WO1995031173A1 - Hair care compositions containing dual dispersion of polysiloxane conditioning agent and polysiloxane shine agent - Google Patents

Abstract

A hair care composition for conditioning and providing shine to the hair, said composition comprising (a) a dispersed hair conditioning component, comprising from about 0.01 % to about 10 %, by weight of the composition, of a nonvolatile, insoluble polysiloxane fluid, said polysiloxane fluid having a viscosity at 25 °C of at least about 5,000 centipoise, and said hair conditioning component having a refractive index of less than 1.48; (b) a dispersed hair shine component, comprising from about 0.005 % to about 5 %, by weight of the composition, of a nonvolatile, insoluble polysiloxane fluid, said hair shine component having a refractive index of 1.48 or more; (c) an aqueous carrier suitable for topical application to the hair; wherein said hair conditioning component and said hair shine component exist in said composition as distinct, discontinuous phases.

Description

HAIR CARE COMPOSITIONS CONTAINING DUAL DISPERSION OF POLYSILOXANE CONDITIONING AGENT AND POLYSILOXANE

SHINE AGENT

TECHNICAL FIELD

This invention relates to hair care compositions that provide conditioning and shine to the hair, through the use of polysiloxane hair conditioning agents and polysiloxane hair shine agents.

BACKGROUND OF THE INVENTION The shampooing of hair conventionally is performed utilizing any of numerous detersive surfactant-containing compositions known in the art. Whereas it is well known how to formulate shampoos that can efficiently clean the hair, substantial segments of consumers also want to condition their hair so that it is more manageable and has a softer feel. They also want their hair to look pleasing and healthy.

Common methods of conditioning the hair, i. e. providing softer feel and manageablity, include the use of hair conditioning agents such as cationic, quaternary ammonium surfactants and polymers, silicone fluids, and hydrocarbons and other organic oils (e.g. fatty esters, fatty alcohols).

Techniques to improve the appearance of hair and to allow it to look healthier include the use of hair shine agents such as shellac, high refractive index silicones (e.g. phenylated dimethicone), and organic oils. The effect of hair shine actives is to increase the amount of light reflecting off the hair surface. Hair shine can be defined as the contrast between the specular and diffuse light reflected off the hair fibers. This contrast creates a perception of "sheen" or "gloss" strongly associated by the consumer with healthy hair.

Although high refractive index silicones can be quite effective at enhancing shine, they are generally not as effective as would be desired for conditioning the hair Low refractive index polysiloxanes (e.g. dimethicone) are high desirable for the hair conditioning benefits they provide, particularly dry hair conditioning. On the other hand, they unfortunately do not provide good hair shine. Cationic surfactants provide good wet hair conditioning, but are generally not as effective as dimethicone for providing dry hair conditioning.

Some hair care ingredients are effective at both conditioning and enhancing shine. These include hydrocarbon oils and fatty esters.

However, they can only be used at limited levels without causing adverse effects on hair appearance or feel, such as causing the hair to appear and feel greasy, and to resoil more quickly.

Whereas a wide variety of conditioning compositions and hair shine compositions are known in the art, it remains highly desirable to provide improved hair care compositions that provide both shine and conditioning to the hair without necessarily incurring the aesthetic disadvantages that would be incurred by using high levels of hydrocarbons and fatty esters.

It has recently been found that particularly good hair shine can be obtained when the hair is treated with a high refractive index silicone used in combination with a spreading agent, such as a silicne resin or a surfactant. Unfortunately combining such hair shine agents with conventional, low refractive index silicone conditioning agents tends to substantially decrease the amount of hair shine that can be obtained. Thus, it is an object of this invention to provide hair care compositions which can provide both excellent hair conditioning, particularly dry hair conditioning, and hair shine from a single composition.

It is yet another object of this invention to provide a shampoo composition that cleanses the hair, as well as provides both hair shine and conditioning, especially dry hair conditioning, through the use of high refractive index polysiloxane hair shine agents and polysiloxane hair conditioning agents.

It is another object of this invention to provide a method for providing improved shine and conditioning, especially dry hair conditioning, by application of a single composition.

It is yet another object of this invention to provide a method for cleansing the hair, as well as providing improved shine and conditioning, especially dry hair conditioning, by application of a single composition.

It is still another object of this invention to provide a process for making compositions that meet the above objects. These and other benefits as may be discussed herein or apparent to one skilled in the art can be provided according to the invention which is described below.

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

The invention hereof can comprise, consist of, or consist essentially of the essential elements described herein as well as any of the preferred or optional ingredients also described herein. SUMMARY OF THE INVENTION The present invention provides a hair care composition that comprises:

(a) a dispersed hair conditioning component comprising from about 0.01 % to about 10%, by weight of the composition, of a nonvolatile, insoluble polysiloxane fluid, said polysiloxane fluid having a viscosity at 25°C of at least about 5,000 centipoise, and said hair conditioning component having a refractive index of less than 1.48;

(b) a dispersed hair shine component comprising from about 0.005% to about 5%, by weight of the composition, of a nonvolatile, insoluble polysiloxane fluid, said hair shine component having a refractive index of 1.48 or more;

(c) an aqueous carrier suitable for topical application to the hair; wherein said hair conditioning component and said hair shine component exist in said composition as distinct, discontinuous phases. The compositions and methods of the present invention are advantageous for utilization in connection with a wide variety of hair care products including but not limited to leave-on compositions, such as hair lotions, tonics, gels, mousses, sprays, etc., as well as rinse-off compositions, such as shampoos and hair conditioning rinses. The present invention including various optional and preferred embodiments thereof, is described in more detail below.

DETAILED DESCRIPTION OF THE INVENTION The essential components and aspects of the invention, as well as various optional and preferred ingredients and embodiments of the invention, are described below.

"Insoluble", in reference to a particular ingredient, refers to insolubility in the product composition unless otherwise specifically indicated.

The term "nonvolatile", as used herein, means the material referred to exhibits very low or no significant vapor pressure at ambient conditions, as well-known and understood in the art. The nonvolatile materials hereof will generally exhibit no more than 0.2mm Hg at 25°C and one atmosphere. The nonvolatile materials hereof will also o generally have a boiling point at one atmosphere of at least 275 C, preferably at least 300°C.

The term "polysiloxane fluid", as used herein, encompasses all such fluids, including the high molecular weight, high viscosity polysiloxanes commonly referred to as polysiloxane "gums", which are further described below.

