scattering from Nonionic Surfactants of the Sugar 4,973,473 ll/1990 Lipid Hybrid Type in Aqueous Solution, Denkinger et al., J. 5,037,973 8/1991 Phys. Chem, 1989, 93, PP. 1428-1434. 5,084,270 l/1992 Investigations of a Series of Nonionic Surfactants of Sugar FOREIGN PATENT DOCUMENTS Lipid Hybrids by Light Scattering and Electron Microscopy, Denldnger et al., Colloid & Polymer Science 268:513 527 2523962 9/1983 France . 2321752 1111974 Gennany . (1990). 2338087 l/1975 Germany . Mouolayers from Synthetic Glycolipids, Emmerling, Poly 62-327860 7/1989 Japan . mer Bulletin 6, 305-308 (1982). 94/12511 6/1994 WIPO . Synthesis of New Fluorinated Nonionic Surfactants Derived UT HER PUBLICATIONS from Lactose, Ghoul, Journal of Fluoride Chemistry, 59 (1992) 107-112. ~ Synthetic Ernulsifying Agents, Fieser et al., Jun. 20, 1956, Conformational Effects of 1,3-syn-Diaxial Repulsion and vol. 78, pp. 2825-2832. 1,2-gauche Attraction Between Hydroxy Groups in Mono Linking Sugars with Amino Acid Esters of Lipophilic Alco molecular N-Octyl-D-Hexonamide Solutions, Svenson et hols to Form Surface-Active Sugar Derivatives, Geyer, vol. al., J. Chem. Soc., Perkin Trans 2, 1994,pp. 1023-1028. 330 9 (1963), pp.182-188 (English Translation). Reaction of Aliphatic Diamines with D-Gluconic Acid 8-Lactone, Geyer, vol. 97 (1964), pp. 2271-2275 (English Primary Examiner-Sane M. Gardner Translation). Attorney, Agent, or Firm-—R0nald A. Koatz Amphiphilic Properties of Synthetic Glycolipids Based on Amide Linkages, 1. Electron Microscopic Studies on Aque [57] ABSTRACT ous Gels, Chem. & Physics of Lipids 37 (1985) 227-240. The invention relates to hair care compositions containing The Chiral Bilayer Effect Stabilizes Micellar Fibers, heteroatom containing alkyl aldonamide compounds and Fuhrhop et al., J.Am. Chem. Soc., vol. 109, No. 11; pp. hair conditioning agents. Unexpectedly, applicants have 3386-3390 & Supplemental Material. found that when these heteroatom containing alkyl aldona Lipid Bilayer Fibers from Diastereomeric and Enantiomeric N-Octylaldonamides, Fuhrhop et al., I. Am. Chem. Soc., mides are used, bene?ts such as enhanced stability and/or 1988, 110, pp. 2861-2867. enhanced viscosity are obtained relative to the use of other Stereochemistry and Curvature E?’ects in Supramolecular known thickeners or non-heteroatom containing aldona Organization and Separation Process of Mieellar N-Alky mides. laldonamide Mixtures, Fuhrhop et al., I. Am. Chem. Soc., 1990, 112, pp. 1768-1775. 1 Claim, No Drawings 5,641,480 1 2 HAIR CARE COMPOSITIONS COMPRISING Viscosity/Clarity HETEROATOM CONTAINING ALKYL The viscosity or thiclmess of a hair care composition also ALDONAMIDE COMPOUNDS plays an important role in the selection of that product, since consumers are accustomed to, and expect hair care compo TECHNICAL FIELD sitions to be thick and viscous. If a hair care composition is The present invention is related to new hair care compo thin and nonviscous, a consumer may conclude that the sitions that have improved foam, viscosity, clarity and product is inferior. Furthermore, successful hair care com conditioning characteristics due to the inclusion of a new positions must have good shelf life and should not become type of alkyl aldonamide compound. speci?cally heteroatom turbid or produce sedimentation upon standing. Ideal hair containing alkyl aldonamide compounds. care compositions should cleanse the hair gently and should not overdry the scalp. Surprising the hair care compositions BACKGROUND OF THE INVENTION of the present invention that comprise a heteroatom con The hair of the head has been associated with beauty and taining alkyl aldonamide compound produce clear, stable, social distinction. For this reason, a special importance is thick liquid compositions with good conditioning properties. attached in the cosmetic area to hair care products such as 15 This is unusual and unexpected, since alkyl aldonamides rinses, conditioners, shampoos, conditioning shampoos and that lack heteroatoms generally form opaque, nontransparent the like. liquid compositions which are instead useful as opacifying The primary function of a hair care composition is to or pearlescent agents. cleanse the hair and scalp from soil without stinging or Background Art Alkyl Aldonamides irritating the eyes and scalp. Hair soil includes natural skin An aldonamide is de?ned as the amide of an aldonic acid secretions (such as sebum), skin debris, dirt from the envi (or aldonolactone) and an aldonic acid, in turn is de?ned as ronment and residue from hair-grooming products applied a sugar substance in which the pseudoaldehyde or pseudoke by the consumer. After accomplishing the cleansing action, tose group, generally found at the C1 or C2 position on the the shampoo should not excessively remove the natural oil 25 sugar, has been oxidized to a carboxylic acid group which from the scalp and should leave the hair soft, lustrous and upon drying cyclizes to an aldonolactone. manageable while simultaneously providing a rich copious Aldonamides may be based on compounds comprising foam or lather. This has become a difficult challenge to meet one saccharide unit (e.g., ribonamides, gluconarnides or and it is not surprising to ?nd that considerable resource and glucoheptonamides), two saccharide units (e.g., effort have been directed towards the discovery and devel opment of new ingredients that provide improved foam, lactobionamides, maltobionamides, melibionarnides, viscosity, clarity and conditioning characteristics. The patent cellobionamides, gentiobionamides or D-glucopyranosyl literature, cosmetic journals and forrnularies describe many (1-5)-D-arabinonamides) or they may be based on com such ingredients, however, they still do not provide all the pounds comprising more than two saccharide units. Any answers to the problems encountered in making a totally carbohydrate can be used as long as the sugar has a satisfactory product. 35 pseudoaldehyde or pseudoketose group available for oxida tion to a carboxylic acid group. It has now been found that the inclusion of a heteroatom While alkyl aldonamides are known in the art, there is no containing alkyl aldonamide compound in a hair care com teaching or suggestion of using heteroatom containing alkyl position of the invention, surprisingly provides improved aldonamide compounds of the invention as foam stabilizers, foam, viscosity, clarity and conditioning characteristics. viscosity modi?ers or conditioning agents in hair care com These ?ndings are quite unexpected and have not been positions. recognized or appreciated in the art. In particular, there is no teaching that using heteroatom The hair care compositions of the present invention may containing alkyl aldonamide compounds in hair care com be in aerosol, liquid, gel, creme (cream), lotion, paste, positions alone or with, for example, anionic surfactants granular, powdered, tablet or bar form. Included among the 45 (e.g., sodium or ammonium salts of alkyl sulfates, alkyl hair care compositions are rinses, conditioners, shampoos, ether sulfates), nonionic surfactants (e.g., alkyl polyoxy conditioning shampoos, antidandruif shampoos and the like. alkylene sorbitau esters or alkyl polyglycosides), amphoteric However, the conditioners, shampoos, conditioning sham surfactants (e.g., alkyl carboxybetaines) and mixtures poos and antidandruff shampoos are the preferred compo thereof, could result in a clear thickened hair care compo sitions. sition that foams copiously and leaves the hair soft, lustrous Foam and manageable. US. Pat. No. 2,662,073 to Mehltretter, et al. for example, The ability of a hair care composition to create a desirable teaches gluconamide compounds of the formula: rich lather is a signi?cant driving force in the selection of that product. This important psychological stimulus derived 55 0 from tactile and visual perceptions by the consumer, make it necessary to formulate compositions with ingredients that generate a high level of stable foam or lather. Furthermore, the generation of a thick, persistent lather also serves as a wherein R is an aliphatic hydrocarbon radical having 8 to 18 vehicle to suspend dirt and prevent redeposition during the carbon atoms, a cycloaliphatic radical having 8 to 18 carbon rinse cycle. Surprisingly the hair care compositions of the atoms or a rosin radical. The compounds are said to be invention that comprise a heteroatom containing alkyl valuable wetting agents for use in the mercerization of aldonamide compound produce an enhanced, thick, copious, cotton and in the manufacture of viscose yarn. There is persistent foam and lather. clearly no teaching on suggestion of using heteroatom By contrast, compositions that lack a heteroatom contain 65 containing alkyl aldonamide compounds of the invention in ing alkyl aldonamide compound exhibit low viscosity and liquid hair care compositions for improved foam. viscosity, poor foam. clarity and conditioning bene?ts. 5,641,480 3 4 US. Pat. No 2,776,951 to Melamed teaches the prepara French Patent No. 2,523,962 to Monsigny teaches the tion of vinyloxyethyl gluconamides as polymer precursors. compounds: The polymers are said to be useful as wetting agents and as paper, leather or textile ?nishing agents. There is clearly no 0 teaching or suggestion of using heteroatom containing alkyl ll aldonarnide compounds of the invention in liquid hair care nocrmcrrommcnrmg compositions for improved foam, viscosity, clarity and con ditioning bene?ts. wherein mis 2 to 6 and R3 is a linear or branched alkyl group US. Pat. No. 2,721,211 to Buc teaches alkyl fonnyl containing 6 to 18 carbons. The patent further teaches phenylene gluconamides as solubilizing agents for vat dye polyoxyethylene, polyoxypropylene or polyglycerol deriva stuffs. The alkyl formyl phenylene radical (R) of these 10 tives of the formula. Again, however, there is no teaching of compounds are structurally unrelated to the compounds of a hydrocarbon radical (R) When interrupted by a heteroatom, the invention which contain a hydrocarbon radical inter would provide liquid hair care compositions with improved rupted by a heteroatom. Also, US. Pat. No. 4,190,429 to foam, viscosity, clarity and conditioning bene?ts. Rutter, et al. teaches adamantyl gluconamides as antimicro US. Pat. No. 4,973,473 to Schneider, et al. teaches skin bial agents. In both of these patents, there is clearly no treatment compositions in which the primary moisturizing teaching or suggestion of using heteroatom containing alkyl agent may be a gluconamide compound. Methyloxypropyl aldonarnide compounds of the invention in liquid hair care gluconarnide is the only example of this ingredient which compositions for improved foam, viscosity, clarity and con has the formula: ditioning bene?ts. Fieser, et al. in J. Am. Chem. Soc. 7822825 (1956) teaches 20 0 the preparation of a series of N-alkyl arabinonamides and N-alkyl gluconamides for use as an emulsifying agents, nocrrxcrrorrycrvmcnmocrr, where the attached aliphatic radical (R) is from C10 to C18. The reference teaches that such compounds are poor emul Since this compound is clearly hydrophilic (not surface sifying agents and are therefore expected to be poor surfac active), it cannot be used as a foam stabilizer, viscosity tants. Also, there is clearly no teaching or suggestion that the modi?er or conditioning agent. There is no suggestion to addition of oxygen or other heteroatoms in the alkyl radical utilize alkyl chains greater than methyl and there is clearly can enhance the foam, viscosity, clarity and conditioning no teaching or suggestion that aldonarnides with interrupted bene?ts in liquid hair care compositions. long alkyl chains can provide improved foam, viscosity, Furthermore, the fact that the monosaccharide alkyl clarity and conditioning bene?ts in liquid hair care compo aldonamides, where the alkyl group is C10 or greater, are 30 sitions. poor emulsi?ers is also recognized in German Pat. Nos. Schneider et al. in Hoppe-Seyler’s Z Physiol. Chem. 2,321,752 and 2,338,087, both to Reiser, et a1. (1975). 3301182 (1963) teaches alkyl gluconyl glycinate compounds Speci?cally, DE 2,321,752 is directed to the preparation having the formula: of N,N-dialkyl polyhydroxyamide compounds having the 35 formula: 0 0 II II 0 HOCH;(CHOH)4CNHCH2COR4,

wherein R4=C8 to C10 While this paper does teach monosaccharide aldonarnides wherein n is 3 to 5; R1 is hydrogen or a linear alkyl group containing an alkyl group interrupted with an ester containing 1 to 3 carbon atoms; and R2 is an aliphatic functionality, there is no teaching or suggestion that such hydrocarbon radical having 4 to 7 carbons in normal or alkyl groups may be interrupted with, for example, an ether, branched arrangement (optionally interrupted by oxygen, sul?de or amine or that the use of such groups will provide sulfur or hydroxyl group). The principal patent DE 2,321, 45 improved foam, viscosity, clarity and conditioning bene?ts 752, teaches that alkyl aldonarnides having long chained in liquid hair care compositions. ' radical (R) groups such as lauryl (12 carbons), cetyl (16 Geyer in Chernische Berichte 97:2271 (1964) describes carbons) or stearyl (18 carbons), do not form stable water the preparation of N-alkanoyl-N-gluconoyl ethylene dia emulsions. Therefore, it was surprising to ?nd that: the liquid mide compounds having the structure: hair care compositions of the invention, which comprise 50 heteroatom containing alkyl aldonarnide compounds, pro vide clear compositions with improved foam, viscosity and conditioning bene?ts. Japanese Patent 1-168653 again recognizes that the monosaccharide aldonamides of the art (e.g., N-alkyl 55 wherein R5=C15, C6; and Pfannemueller, et al. in Chemistry gluconamides) do not show suf?cient emulsifying properties and Physics of Lipids 37:227 (1985) describes the prepara (poor surface-activity). Again, there is a recognition that tion of N-alkanoyl-N-methyl-N-gluconyl ethylene diamide such compounds are poor emulsi?ers and are therefore not compounds of the formula: expected to be useful as ingredients in liquid hair care compositions. The Japanese patent seeks to address this problem by it’ it’ using N,N-dialkyl polyhydroxyamide compounds where one alkyl group (R) is C8-C18 and the other is C1-C4. There CH3 is clearly no teaching or suggestion of using heteroatom containing alkyl aldonarnide compounds of the invention in These references teach monosaccharide aldonarnides con liquid hair care compositions for improved foam, viscosity, taining an alkyl group that is interrupted with an amide clarity and conditioning bene?ts. group, not an amine group. Again, there is no teaching or 5,641,480 5 6 suggestion of alkyl aldonamides with alkyl groups inter example, J .Am. Chem. Soc. 109(11)::3387 (1987), 11022861 rupted with an ether, sul?de or amine linkage or that such (1988) and 112:1768 (1990) to Fuhrhop, et al.; Mol. Cryst. interrupting groups provide greater foam, viscosity, clarity Liq. Cryst. 