High Refractive Index Polysiloxane Fluid-Containing Hair Shine Component The compositions hereof will contain a hair shine component, dispersed in the composition, which comprises a nonvolatile, insoluble, high refractive index polysiloxane fluid as a hair shine agent. The hair shine component may further comprise other ingredients that are compatible with the hsir shine agent, such as a spreading agent or diluent. Thus, the polysiloxane fluid-containing hair shine component includes the polysiloxane fluids present, as well as any additional ingredients present in the same dispersed phase of the composition. By "compatible" what is meant is that the ingredients can stably coexist in the same phase, such as by being soluble or miscible. The compositions hereof will comprise from about 0.005% to about 5%, by weight, of such hair shine component, preferably from about 0.01 % to about 3%, more preferably from about 0.1 % to about 3%, most preferably from about 0.2% to about 2%. The level of the high refractive index polysiloxane hair shine agent will also preferably be within the above ranges.

The hair shine component, as well as the hair shine agent will have a refractive index of 1.48 or more, preferably at least about 1.50, more preferably at least about 1.52. Although not intended to necessarily limit the invention, the refractive index will generally be about 1.70 or less, preferably about 1.60 or less, more preferably about 1.56 or less, most preferably about 1.54 or less.

As is well known in the art, "refractive index" refers to the change in direction (i.e. apparent bending) of a light ray passing from one medium to another. Refractive index shall herein refer to the light ray passing from air to a polysiloxane fluid, hair shine component, or hair conditioning component.

Refractive index of a polysiloxane fluid hair shine component can be determined using standard equipment commonly available and know in the art, such as an Abbe refractometer. Techniques for measuring refractive index are described, for example, in the Handbook of Chemical Microscopy, Volume I - Chemical Methods and Inorganic Qualitative Analysis, Chemot and Mason, ed., John Wiley & Sons, Inc., New York, 1958, pp 311-334.

The polysiloxane fluid hair shine component for use herein will generally have an average viscosity of at least about 10 centipoise at 25°C, preferably from about 50 to about 1,000,000 centipoise, more preferably from about 100 to about 100,000 centipoise, more preferably from about 200 to about 50,000 centipoise, most preferably from about 500 to about 10,000 centipoise. The average viscosity can be measured by means of a glass capillary viscometer as set forth in Dow Corning Corporate Test Method CTM0004, July 20, 1970. Viscosity above or below these ranges can be used in the present invention as long as the other requirements and objects of the invention are met.

The polysiloxane fluid suitable for purposes hereof includes those represented by general Formula (I):

wherein each R independently is substituted or unsubstituted aliphatic (e.g. alkyl or alkenyl), aryl, aryloxy, alkaryl, alkoxy, alkamino (e.g. alkyl or alkenyl amino groups), hydroxy, or hydrogen, or combinations thereof; and n is an integer of at least about 1 , preferably from about 1 to about 10,000, more preferably from about 1 to about 1 ,000. The R substituents can also include combinations of ether groups, hydroxy groups, and amine groups, as well as other functional groups, such as halogens and halogen-substituted functionalities, e.g. halogen-substituted aliphatic and aryl groups. The polysiloxane fluid can be cyclic or linear. Linear polysiloxanes are exemplified above by Formula I. Branched chain can also be used. Cyclic polysiloxanes include those represented by Formula (II):

wherein R is as defined above, n is from 3 to 7, preferably from 3 to 5.

The substituents on the siloxane chain (R) may have any structure as long as the resulting polysiloxanes remain fluid at room temperature, are hydrophobic, are neither irritating, toxic nor otherwise harmful when applied to the hair, are compatible with the other components of the composition, are chemically stable under normal use and storage conditions, are capable of being deposited on the hair, and the resulting polysiloxane fluid has a refractive index as set forth above.

Preferred alkyl and alkenyl substitutes are C-.-C5 alkyls and alkenyls, more preferably from C₁-C₄, most preferably from CΛ -C^ The aliphatic portions of other alkyl-, alkenyl-, or alkynyl- containing groups (such as alkoxy, alkaryl, and alkamino) can be straight or branched chains and preferably have from one to five carbon atoms, more preferably from one to four carbon atoms, even more preferably from one to three carbon atoms, most preferably from one to two carbon atoms. As discussed above, the R substituents hereof can also, contain amino functionalities, e.g., alkamino groups, which can be primary, secondary or tertiary amines or quaternary ammonium. These include mono-, di-, and tri- alkylamino and alkoxyamino groups wherein the aliphatic portion chain length is preferably as described above. The R substituents can also be substituted with other groups, such as halogens (e.g. chloride, fluoride, and bromide), halogenated aliphatic or aryl groups, and hydroxy (e.g. hydroxy substituted aliphatic groups). Suitable halogenated R groups could include, for example, t -halogenated (preferably fluoro) 8 High refractive index polysiloxane are available commercially from General Electric Silicones (Waterford, New York, U.S.A.), Dow Corning Corporation (Midland, Michigan, U.S.A.), Huls America (Piscataway, New Jersey, U.S.A.). The high refractive index polysiloxanes that are used as the hair shine agents herein provide the hair with an enhanced shinny appearance. Specular reflectance is a useful means for measuring shininess of hair. In general, specular reflectance refers to the fraction, or percentage, of incident light reflected from a surface in the mirror direction (i.e. light reflected in the direction that is 180° from the light flowing from the light source toward the reflective surface) within a specified angular tolerance. Further background in specular reflectance and its use in evaluating shininess of hair can be found in R. F. Stamm, M. L. Garcia, and J. J. Fuchs, 'The Optical Properties of Human Hair-I. Fundamental Considerations and Goniophotometer Curves, and II. The Lustre of Human Hair Fibers," J. Soc. Cosmet. Chem. 28, 571-599 and 601-609 (September 1977).

Specular reflectance that is measured from a coating of the compositions hereof on a collagen-coated black ceramic plate correlates with shininess of hair. Specular reflectance on such collagen-coated black ceramic plates for purposes of the present invention may be determined according to the procedure as described below and set forth in the Experimental section, referred to herein as "Glossmeter Specular Reflectance." In general, Glossmeter Specular Reflectance ("GSR") is measured as follows. A 1.0% solution is prepared using the high refractive index polysiloxane fluid hair shine component. The same solvent or diluent used in the composition, if any, for the hair shine agent is used to dilute the 1.0% solution. If the polysiloxane fluid is not diluted with a separate solvent in the composition, cyclomethicone should be used to prepare the 1.0% solution. If necessary for solubility or miscibility purposes, cyclomethicone/ethanol solutions can be used to form the 1.0% solution for purposes of the GSR test. The test solution is deposited on a collagen-coated, black ceramic tile and allowed to dry. Specular reflectance is measured with a spectrophotometer suitable for measuring specular reflectance from flat surfaces, e.g. a glossmeter. Suitable glossmeters are commercially available and known in the art. These include the "micro-gloss" glossmeter available from BYK-Gardner, Ind., 7

1 1 alkyl groups such as -R -C(F)₃, wherein R is C^Cg alkyl. Examples of such polysiloxanes include polymethyl -3,3,3 trifluoropropylsiloxane.

The high refractive index polysiloxane fluids hereof will generally contain aryl-containing R substituents at a sufficient level to increase the refractive index to the desired level.

Aryl-containing substituents contain alicyclic and heterocyclic five and six membered aryl rings, and substituents containing fused five or six membered rings. The aryl rings themselves can be substituted or unsubstituted. Substituents include aliphatic substituents, and can also include alkoxy substituents, acyl substituents, ketones, halogens (e.g., Cl and Br), amines, etc. Exemplary aryl-containing groups include sub¬ stituted and unsubstituted arenes, such as phenyl, and phenyl derivatives such as phenyls with C..-Cc alkyl or alkenyl substituents, e.g., allylphenyl, methyl phenyl and ethyl phenyl, vinyl phenyls such as styrenyl, and phenyl alkynes (e.g. phenyl C₂-C₄ alkynes). Heterocyclic aryl groups include substituents derived from furan, imidazole, pyrrole, pyridine, etc. Fused aryl ring substituents include, for example, napthalene, coumarin, and purine.

In general, the high refractive index polysiloxane fluids hereof will have a degree of aryl-containing substituents of at least about 15%, preferably at least about 20%, more preferably at least about 25%, even more preferably at least about 35%, most preferably at least about 50%. Typically, although it is not intended to necessarily limit the invention, the degree of aryl substitution will be less than about 90%, more generally less than about 85%, preferably from about 55% to about 80%.

The high refractive index polysiloxane fluids may also be characterized by relatively high surface tensions as a result of their aryl substitution. In general, the polysiloxane fluids hereof will have a

2 Surface Tension of at least about 24 dynes/cm , typically at least about 2 27 dynes/cm . Surface Tension, for purposes hereof, is measured by a de Nouy ring tensiometer according to Dow Corning Corporate Test

Method CTM 0461 , November 23, 1971.

The preferred polysiloxane fluids hereof will have a combination of phenyl or phenyl derivative substituents (preferably phenyl), with alkyl substituents, preferably C..-C ., alkyl (most preferably methyl) hydroxy,

1 ? 1 2 alkyiamino (especially -R NHR NH2 where each R and R independently is a C.-C-, alkyl, alkenyl, and/or alkoxy. Silver spring, MD, USA. The hair shine component hereof should provide an increase ("Δ") in Glossmeter Specular Reflectance relative to the control of at least about Δ 1.0% (based on 100% of the original light intensity) preferably at least about Δ 5%, more preferably at least about Δ 10%, more preferably at least about Δ 20%, most preferably at least about Δ 30%. Spreading Agent

The hair shine component in the compositions of the present invention optionally, and preferably, comprise a compatible nonvolatile spreading agent for the high refractive index polysiloxane fluid.

The term "nonvolatile" is as defined previously herein. By "compatible" what is meant is that the spreading agent is soluble in, dispersible in, or miscible with the high refractive index polysiloxane fluid, such that these two components can remain intermixed in the same phase of the composition. The spreading agent and the polysiloxane fluid form a mixture wherein the spreading agent reduces the Surface Tension of the polysiloxane fluid.

The compositions hereof preferably contain a sufficient amount of the spreading agent to reduce the Surface Tension of the high refractive index polysiloxane fluid, or the polysiloxane-containing hair shine component, by at least about 5%, preferably at least about 10%, more preferably at least about 15%, even more preferably at least about 20%, most preferably at least about 25%. Reductions in Surface Tension of the high refractive index polysiloxane fluid/spreading agent mixture can result in improved shine enhancement of the hair. Although it is not intended to necessarily limit the maximum degree of Surface Tension reduction to any particular amount, in the preferred compositions hereof

Surface Tension will generally be reduced by from about 20% to about

35%, more generally from about 25% to about 30%. The spreading agent will also preferably reduce the Surface

2 Tension by at least about 2 dynes/cm , preferably at least about 3

2 2 dynes/cm , even more preferably at least about 4 dynes/cm , most

2 preferably at least about 5 dynes/cm .

The Surface Tension of the hair shine component in the final

2 product, is preferably 30 dynes/cm or less, more preferably about 28 2 2 dynes/cm or less most preferably about 25 dynes/c or less. Typically the Surface Tension will be in the range of from about 15 to about 30, more typically from about 18 to about 28, and most generally from about 2 20 to about 25 dynes/cm . Changes in Surface Tension can be measured according to the above test method or according to ASTM

Method D 1331.

The hair shine component also preferably contains a sufficient amount of the spreading agent to increase the Glossmeter Specular

Reflectance by at least about "delta 1.0%" (hereinafter "Δ 1.0%", wherein delta refers to a change in percentage specular reflectance based upon

100% of the original light intensity). Preferably, the increase in

Glossmeter Specular Reflectance is at least about Δ2.0%, more preferably at least about Δ5.0%, even more preferably at least about Δ 7.5%, most preferably at least about Δ10.0%.

The weight ratio of the high refractive index polysiloxane fluid to the spreading agent will preferably be between about 1000:1 and about 1 :10, preferably between about 100:1 and about 1 :1 , more preferably between about 50:1 and about 2:1, most preferably from about 25:1 to about 2:1. For hair rinse compositions it is particularly preferred for the ratio to be between about 10:1 and about 2:1. When fluorinated surfactants are used, particularly high refractive index polysiloxane: spreading agent ratios may be effective due to the efficiency of these surfactants. Thus, it is contemplated that ratios significantly above 1000:1 may be used.