135:93 (1986) to Baeyens-Volant, et al., 185 2209 and conditioning bene?ts than others. Furthermore, there is (1990) to Je?ery and 1981381 (1991) to Van Doren, et a1.; clearly no teaching or suggestion of using sugar compounds Chemistry and Physics of Lipids 39:313 (1986) to Zabel, et having two saccharide units or greater (e.g., al.; Liquid Crystals 1(4):357 (1986) and Makrolmol. Chem. lactobionamides) together within an interrupted alkyl group 189:2433 (1988) to Pfannemueller, et al.; Carbohydrate for providing improved foam, viscosity, clarity and condi Research 176:165 (1988) to Farnow, et al. and J. Am Chem. tioning bene?ts in liquid hair care compositions. Soc. 113:7436 (1991) to Frankel, et al. There is clearly no U.S. Pat. No. 5,037,973 to Meinetsbeger teaches a series 10 teaching or suggestion in any of these references, of using of bis-alkyl aldonamide compounds as intermediates for heteroatom containing alkyl aldonamide compounds of the pharmacological applications. While this paper does teach invention in liquid hair care compositions for improved bis-alkyl aldonamide compounds containing heteroatoms, foam, viscosity, clarity and conditioning bene?ts. there is no teaching or suggestion that the use of such radicals will provide improved foam, viscosity, clarity and Alkyl Aldobionamides conditioning bene?ts in liquid hair care compositions. In addition, the heteroatom containing alkyl aldonamides of U.S. Pat. Nos. 2,752,334 to Walton and 2,785,152 to this invention are monomeric in nature (structurally very Jones teach aldobionamide compounds prepared by the di?erent) whereas the bis-alkyl aldonamide compounds of reaction of aldobionic acids or aldobionolactones with fatty U.S. Pat. No. 5,037,973 are dimeric in nature and would not amines or fatty amino acid esters. The compounds are said be considered as useful ingredients in liquid hair care to be useful as an emulsi?er in food compositions and as compositions. antimycotic agents. There is no teaching or suggestion that U.S. Pat. Nos. 3,766,367 and 3,855,290 to Zak, et al. as the use of a heteroatom (e. g., oxygen, nitrogen or sulfur) in well as U.S. Pat. Nos. 4,038,294 and 4,342,706 to Conner, the aliphatic hydrocarbon radical of an alkyl aldobionamide compound can improve foam, viscosity, clarity and condi et a1. teach quaternary halide gluconamide compounds of the 25 formulas: tioning bene?ts in liquid hair care compositions. Williams, et al. in Archives of Blochem. and Biophysics, 195(1): 145 (1979) and Carbohydrate Research 67:C1—C3 (1978) teach aldobionamide compounds prepared by the 30 reaction of aldobionic acids with alkyl amines. Again, there is no teaching or suggestion that the alkyl group of the alkyl amine may contain a heteroatom, nor is there any teaching or suggestion of using heteroatom containing alkyl aldo bionamide compounds for enhanced foam, viscosity, clarity 35 and conditioning bene?ts in liquid hair care compositions. Scholnick, et al. in J. Dairy Sci. 63(3):471 (1980) teach aldobionamide compounds as effective chelating agents of ferric ion. There is clearly no teaching or suggestion of using heteroatom containing alkyl aldobionamide compounds of the invention in liquid hair care compositions for improved foam, viscosity, clarity and conditioning bene?ts. In copending application, U.S. Ser. No. 816,419, the assignee of the subject application has ?led an application directed to the use of the broad class of aldonamide surfac 45 tants in personal products or detergent compositions. The application, U.S. Ser. No. 981,644, has been ?led as a separate applicau'on on the same date as U.S. Ser. No. 816,419. These applications have a few examples of using a heteroatom (i.e., ether and ester in the aliphatic hydrocarbon), however there is no teaching or suggestion that this heteroatom is responsible for improved foam, These compounds are said to be useful as emollients viscosity, clarity and conditioning bene?ts in hair care which are substantive to skin or hair and are further taught compositions. Also, U.S. Ser. No. 981,644 has been ?led as in U.S. Pat. Nos. 3,990,991 to Gerstein, 4,534,964 to Her world application WO 94/12511. On page 17 of WO stein et a1. and 4,529,588 to Smith et al. which all describe 55 94/12511 it is mentioned, along with a broad recital of conditioning shampoo compositions comprising quaternary multiple product types, that aldonamide compounds may be halide gluconamide compounds. There is clearly no teaching used as surfactants in hair care compositions. There is or suggestion in any of these references, of using heteroatom absolutely no exempli?cation or teaching of the heteroatom containing alkyl aldonamide compounds of the invention in containing alkyl aldonamide compounds of the invention in liquid hair care compositions for improved foam, viscosity, compositions with for example, certain essential ingredients clarity and conditioning bene?ts. Also the heteroatom con such as cosurfactants, antidandruif agents, hair conditioning taining alkyl aldonamide compounds of the present inven agents, suspending agents, auxiliary thickening agents, tion are structurally very different and do not contain a water and other auxilary agents (see claim 4). There is also quaternary ammonium functional group which is respon clearly no teaching of improved foam, viscosity, clarity and sible for the emolliency and conditioning effect. 65 conditioning bene?ts that are provided when heteroatom Finally, there are several references teaching the molecu containing alkyl aldonamide compounds of the invention are lar and liquid crystal structure of alkyl aldonamides, see for formulated in hair care compositions. The individual ingre 5,641,480 7 8 dients have to ful?ll, in part, wholly different functions while ditioning characteristics due to the inclusion of a new type at the same time each ingredient must complement and of alkyl aldonamide compound, speci?cally hereroatom increase the effect of other substances. This has always been containing alkyl aldonamide compounds of the formula: a di?icult challenge to meet and ?nding the right combina tion of ingredients for improved foam, viscosity, clarity and 5 conditioning is a signi?cant achievement. Finally, there are several references teaching the molecu lar and micellar structure of alkyl aldobionamides generally, but are otherwise unrelated to the compounds of the invention, see for example, J. Phys. Chem. 93(4):1482 10 (1989) and Colloid Poylm. Sci. 268(6):513 (1990) to wherein: Denkinger, et al. and Polym. Bull. (Berlin) 6(5—6):305 (1982) to Emmerling. Since most hair care compositions are based on petro X=H, a C1-C4 alkyl group or mixtures thereof; chemical ingredients, it would be most desirable to use Y=NA, *NHZ, +NHA, O, S, SO, S02, materials which are instead naturally derived, such as car bohydrates. These renewable raw materials have the distinct 0 0 o 0 advantage of being readily available, inexpensive, II II II H biodegradable, aquatically favorable and optically pure. CO, OC,CNA, NAC Thus the ability to ?nd a naturally derived, environmen tally friendly compound, that simultaneously provides an 20 or mixtures thereof; enhanced copious persistent lather, thick viscosity, clarity and conditioning e?tect in clear liquid hair care compositions G=H, a mono-, di-, oligo-, polysaccharide group, a is a signi?cant achievement. ’ (CHZCHZO) —--H, (CH2CHCH3O),—-H group or mix Accordingly, it is an object of the present invention to tures thereo ; provide hair care compositions that have excellent lathering 25 and foaming characteristics. It is another object of the present invention to provide hair A=H, a hydroxy C1-C18 is alkyl group, C1-C18 straight care compositions that have stiif consistencies which allow or branched chain, saturated or unsaturated hydrocar e?‘ective bottle and tube packaging. bon which may be unsubstituted or substituted with an It is another object of the present invention to provide 30 aromatic, cycloaliphatic, mixed aromatic aliphatic radi viscous hair care compositions which are resist to spillage cal or a and effectively cling to the hand before shampooing. It is another object of the present invention to provide stable clear hair care compositions comprising of a heteroa pH Y tIQH Y]—R12 tom containing alkyl aidonamide compound which do not 35 X Ill X m p become turbid or produce sedimentation upon standing. It is still another object of the present invention to provide group or mixtures thereof; wherein X, m, Y and p are de?ned mild hair care compositions that ef?ciently remove surface as above; and R12 is a straight or branched chain, saturated grease, dirt and skin debris from the hair shaft and scalp. or unsaturated hydrocarbon which may be unsubstituted or It is still another object of the present invention to provide substituted with an aromatic, cycloaliphatic, or mixed aro new and improved hair care compositions that leave the hair matic aliphatic radical comprising one or more carbon fragrant, lustrous, soft, conditioned and in a manageable atoms, preferably from about 1 to about 28 carbon atoms. state. Preferably, It is a ?nal object of the present invention to provide an 45 n=2—5; improved method of shampooing and conditioning the hair. m=1—4; These and other objects will become readily apparent from X=H, a C1 alkyl group or mixtures thereof; the detailed description which follows. Y=NA, +NH2, *NHA, O, SUMMARY OF THE INVENTION o o o 0 The present invention provides new hair care composi 50 II II II II tions for use in home shampooing and conditioning opera co, 0c, CNA, NAC tions. The present invention is based on the discovery that heteroatom containing alkyl aldonamide compounds pounds or mixtures thereof; - are useful as foam stabilizers, viscosity modi?ers and con ditioning agents in a variety of hair care compositions. 55 Included among the hair care compositions of the present G=H, a monosaccharide group, a (CH2CH2O)q—H, invention are rinses, conditioners, shampoos, conditioning (CH2CHCH3O),—H group or mixtures thereof; shampoos, antidandrutf shampoos and the like. However, q=1-25 the conditioners, shampoos, conditioning shampoos and antidandruff shampoos are the preferred compositions and A=H, a hydroxy C1—C8 alkyl group, a C1—C8 straight or the components found in such compositions are described in branched chain, saturated or unsaturated hydrocarbon the detailed description that follows. group or mixtures thereof: and R12 is a straight or branched chain, saturated or unsaturated hydrocarbon DETAILED DESCRIPTION OF THE which may be unsubstituted or substituted with an INVENTION 65 aromatic, cycloaliphatic, or mixed aromatic aliphatic The present invention provides new hair care composi radical comprising from about 7 to about 24 carbon tions that have improved foam, viscosity, clarity and con atoms. 5,641,480 9 10 Most preferably, R12=C12H25 (25%), C13H27 (39%), C14H29 (21%), 11=3—5; C15H31 (15) m=1__3, Yet another speci?c example of a monosaccharide het __ . _ eroatom containing alkyl aldonamide compound of the X_H’ a C1 alkyl group or mums thereof’ 5 invention is N-gluconyl dodecyldi(oxyethyl) glycinate, also Y=NA’ +NH2’ ‘PNHA, 0’ known as N-gluconyl dodecyl(diethylene glycol) ether glycinate, N-gluconyl (diethylene glycol) monododecyl if 3 if H ether glycinate and as N-gluconyl dodecyl(dioxyethylene) CO’ OC’CNA, NAC glycinate having the formula: 10 or mixtures thereof; Em |(|) ‘(1) P=O_6 HOCH2€H(|IHCH(|3HCNHCH2COCH2CH2OCH1CH2OC12H25 G=H, a monosaccharide group, a (CH2CH2O)q——H, OH OH (CH2CHCH3O),—H group or mixtures thereof; 15 OH q=1—15 1:145 wherein: A=H, a hydroxy C1—C6 alkyl group, a Cl-C6 straight or “:4; branched chain, saturated or unsaturated hydrocarbon 20 111:1 or 2; group or mixtures thereof; and R12 is a straight or X =hydrogen; branched chain, saturated or unsaturated hydro carbon Y =ester (COO) or oxygen (0); radical comprising from about 8 to about 22 carbon 2 atoms p:G=hydrogen; ’ A speci?c example of a monosacchande hetero,atom 25 A=hydmgem and containing alkyl aldonamide compound of the invention is C C 0 r0 1 D- uconamide havin the formula: R12=C12H25 8/ 10 Xyp py g1 g A speci?c example of a disaccharide heteroatom contain OH 0 ing alkyl aldonamide compound of the invention is dode I ll cyloxypropyl D-lactobionamide having the formula: HOCH2(‘3HCHCH(|3HCNH(CH;)3OCsH17/C1oH21 30 OH OH clm 3 OH HOCHZ(IIHCHCH$HCNH(CH2)3OCQHZ5 wherein: 35 OH OH n=4; OH 0 m=3; HO 0 X=hydrogen; Y=oxygen (O); OH p=0; 40 G=hydrogen; OH A=hydrogen; and h _ . R12=C6H13 (1%), 081117 (59%), CmHn (39%), CQH” w 63"‘ (1%)‘ 4s 11 ’ Another speci?c example of a monosaccharide heteroa- 111:3; torn containing alkyl aldonamide compound of the invention X=hY<1r<>g@n; is C12—C15 oxypropylaminopropyl D-glucoheptonamide Y=oxygen (0); having the formula: F0;

(In.I ll HOCHzCHfHCHCH?IHCNHCHZCHZCHZNHCHZCHZCHZOCEH5—C15H31 0H OH OH OH

wherein: : G=hydrogen or galactose; n=5. A=hydr0gen: and _?;, 60 R12=C12H25' m- ’ Another speci?c example of a disaccharide heteroatom X=hydrogem containing alkyl aldonamide compound of the invention is =oxygen (O) or nitrogen (NH); dodecyltl?oxycthyl) OXYPI'OPYl D-g1uc°PyIa?°sy1'(1-5)'D' p___1, _ ‘_ arabinonamide, also known as dodecyl (uiethylene glycol) G=h’ydmgen; 65 propylene glycol ether D-g1ucopyranosyl-(l-5)-D arabinonamide, (triethylene glycol)propylene glycol A=hydrogen; and monodoclecyl ether D-glucopyranosy1-(1-5)-D

5,641,480 13 14 alkyloxypropyl D-gluconamide heptaoxyethylene ether sulfonic acid, ethanesulfonic acid, toluenesulfonic acid and alkyloxypropyl D-gluconamide octaoxyethylene ether mixtures thereof or by reaction with, for example an alky alkyloxypropyl D-gluconamide nonaoxyethylene ether lating agent such as chloromethane, dirnethyl sulfate, diethyl alkyloxypropyl D-gluconamide decaoxyethylene ether sulfate and benzyl chloride. The presence of an amino group, or a salt of an amino alkyloxypropyl D-gluconamide trioxypropylene ether group in the alkyl chain of a heteroatom containing alkyl alkyloxypropyl D-gluconamide oxyethylenedioxypropy aldonamide compound of the present invention, provides a lene ether functionality that is substantive to the hair. The ?nal result alkyloxyethyl D-gluconamide dioxyethylenetrioxypropy is a conditioning effect which provides desirable qualities lene ether 10 such as ease of combing, detangling, body, shine, texture, alkyloxyethyl D-gluconamide trioxypropylenedioxyeth split-end mending, manageability and static buildup preven ylene ether tion. alkyloxypropyl D-lactobionamide monooxyethylene The heteroatom containing alkyl aldonamide compounds ether of the present invention can also be ethoxylated, propoxy alkyloxypropyl D-lactobionamide dioxyethylene ether lated or butoxylated with ethylene oxide, propylene oxide, alkyloxypropyl D-lactobionamide trioxyethylene ether butylene oxide or mixtures thereof to give a series of polyoxyalkylene ether sugar surfactants. alkyloxypropyl D-lactobionamide tetraoxyethylene ether Typical levels of heteroatom containing alkyl aldonamide alkyloxypropyl D-maltobionamide dioxyethylene ether compound are from about 0.1% to about 40%, preferably alkyloxypropyl D-maltobionamide pentaoxypropylene 20 from about 0.2% to about 35%, even more preferably from ether about 0.3% to about 30% by weight of the composition. alkyloxypropyl D-maltobionamide decaoxypropylene There are a wide variety of essential ingredients that can ether be used in hair care compositions depending on the charac Wherein the alkyl group contains from about 1 to about 28 teristics and end purpose sought. Such ingredients are well carbon atoms, preferably from about 7 to about 24 carbon 25 known to those skilled in the art and include, but are not atoms and even more preferably from about 8 to about 22 limited to cosurfactants, antidandrutf agents, hair condition carbon atoms. ing agents, suspending agents, auxiliary thickening agents, The A group is preferably hydrogen, although it may be water and other optional ingredients (auxilary agents). a hydroxy C1-C4 alkyl group or a C1 to C18 straight or The individual ingredients have to ful?ll, in part, wholly branched chain, saturated or unsaturated hydrocarbon radi 30 different functions while at the same time each ingredient cal. The A group may also be interrupted by a hetero-atom must complement and increase the effect of other sub and may have the same structure as the group attached to the stances. This has always been a di?icult challenge to meet nitrogen atom. and ?nding the right combination of ingredients for If the A or R12 group is an aliphatic radical, suitable improved foam, viscosity, clarity and conditioning is a examples include methyl, ethyl, propyl, butyl, pentyl, hexyl, 35 signi?cant achievement. heptyl, octyl, nonyl, decyl, undecyl, dodecyl, tridecyl, tetradecyl, pentadecyl, hexadecyl, heptadecyl, octadecyl, COMPOSITIONS coco, soya, tallow, tall oil, castor, corn, cottonseed, palm, The essential and optional ingredients of the present rapeseed, sa?lower, sesame, sun?ower, ?sh oil, allyl, octenyl, nonenyl, decenyl, undecenyl, dodecenyl, tridecenyl, invention are given in the following paragraphs. tetradecenyl, pentadecenyl, hexadecenyl, heptadecenyl, Cosuifactants (Cleansing Agents) octadecenyl (oleyl), linoleyl and linolenyl. If the A or Rl2 group is interrupted by an aromatic radical, An essential component of the present invention is a the aromatic group may be for example, benzyl or aniline. cosurfactant. The term “cosurfactant” is used to denote both Cycloaliphatic radicals are exempli?ed but are not limited to 45 soap and nonsoap surface-active agents. The nonsoap cyclopentyl and cyclohexyl. Suitable mixed aromatic ali surface-active agents include anionic, nonionic, amphoteric, phatic radicals are exempli?ed by benzylpropyl, zwitterionic and cationic surfactants. phenylethyl, phenoxyethyl and vinylbenzyl. The G group may be hydrogen or an attached mono-, di-, Soaps oligo-, or polysaccharide. Examples of suitable saccharides Suitable soaps are exempli?ed as alkali metal, ammonium that can be oxidized to sugar acids [GOCH2(CHOG) or alkanolammonium salts of aliphatic alkane or alkene RCOOH] include but are not limited to, erythrose, threose, monocarboxylic acids having about 8 to about 18 carbon ribose, arabinose, xylose, lyxose, allose, altrose, idose, atoms. Sodium, potassium, ammonium, mono-, di-, and talose, glucose, galactose, mannose, gulose, fructose, triethanolammonium cations or combinations thereof, are sorbose, sucrose, isomaltose, isomalt, isomaltulose 55 (palatinose), trehalulose, 3-ketosucrose, leucrose, lactulose, preferred. Soaps may be prepared by either direct saponi? gentiobiose, maltose, lactose, melibose, cellobiose, cation of fats and oils or by neutralizan‘on of free fatty acids. triglucose, tetraglucose, starch and cellulose. Particularly useful are the sodium, potassium, ammonium and alkanolammonium salts of lauric acid, myristic acid, When an amino group is present it may be converted to the corresponding salt by reaction with, for example an palmitic acid, stearic acid, oleic acid, linoleic acid, ricinoleic organic or inorganic acid such as hydrochloric acid, sulftnic acid, coconut fatty acid and tallow fatty acid. acid, phosphoric acid, boric acid, oxalic acid, malonic acid, glutaric acid, adipic acid, sebacic acid, tricarballylic acid, Anionic Stn'factants butanetetracarboxylic acid, itaconic acid, maleic acid, malic Suitable anionic surfactants are broadly exempli?ed as acid, fumaric acid, citraconic acid, glutaconic acid, bis 65 alkali metal, ammonium or alkanolammonium salts of (hydroxymethyl)propionic acid, tartaric acid, citric acid, organic reaction products having an aliphatic alkyl, alkene formic acid, lactic acid, acetic acid, benzoic acid, methane or alkyl aromatic group with about 8 to about 18 carbon 5,641,480 15 16 atoms and at least one water solubilizing radical selected lene N-methyl taurine. Preferred alkyl ether isethionates and from the group consisting of phosphate, phosphonate, alkyl ether taurinates are those comprising an average alkyl sulfonate, sulfate or carboxylate. Examples of suitable chain length of about 10 to about 16 carbon atoms and an anionic surfactants useful in the present invention include average degree of alkoxylation of about 1 to about 6 moles the sodium, potassium, ammonium, mono-, di- and trietha of ethylene oxide. Speci?c examples of alkyl isethionates, nolarmnonium salts of; C8-C3 alkyl phosphates, C8—C18 alkyl ether isethionates, alkyl taurinates and alkyl ether alkyl ether phosphates with about 1 to about 25 moles of taurinates useful in the present invention include sodium alkylene oxide, C8—C18 acyl isethionates, C,3—C18 acyl ether dodecyl isethionate, potassium dodecyl isethionate, ammo isethionates with about 1 to about 25 moles of alkylene nium dodecyl isethionate, sodium tetradecyl isethionate, oxide, C8-C18 acyl taurinates, C8—C18 acyl ether taurinates ammonium tetradecyl isethionate, sodium coconut with about 1 to about 25 moles of alkylene oxide, C8-C3 isethionate, ammonium coconut isethionate, sodium dodecyl alkyl benzene sulfonates, C8—C18 alkyl ether benzene sul (ethylene glycol) ether isethionate, sodium coconut fates With about 1 to about 25 moles of alkylene oxide, (diethylene glycol) ether isethionate, sodium dodecyl C8—C18 alkyl paraf?n sulfonates (primary and secondary), taurinate, sodium coconut(ethylene glycol) ether taurinate, Cs-C18 alkanolamide sulfates, C,,—C18 alkanolamide ether 15 sodium dodecyl N-methyl taurinate, ammonium dodecyl sulfates with about 1 to about 25 moles of alkylene oxide, N-methyl taurinate, sodium tetradecyl N-methyl taurinate, C8—C18 alkyl ot-sulfomonocarboxylates, Cs-Cls alkyl glyc sodium coconut N-methyl taurinate, ammonium coconut eryl sulfates, C8-C118 alkyl glyceryl ether sulfates with about N -methyl taurinate, sodium tetradecyl(ethylene glycol) 1 to about 25 moles of alkylene oxide, C8—C18 alkyl glyceryl ether taurinate, ammonium coconut(tn'ethylene glycol) ether sulfonates, C8—C18 alkyl glyceryl ether sulfonates with 20 N-methyl taun'nate and mixtures thereof. about 1 to about 25 moles of alkylene oxide, C8—C18 alkyl Another suitable class of anionic surfactant useful in the ether methylcarboxylates with about 1 to about 25 moles of present invention are the sodium, potassium and ammonium alkylene oxide, C8—C18 alkyl sarcosinates/glycinates/ salts of alkyl benzene sulfonates in which the alkyl group hydrolysates, Cs-Cls monoalkyl sulfosucciuates, C8—C18 contains from about 8 to about 18 carbon atoms in branched monoalkyl sulfosuccinamates, C5-C1‘, dialkyl 25 or preferably in straight chain con?guration. Alkyl benzene sulfosuccinates, Cs-C1o dialkyl sulfosuccinamates, C8—C18 sulfonates are prepared by sulfonation of linear C8—C18 alkyl ot-ole?n sulfonates, C8—C18 alkyl sulfates and C8-C1,; alkyl benzenes with sulfur trioxide in a falling ?lm or tube bundle ether sulfates with about 1 to about 25 moles of alkylene reactor followed by neutralization with base. Other suitable oxide. sulfonating agents used to prepare C8-C18 alkyl benzene sulfonates include oleum, chlorosulfonic acid, sulfuric acid Description of Anionic Surfactants or sulfur trioxide complexes. Examples of suitable alkali The sodium, potassium and ammonium salts of alkyl metal, ammonium and alkanolammonium salts of alkyl phosphates and alkyl ether phosphates having about 8 to benzene sulfonates are disclosed in US. Pat Nos. 2,220,099 about 18 carbon atoms and about 1 to about 25 moles of and 2,477,383 both of which are incorporated herein by alkylene oxide represent a suitable class of anionic surfac 35 reference. Speci?c examples of alkyl benzene sulfonates tant useful in the present invention. Alkyl phosphates and useful in the present invention include sodium dodecyl alkyl ether phosphates are prepared by reacting C,_,—C18 alkyl benzene sulfonate, potassium dodecyl benzene sulfonate, fatty alcohols, C8—C18 alkyl fatty alcohol alkoxylates or ammonium dodecyl benzene sulfonate, sodium C11—C13 Gig-C18 alkyl phenol alkoxylates with either phosphorous alkyl benzene sulfonate, sodium tetradecyl benzene peutoxide, phosphorous oxychloride, phosphoric acid or sulfonate, ammonium tetradecyl benzene sulfonate and mix polyphosphoric acid to give a mixture of monoalkyl and tures thereof. dialkyl phosphate esters that may be neutralized with base. Another suitable class of anionic surfactant useful in the Preferred alkyl ether phosphates are those comprising an present invention are the sodium, potassium and ammonium average alkyl chain length of about 10 to about 16 carbon salts of alkyl benzene ether sulfates in which the alkyl group atoms and an average degree of alkoxylation of about 1 to 45 contains from about 8 to about 18 carbon atoms in branched about 16 moles of ethylene oxide, propylene oxide or or preferably in straight chain con?guration with about 1 to mixtures thereof. Speci?c examples of alkyl phosphate about 25 moles of alkylene oxide. Alkyl benzene ether esters and alkyl ether phosphates useful in the present sulfates are prepared by sulfation of linear C3—C18 alkyl invention include sodium dodecyl phosphate, ammonium phenol alkoxylates with sulfur trioxide, oleum, chlorosul dodecyl phosphate, ammonium tetradecyl phosphate, 50 fonic acid, sulfuric acid or sulfur trioxide complexes fol sodium Clo-C16 alkyl phosphate, sodium dodecyl lowed by neutralization with base. Preferred alkyl benzene (diethylene glycol) ether phosphate, sodium tetradecyl ether sulfates are those comprising an average alkyl chain (triethylene glycol) ether phosphate, PPG-S ceteth-lO length of about 10 to about 16 carbon atoms and an average phosphate, oleth-lO phosphate and mixtures thereof. degree of alkoxylation of about 1 to about 6 moles of The sodium, potassium and ammonium salts of alkyl 55 ethylene oxide. Specific examples of alkyl benzene ether isethionates, alkyl ether isethionates, alkyl taurinates and sulfates useful in the present invention include sodium alkyl ether taurinates having about 8 to about 18 carbon nonylphenol(diethylene glycol) ether sulfate, sodium atoms and about 1 to about 25 moles of alkylene oxide nonylphenol(triethylene glycol) ether sulfate, sodium represent another suitable class of anionic surfactant useful dinonylphenol(triethylene glycol) ether sulfate, sodium in the present invention. Alkyl isethionates, alkyl ether dodecylphenol(tetraethylene glycol) ether sulfate, ammo isethionates, alkyl taurinates and alkyl ether taurinates are nium dodecylphenol(diethylene glycol) ether sulfate and prepared by reacting C8—C18 alkyl fatty acids, C,3—C18 alkyl mixtures thereof. fatty acid halides, C8-C18 alkyl ether C1—C3 alkylcarboxylic Still another suitable class of anionic surfactant useful in acids or Cs-C18 alkyl ether C1—C3 alkylcarboxylic acid the present invention are the sodium, potassium and ammo halides with either the sodium, potassium or ammonium ' nium salts of paraf?n sulfonates having about 8 to about 18 salts of isethionate, polyoxyalkylene isethionate, tamine, carbon atoms, more desirably from about 12 to about 16 polyoxyalkylene taurine, N-methyl taurine or polyoxyalky carbon atoms. Para?in sulfonates are preferably prepared by 5,641,480 17 18 sulfoxidation of a speci?c cut of para?in with sulfur dioxide rapeseed, saftlower, sesame, sun?ower, ?sh, and tall oil. and oxygen. The product consists mainly of secondary Preferred alkyl glyceryl ether sulfates are those comprising sulfonic acids along With some primary sulfonic acids which an average chain length of about 10 to about 16 carbon are neutralized with a suitable base to provide a water atoms and an average degree of alkoxylation of about 1 to soluble para?in sulfonate. Similarly, para?in sulfonates may about 6 moles of ethylene oxide. Speci?c examples of alkyl also be obtained by sulfochlorination which utilizes a mix glyceryl sulfates useful in the present invention include ture of sulfur dioxide, chlorine and actinic light as the sodium dodecyl glyceryl sulfate, potassium dodecyl glyceryl sulfonating agent It is most desirable to prepare paraf?n sulfate. ammonium dodecyl glyceryl sulfate, sodium tet sulfonates as the monosulfonate, having no unreacted start radecyl glyceryl sulfate, ammonium oleyl glyceryl sulfate, ing para?in hydrocarbon (or having a limited portion thereof ammonium tetradecyl glyceryl sulfate. sodium coconut present) and little or no inorganic salt by-product. Similarly glyceryl sulfate, sodium coconut(ethylene glycol) glyceryl the proportions of disulfonate or higher sulfonate should be ether sulfate, sodium coconut(diethylene glycol) glyceryl minimized, although some may be present. Speci?c ether sulfate, sodium coconut(triethylene glycol) glyceryl examples of para?in sulfonate useful in the present inven ether sulfate and mixtures thereof. tion include sodium C1._,-C13 para?in sulfonate, sodium Still another suitable class of anionic surfactant useful in C12-Cl4 para?in sulfonate, sodium C12—C15 para?ln the present invention are the sodium, potassium and ammo sulfonate, sodium C13-C15 paraf?n sulfonate potassium nium salts of alkyl glyceryl sulfonates and alkyl glyceryl C12—C15 paraf?n sulfonate, ammonium C13—C15 para?in ether sulfonates having about 8 to about 18 carbon atoms sulfonate, sodium C12—C16 para?in sulfonate and mixtures and about 1 to about 25 moles of alkylene oxide. Alkyl thereof. glyceryl sulfonates and alkyl glyceryl ether sulfonates are Still another suitable class of anionic surfactant, useful in prepared by the Strecker reaction of a higher C8-C18 alkyl the present invention are the sodium, potassium and ammo chlorohydrin ether or C8-C18 alkyl polyoxyalkylene chlo nium salts of alkanolamide sulfates and alkanolamide ether rohydrin ether with alkali sul?te, alkali bisul?te or analo sulfates having about 8 to about 18 carbon atoms with about gous type salt. Preferred alkyl glyceryl sulfonates are those 1 to about 25 moles of alkylene oxide. Alkanolamide sul 25 comprising an average chain length of about 10 to about 16 fates