Preferred spreading agents for use herein include silicone resins, and surfactants, which include both polyether siloxane copolymers and non-silicone-containing organic surfactants. Especially preferred spreading agents are the silicone resins. Silicone Resin

Silicone resins are highly crosslinked polymeric siloxane systems. The crosslinking is introduced through the incorporation of trifunctional and tetrafunctional silanes with monofunctional or difunctional monomer units, or both, during manufacture of the silicone resin. As is well understood in the art, the degree of crosslinking that is required in order to result in a silicone resin will vary according to the specific silane units incorporated into the silicone resin. In general, silicone materials which have a sufficient level of trifunctional and tetrafunctional siloxane monomer units (and hence, a sufficient level of crosslinking) such that they dry down to a rigid, or hard, film are considered to be silicone resins. The ratio of oxygen atoms to silicon atoms is indicative of the level of crosslinking in a particular silicone material. Silicone resins will generally have at least about 1.1 oxygen atoms per silicon atom. Preferably, the ratio of oxygen:silicon atoms is at least about 1.2:1.0. Typical silanes used in the manufacture of silicone resins are monomethyl-, dimethyl-, monophenyl-, diphenyl-, methylphenyl-, monovinyl-, and methylvinyl-chlorosilanes, and tetrachlorosilane. Preferred resins are the methyl substituted silicone resins, such as those offered by General Electric as GE SS4230 and SS4267. Commercially available silicone resins will generally be supplied in an unhardened form in a low viscosity volatile or, preferably, nonvolatile silicone fluid. The silicone resins for use herein will be present in the compositions hereof in non-hardened form rather than as a hardened resin, as will be readily apparent to those skilled in the art. Background material on silicones including sections discussing silicone fluids, gums, and resins, as well as manufacture of silicones, can be found in Encyclopedia of Polymer Science and Engineering, Volume 15, Second Edition, pp 204-308, John Wiley & Sons, Inc., 1989, and Chemistry and Technology of Silicones, Walter Noll, Academic Press, Inc. (Harcourt Bruce Javanovich, Publishers, New York), 1968, pp 282-287 and 409-426, both incorporated herein by reference. Silicone materials and silicone resins in particular, can conveniently be identified according to a shorthand nomenclature system well known to those skilled in the art as "MDTQ" nomenclature. Under this system, the silicone is described according to presence of various siloxane monomer units which make up the silicone. Briefly, the symbol M denotes the monofunctional unit (CH3)3SiO)o.5, D denotes the difunctional unit (CH3)2SiO; T denotes the trifunctional unit (CH3)Sr-j 5; and Q denotes the quadri- or tetra-functional unit Siθ2- Primes of the unit symbols, e.g., M', D', T, and Q' denote substituents other than methyl, and must be specifically defined for each occurrence. Typical alternate substituents include groups such as vinyl, phenyls, amines, hydroxyls, etc. The molar ratios of the various units, either in terms of subscripts to the symbols indicating the total number of each type of unit in the silicone (or an average thereof) or as specifically indicated ratios in combination with molecular weight complete the description of the silicone material under the MDTQ system. Higher relative molar amounts of T, Q, T and/or Q' to D, D', M and/or or M' in a silicone resin is indicative of higher levels of crosslinking. As discussed before, however, the overall level of crosslinking can also be indicated by the oxygen to silicon ratio.

The silicone resins for use herein which are preferred are MQ,

MT, MTQ, and MDTQ resins. Thus, the preferred silicone substituent is methyl. Especially preferred are MQ resins particularly those wherein the M:Q molar ratio is from about 0.5:1.0 to about 1.5:1.0 and the average molecular weight of the resin is from about 500 to about 10,000, generally from about 1 ,000 to about 10,000.

Other spreading Agents Other spreading agents which can be used for the high refractive index polysiloxane hair shine agent include surfactants. A wide variety of surfactants that can be used are discribed below.

Surfactants

Surfactants that are compatible with the high refractive index polysiloxane fluid hereof and which is suitable for application to the hair can also be used as spreading agents. The surfactants can be anionic, cationic, nonionic, or amphoteric or a combination thereof. Surfactants can also be utilized for other purposes that are known in the art. For example, anionic, nonionic, amphoteric, and zwitterionic surfactants can be used as cleansing agents and emulsifying agents. Cationic surfactants can be used as conditioning agents. For convenience, a wide variety of surfactants suitable for use herein are further described in the nonlimiting disclosure below.

Polvether Siloxane Copolvmer Polyether siloxane copolymers, or silicone "copolyols" as they are sometimes referred to, are silicone-containing surfactants that can be utilized as spreading agents for the polysiloxane fluid, for emulsifying agents for polysiloxane fluids, or for conditioning agents for the hair.

Silicone copolyols are surfactants characterized by a hydrophobic polysiloxane chain and a hydrophilic alkoxy portion.

Silicone copolyols which may be used include polyalkylene oxide modified polydimethylsiloxanes of the following formulae:

and

R' - Si~[-0 Si(CH3)2]_χ-(OC₂H4)_a - (OC₃H₆)_b - OR" ³ wherein R is hydrogen, an alkyl group having from 1 to about 12 carbon atoms, an alkoxy group having from 1 to about 6 carbon atoms or a hydroxyl group; R' and R" are alkyl groups having from 1 to about 12 carbon atoms; x is an integer of from 1 to 100, preferably from 20 to 30; y is an integer of 1 to 20, preferably from 2 to 10; and a and b are integers of from 0 to 50, preferably from 20 to 30.

Silicone copolyols among those useful herein are also disclosed in the following patent documents, all incorporated by reference herein: U.S. Patent 4,122,029, Geen, et al., issued October 24, 1978; U.S. Patent 4,265,878, Keil, issued May 5, 1981 ; and U.S. Patent 4,421 ,769, Dixon, et al., issued December 20, 1983. Such silicone copolyol materials are also disclosed, in hair compositions, in British Patent Application 2,066,659, Abe, published July 15, 1981 (incorporated by reference herein) and Canadian Patent 727,588, Kuehns, issued February 8, 1966 (incorporated by reference herein). Commercially available silicone copolyols which can be used herein, include Silwet Surface Active Copolymers (manufactured by the Union Carbide Corporation); and Dow Corning Silicone Surfactants (manufactured by the Dow Corning Corporation). In addition to silicone-containing surfactants, non-silicone- containing organic surfactants can also be used in the present invention. A wide variety are described below. Anionic Surfactants

Anionic surfactants useful herein include alkyl and alkyl ether sulfates. These materials typically have the respective formulae ROSO₃M and RO(C₂H₄O)_χSO₃M, wherein R is alkyl or alkenyl of from about 10 to about 20 carbon atoms, x is 1 to 10, and M is a water-soluble cation such as ammonium, sodium, potassium and triethanolamine. Another suitable class of anionic surfactants are the water-soluble salts of the organic, sulfuric acid reaction products of the general formula:

R₁-S0₃-M wherein R₁ is chosen from the group consisting of a straight or branched chain, saturated aliphatic hydrocarbon radical having from about 8 to about 24, preferably about 12 to about 18, carbon atoms; and M is a cation. Important examples are the salts of an organic sulfuric acid reaction product of a hydrocarbon of the methane series, including iso-, neo-, and n-paraffins, having about 8 to about 24 carbon atoms, preferably about 12 to about 18 carbon atoms and a sulfonating agent, e.g., S0₃, H2S0₄, oleum, obtained according to known sulfonation methods, including bleaching and hydrolysis. Preferred are alkali metal and ammonium sulfonated

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

Still other anionic surfactants include the class designated as succinamates. This class includes such surface active agents as disodium N-octadecylsulfosuccinamate; tetrasodium

N-(1 ,2-dicarboxyethyl)-N-octadecylsulfosuccinamate; diamyl ester of sodium sulfosuccinic acid; dihexyl ester of sodium sulfosuccinic acid; dioctyl esters of sodium sulfosuccinic acid.