and alkanolarnide ether sulfates are prepared by sul carbon atoms and an average degree of alkoxylation of about fating C8-C1,‘ alkanolamides or C8-C18 alkanolamide 1 to about 6 moles of ethylene oxide. Speci?c examples of alkoxylates with sulfur trioxide, oleum, chlorosulfonic acid, alkyl glyceryl sulfonates useful in the present invention sulfuric acid or sulfur trioxide complexes followed by include sodium dodecyl glyceryl sulfonate, potassium dode neutralization with base. Speci?c examples of alkanolamide 30 cyl glyceryl sulfonate, ammonium dodecyl glyceryl sulfates and alkanolamide ether sulfates useful in the present sulfonate, sodium tetradecyl glyceryl sulfonate. ammonium invention include sodium dodecyl monoethanolamide oleyl glyceryl sulfonate, ammonium tetradecyl glyceryl sulfate, sodium tetradecyl diethanolamide monosulfate, sulfonate, sodium coconut glyceryl sulfonate, sodium sodium tetradecyl diethanolamide disulfate, sodium coconut coconut(ethylene glycol) glyceryl ether sulfonate, sodium monoethanolamide sulfate, ammonium coconut diethanola 35 coconut(diethylene glycol) glyceryl ether sulfonate, sodium mide monosulfate, sodium coconut diethanolamide coconut(triethylene glycol) glyceryl ether sulfonate and sesquisulfate, sodium coconut monoethanolamide mixtures thereof. (diethylene glycol) ether sulfate, sodium coconut Still another suitable class of anionic surfactant useful in monoethanolamide(triethylene glycol) ether sulfate and the present invention are the sodium, potassium and ammo mixtures thereof. nium salts of alkyl ether methylcarboxylates having about 8 Still another suitable class of anionic surfactant useful in to about 18 carbon atoms and about 1 to about 25 moles of the present invention are the sodium, potassium and ammo alkylene oxide. Alkyl ether methylcarboxylates are prepared nium salts of alkyl ot-sulfomonocarboxylates having about 8 by carboxymethylating the condensation products of alky to about 18 carbon atoms. Alkyl ot-sulfomonocar’ooxylates lene oxide and higher Cg-C18 alkyl alcohols with halo-acetic monocarboxylates are prepared by sulfonation of C8—C18 45 acid salts or by chemical oxidation. The alcohols can be alkyl fatty acids, C8—C18 alkyl fatty acid esters with sulfur derived synthetically or naturally from fats or oils. Dodecyl trioxide, oleum, chlorosulfonic acid, sulfuric acid or sulfur alcohol, tetradecyl alcohol and coconut oil are preferred nioxide complexes followed by neutralization with base; or herein. Such alcohols are reacted with about 1 to about 25 by esteri?cation of sulfoacetic acid, ot-sulfopropionic acid or moles of alkylene oxide followed by carboxymetoxide and ot-sulfobutyric acid with higher C8—C18 alkyl alcohols fol 50 neutralization with base. Preferred alkyl ether methylcar lowed by neutralization with base. Speci?c examples of boxylates are those comprising an average alkyl chain length alkyl ot-sulfomonocarboxylates useful in the present inven of about 10 to about 16 carbon atoms and an average degree tion include sodium methyl ot-sulfolaurate, potassium ethyl of alkoxylation of about 1 to about 15 moles of ethylene Ot-sulfolaurate, sodium methyl ot-sulfomyristate, ammonium oxide, propylene oxide or mixtures thereof. Speci?c ethyl ot-sulfomyristate, sodium decyl ot-sulfobutyrate, 55 examples of alkyl ether methylcarboxylates useful in the sodium dodecyl sulfoacetate, sodium coconut sulfoacetate, present invention include sodium dodecyl ether ammonium dodecyl ot-sulfopropionate and mixtures thereof. methylcarboxylate, sodium dodecyl(ethylene glycol) ether Still another suitable class of anionic surfactant useful in methylcarboxylate, sodium dodecyl(diethylene glycol) ether the present invention are the sodium, potassium and ammo methylcarboxylate, ammonium dodecyl(triethylene glycol) nium salts of alkyl glyceryl sulfates and alkyl glyceryl ether ether methylcarboxylate, sodium tetradecyl(triethylene sulfates having about 8 to about 18 carbon atoms and about glycol) ether methylcarboxylate, sodium tetradecyl(tetra 1 to about 25 moles of alkylene oxide. Alkyl glyceryl ethylene glycol) ether methylcarboxylate, trideceth-7 sulfates and alkyl glyceryl ether sulfates are prepared by carboxylate, laureth—l3 carboxylate and mixtures thereof. sulfation of C$--C18 alkyl monoglycerides, C5-C1‘, dialkyl Still another suitable class of anionic surfactant useful in glycerides, C3—C18 alkyl monoglyceride alkoxylates. fats or 65 the present invention are the sodium, potassium, ammonium oils with sulfuric acid. Suitable examples of fats and oils and alkanolammonium salts of alkyl sarcosinates having include coconut, soya, tallow, castor, corn, cottonseed, palm, about 8 to about 18 carbon atoms. Alkyl sarcosinates are 5,641,480 19 20 generally considered to be acylated amino acid salts pre ethylene or from thermocracking of certain hydrocarbons. pared by amidation of C8—C18 alkyl fatty acids, (Is-C18 alkyl Suitable examples of l-alkenes include l-dodecene, fatty acid esters or Gig-C18 alkyl fatty acid halides with an l-tetradecene and l-hexadecene. The sulfonation of amino acid sarcosine salt. Speci?c examples of alkyl sarco l-allrenes results in a fairly complex mixture of products sinates useful in the present invention include sodium dode comprised of alkene sulfonate, hydroxyalkane sulfonate and cyl sarcosinate, potassium dodecyl sarcosinate, ammonium alkyl disulfonate in a ratio of about (60—70):(20-30):(4—l2) dodecyl sarcosinate, sodium tetradecyl sarcosinate, ammo respectively. Preferred ot-ole?n sulfonates are those com nium tetradecyl sarcosinate, sodium coconut sarcosinate, prising a mixture of individual compounds having an aver ammonium coconut sarcosinate, triethanolarnine oleyl sar age chain length of about 12 to about 16 carbon atoms. Such cosinate and mixtures thereof. Examples of other suitable 10 mixtures can comprise from about 0% to about 30% by acylated amino acid salts useful in the present invention weight C12 ole?n sulfonate, from about 55% to about 75% include the sodium, potassium and ammonium salts of by weight C14 ole?n sulfonate and from about 25% to about C8-C18 alkyl alaninate, C,,—C18 alkyl B-alaninate, C8—C18 45% by weight C1,5 ole?n sulfonate. Speci?c examples of alkyl N-methyl alaninate, C,,—C18 alkyl ot-aminoisobutyrate, ot-ole?n sulfonates useful in the present invention include C8—C18 alkyl ot-aminobutyrate, C3—C8 alkyl sodium C12—C13 ot-ole?n sulfonate, sodium C12—C14 ot-aminocaproicate, C,,—C18 alkyl glycinate, C3-C18 alkyl Ot-ole?n sulfonate, sodium C13-C14 ot-ole?n sulfonate, N-ethyl glycinate, C3-C18 alkyl N-propyl glycinate, C8-C18 sodium C13—C15 ot-ole?n sulfonate, sodium C12—C16 alkyl N-butyl glycinate, C8-C1,3 alkyl leucinate, C8—C18 ot-ole?n sulfonate, potassium C12—C16 ot-ole?n sulfonate, alkyl methioninate, C8—C18 alkyl serinate, C8—C18 alkyl ammonium C12—C16 ot-ole?n sulfonate and mixtures dlnorvalinate, C8—C18 alkyl aspartate, C8—C18 alkyl 20 thereof. Further examples of ot-ole?n sulfonates are glutamate and mixtures thereof. Preferred acylated amino described more fully in US. Pat. No. 3,332,880 which is acid salts useful in the present invention include the sodium, incorporated herein by reference. potassium and ammonium salts of dodecyl, tetradecyl and Apreferred class of anionic surfactant found to be useful coconut glycinate, sarcosinate and mixtures thereof. Besides in the present invention are the sodium, potassium and amidating amino acids salts, mixtures of amino acids or 25 ammonium salts of alkyl sulfates, especially those obtained polypeptides, obtained by hydrolyzing proteins, may be by sulfating higher C8—C18 alkyl alcohols produced natu amidated with C$-C18 alkyl fatty acids, C8-C18 alkyl fatty rally from coconut oil or those prepared synthetically from acid esters or C8-C18 alkyl fatty acid halides. Suitable petroleum sources. Speci?c examples of alkyl sulfates use examples of hydrolyzable proteins include collagen, corn, ful in the present invention include sodium dodecyl sulfate, keratin, silk, soy, scrapleather, wheat gluten and albumin. 30 potassium dodecyl sulfate, ammonium dodecyl sulfate, Preferred polypeptide amino acid salts useful in the present monoethanolammonium dodecyl sulfate, diethanolammo invention include the sodium, potassium and ammonium nium dodecyl sulfate, triethanolammonium dodecyl sulfate, salts of dodecyl, tetradecyl, coconut and oleyl leather sodium tetradecyl sulfate, potassium tetradecyl sulfate, hydrolysate or collagen hydrolysate (animal protein). ammonium tetradecyl sulfate, monoethanolamrnonium tet Yet another suitable class of anionic surfactant useful in 35 radecyl sulfate, triethanolammonium tetradecyl sulfate, the present invention are the sodium, potassium and ammo sodium hexadecyl sulfate, ammonium hexadecyl sulfate, nium salts of alkyl or dialkyl sulfosuccinates and sulfosuc sodium coconut sulfate, sodium C12—C15 alkyl sulfate and cinamates having from ,about 8 to about 18 carbon atoms. mixtures thereof. Alkyl sulfates are sold commercially under Alkyl sulfosuccinates and sulfosuccinamates are prepared several trade names which includes Carsonol ALS and by the reaction of maleic anhydride, maleic and/or fumaric Carsonol DLS, Carsonol SLS and Carsonol sold by Lonza acid with one or two equivalents of an appropriate reactive Inc.; Duponol QC, Duponol D Paste, Duponol EP, Duponol moiety containing a labile hydrogen, followed by sulfona G, Duponol LB Paste and Duponol WA Paste sold by Vidtco tion with sodium bisul?te, sodium sul?te, sodium met Corporation; Rhodapon CAV, Rhodapon L22, Rhodapon abisul?te or analogous type salt. Suitable examples of LSB, Rhodapon LT-6 and Rhodapon TDS sold by Rhone appropriate labile reactants are the C,,—C18 alkyl fatty 45 Poulenc; Standpol A and Standpol DEA sold by Henkel amines, C8-C18 alkyl fatty alcohols, C,;—C18 alkyl fatty Corpoporation; Sulfochem Sulfochem ALS, Sulfochem alcohol alkoxylates, C8—C18 alkyl fatty amides, C8—C18 DLS, SulfochemTLS and Sulfochem SLS sold by Chemron. alkyl fatty alkanolamides and C8--C18 alkyl fatty alkanola Another preferred class of anionic surfactant found to be mide alkoxylates. Preferred are the alkyl sulfosuccinates, most useful in the present invention are the sodium, potas particularly sodium dioctyl sulfosuccinate, disodium dode 50 sium and ammonium salts of alkyl ether sulfates which are cyl sulfosuccinate, diammonium tetradecyl sulfosuccinate, obtained by sulfating the higher C8—C18 alcohol ethoxylates. disodium dodecyl(diethylene glycol) ether sulfosuccinate, Such alcohols are reacted with about 1 to about 25 moles of disodium coconut(t1iethylene glycol) ether sulfosuccinate, alkylene oxide followed by sulfation and neutralization with disodium undecylenamido MEA sulfosuccinate, disodium base. Most highly preferred alkyl ether sulfates useful in the laurethsulfosuccinate, disodium lauramido MEA 55 present invention include those comprising a mixture of sulfosuccinate, disodium cocoamidosulfosuccinate, diso individual compounds having an average chain length of dium cocoamido MIPA sulfosuccinate, disodium oleamido about 10 to about 18 carbon atoms and an average degree of MEA sulfosuccinate, disodium oleamido PEG-2 alkoxylation of about 1 to about 4 moles of ethylene oxide. sulfosuccinate, disodium oleamidosulfosuccinate, disodium Such a mixture can comprise from about 0% to about 50% cocoamido(tetraethylene glycol) ether sulfosuccinate, diso by weight Clo-C11 alkyl ether sulfate, from about 20% to dium ricinoleyl MEA sulfosuccinate and mixtures thereof. about 100% by weight C12 alkyl ether sulfate, from about Yet another suitable class of anionic surfactant useful in 0% to about 80% by weight C13—C14-C15—C16 alkyl ether the present invention are the sodium, potassium and ammo sulfates and from about 0% to about 30% by weight C17-C18 nium salts of ot-ole?n sulfonates having about 8 to about 18 alkyl ether sulfates; and from about 5% to about 90% by carbon atoms. ot-Ole?n sulfonates are prepared by continu 65 weight of compounds having a degree of alkoxylation of 0; ous sulfonation of l-alkenes with liquid or gaseous sulfur from about 7% to about 95% by weight of compounds tn'oxide. The l-alkenes are derived from oligomerization of having a degree of alkoxylation of l to 4; and from about 0% 5,641,480 21 22 to about 35% by weight of compounds having a degree of about 2 to about 60 moles of alkylene oxide, even more alkoxylation greater than 5. Speci?c examples of alkyl ether preferably from about 3 to about 25 moles alkylene oxide. sulfates useful in the present invention include sodium laureth-l sulfate, sodium laureth-2 sulfate, sodium laureth-3 Description of Nonionic Surfactants sulfate, potassium laureth-l sulfate, potassium laureth-2 sulfate, potassium laureth-3 sulfate, ammonium laureth-l The polyoxyalkylene esters of alkyl fatty acids, the poly sulfate, ammonium laureth-2 sulfate, ammonium laureth-3 oxyalkylene alkyl mercaptans, the polyoxyalkylene alkyl sulfate, monoethanolammonium laureth-l sulfate, monoet hanolammonium 1aureth-2 sulfate, monoethanolammonium fatty amides and the polyoxyalkylene alkyl fatty alkanola laureth-3 sulfate, diethanolammonium laureth-l sulfate, mides having an average alkyl chain length of about 8 to diethanolammonium laureth-2 sulfate, diethanolammonium about 18 carbon atoms and from about 3 to about 25 moles laureth-3 sulfate, triethanolammonium laureth-l sulfate, tri of ethylene oxide represent a suitable class of nonionic ethanolammonium laureth-2 sulfate, triethanolammonium surfactant useful in the present invention. Speci?c examples laureth-3 sulfate, sodium myreth-l sulfate, sodium myreth-2 of such surfactants useful in the present invention include sulfate, sodium myreth-3 sulfate, ammonium myreth-l polyoxyethylene (8) lauryl mercaptan, polyoxyethylene (6) sulfate, ammonium myreth-Z sulfate, ammonium myreth-3 lauryl ester, polyoxyethylene (8) lauryl ester, polyoxyethyl sulfate, sodium Clo-C16 alkyl (1) ether surfate, sodium ene (8) myristyl ester, polyoxyethylene (10) myristyl ester, Clo-C16 alkyl (2) ether sulfate, sodium Clo-C16 alkyl (3) polyoxyethylene (14) myristyl ester, polyoxyethylene (15) ether sulfate and mixtures thereof. Alkyl ether sulfates are coconut ester, polyoxyethylene (7) laurylamide, polyoxy sold commercially under several trade names which includes 20 Carson SLES-2 and Carson SES-A sold by Lonza Inc.; ethylene (10) laurylamide, polyoxyethylene (20) Duponol FAS sold by Witco Corporation; Norfox SLES-03 laurylamide, polyoxyethylene (16) myristylamide, polyoxy and Norfox SLES-60 sold by Norma, Fox & Co.; Standpol ethylene (l2) cocoaide, polyoxyethylene (20) cocotrietha EA-l, Standpol EA-2, Standpol EA-3, Standpol EA-40, nolamide and mixtures thereof. Standpol ES-l, Standpol ES-2, Standpol ES-3, Standpol 25 ES-40, Standpol ES-50, Standpol ES-250 and Standpol 350 Another suitable class of nonionic surfactant useful in the sold by Henkel Corporation; Sulfochem EA-l, Sulfochem present invention are the polyoxyalkylene oxide block EA-2, Sulfochem EA-3, Sulfochem EA-60, Sulfochem copolymers such as those obtained by the condensation of EA-70, Sulfochem ES-l, Sulfochem ES-2, Sulfochem ES-3, hydrophilic ethylene oxide with hydrophobic polyoxypro Sulfochem ES-60, Sulfochem ES-70 and Sulfochem K sold pylene glycol. The hydrophobic portion of these compounds by Chemron. preferably has a molecular weight of about 1500 to about 1800 and exhibits water insolubility. The addition of poly Nonionic Surfactants oxyethylene units to this hydrophobic portion tends to Suitable commercial nonionic surfactants are broadly increase the water solubility of the molecule as a whole and exempli?ed as the polyoxyalkylene oxide condensation 35 the liquid character of the product. Preferred surfactancy is products of hydrophobic alkyl, alkene, or alkyl aromatic retained up to the point where the polyoxyethylene content functional groups having a free reactive hydrogen available is from about 10% to about 50% by weight of the total for condensation with hydrophilic alkylene oxide, such as condensation product. This corresponds to condensation of ethylene oxide, propylene oxide, butylene oxide, polyethyl about 4 moles to about 40 moles ethylene oxide. Speci?c ene oxide or polyethylene glycol to form nonionic surfac examples of commercially available polyoxyalkylene oxide tants. Examples of such hydrophobic functional groups block copolymers useful in the present invention include include hydroxy, carboxy, mercapto, amino or amido Pluronic L61, Pluronic L62, Pluronic L62D, Pluronic groups. L62LF, Pluronic L63, Pluronic L64, Pluronic P65, and The overall reaction may be expressed as: Pluronic F68 sold by BASF wherein the pre?xes L, P and F 45 before the numbers represent liquid, paste or ?ake form O respectively. (Pluronic L62D is a low foaming version of Pluronic L62 and Pluronic L62LF is a mixture of 10% Pluronic L61 and 90% Pluronic L62). wherein R13 is a hydrophobic alkene or alkane group having Another suitable class of nonionic surfactant useful in the about 8 to about 18 carbon atoms: R14 is hydrogen or an present invention are the polyoxyalkylene oxide block alkyl group with about 1 to about 2 carbon atoms; 11 is from copolymers such as those obtained by the condensation of about 1 to about 100; X is selected from the group consisting hydrophilic ethylene oxide with hydrophobic polyoxypro of O, C6H4O, C6H3R13O, COO, S, NH, NR15, CONH, pylene ethylenediamine or polyoxypropylene tn'ethylenetet CONRIS, CONR15(CH2)a(NR15)2and COl\IR15(CI*I2),,I\1R15 55 ramine The hydrophobic portion of these compounds pref (CH2)cN(R,5)2; where R15 is selected from the group con sisting of H, (CH2CH2O),,, (CH2CHCH3O)¢and mixtures erably has a molecular weight of about 2500 to about 4500 thereof; a+b+c is from about 1 to about 10; and d+e is from and exhibits water insolubility. The addition of polyoxyeth about 1 to about 100. ylene units to this hydrophobic portion tends to increase the Examples of useful hydrophobes of commercial nonionic water solubility of the molecule as a whole and the liquid surfactants include higher C8—C18 alkyl fatty alcohols, character of the product. Preferred surfactancy is retained up middle C8-C14 alkyl phenols, higher C8—C18 alkyl fatty to the point where the polyoxyethylene content is from about acids, higher C8—C18 alkyl mercaptans, higher C8--C18 alkyl 20% to about 90% by weight of the total condensation fatty amines, higher C8-C1,3 alkyl amides and higher C8—C18 product. Speci?c examples of commercially available alkyl fatty alkanolamides. The polyoxyalkylene oxide con 65 polyoxyethylene-polyoxypropylene ethylenediamines use densate products of such materials may comprise from about ful in the present invention includes Tetronic 702, Tetronic 1 to about 100 moles of alkylene oxide, preferably from 704 and Tetronic 804 sold by BASF having the formula: 5,641,480 23 24 mannitol/mannitan esters, alkyl glucoside esters, glucose esters and sucrose esters. Preferred polyhydroxypolyoxy NCHZCHZN alkylene alkyl esters useful in the present invention include the polyoxyaikylene sorbitan, and mannitan esters having H(0C2H4)>'(oC3H6)x (C3H60)’(CzH40)>~H about 8 to about 18 carbon atoms and about 3 to about 45 moles of ethylene oxide. Speci?c examples of polyoxyalky wherein x is from about 43 to about 78 of a polyoxypropy lene sorbitan and mannitan esters include the Tweens, such lene group, which corresponds to an average molecular as polyoxyethylene (10) sorbitan monolaurate, polyoxyeth weight of about 2500 to about 4500; and y is from about 14 ylene (20) sorbitan monolaurate, polyoxyethylene (44) sor to about 920 of a polyoxyethylene group, which corresponds 10 bitan monolaurate, polyoxyethylene (20) monopalmitate, to an average molecular weight of about 625 to about 40,500 polyoxyethylene (20) sorbitan monostearate, polyoxyethyl or about 20% to about 90% by weight of the total product. ene (10) sorbitan monococoate, polyoxyethylene (20) sor Still another suitable class of nonionic surfactant useful in bitan monococoate, polyoxyethylene (30) mannitan dilau the present invention are the alkylmonoglycosides and alky rate and mixtures thereof. lpolyglycosides as those disclosed in US Pat. No. 4,565, Still another suitable class of nonionic suifactant useful in _ 647 having the formula R160 (CnHznO)x(glycosyl)y wherein the present invention are the amine oxides of the formula: R16 is selected from the group consisting of alkyl, alkene, alkylphenyl, hydroxyalkyl, hydroxyalkylphenyl and mix tures thereof containing from about 8 to about 18 carbon wherein R17 is alkyl, alkene, hydroxyaikyl, acylamidopropyl atoms; preferably containing from about 10 to about 16 20 and alkylphenyl group or mixtures thereof, containing about carbon atoms: 11 is 2 or 3, preferably 11 is 2; x is from about 8 to about 18 carbon atoms, preferably from about 10 to 0 to about 15, preferably x is 0; and y is from about 1 to about 16 carbon atoms; R18 is an alkylene or hydroxyalky about 8, preferably y is from about 1.1 to about 5, most lene group containing from about 2 to about 3 carbon atoms, preferably y is from about 1.2 to about 2.5. The glycosyl preferably 2 carbon atoms; x is from about 0 to about 3, group may be derived from glucose, galactose, lactose, 25 preferably x is 0; and each R19 is an alkyl or hydroxyalkyl maltose, sucrose, starch, cellulose, fructose and mixtures group containing from about 1 to about 3 carbon atoms, thereof; preferably, however, the glycosyl is derived from preferably from about 1 to about 2 carbon atoms, or a high dextrose corn syrup, glucose or starch. Alkylpolygly polyoxyethylene group having about 1 to about 3 moles of cosides are prepared by the reaction of C8-C18 alkyl alco ethylene oxide, preferably from about 1 mole of ethylene hols or C8—C18 alkylpolyoxyalkyleue alcohols with glucose 30 oxide. The R19 group can also be attached to each other e.g., or a source of glucose at the anomeric position (carbon 1 through an oxygen or nitrogen atom to form a ring structure. hydroxyl group position) to form a glycoside. Additional Speci?c examples of amine oxides useful in the present glycosyl units can then be attached to the 2, 3, 4, and/or 6 invention include dimethyloctylamine oxide, diethyldecy hydroxyl group position of the newly formed glycoside to lamine oxide, dimethyldodecylamine oxide, diethyldodecy produce an alkylpolyglycoside. Optionally and less desir 35 lamine oxide, dimethyltetradecylarnine oxide, dimethyl ably the alkylpolyglycoside may be alkoxylated with alky Alfol 1214 amine oxide, methylethylhexadecylamine oxide, lene oxide to form a polyoxyalkylene alkylpolyglycoside diethyloctadecylamine oxide, dimethylcocoamine oxide, with about 8 to about 18 carbon atoms and about 1 to about dimethyl-2-hydroxydodecylamine oxide, bis(2 100 moles of ethylene oxide, preferably from about 2 to hydroxyethy1)dodecylamine oxide, bis(2-hydroxyethyl) about 7 moles of ethylene oxide. Speci?c examples of 40 cocoamine oxide, bis(2-hydroxyethyl)oleylarnine oxide, bis alkylmonoglycosides useful in the present invention include (2-hydroxyethyl) C12—C15 alkoxypropylamine oxide, dodecyl glucoside, tetradecyl glucoside and coconut gluco dimethyldodecyloxyethylamine oxide, dodecylarnidopropy side. Speci?c examples of alkylpolyglycosides useful in the ldimethylarnine oxide, tetradecylamidopropyldimethylaine present invention include dodecyl polyglucoside with a oxide, cocoarnidopropyldimethylamine oxide and mixtures degree of polymerization of 1.2, dodecyl polyglucoside with 45 thereof. Preferred amine oxide are the Clo-C18 alkyldim a degree of polymerization of 1.3, dodecyl polyglucoside ethylarnine oxides and the Clo-C18 acylamidoalkyldimethy with a degree of polymerization of 1.5, tetradecyl polyglu lamine oxides. coside with a degree of polymerization of 1.2, tetradecyl Still another suitable class of nonionic surfactant useful in polyglucoside with a degree of polymerization of 1.4, tet the present invention are the polyhydroxy fatty acid amides radecyl polyglucoside with a degree of polymerization of 50 of the formula: 1.6, Clo-C16 alkyl polyglucoside with a degree of polymer ization of 1.2, Clo-C16 alkyl polyglucoside with a degree of polymerization of 1.4, coconut polyglucoside with a degree of polymerization of 1.2, coconut polyglucoside with a degree of polymerization of 1.3, coconut polyglucoside with 55 R20 a degree of polymerization of 1.5, coconut polyglucoside with a degree of polymerization of 2.1 and mixtures thereof. wherein R20 is H, a C1-C4 alkyl, 2-hydroxyethyl, Still another suitable class of nonionic surfactant useful in 2-hydroxypropyl group or mixtures thereof, preferably R20 the present invention are the alkene oxide condensation is methyl; and R21 is a straight or branched chain C5-C131 products of polyhydroxyalkyl esters having about 8 to about alkyl, alkenyl, alkylphenyl, hydroxyalkyl, hydroxyalkylphe 18 carbon atoms and about 1 to about 100 moles of ethylene nyl group, preferably a straight chain C9-C1‘7 alkyl or alkene oxide, preferably from about 3 to about 45 moles of ethylene group; and Z is a polyhydroxy group containing at least 2 oxide. Examples of polyhydroxyalkyl esters include those hydroxyl groups or an alkoxylated derivative thereof having about 2 to about 7 hydroxyl groups per alkyl chain (preferably an ethoxylated or propoxylated derivative). Z such as ethylene glycol esters. propylene glycol esters, 65 may be derived from a reducing sugar in a reductive glycerol esters, polyglycerol esters, erythritol esters, xylitol amination reaction and is preferably a glycityl. Examples of esters, pentaerythritol esters, sorbitol/sorbitan esters, suitable reducing sugars include glucose, fructose, sucrose, 5,641,480 25 26 maltose, lactose, galactose, mannose, xylose, starch and galactose, mannose, xylose, starch and cellulose. As for cellulose. As for commercial raw materials, high dextrose commercial raw materials, high dextrose corn syrup, high corn syrup, high fructose corn syrup and high maltose corn fructose corn syrup and high maltose corn syrup can be syrup can be utilized and may be preferred in some cases utilized and may be preferred in some cases over the over the individual sugar components. Z may be selected individual sugar components. Examples of ZOR23 include from the group consisting of HOCH2(CHOH),,CH2—or methyl glucoside. ethyl glucoside, hydroxyethyl glucoside, HOCH2(CHOH)CHOR22(CHOH)2CH2—where n is an methyl galactoside, methyl fructoside, ethyl fructoside, integer from about 2 to about 6, inclusive, and R22 is H or methyl lactoside and ethyl sucroside.Alky1 glycoside esters a cyclic or aliphatic monosaccharide. Most preferred are are prepared by enzymatic esteri?cation of C8-C18 fatty glycityls wherein n is 4, particularly HOCH2(CHOH) acids or by alkaline transesteri?cation of C8—C18 fatty acid 4CH2-—. Examples of R1,0 include N-methyl, N-ethyl, esters/triglycerides with alkyl glycosides such as methyl or N-propyl, N-isopropyl, N-butyl, N-2-hydroxyethyl and N-2 ethyl glucoside at elevated temperature. The alkyl glycoside esters may also be ethoxylated or propoxylated with about 1 hydroxypropyl. Examples of >NCOR21 include lauramide, to about 150 moles of ethylene oxide. propylene oxide or myristamide, palmitamide, stearamide, oleamide, cocoarn mixtures thereof. Speci?c examples of alkyl glycoside esters ide and tallowamide. Examples of Z include useful in the present invention include methyl glucoside l-deoxyglucityl, 2-deoxyfructityl, l-deoxymaltityl, monococoate, ethyl glucoside monolaurate, ethyl glucoside l-deoxylactityl, l-deoxygalactityl, l-deoxymannityl and monomyristrate, ethyl glucoside monococoate, ethyl glu l-deoxymaltotriotityl. Optionally the polyhydroxy fatty acid cose sesquicocoate, ethyl glucose dicocoate, methyl fructo aide may be alkoxylated with alkylene oxide to form a side monococoate, methyl lactoside monococoate, methyl polyoxyalkylene polyhydroxy fatty acid aide with about 8 to sucroside monococoate, sucrose cocoate, methyl gluceth-20 about 18 carbon atoms and about 1 to about 100 moles of sesquistearate, PEG-120 methyl glucose dioleate, methyl ethylene oxide, preferably from about 2 to about 7 moles of gluceth-10, methyl gluceth-20 and mixtures thereof. ethylene oxide. Methods for making polyhydroxy fatty acid Apreferred class of nonionic surfactant found to be useful aides are known in the art. In general, they are prepared by in the present invention are the polyoxyalkylene alkyl alco the reaction of an alkyl amine with a reducing sugar fol 25 hols having about 8 to about 18 carbon atoms in either lowed by reductive amination to form the corresponding branched or preferably straight chain con?guration and N-alkyl polyhydroxyarnine, which is then reacted with a about 1 to about 100 moles of ethylene oxide. Particularly fatty aliphatic ester or triglyceride in a condensation] preferred are the condensation products of alcohols having arnidation step to form the ?nal N-alkyl N-polyhydroxy fatty an alkyl group containing about 10 to about 16 carbon atoms acid aide product. Processes for making polyhydroxy fatty with from about 3 to about 45 moles of ethylene oxide per acid aides are disclosed in for example, US. Pat. No. mole of alcohol. Speci?c examples of commercially avail 1,985,424 to Piggott, US. Pat. No. 2,703,798 to Schwartz able nonionic surfactants of this type include Tergitol 15 -S-9 and U.S. Pat. No. 2,965,576 to Wilson all of which are (the condensation product of C11—C 15 linear secondary alco incorporated herein by reference. hol with 9 moles of ethylene oxide and a narrow molecular Yet another suitable class of nonionic surfactant useful in 35 weight distribution) and Tergitol 24-L-6NMW (the conden the present invention are the non-heteroatom containing sation product of C12—C14 primary alcohol with 6 moles of alkyl aldonarnides and aldobionamides having about 8 to ethylene oxide) both sold by Union Carbide Corporation; about 18 carbon atoms. Alkyl aldonamides