Other suitable anionic surfactants utilizable herein are olefin sulfonates having about 12 to about 24 carbon atoms. The term "olefin sulfonates" is used herein to mean compounds which can be produced by the sulfonation of a-olefins by means of uncomplexed sulfur trioxide, followed by neutralization of the acid reaction mixture in conditions such that any sultones which have been formed in the reaction are hydrolyzed to give the corresponding hydroxy-alkanesulfonates. The a-olefins from which the olefin sulfonates are derived are mono-olefins having about 12 to about 24 carbon atoms, preferably about 14 to about 16 carbon atoms. Another class of anionic organic surfactants are the b-alkyloxy alkane sulfonates.

Other anionic surfactants include N-acyl amino acid surfactants and salts thereof (alkali, alkaline earth, and ammonium salts) such as those represented by the Formula

0 R2

II I R1 . c - N— (R³)_n— COOM

wherein: R¹ is a C8-C24 alkyl or alkenyl radical, preferably C10-C18' R^ is -H, C1-C4 alkyl, phenyl, or -CH2COOM, preferably C1-C4 alkyl, more preferably C1-C2 alkyl; R³ is -CR⁴2- or C1-C2 alkoxy, wherein each R⁴ independently is -H or C^ -CQ alkyl or alkylester, and n is from 1 to 4, preferably 1 or 2; and M is -H or a salt-forming cation as described above, preferably an alkali metal such as sodium or potassium.

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

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

Another common anionic surfactant includes the water soluble soaps, e.g., salts of C10-C20 fatty acids, such as coconut-and tallow- based soaps. Preferred salts are ammonium, potassium, and sodium salts. Nonionic Surfactants

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

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

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

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

4. Long chain tertiary amine oxides such as those corresponding to the following general formula: R₁ R₂R₃N > O wherein R^ contains an alkyl, alkenyl or monohydroxy alkyl radical of from about 8 to about 18 carbon atoms, from 0 to about 10 ethylene oxide moieties, and from 0 to about 1 glyceryl moiety, and R₂ and R₃ contain from about 1 to about 3 carbon atoms and from 0 to about 1 hydroxy group, e.g., methyl, ethyl, propyl, hydroxyethyl, or hydroxypropyl radicals (the arrow in the formula represents a semipolar bond).

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

RR'R-p > o wherein R contains an alkyl, alkenyl or monohydroxyalkyi radical ranging from about 8 to about 18 carbon atoms in chain length, from 0 to about 10 ethylene oxide moieties and from 0 to about 1 glyceryl moiety and R' and R" are each alkyl or monohydroxyalkyi groups containing from about 1 to about 3 carbon atoms. The arrow in the formula represents a semipolar bond.

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

7. Polysorbates, e.g., sucrose esters of fatty acids. Such materials are described in U.S. Patent 3,480,616, e.g., sucrose cocoate (a mixture of sucrose esters of a coconut acid, consisting primarily of monoesters, and sold under the tradenames GRILLOTEN LSE 87K from RITA, and CRODESTA SL-40 from Croda).

8. Alkyl polysaccharide nonionic surfactants are disclosed in U.S. Patent 4,565,647, Llenado, issued January 21 , 1986, having a hydrophobic group containing from about 6 to about 30 carbon atoms, preferably from about 10 to about 16 carbon atoms and a polysaccharide, e.g., a polyglycoside, hydrophilic group. The polysaccharide can contain from about 1.0 to about 10, preferably from about 1.3 to about 3, most preferably from about 1.3 to about 2.7 saccharide units. Any reducing saccharide containing 5 or 6 carbon atoms can be used, e.g., glucose, galactose and galactosyl moieties can be substituted for the glucosyl moieties. (Optionally the hydrophobic group is attached at the 2-, 3-, 4-, etc. positions thus giving a glucose or galactose as opposed to a glucoside or galactoside.) The intersaccharide bonds can be, e.g., between the one position of the additional saccharide units and the 2-, 3-, 4-, and/or 6-positions on the preceding saccharide units. Optionally there can be a polyalkyleneoxide chain joining the hydrophobic moiety and the polysaccharide moiety. The alkyl group preferably contains up to about 3 hydroxy groups and/or the polyalkyleneoxide chain can contain up to about 10, preferably less than 5, alkylene moieties. Suitable alkyl polysaccha des are octyl, nonyldecyl, undecyldodecyl, t decyl, tetradecyl, pentadecyl, hexadecyl, heptadecyl, and octadecyl, di-, tri-, tetra-, penta-, and hexaglucosides, galactosides, lactosides, glucoses, fructosides, fructoses and/or galactoses.

9. Polyethylene glycol (PEG) glyceryl fatty esters, as depicted by the formula RC(0)OCH₂CH(OH)CH₂(OCH₂CH₂)_nOH wherein n is from about 5 to about 200, preferably from about 20 to about 100, more preferably from about 30 to about 85, and RC(O)- is an ester wherein R comprises an aliphatic radical having from about 7 to 19 carbon atoms, preferably from about 9 to 17 carbon atoms, more preferably from about 11 to 17 carbon atoms, most preferably from about 11 to 14 carbon atoms. The combinations of n from about 20 to about 100, with

^esters. f°^r minimized adverse effect on foaming, is preferred.

10. Other surfactants that can be used include the C10-C18 N- alkyl (Ci-Cβ) polyhydroxy fatty acid amides. Typical examples include the C12-C18 N-methylglucamides. See WO 9,206,154 and US Patent 5,194,639, incorporated herein by reference. Other sugar-derived surfactants include the N-alkoxy polyhydroxy fatty acid amides, such as C-|0"Cl8 N-(3-methoxypropyl) glucamide. The N-propyl through N-hexyl C12-C18 glucamides would be preferred for applications wherein low sudsing is desired. Cationic Surfactants

Cationic surfactants useful in compositions of the present invention, particularly the conditioner compositions, contain amino or quaternary ammonium hydrophilic moieties which are positively charged when dissolved in the aqueous composition of the present invention. Cationic surfactants among those useful herein are disclosed in the following documents, all incorporated by reference herein: M.C. Publishing Co., McCutcheon's, Detergents & Emulsifiers. (North American edition 1979); Schwartz, et al., Surface Active Agents. Their Chemistry and Technology. New York: Interscience Publishers, 1949; U.S. Patent 3,155,591, Hilfer, issued November 3, 1964; U.S. Patent 3,929,678, Laughlin, et al., issued December 30, 1975; U.S. Patent 3,959,461 , Bailey, et al., issued May 25, 1976; and U.S. Patent 4,387,090, Bolich, Jr., issued June 7, 1983.