and aldobiona Neodol 45-7 (the condensation product of CM-C15 linear mides are prepared by the reaction of an aldonic acid, alcohol with 7 moles of ethylene oxide), Neodol 45-9 (the aldobionic acid, aldonolactone or aldobionolactone with a condensation product of C14-C15 linear alcohol with 9 non-heteroatom containing alkyl amine such as decylamine, moles of ethylene oxide), Neodol 23-65 (the condensation dodecylamine, tetradecylamine, hexadecylamine, product of C12—Cl3 linear alcohol with 6.5 moles of ethyl octadecylamine, oleylarnine and cocoarnine in an organic ene oxide), Neodol 45-4 (the condensation product of solvent. Speci?c examples of alkyl aldonamides and aldo C14—C15 linear alcohol with 4 moles of ethylene oxide), bionamides useful in the present invention include dodecyl 45 Neodol 25-7 (the condensation product of C12-C15 linear gluconamide, tetradecyl gluconarnide, coco gluconamide, alcohol with 7 moles of ethylene oxide and Neodol 25-9 (the coco glucoheptonamide, decyl lactobionamide, dodecyl condensation product of C12-C15 linear alcohol with 9 lactobionamide, tetradecyl lactobionamide, hexadecyl moles of ethylene oxide) all sold by Shell Chemical Com lactobionamide, octadecyl lactobionamide, oleyl pany. The CI‘FA adopted name for this class of nonionic lactobionamide, coco lactobionamide, coco maltobionamide surfactant is laureth-x (PEG-x lauryl ether), isolaureth-x and mixtures thereof. (PEG-x isolauryl ether), myreth-x (PEG-x myristyl ether), Yet another suitable class of nonionic surfactant useful in ceteth-x (PEG-x cetyl ether), steareth-x (PEG-x stearyl the present invention are the alkyl glycoside esters having ether), oleth-x (PEG-x oleyl ether), cetoleth-x (PEG-x cetyl/ the formula: oleyl ether) and ceteareth-x (PEG-x cethyl/stearyl ether) 55 wherein x is about 1 to about 60 and represents the degree of ethoxyltion. Preferred are laureth-4 through 25, myreth-4 through 10, ceteth-5 through 30 and stearth-3 through 40. Another preferred class of nonionic surfactant found to be useful in the present invention are the polyoxyalkylene wherein R73 is H, a Cl-C6 alkyl, hydroxyethyl or hydrox alkylphenols having about 8 to about 14 carbon atoms in ypropyl group; preferably R23 is methyl or ethyl; n is from either branched or preferably straight chain con?guration about 1 to about 3; R24 is a straight or branched chain alkyl, and about 1 to about 100 moles of ethylene oxide, preferably alkene, alkylphenyl, hydroxyalkyl, hydroxyalkylphenyl from about 5 to about 23 moles of ethylene oxide. Speci?c group having about 7 to about 17 carbon atoms and ZOR23 examples of commercially available nonionic surfactants of is a polyhydroxy sugar group derived from the glycosidation 65 this type include Igepal CO-610 (the condensation product of reducing sugars. Examples of suitable reducing sugars of nonylphenol with about 7 to about 8.5 moles of ethylene include glucose, fructose, sucrose, maltose, lactose, oxide), Igepal CO-630 (the condensation product of non 5,641,480 27 28 ylphenol with 9 moles of ethylene oxide), Igepal RC-620 cocoamphopropionate , cocoamphoglycinate, (the condensation product of dodecylphenol with about 10 cocoamphocarboxyglycinate, cocoamphopropylsulfonate, moles of ethylene oxide, Igepal RC-630 (the condensation cocoamphocarboxypropionic acid and mixtures thereof. The product of dodecylphenol with about 12 moles of ethylene CTFA adopted name for this class of arnphoteric surfactant oxide), Igepal DM-710 (the condensation product of is amphoteric-l through 20. Preferred are amphoteric-l, dinonylphenol with about 15 moles of ethylene oxide) all amphoteric-2, arnphoteric-6, amphoteric-lO, arnphoteric- 12, sold by GAF Corporation and Triton X-114 (the condensa amphoteric- 1 7 , amphoteric- 1 8 , amphoteri c- 1 9 and tion product of octylphenol with about 7 to about 8 moles of amphoteric-ZO. ethylene oxide), Triton X-100 (the condensation product of octylphenol with about 9 to about 10 moles of ethylene 10 Zwitterionic Surfactants oxide) and Triton X-l02 (the condensation product of octylphenol with about 12 to about 13 moles of ethylene Suitable zwitterionic surfactants are exempli?ed as those oxide) all sold by Rohm & Haas Company. The CTFA which can be broadly described as derivatives of aliphatic adopted name for this class of nonionic surfactant is quaternary ammonium, sulfonium and phosphoniurn com pounds with one long chain group having about 8 to about octoxynol, nonoxynol and dodoxynol. Preferred are 15 octoxynol-S through 20, nonoxynol-S through 23 and 18 carbon atoms and at least one water solubilizing radical dodoxynol-S through 12. selected from the group consisting of sulfate, sulfonate, carboxylate, phosphate or phosphonate. A general formula Amphoteric Surfactants for these compounds is: There are two classes of amphoteric surfactant; those that are pH sensitive (arnphoteric) and those that are pH insen sitive (zwitterionic). wherein R25 contains an alkyl, alkene or hydroxyalkyl group Suitable amphoteric surfactants are exempli?ed as those With about 8 to about 18 carbon atoms, from about 0 to about which can be broadly classi?ed as derivatives of aliphatic 10 moles of ethylene oxide and from about 0 to about 2 secondary and tertiary amines which contain a quaternary 25 glyceryl units; Y is a nitrogen, sulfur or phosphorous atom; ammonium or non-quaternary ammonium group and one R26 is an alkyl or hydroxyalkyl group with about 1 to about long chained alkyl or alkene group having about 8 to about 3 carbon atoms; x is 1 when Y is a sulfur atom and 2 when 18 carbon atoms and at least water solubilizing radical Y is a nitrogen or phosphorous atom; R27 is an alkyl or selected from the group consisting of sulfates, sulfonates, hydroxyalkyl group with about 1 to about 5 carbon atoms carboxylates, phosphates or phosphonates. 30 andZ is radical selected from the group consisting of sulfate, Examples of such amphoteric surfactants include the sulfonate, carboxylate, phosphate or phosphonate. Examples N-alkyl B-amino propionates, such as sodium(dodecyl of such zwitterionic surfactants include the sulfatobetaines, [5-amino)propionate (sodium laurarninopropionate), dietha such as 3-(dodecyldimethylarnmonio)- l-propane sulfate and nolamine laurarninopropionate and sodium cocoaminopro 2-(cocodimethylammonio)-l-ethane sulfate; the pionate; the N-alkyl ?-imino dipropionates, such as 35 sulfobetaines, such as 3-(dodecyldimethylammonio)-2 disodium(dodecyl B-imino)dipropionate (sodium hydroxy-l-propane sulfonate, laurirninodipropionate) and cocoirninodipropionate; the 3-(tetradecyldimethylammonio)-l-propane sulfonate, alkyl taurinates, such as monoethanolammonium coconut 3 -( C 12-C14 alkylamidopropyldimethylammoni o)-2 taminate as taught in U.S. Pat. No. 2,658,072 which is hydroxy- l-propane sulfonate, 3-(cocodimethylammonio)-1 incorporated herein by reference and the derivatives derived propane sulfonate; the carboxybetaine such as from 2-alkyl-2-imidazoline, such as those sold under the (dodecyldimethylammonio)acetate (lauryl betaine), trade name Miranol as taught in U.S. Pat. Nos. 2,528,378, (tetradecyldimethylammonio)acetate (myristyl betaine), 2,773,068, 2,781,354 and 2,781,357 all of which are incor (cocodimethylammonio)acetate (coconut betaine), porated herein by reference. The amphoteric imidazoline (oleyldimethylammonio)acetate (oleyl betaine), derived surfactants are a preferred class of amphoteric 45 (do decyloxymethyldimethylammonio)acetate, surfactant and are prepared by condensing (tetradecyloxyhydroxylpropyldimethylammonio)acetate, aminoethylethanolamine, diethylenetriamine or ethylenedi [cocodi(polyethoxyethanol)ammonio] acetate, amine with a fatty acid having about 8 to about 18 carbon (dodecyldimethylammonio)propionate, atoms to form a ?ve-membered imidazoline ring which may (dodecylamidopropyldimethylammonio)acetate, be ionized by an anionizable alkylating agent such as 50 (cocoamidopropyldimethylammonio)acetate (also known as sodium chloroacetate, methyl or ethyl acrylate, acrylic acid, cocoamidopropyl betaine); the sulfoniobetaines such as 2-hydroxy-1,3-propane sultone, 3-chloro-2-hydroxypropane (dodecyldimethylsulfonio)acetate and sulfonic acid and 1,3-propane suitone on or near the cyclic 3-(cocodimethylsulfonio)- l-propane sulfonate and the phos portion or cationic portion of the molecule. Alkylations may phoniobetaines such as 4-(trimethylphosphonio)-1 be done with or without solvent or in aqueous solution. In 55 hexadecane sulfonate 3-(dodecyldimethylphosphonio)-l aqueous solution, the imidazoline ring may be hydrolytically propanesulfonate, 2-dodecyldimethylphosphonio)-l-ethane opened to form a mixture of imidazoline and linear amide. sul?te and mixtures thereof. Speci?c examples of amphoteric imidazoline-derived sur Means for preparing many of the surfactant compounds of factants useful in the present invention include this class are described in U.S. Pat. Nos. 2,129,264, 2,697, lauroamphocarboxypropionate, lauroamphopropionate, 656, 2,774,786, 2,813,898, 2,828,332, 3,265,719, 3,529,521 lauroamphoglycinate, lauroamphocarboxyglycinate, and German Pat. No. 1,018,421, all of which are incorpo lauroamphopropylsulfonate, lauroamphocarboxypropionic rated herein by reference. acid, myristoamphocarboxypropionate, Of all the above described types of zwitterionic myristoamphopropionate, myristoamphoglycinate, surfactants, preferred compounds include the sulfobetaines myristoamphocarboxyglycinate, 65 such as 3-(cocodimethylammonio)-l-propanesulfonate, myristoamphopropylsulfonate, myristoarnphocarboxypropi 3-(cocodimethylammonio)-2-hydroxy-l-propanesulfonate onic acid, cocoamphocarboxypropionate, and the carboxybetaines such as (cocodimethylammonio) 5,641,480 29 30 acetate, (dodecylamidopropylammonio)acetate and Hair Conditioning Agents (cocoamidopropylammonio)acetate (cocoamidopropyl Various materials have been taught in the art for use as betaine). agents that condition the hair. In general, such conditioning Cationic Surfactants agents are designed to enhance fullness, body, manageability, softness, luster and overall attractive appear Cationic surfactants have been taught in the art as con ance and handling properties of the hair. Examples of such ditioning agents for the hair. Suitable cationic surfactants are conditioning agents include, lanolin and its derivatives, long broadly exempli?ed as those of the general formula: chain esters such as isopropyl myristate, butyl palmitate, stearyl stearate, carylic/capric triglycerides, polyols such as 10 glycerol (glycerin), propylene glycol and the like, oils, wherein R28 contains an alkyl, alkene or alkylphenyl group amine oxides, fatty alcohols, carbohydrates, fatty acids, with about 10 to about 24 carbon atoms; R29, R30 and R31 alkyl pyrrolidones, polyvinylpyrrolidone (PVP), sodium contains an alkyl, alkene or alkylphenyl group with about 10 PCA, vitamins, amino acids, silicones and certain cationic surfactants. It is to be understood that any such conditioning to about 24 carbon atoms, or an alkyl or alkylhydroxy group 15 with about 1 to about 5 carbon atoms; and A- can be any salt agent can be employed herein, depending on the formula forming anion such as halide, hydroxide, sulfate, carbonate tions desires, however, the silicones and cationics are par and phosphate. ticularly preferred. Examples of such cationic surfactants include myristylt Suitable non-volatile silicone ?uids are exempli?ed as rimethyl ammonium chloride, cetyltrimethylammonium 20 polyalkylsiloxane, polyarylsiloxane, polyalkylarylsiloxane chloride, stearyltrimethylammonium chloride, oleyltrim and polyethersiloxane copolymers which are present at ethylammonium chloride, tallowtrimethylammonium about 0% to about 10%, preferably from about 0% to about chloride, dimyristyldimethylammonium chloride, dice 8%, even more preferably from about 0% to about 6% by tyldimethylammonium chloride, distearyldimethylammo weight of the composition. Mixtures of these ?uids may also nium chloride, distearyldiethylammonium bromide, dioley 25 be used and are preferred in certain executions. The silicone ldimethylammonium chloride, ditallowdimethylammonium ?uid should be insoluble in the shampoo matrix and present chloride, stearyldimethylbenzyl ammonium chloride as a dispersion. (stearalkonium chloride), PPG-9 diethylmonium chloride, Examples of non-volatile polyalkylsiloxane ?uids useful PPG-25 diethylmonium chloride, PPG-40 diethylmonium in the present invention include, for example, the polydim chloride, tritnyristylmethyl armnonium chloride, tricetylm 30 ethylsiloxanes having viscosities from about 5 to about ethylammonium chloride, tristearylmethylammonium 600,000 centistokes at 25 ° C., preferably from about 350 to chloride, bishydroxyethyl dihydroxypropyl steramonium about 100,000 centistokes at 25° C. chloride, gaur hydroxypropyltrimonium chloride, benzyl Examples of non-volatile polyalkylarylsiloxane ?uids trimethylammonium hydrolyzed animal protein or mixtures useful in the present invention include, for example, the thereof. The CI'FA adopted name for this class of cationic 35 polymethylphenylsiloxanes having viscosities from about surfactant is quaternium. Preferred cationic surfactants are 15 to about 30,000 centistokes at 25° C. quaternium-l through 84, most preferably quaternium-6, Examples of non-volatile polyethersiloxane copolymer quaternium-l6, quaternium-l9, quaternium-20, quaternium ?uids useful in the present invention include, for example, 22, quaternium-23, quaternium-26, quaternium-32, the polyethylene oxide modi?ed dimethylpolysiloxanes quaternium-33, quaternium-41, quaternium-60 and (dimethicone copolyol), polypropylene oxide modi?ed dim quaternium-70. The polymeric cationic surfactants such as ethylpolysiloxanes and polyethylene oxide/polypropylene polyquaternium-l through 39 are useful as well, preferably polyquaternium-7, polyquaternium-8, polyquaternium-lO, oxide modi?ed dimethylpolysiloxanes and mixtures thereof. and polyquaternium-ll. Other silicone materials useful in the present composi tions are the silicone gums as described in U.S. Pat. No. Many additional non-soap surfactants are described in 45 McCutcheon’s Detergents and Emulsi?ers (Vol. 1) and 4,152,416 and in Chemistry and Technology of Silicones McCutcheon’s Functional Materials (Vol. 2), 1992 Annual, published by Academic Press (1968) both of which are published by MC Publishing Co. as well as the CI‘FA incorporated herein by reference. Silicone gums are gener (Cosmetic, Toiletry and Fragrance Association) 1992 Inter ally high molecular weight polydiorganosiloxanes having a mean molecular weight from about 200,000 to about 1,000, national Buyers Guide, published by CI‘FA Publications and 50 OPD 1993 Chemical Buyers Directory 80th Annual Edition, 000. Speci?c examples of silicone gums include published by Schnell Publishing Co. which are all incorpo polydimethylsiloxane, (polydimethylsiloxane) rated herein by reference. (methylvinylsiloxane) copolymer, poly The above mentioned