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

wherein R1-R4 are independently an aliphatic group of from about 1 to about 22 carbon atoms, or an aromatic, alkoxy, polyoxyalkylene, alkylamido, hydroxyalkyl, aryl or alkylaryl group having from about 12 to about 22 carbon atoms; and X is an anion selected from halogen, acetate, phosphate, nitrate and alkylsulfate radicals. The aliphatic groups may contain, in addition to carbon and hydrogen atoms, ether linkages, and other groups such as amino groups. The longer chain aliphatic groups, e.g., those of about 12 carbons, or higher, can be saturated or unsaturated.

Salts of primary, secondary and tertiary fatty amines are also suitable cationic surfactant materials. The alkyl groups of such amines preferably have from about 12 to about 22 carbon atoms, and may be substituted or unsubstituted. Such amines, useful herein, include stearamido propyl dimethyl amine, diethyl amino ethyl stearamide, dimethyl stearamine, dimethyl soyamine, soyamine, myristyl amine, tridecyl amine, ethyl stearylamine, N-tallowpropane diamine, ethoxylated (5 moles E.O.) stearylamine, dihydroxy ethyl stearylamine, and arachidylbehenylamine. Suitable amine salts include the halogen, acetate, phosphate, nitrate, citrate, lactate and alkyl sulfate salts. Such salts include stearylamine hydrochloride, soyamine chloride, stearylamine formate, N-tallowpropane diamine dichloride and stearamidopropyl dimethylamine citrate. Cationic amine surfactants included among those useful in the present invention are disclosed in U.S. Patent 4,275,055, Nachtigal, et al., issued June 23, 1981 , incorporated by reference herein. Amphoteric Surfactants Examples of amphoteric surfactants which can be used in the compositions of the present invention are those which are broadly described as derivatives of aliphatic secondary and tertiary amines in which the aliphatic radical can be straight or branched chain and wherein one of the aliphatic substituents contains from about 8 to about 18 carbon atoms and one contains an anionic water solubilizing group, e.g., carboxy, sulfonate, sulfate, phosphate, or phosphonate. Examples of compounds falling within this definition are sodium 3-dodecyl-aminopropionate, sodium 3-dodecylaminopropane sulfonate, N-alkyltaurines such as the one prepared by reacting dodecylamine with sodium isethionate according to the teaching of U.S. Patent 2,658,072, N-higher alkyl aspartic acids such as those produced according to the teaching of U.S. Patent 2,438,091 , and the products sold under the trade name "Miranol" and described in U.S. Patent 2,528,378, both of which patents are incorporated herein by reference. The amphoteric surfactant hereof include the imidazolinium amphoteric surfactants such as those depicted by the Formula:

R3

R¹CON (CH₂ ) _n N⁺-CH₂ Z

I I

R⁴ R2 wherein R1 is C8-C22 alkyl or alkenyl, preferably C12-C16' R^ '^s hydrogen or CH2CO2M, R³ is CH₂CH₂OH or CH₂CH₂OCH2CH COOM, R⁴ is hydrogen, CH₂CH₂OH, or CH₂CH₂OCH₂CH2COOM, Z is C0₂M or CH2CO2M, n is 2 or 3, preferably 2, M is hydrogen or a cation, such as alkali metal, alkaline earth metal, ammonium, or alkonol ammonium. Suitable materials of this type are marketed under the tradename MIRANOL and are understood to comprise a complex mixture of species, and can exist in protonated and non-protonated species depending upon pH with respect to species that can have a hydrogen at R2. The imidazolinum amphoteric surfactant hereof can be derived via an imidazolinium intermediate. However, it will be recognized by thosed in the art that it needn't necessarily be derived via an imidazolinium.

Preferred amphoteric surfactants of are monocarboxylates and dicarboxylates. Examples of these materials include cocoamphocarboxypropionate, cocoamphocarboxypropionic acid, cocoamphocarboxyglycinate (alternately referred to as cocoamphodiacetate), and cocoamphoacetate.

Specific commercial products providing the imidazolinium derivative component of the present compositions include those sold under the trade names MIRANOL C2M CONC. N.P., MIRANOL C2M CONC. O.P., MIRANOL C2M SF, MIRANOL CM SPECIAL (Miranol, Inc.); ALKATERIC 2CIP (Alkaril Chemicals); AMPHOTERGE W-2 (Lonza, Inc.); MONATERIC CDX-38, MONATERIC CSH-32 (Mona Industries); REWOTERIC AM-2C (Rewo Chemical Group); and SCHEROTERIC MS- 2 (Scher Chemicals).

Amphoteric surfactants also include aminoalkanoates of the formula:

R-NH(CH₂)_nCOOM; and

iminodialkanoates of the formula:

R-N[(CH₂)_mCOOM]2 and mixtures thereof; wherein n and m are numbers from 1 to 4, R is Cs- C22 alky' or alkenyl, and M is hydrogen, alkali metal, alkaline earth metal, ammonium or alkanolammonium.

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

Zwitterionic surfactants can be considered as amphoteric surfactants exemplified by those which are broadly described as derivatives of aliphatic quaternary ammonium, phosphonium, and sulfonium compounds, in which the aliphatic radicals can be straight or branched chain, and wherein one of the aliphatic substituents contains from about 8 to about 18 carbon atoms and one contains an anionic water-solubilizing group, e.g., carboxy, sulfonate, sulfate, phosphate, or phosphonate. A general formula for these compounds is:

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

Zwitterionics include, for example, betaines. Examples of betaines include the high alkyl betaines, such as coco dimethyl carboxymethyl betaine, lauryl dimethyl carboxymethyl betaine, lauryl dimethyl alphacarboxyethyl betaine, cetyl dimethyl carboxymethyl betaine, lauryl bis-(2-hydroxyethyl) carboxymethyl betaine, stearyl bis-(2- -hydroxypropyl) carboxymethyl betaine, oleyl dimethyl gamma- -carboxypropyl betaine, and lauryl bis-(2-hydroxypropyl)alpha- -carboxyethyl betaine. The sulfobetaines may be represented by coco dimethyl sulfopropyl betaine, stearyl dimethyl sulfopropyl betaine, lauryl dimethyl sulfoethyl betaine, lauryl bis-(2-hydroxyethyl) sulfopropyl betaine and the like; amidobetaines and amidosulfobetaines, wherein the RCONH(CH₂)₃ radical is attached to the nitrogen atom of the betaine are also useful in this invention.