cosurfactants (anionic, nonionic, (dimethylsiloxanediphenyl)(methylvinylsiloxane) copoly mer and mixtures thereof. References that describe suitable amphoteric, zwitterionic, cationic surfactant and mixtures 55 thereof) are used in combination with the heteroatom con silicone ?uids include U.S. Pat. Nos. 2,826,551, 3,964,500, taining alkyl aldonamides in hair care compositions of the 4,364,837, British Pat. No. 849,433 and Silicon Compounds present invention. The anionic surfactants, particularly the distributed by Petrarch Systems, Inc. all of which are alkyl sulfates and the alkyl ether sulfates, the nonionic incorporated herein by reference. surfactants, particularly the alkyl polyoxyalkylene sorbitan The silicone ?uids are present from about 0% to about esters and the alkyl polyglycosides, and the amphoteric 10%, preferably ?om about 0% to about 8%, even more surfactants particularly, the alkyl carboxybetaines are pre preferably from about 0% to about by weight of the com ferred for use herein. position. Typical levels of cosurfactant are from about 0% to about Auxiliary Thickening Agents 45%, preferably from about 0.1% to about 40%, even more 65 preferably from about 0.2% to about 35% by weight of the Various materials have been taught in the art as auxiliary composition. thickening agents that are useful in combination with het 5,641,480 31 32 eroatom containing alkyl aldonamide compounds of the Examples of traditional antidandrulf agents include present invention for enhancing viscosity and rendering the menthol, sulfur, salicylic acid, piroctone olamine composition more acceptable. (octopirox), hexachlorophene, resorcinol, coal tar coal, tar Examples of common thickening agents include fumed extract, coal tar solution and certain cationics such as silica, bentonite (hydrated aluminum silicone dioxide), PEG cetyldimethylbenzylammonium bromide. Currently 55 propylene glycol oleate, PEG 6000 distearate, cellulose however, most authorities in this area recognize that anti gum, hydroxypropyl cellulose, hydroxyethyl cellulose, dandruif agents based on pyridinethione salts, piroctone hydroxypropyl methyl cellulose, sodium carboxymethyl olamine or selenium sul?de are most effective against cellulose, carrageenan, veegum (magnesium aluminum dandruff, and such materials are preferred. It should be silicate), xanthan gum, gaur hydroxypropyltrimonium 10 understood that any such antidandruff agent can be chloride, gaur gum, pectin, amine oxides, glucose glutmate, employed herein, depending on the formulators desires, stearamidopropyldimethylamine lactate and the alkanola however, the pyridinethione salts are most especially pre mides. ferred. The pyridinethione salts are based on suitable heavy Examples of another type of thickening agent (gelling metals such as in zinc, cadmium, magnesium, tin, aluminum agent/viscosity control agent) found to be useful in the 15 and zirconium, however, zinc as in zinc pyridinethione (zinc present invention include the poly(oxyethylene)-poly pyrithione) is highly preferred. The use of pyridinethione (oxypropylene) block copolymers such as poloxamer 101 salts as antidandruif agents in shampoos and hair rinses are through 941 sold by BASF, ICIAmericas and Hodag. Of this class of thickening agent, poloxamer 101, poloxamer 182, disclosed in the U.S. Pat. Nos. 2,809,971, 3,236,733, 3,723, poloxamer 238, poloxamer 934 and poloxamer 941 and 325, 3, 753,916, 3,761,417 and 3,761,418 all of which are mixtures thereof are preferred and poloxamer 188, polox incorporated herein by reference. amer 237, poloxamer 338, poloxamer 407 and mixtures 'Iypical levels of antidandruff agent are from about 0% to thereof are highly preferred. The poly(oxyethylene)-poly about 8%, preferably from about 0% to about 6%, even more (oxypropylene) block polymers are of the formula: preferably from about 0% to about 4% by weight of the composition. Mixtures of antidandru?’ agents can also be 25 used. Suspending Agents Various materials have been taught in the art as agents that wherein: are useful in suspending certain performance ingredients X=75 and Y=30 for poloxamer 188 30 such as zinc pyridinethione platelets, silicone ?uids, and the X=62 and Y=39 for poloxamer 237 like, uniformly, thereby assisting in the delivery of the desirable performance attributes associated with these ingre X=128 and Y=54 for poloxamer 338 dients. The suspending agent useful in the present invention X=98 and Y=67 for poloxamer 407 can be any of several long chain acyl derivatives or mixtures These products are complex mixtures of copolymer pro 35 thereof. Included are the glycol mono-, di- and tiiesters duced in a Wide range of molecular Weights (l,100—l4,000) having about 14 to about 22 carbon atoms. Preferred glycol with varying degrees of ethylene oxide and propylene oxide. esters include the ethylene glycol mono- and distearates, The block polymers are prepared by polymerizing propylene glyceryl stearates, palm 01f glyceride, tripalmitin, tristearin oxide in a controlled fashion to give a desired weight and mixtures thereof. followed by ethoxylation with ethylene oxide. The ethoxy Another example of a suspending agent useful in the lated portions of the block polymer can provide from about present invention include the alkanolamides having from 10% to about 80% by weight of the ?nal product. about 14 to about 22 carbon atoms. Preferred alkanolamides Preferred thickeners are the alkanolamides which are are stearic monoethanolamide, steric diethanolamide, stearic prepared by the reaction of a C,;—C18 alkyl fatty acid, C8—C18 monoisopropanolamide, stearic monoethanolamide stearate alkyl fatty acid ester or C8—C18 alkyl fatty acid halide with and mixtures thereof. a hydroxyl alkylamine such as monoethanolamine or dietha 45 nolarnine. Suitable examples of alkanolamides useful as Still another example of a suspending agent useful in the auxiliary thickening agents include lauric present invention include the long chain fatty acid esters such as stearyl stearate, stearyl palmirate and palmityl monoethanolamide, lauric diethanolamide, myristic palmirate. monoethanolamide, myristic diethanolamide, coco monoethanolamide, coco diethanolamide, palmitic 50 Still another example of a suitable suspending agent monoethanolamide, linoleic monoethanolamide, linoleic useful in the present invention include the long chain amine diethanolamide, hydroxystearyl monoethanolamide, almond oxides having from about 14 to about 22 carbon atoms. diethanolamide, palm kernel diethanolamide, oleic monoet Preferred mine oxides are hexadecyldimethylamine oxide hanolamide and mixtures thereof. Most highly preferred and octadecyldimethylamide oxide. auxiliary thickening agent useful in the present invention 55 Yet another example of a suitable suspending agent (or include are lauric monoethanolamide (lauramide MEA), thickening agent) useful in the present invention include the lauric diethanolamide (lauramide DEA), coco monoethano carbohydrate gums such as cellulose gum, microcrystalline lamide (cocoamide MBA) and coco diethanolamide cellulose, cellulose gel, hydroxyethyl cellulose, hydroxypro (cocoamide DEA) which may be present from about 0% to pyl cellulose, sodium carboxymethylcellulose, hydroxym about 10%, preferably at about 0% to about 8%, even more ethyl carboxymethyl cellulose, hydroxymethyl carboxypro preferably from about 0% to about 6% by weight of the pyl cellulose, methyl cellulose, ethyl cellulose, guar gum, composition. gum karaya, gmn tragacanth, gum arabic, gum acacia, gum agar, xanthan gum and mixtures thereof. Preferred carbo Antidandruff Agents hydrate gums are the cellulose gums and xanthan gum. Various materials have been taught in the art as agents that 65 Of all the above described types of suspending agents, are useful in removing or preventing the fonnation of a preferred compounds include the long chain glycol esters ?aky, itchy condition generally known as dandruff. and the carbohydrate gums. 5,641 ,480 33 34 The suspending agent or mixtures of agent may be present the formulators desires. Typical levels of salt used to control from about 0% to about 7%, preferably from about 0% to composition viscosity are from about 0. 1% to about 10% by about 5%, even more preferably from about 0% to about 4% weight of the composition. by weight of the composition. Examples of emulsi?ers/emollients (refattying agents) or dispersants useful in the present invention which condition Water the hair and scalp and assist in the ease of combing, Water is the last essential component of the present detangling, body, shine, manageability, split-end mending invention and forms the remainder of the composition. and prevent static build-up include dimethicone, cyclomethicone, amodimethicone, lanolin oil, lanolin fatty Water is generally present from about 1% to about 95%, 10 acid, lanolin alcohol, acetylated lanolin alcohol, acetylated preferably ?om about 45% to about 90%. alkoxylated lanolin such as laneth-9 acetate and laneth-lO Optional Ingredients (Auxilary Agents) acetate, alkoxylated lanolin having about 30 to about 75 moles of ethylene oxide or propylene oxide such as PEG-l6 The shampoos herein can contain a variety of less essen lanolin, PEG-27 lanolin, PEG-40 lanolin, PEG-75 lanolin tial optional ingredients (auxilary agents) suitable for ren and PPG-l2-PEG-50 lanolin, long chain esters such as cetyl dering such compositions more acceptable. Such ingredients acetate, stearyl acetate, oleyl acetate, lauryl lactate, myristyl are well known to those skilled in the art and include, but are lactate, cetyl lactate, stearyl lactate, decyl neopentanoate, not limited to, hair styling agents, viscosity control agents, decyl oleate, isopropyl myristate, lauryl myristate, myristyl emulsi?ers/emollients, dispersants, conditioning emollient myristate, myreth-3-myristate, palmityl myristate, stearyl oils, conditioning extracts, humectants. solubilizing/ my1istate,isopropylpalmitate, octyl palrnitate, 2-ethylhexyl clarifying agents, stabilizers, sun-screens/UV absorbers, palmirate, lauryl palmirate, myristyl palrnitate, palmityl opaci?ers/pearlescent agents, vitamins amino acids, palmirate, stearyl palrnitate, butyl stearate, myristyl stearate, proteins, curl enhancing agents, hair coloring agents, palmityl stearate, isocetyl stearate, isostearyl isostearate, chelating/sequestering agents, hydrotropes, anti-lice agents, myristyl alcohol, cetyl alcohol, isocetyl alcohol, stearyl hair straightening agents, preservatives/antimicrobial 25 alcohol, oleyl alcohol, dioctyl succinate, didecyl succinate, agents, bactericides/fungicides, antioxidants, brightening caprylic/capric triglycerides, ethoxylated cholesterol, PEG agents (bleaches), pH control agents, buffering agents, colo 16 soya sterol, and mixtures thereof. Typical levels of rants and perfumes/fragrances. These ingredients, when emulsi?er or emollient are from about 0% to about 10% by used, are added at their usual levels, each generally up to weight of the composition. about 10% by weight of the composition and usually totaling 30 Examples of conditioning emollient oils useful in the up to about 0.001% to about 35% by weight of the compo present invention which condition the hair and scalp and sition. assist in the ease of combing, detangling, body, shine, Examples of hair styling agents useful in the present manageability, split-end mending and prevent static build-up invention include styling polymers such as vinyl include arnica blossom oil, apricot kernel oil, avocado oil, pyrrolidone/vinyl acetate copolymers (30/70 by weight), 35 babassa oil, balm mint oil, basil oil, bergamot oil, bitter vinyl acetate homopolymer, t-butyl acrylate homopolymer, almond oil, bitter orange oil, castor oil, calendula oil, t-butyl sterene/ethyl hexyl methacrylate copolymer (50/50 coconut oil, collagen/lanolin oil, cod liver oil, cucumber oil, by weight), dimethyl acrylamide/t-butyl acrylate/ethylhexyl corn oil, carrot oil, egg oil, eucalyptus oil, evening primrose methacrylate copolymer (10/45/45 by weight), ethylene] oil, geranium oil, gardenia oil, grapefruit oil, grape seed oil, vinyl acetate copolymer (12.5/ 87.5 by weight), allyl alcohol/ 40 hybrid safflower oil, jasmine oil, jojoba oil, kiwi oil, light styrene copolymer (19/81 by weight), vinyl chloride/vinyl mineral oil, lemon oil, mandarin orange oil, orange ?ower acetate copolymer (83/17 by weight and lower), vinyl oil, orange oil, mink oil, olive oil, palm oil, peach kernel oil, pyrrolidone/vinyl acetate/butyl acrylate copolymer (1017 8/ passionflower oil, rapeseed oil, sesame oil, soybean oil, l2 and 10/70/20 by weight), vinyl pyrrolidone/vinyl acetate/ safflower oil, sun?ower oil, sweet almond oil, wheat germ butyl acrylate/styrene sulfonate copolymer (10/70/ 15/5 by 45 oil and mixtures thereof. Typical levels of conditioning weight), vinyl pyrrolidone/vinyl propionate copolymer emollient oil are from about 0% to about 10% by weight of (5/95 by weight), vinyl caprolactam/vinyl acetate copolymer the composition. (5/95 by weight), ethyl acrylate/acrylic acid/t-butyl acryla Examples of conditioning extracts useful in the present mide copolymer, vinyl acetate/crotonic acid copolymer (90/ invention which condition the hair and scalp and assist in the 10 by weight), vinyl acetate/vinyl propionate/crotonic acid 50 ease of combing, detangling, body, shine, manageability, (50/40/10 by weight) and vinyl acetate/vinyl neodecanoate/ split-end mending and prevent static build-up include aloe crotonic acid copolymer. Typical levels of hair styling agent extract, aloe ?ower extract, aloe vera gel extract, apple which are designed to assist the user in having the sham extract, apple leaf extract, apple pectin extract, balsam pooed hair retain a particular shape are from about 0% to canada extract, balsa oregon extract, balsam peru extract, about 10% by weight of the composition. 