Polysiloxane Fluid-Containing Hair Conditioning Component The compositions hereof will also contain a hair conditioning component dispersed in the composition which comprises from about 0.01 % to about 10%, by weight of the composition, preferably from about 0.05% to about 5%, more preferably from about 0.5% to about 3%, of a nonvolatile, insoluble polysiloxane fluid as the hair conditioning agent. The level of the dispersed hair conditioning component, as a whole, will also generally fall within the above ranges. The polysiloxane-containing hair conditioning component and preferably the polysiloxane hair conditioning agent therein, will have a refractive index of less than 1.48, preferably about 1.46 or less, more preferably from about 1.40 to about 1.45, most preferably from about 1.42 to about 1.44. The polysiloxane hair conditioning agent, and preferably the hair conditioning component, will also have an average viscosities at 25°C of at least about 5,000 centipoise, preferably from about 50,000 to about 5,000,000 centipoise, more preferably from about 75,000 to about 2,000,000 centipoise, most preferably from about 100,000 to about 1 ,500,000 centipoise. Viscosity can be measured as previously described. The polysiloxane fluid hair conditioning agent can have other ingredients in the same dispersed phase, e.g., silicone resins (such as described above) to aid in disposition on the hair. The combination of any such additional ingredients in the same dispersed phase as the polysiloxane fluid hair conditioning agent is referred to herein as the polysiloxane fluid- containing hair conditioning component.

The polysiloxane fluid can have a structure as set forth above under Formula I, except that the level of aryl substitution must be sufficiently low such that the refractive index is as described above. Preferably the degree of aryl substitution will be less than about 15%, more preferably less than about 10%, even more preferably less than about 5%, most preferably zero percent. The most preferred conditioning agent is polydimethylsiloxane.

Preferred hair conditioning agents are combinations of lower viscosity nonvolatile silicone fluids, having average viscosities at 25°C of about 50 to about 10,000 centipoise, more preferably from about 100 to about 1000 centipoise, and silicone gums having viscosities of greater than 1 ,000,000 centipoise, at 25°C. The gums will generally, though not necessarily, have an average viscosity of from about 2,000,000 to about 10,000,000 centipoise at 25°C. Solvent Depending upon the particular choice of spreading agent (if any) and high refractive index polysiloxane fluid, it may be necessary or desirable to incorporate an additional solvent in the hair shine component phase to ensure that the resin and polysiloxane fluid are compatible with one another. If the solvent has a refractive index below about 1.46, or is otherwise below the refractive index of the polysiloxane fluid, it may be desirable to use a solvent which is volatile (materials that exhibit greater than 0.2mmHg at 25° C and one atmosphere, generally with a boiling point of less than 275° C), so that it does not remain on the hair and potentially impair the shine performance obtained according to the present invention. Suitable solvents include: cyclomethicone, other cyclic siloxanes such as those described herein as carrier fluids, linear polysiloxane polymers such as dimethicone, and other low viscosity analogues of the polysiloxane materials described in Formulas I and II, preferably having viscosity at 25°C of about 10 centistokes or less, such materials generally having lower (or zero) degree of aryl-containing substituents than the highly arylated, high refractive index polysiloxane of the present invention; volatile liquid hydrocarbons, such as straight or branched chain hydrocarbons having from about 4 to about 16 carbon atoms (e.g., hexane, isobutane, decane, dodecane, tetradecane, tridecane); lower alcohols (e.g. C₂-C₄ alcohols such as ethanol and isopropanol); hydrocarbon esters, preferably with a total of about 10 carbon atoms or less (e.g. ethyl acetate); halogenated hydrocarbons (e.g. freon); volatile ketones (e.g. acetone); and mixtures thereof. Especially preferred is cyclomethicone. The present invention does not, however, exclude the use of nonvolatile solvents for the resin/phenylated polysiloxane solvent.

When used, solvents as described above will be used typically at a weight ratio of (solvent) to (highly arylated nonvolatile polysiloxane plus spreading agent) of up to about 100:1 , more typically up to about 50:1 , for rinse-off hair care products, preferably from about 2:1 to about 10:1 for hair rinse products. For leave-on products, high levels of volatile solvents may be used as carrier ingredients, as described later. Dual Dispersed Polvsiloxane-Containing Hair Shine And Hair Conditioning Components

It is an essential aspect of the present invention that the polysiloxane-containing hair conditioning component and polysiloxane- containing hair shine component be dual dispersed in the composition. By this what is meant is that the hair shine and hair conditioning components each exist in the composition as distinct, discontinuous phases. The dispersed components will be present in the composition in the form of droplets. By "distinct, discontinuous phases", what is meant is that the droplets of the hair shine component and the droplets of the hair conditioning component exist in the composition as separate species of droplets. This has been found to be critical for providing conditioning with the unexpectedly improved hair shine. On the other hand, intermixing of the components of the high refractive index hair shine agent and the lower refractive index hair conditioning agent to form a single type of droplet would result in shine performance that would be substantially degraded.

The compositions of the present invention can be made by first preparing, or otherwise obtaining, separate dispersions of the polysiloxane hair shine agent and the polysiloxane hair conditioning agent, and then combining the two dispersions together, together with any additional ingredients, to form the final product. Conventional methods known in the art for preparing premix dispersions may be utilized. Preferably, the dispersions will be in the form of emulsions, formulated by separately mixing the ingredients of the polysiloxane hair shine component and the ingredients of the polysiloxane hair conditioning component, respectively, in water with an emulsifying agent. Suitable emulsifying agents include surfactants, including the anionic, nonionic, cationic, and amphoteric surfactants, and combinations thereof, as previously described. Preferred are anionic, amphoteric and nonionic surfactants. Especially preferred are anionic and nonionic surfactants. Most preferred, particularly for shampoos or other foaming or lathering compositions, are anionic surfactants. Especially preferred are alkyl and alkyl ethoxyglated sulfates. The weight ratio of the surfactant to polysiloxane hair conditioning agent or polysiloxane hair shine agent in the premix dispersions is preferably from about 1 :30 to about 6:5, more preferably from about 1 :12 to about 1 :4 It is also contemplated to add soluble salts such as sodium chloride or other viscosity modifying agents to the premix, to thicken the surfactant phase and ease emulsification, particularly when viscous polysiloxanes are to be emulsified. In general, from about 0.01 % to about 10%, by weight of the premix, of such salts are used. In general, the level of water in the premixes will be from about 1 % to about 20%, preferably from about 5% to about 10%, by weight of the premix.