55 balsam tolu extract, balm mint extract, black walnut extract, Examples of organic viscosity modifying agents useful in birch leaf extract, birch sap extract, calendula extract, cha the present invention include C8-C18 alkyl fatty alcohols, momile extract. colocynth extract, comfrey extract, comfrey C8-C18 alkyl fatty acids, C8—C1,; alkyl fatty esters, ethanol, leaf extract, coltsfoot extract, clover blossom extract, cus isopropanol and benzyl alcohol. Examples of inorganic tard apple extract, egg extract, fennel extract, gelatin extract, viscosity modifying agents include ionizable salts such as 60 geranium extract, grapefruit extract, horsetail extract, henna sodium chloride, potassium chloride, calcium chloride, mag extract, hazel extract, hops extract, honey extract, indian nesium chloride, potassium bromide, ammonium chloride, cress extract, kelp extract, lemon extract, lemon juice sodium sulfate, potassium sulfate, magnesium sulfate and extract, lemon peel extract, lime extract, malt extract, man sodium thiosulfate. The ionizable salts are particularly use- . darin orange extract, matricaria extract, mint extract, nettle ful for obtaining or modifying a desired viscosity. The as" extract, oakmoss extract, orange extract, orange peel extract, amount of ionizable salt used depends on the amount of ponkan extract, papaya extract, pummelo extract, red rasp active ingredient present and can be adjusted according to berry extract, red raspberry leaf exnact, rhubarb extract, 5,641,480 35 36 rosemary extract, thyme extract, tamarind extract, tangerine octadecanol, tallow alcohol, oleyl alcohol, ethylene glycol extract, sage extract, strawberry extract, strawberry leaf monostearate, ethylene glycol distearate, diethylene glycol extract, Valerian extract, witch hazel extract, autolyzed yeast distearate, triethylene glycol distearate, glycerol mono/ extract, yarrow extract and mixtures thereof. Preferred distearate, PEG 400 stearate, PEG 600 oleate, PEG-4 to PEG extracts are balsam canada, balsam oregon, balsam peru, 150 laurate/dilaurate, PEG 4 to PEG 150 stearate/distearate, balsam tolu and honey. Typical levels of conditioning extract PEG-4 to PEG 150 oleate/dioleate, coco gluconamide, tal are from about 0% to about 10% by weight of the compo low gluconamide, dodecyl gluconamide hexadecyl sition. gluconamide, octadecyl gluconamide, coco Examples of humectants useful in the present invention glucoheptonamide, tallow lactobionamide, octadecyl which provide moisture to the hair and scalp include pro lactobionamide, tallow maltobionamide, pylene glycol (PG), butylene glycol, hexylene glycol, PEG bismuthoxychloride, spermaceti, magnesium silicate, cal (polyethylene glycol), PEG-5M, PEG-6, PEG-9, PEG-10, cium silicate, guanine, zinc oxide, titanium dioxide (anatose PEG- 14M, PPG-12-buteth-16, PPG-12-buteth-16, PPG-28 form or rutile form), titanium dioxide coated mica and buteth-35, glycerol (glycerin), erythiitol, xylitol, sorbitol, coloured pigments coated mica and as well as the zinc, mannitol, lactitol, hydrogenated starch hydrolyzates, sodium calcium and magnesium salts of fatty acids such as myristic pyrrolidone carboxylic acid (sodium PCA), ethoxylatedl acid, palmitic acid, stearic acid, behenic acid, coconut fatty propoxylated methyl glucose, lactic acid, acetamide MEA, acid. Preferred are the non-hetero-atom containing alkyl lactamide MEA, wheat germamidopropyldimethyl lactate, aldonamides/aldobionamides and the ethylene glycol esters C12-C15 lactate, stearamidopropyldimethyl lactate and mix such as ethylene glycol monostearate and distearate. Typical tures thereof. Preferred humectants are propylene glycol, 20 levels of opaci?ers or pearlescent agent are from about 0% glycerol, hydrogenated starch hydrolyzates acetamide MEA, to about 7% by weight of the composition. lactamide MEA and sodium pyirolidone carboxylic acid. Examples of vitamins useful in the present invention Typical levels of humectant are from about 0% to about 10% which provide the hair with valuable nutrition include by weight of the composition. vitamin A (as retinyl acetate, propionate or palmitate) pro Examples of solubilizing or clarifying agents useful in the 25 vitamin A (based on earrot extract, as ?-carotene), vitamin present invention which assist in maintaining hair care B1 (as thiamine mononitrate), vitamin B2 (as ribo?avin), composition clarity by solubilizing poorly soluble ingredi vitamin B3 (as niacinamide, vitamin B5 (as pantothenic ents include methanol, ethanol, propanol, isopropanol, acid), provitamin B5 (as panthenol), vitamin B6 (as pyri butanol, ethoxydiglycol, phenyl e?ianol, phenyl propanol, doxine hydrochloride, dioctenoate, dilaurate, dipalmitate or benzyl alcohol, ethyl buyrate, isopropyl butyrate, diethyl tripalmitate), vitamin B12 (as cyanocobalamin), vitamin B15 phthalate, phenylethyldimethyl carbinol, ethyl-6 (as pangamic acid), vitamin C (as aseorbie add), vitamin D2 acetoxyhexanoate, methyl(2-pentanyl-3-oxy) (as ergocalciferol), vitamin D3 (as cholecalciferol), vitamin cyclopentylacetate, ethylene glycol, diethylene glycol, tri E (as dl-ot-tocopherol acetate, linoleate or nicotinate,), vita ethylene glycol, polyethylene glycol having a molecular min F (as glyceryl linoleate and glyceryl linolenate), vitamin weight of about 200 to about 1000, propylene glycol, 35 K1 (as phytonadione), vitamin K3 (as menadione), paba glycerol, 3,6-dimethyl-4-octyne-3,6-diol, 2-methyl-2,4 (p-aminobenzoic acid), oholine, folio acid, biotin, allantoin pentanediol, 2-ethyl-l,3-hexanediol and nonionic surfac biotin, retinol, inositol, allantoin calcium pantothenate, lici tants particularly polyoxyethylene nonionic surfactants. thin (oholine di-CIG-C13 glycerophosphate), cholesterol, Typical levels of solubilizing or clarifying agent are from PEG 16 soya sterol and mixtures thereof. Preferred vitamins about 0% to about 10% by weight of the composition. 40 are provitamin A, vitamin B1, vitamin B2, provitamin B5, Examples of sunscreens or UV absorbers useful in the vitamin B6, vitamin B12 and vitamin E. Typical levels of present invention which protect the hair and certain sensitive vitamin are from about 0% to about 7% by weight of the ingredients from harmful sunlight include dipropyleneglycol composition. salicylate, octyl salicylate, 2-ethylhexyl Examples of amino acids useful in the present invention p-dimethylaminobenzoate (octyldimethyl-PABA), polyoxy 45 which provide the hair with valuable nutrition include ethylene p-dimethylaminobenzoate (PEG-25 PABA), Tri alanine, B-alanine, N-methylalanine, N-phenylalanine, PABA-panthenol, dromtrizole, 2-ethylhexyl B-aminoisobutyric acid, [S-aminobutyric acid, p-methoxycinnamate, DEA p-methoxycinnamate, butyl ?-aminocaproic acid, e-aminocaproic acid, glycine, methoxybenzoyhnethane, benzophenones 1 through 12 N-ethylglycine, N-propylglycine, N-butylglycine, leucine, particularly, 2,4-dihydroxybenophenone (benzophenone 1), 50 methionine, derivatives of methionine, sarcosine, serine, 2,2’,4,4'-tetrahydroxybenzophenone (benzophenone 2), norvaline, tryptophan, lysine, aspartic acid, glutamic acid, 2-hydroxy-4‘methoxybenzophenone (benzophenone 3), iminodiacetic acid, keratin amino acids (keratin 2-hydroxy-4-methoxybenzophenone-5-sulfonic acid polypeptides), silk amino acids, allantoin acetyl methionine, (benzophenone 4), 2,2'-dihydroxy-4,4' allantoin, deoxyribonucleic acid, protamine/nucleic acid dimethoxybenzophen (benzophenone 6), 2,2'-dihydroxy-4 55 complex, nucleic acid and mixtures thereof. Preferred amino methoxybenzophenone (benzophenone 8), disodium-2,2' acids are glycine, methionine, sarcosine, keratin amino acids dihydroxy-4,4'-dimethoxy-5,5'-disulfobenzophenone and silk amino acids. Typical levels of amino acid are from (benzophenone 9), 2-hydroxy-4-n-octoxybenzophenone, about 0% to about 7% by weight of the composition. menthyl anthranilate, 2-(2-hydroxy-5'-methylphenyl) Examples of proteins useful in the present invention benzotriazole, 2-phenylbenzimidazole-5-sulfonic acid and which provide the hair with valuable nutrition include mixtures thereof. Preferred sunscreens are the benzophe hydrolyzed casein, hydrolyzed collagen (hydrolyzed animal nones 1 through 6, 8, 9 and 11. Typical levels of sunscreen protein), myristoyl hydrolyzed animal protein, hydrolyzed or UV absorber are from about 0% to about 8% by weight corn protein, hydrolyzed glycosaminoglycans, hydrolyzed of the composition. keratin (keratin protein), hydrolyzed milk protein, hydro Examples of opaci?ers and pearlescent agents useful in 65 lyzed pea protein, hydrolyzed potato protein, hydrolyzed the present invention which provide a soft, silvery and rice protein, hydrolyzed silk (silk protein), hydrolyzed soy pearly luster to hair care compositions include hexadecanol, protein, hydrolyzed vegetable protein, hydrolyzed wheat 5,641,480 37 38 gluten, hydrolyzed wheat protein, hydrolyzed yeast protein FCF, alizan'n cyanine green, quinizarin green SS, naphthol and mixtures thereof. Preferred proteins are hydrolyzed green B, orange 11, ammaranth, erythrosine,ponceau SX, collagen, hydrolyzed keratin protein, hydrolyzed silk protein Eosin YS, helindone pink CN, acid fuchsin D, napthalene and hydrolyzed soy protein. Typical levels of protein are red B, acid violet 6B, alizurol purple SS. tartrazine, sunset from about 0% to about 7% by weight of the composition. yellow FCF, quionoline yellow WS, quionoline yellow SS, Examples of curl enhancing agents useful in the present metanti yellow, naphthol yellow S and mixtures thereof. invention which hold the hair in a waved or curled position Examples of semiperrnanent to permanent organic hair dyes include sodium, potassium, ammonium and alkanolammo that remain on the hair after several shampooing sessions nium salts of thioglycolic acid, dithiodiglycolic acid, mer include p-aminodiphenylamine, p-aminodiphenylamine captobutane sulfonic acid, thiolactic acid, thioparaconic hydrochloride, p-aminodiphenylamine sulfonic acid, acid, ot,ot'-dimercaptoadipic acid, formamidine sulfonic 2-arnino-5-hydroxytoluene, 5-amino-2-hydroxyto1uene, acid, li-mercaptoethane sulfonic acid as well as mercaptans 2-amino-4-nitrophenol, 4-amino-2-nitrophenol, such as ot-thiolglycerol, B-aminoethylmercaptan, mercapto o-aminophenol, p-aminophenol, m-aminophenol, ethyl alcohol, ?-mercaptopionamide, p-aminophenol hydrochloride, p-aminophenol sulfate, mercaptoethylacetamide, thioglycolamide, methyl mercap 15 2-aminophenol—4-sulfonic acid, 4-aminophenol-2-sulfonic toethyl sulfone, mercaptoethyl nitrile, mercaptoethyl acid, N-(p-aminophenyl)glycine, o-anisidine, p,p’ tri?uoroacetamide-l,4-dimercapto-2,3-butanediol, cysteine diaminodiphenylamine, p,p’-diamminodiphenylamine and mixtures thereof. Still other examples of curl enhancing sulfonate, p,p'-diaminodiphenylamine methane, 1,8 agents are those that liberate thioglycolic acid by decompo diaminonaphthalene, 2,4-diaminophenol, 2,4 sition or reaction in the presence of water just before or 20 diaminophenol hydrochloride, 2,4-diaminophenol-4 during actual use or are derivatives which are active curling sulfonic acid, 3,4-diaminotoluene, N,N-d.i-sec-butyl-o agents by virtue of thier free thiol (SH) groups. Examples of phenylencdiamine, N,N-dimethyl-p -phenylenediamine, compounds that liberate thioglycolic acid include carbami 4,6-dinitro-2-aminophenol, S-nitro-o-aminophenol, 4-nit1'o nyl thioglycolic acid, ditiocarbamyl derivatives, glycolic o-aminophenol, 5-nitro-2-aminophenol, 4-nitro-2 esters of di- and tiithiocarbonic acid, thioglycolic hydrazide, 25 aminophenol, 2-nitro-o-aminophenol, N-(p-hydroxyphenyl) monothiopropylene glycol, dithiopropyleneglycol, glycine, N-(p-hydroxy-5-nitrophenyl)glycine, bisthioglycolic acid imide, heterocyclic compounds such as p-methylamino phenol surfate, 1,5-naphthalenediol, 4-nitro 2,4-thiazoledione, esters and amides 0f thioglycolic acid o-phenylenediarnine, 2-nitIo-p-phenylenediamine, nitro-m such as the thioglycolic esters of monomethyl-, dimethyl phenylencdiamine, N-(p-nitrophenyl)-glycine, and trimethylsilanol, thioglycolamide, 30 o-phenylenediamine, m-phenylenediamine, B-aminoethylthioglycolamide, thioglycolic amides of amino m-phenylenediamine hydrochloride, p-phenylenediamine, acids and mixtures thereof. Further examples of curling p-phenylenediamine hydrochloride, p-phenylenediamine agents are described in British Patent Nos. 0,771,627, 804, sulfate, 4-methoxy-6-methyl-m-phenylenediamine, 2,5 077, and 0,824,426; German Patent Nos. 0,971,899, 1,067, tolylenedia mine sulfate, m-tolylenediamine, 566 and 1,096,551; French Patent No. 1,174,561; Austrian 35 p-tolylenediamine, p-tolylenediamine sulfate, 2,4,6 Patent No. 0,210,071 and U.S. Pat. No. 3,148,126 all of trinitroaniline, ot-naphtho, 2,4-diaminoanisole, 2,4 which are incorporated herein by reference. Yet other diaminoanisole sulfate, 2,4-diaminophenetole, examples of curl enhancing agents useful in the present hydroxyquinone, hydroxyhydroquinol, phloroglycinol, invention are nonmercaptan reducing agents such as sodium pyrocatechol, resorcinol, xylenol, 1,2,3-trihydroxybenzene sul?te, potassium sul?te, ammonium sul?te, sodium (pyrogallol), 1,2,4-trihydroxybenzene, 2,4,5 bisul?te, potassium bisul?te, ammonium bisul?te, guanidine trihydroxytoluene, 1,5-dihydroxynaphthalene 6-chloro—4 bisul?te, alkyl or aryl substituted guanidinium bisul?tes, nitrophenol, 2,5-diaminopyridine, 2,6-diaminopyridine, 2,5 phosphine derivatives such as tetrakishydroxymethylphos dihydroxypyridine, 2,6-dihydroxypyridine and mixtures phonium chloride as well as the organic or inorganic salts of thereof. Examples of plant hair dyes include henna sulfurous acid and base/sul?te mixtures such as borax/ (2-hydroxy-1,4-naphthoqunione), indigo, camomile (4',5,7 sodium hyposul?te, potassium carbonate/sodium sul?te, trihydroxy?avone), Roman camomile (anthemis nobills), sodium bicarbonate/potassium sul?te, monoethanolaminej German/Hungarian camomile (matricaria chamomilla), potassium sul?te, ammonium carbonate/ammonium sul?te, wood extracts such as brazilin from brazilwood, catechu sodium hydroxiddsodium bisulflte and mixtures thereof. (catechin/1,2-dihydroxybenzene mixture), fustic (2',3,4'5,7 The curling or waving action of sul?tes and bisul?tes can be 50 pentahydroxy?avone/morintannic acid mixture), logwood accelerated through chemical additives such as quinones, (hydroxybrasilin), nutgalls, quercitron (3,3‘, 4'5,7 polyphenols, urea, formamide and denaturants. In principle, pentahydroxy?avone/quercitrin mixture), walnut waving or curling of the hair is accomplished by altering the (S-hydroxy-l,4-naphthoquinone/pyrogallol mixture), chemical con?guration of the hair. In general, curling agents rhubarb, sage, black tea, chrysophanol (1,8-dLhydroxy-3 such as those described above break or rearrange disul?de 55 methylanthraquinone) and mixtures thereof. 'Iypical levels hair linkages which normally hold the hair in a straight hair coloring agent used in coloring shampoo preparations of con?guration. Preferred curl enhancing agents are the the invention are from about 0% to about 7% by weight of sodium, potassium, ammonium salts of thioglycolic acid, the composition. sul?te, bisul?te and mixtures thereof. Typical levels of curl Examples of chelating or sequestering agents (builders) enhancing agent are from about 0% to about 7% by weight useful in the present invention include the sodium, potas of the composition. sium and ammonium salts of diphosphoric acid, triphospho~ Examples of hair coloring agents which effect useful in ric acid, pyrophosphoric acid, orthophosphoric acid, hex the present invention include the temporary, semi-permanent ametaphosphoric acid, l-hydroxyethane-l,l-phosphonic or permanent organic, plant and metallic hair dyes. acid, diethylenetriamine penta(methylene diphosphonic Examples of temporary organic hair dyes which areeasily 65 acid), ethylenediamine tetraacetic acid (EDTA), diethylen removed by shampooing include brilliant blue FCF, indigo etriamine pentaacetic acid (DTPA), N-(hydroxyethyl) eth tine IA, Alphazurine FG erioglaucine, indigo, fast green ylenediamine triacetic acid (HEDTA), propylenediamine