The weight average droplet size (diameter) in the dispersions hereof will generally be from about 0.1 microns to about 500 microns, preferably from about 2 microns to about 250 microns, more preferably from about 5 microns to about 100 microns, most preferably from about 5 microns to about 50 microns. Carrier The compositions of the present invention will comprise an aqueous carrier for the hair shine agent and conditioning agent suitable for application to the hair. The aqueous carrier will comprise water at a level of from about 50% to about 99.99%, by weight of the composition, generally from about 50% to about 99.98%, preferably from about 60% to about 95%, more preferably from about 70% to about 90%. The compositions used herein can include other fluids, as well as other carrier components suitable for application to the hair. As used herein, the phrase "suitable for application to hair" means that the carrier does not damage or negatively affect the aesthetics of hair and is safe for application to the hair and to skin. As will be understood in the art, the choice of appropriate carrier will also depend on the particular polysiloxane fluids to be used, and whether the product is meant to be left on the hair (e.g., hair spray, mousse, tonic) or to be rinsed off after use (e.g., shampoo, hair conditioning rinse). Optional Ingredients

The compositions of the present invention may be formulated in a wide variety of product types, including mousses, gels, lotions, tonics, sprays, shampoos and conditioners. The additional components, in addition to the carrier, required or desirable to formulate such products vary with product type and can be routinely chosen by one skilled in the hair care product art. Additional Carrier Fluids

Suitable additional carrier fluids for use in the present invention include, but are not limited to, lower alcohols (e.g. C^-CQ) monohydhc alcohols, such as ethanol and isopropanol), hydrocarbons (such as isobutane, hexane, decene, acetone), halogenated hydrocarbons (such as Freon), linalool, and hydrocarbon esters (such as ethyl acetate, dibutyl phthalate). Suspending Agents and Thickening Agents

A preferred component in the present composition is a suspending agent for suspending the polysiloxane hair shine component and polysiloxane hair conditioning components in the compositions. Such suspending agents include crystalline suspending agents, gel vehicles, and other suspending and/or thickening agents. Thickening agents may be added to aid in suspending the dispersed, insoluble phases in the aqueous carrier or to merely modify rheology, or both. In general, suspending agents, and thickeners are used at levels of from about 0.1% to about 10%, by weight, of the composition.

Gel vehicles can comprises two components: a lipid and a cationic surfactant. Suitable cationic surfactants are described in detail above. Gel vehicles are generally described in the following documents, all incorporated by reference herein: Barry, 'The Self Bodying Action of the Mixed Emulsifier Sodium Dodecyl Sulfate/Cetyl Alcohol", 28 J. of Colloid and Interface Science 82-91 (1968); Barry, et al., 'The Self-Bodying Action of Alkyltrimethylammonium Bromides/Cetostearyl Alcohol Mixed Emulsifiers; Influence of Quaternary Chain Length", 35 1 of Colloid and Interface Science 689-708 (1971 ); and Barry, et al., "Rheology of Systems Containing Cetomacrogol 1000 - Cetostearyl Alcohol, I. Self Bodying Action", 38 J. of Colloid and Interface Science 616-625 (1972). Gel vehicles are particularly useful for hair rinse compositions, as well as leave-on hair care compositions such as gel conditioners and shine enhancers. Lipid gel vehicle materials are essentially water-insoluble, and contain hydrophobic and hydrophilic moieties. They include naturally or synthetically-derived acids, acid derivatives, alcohols, esters, ethers, ketones, and amides with carbon chains of from about 12 to about 22, preferably from about 16 to about 18, carbon atoms in length. Fatty alcohols and fatty esters are preferred; fatty alcohols are particularly preferred.

Preferred lipids are esters, such as cetyl palmitate and glycerylmonostearate. Cetyl alcohol and stearyl alcohol are preferred alcohols. A particularly preferred lipid vehicle material is comprised of a mixture of cetyl alcohol and stearyl alcohol containing from about 55% to about 65% (by weight of mixture) of cetyl alcohol.

Lipid vehicle materials among those useful herein are also dis¬ closed in Bailey's Industrial Oil and Fat Products. (3rd edition, D. Swern, ed., 1979), incorporated by reference herein. Fatty alcohols included among those useful herein are disclosed in the following documents, all incorporated by reference herein: U.S. Patent 3,155,591 , Hilfer, issued November 3, 1964; U.S. Patent 4,165,369, Watanabe, et al., issued August 21 , 1979; U.S. Patent 4,269,824, Villamarin, et al., issued May 26, 1981 ; British Specification 1 ,532,585, published November 15, 1978; and Fukushima, et al., 'The Effect of Cetostearyl Alcohol in Cosmetic Emulsions", 98 Cosmetics & Toiletries 89-112 (1983). Fatty esters included among those useful herein are disclosed in U.S. Patent 3,341 ,465, Kaufman, et al., issued September 12, 1976 (incorporated by reference herein). If included in the compositions of the present invention, the lipid vehicle material is preferably present at from about 0.1 % to about 8.0% of the composition; the cationic surfactant gel vehicle material is preferable present at from about 0.05% to about 5.0% of the composition.

Suspending agents or thickeners for use in the compositions of the present invention, especially for hair rinses, also include combinations of hydrophobically-modified hydroxyethyl cellulose materials with thickeners (such as locust bean gum), particular surfactants, quaternary ammonium compounds (such as ditallowdimethyl ammonium chloride), and/or chelating agents (such as EDTA). These vehicles are described in detail in the following patents: U.S. Patent 5,106,609, issued April 21 , 1992 to Bolich et al., U.S. Patent 5,100,658, issued March 31 , 1992 to Bolich et al., U.S. Patent 5,104,646, issued April 14, 1992 to Bolich et al, and U.S. Patent 5,100,657, issued March 31 , 1992 to Ansher-Jackson et al., each incorporated herein by reference.

Crystalline suspending agents are preferred components for suspending the hair shine component and hair conditioning component, as well as other immiscible or particulate ingredients (e.g. insoluble, anti-static cationic surfactants which are anti-dandruff actives, such as zinc pyridinethione, selenium disulfite, ant the like). A crystalline suspending agent is particularly preferred in pourable liquid formulations containing hair cleansing-effective amounts of detersive surfactants, such as shampoos.

Preferred suspending agents useful in the present compositions include any of several long chain acyl derivative materials or mixtures of such materials, such as long chain acyl derivatives, long chain amine oxides, and mixtures thereof, wherein such suspending agents are present in the composition in crystalline form. These suspending agents are described in U.S. Patent 4,741 ,855, Grote and Russell, issued May 3, 1988, and U.S. Reissue Patent RE 34,584, Grote and Russell, issued April 12, 1994, both incorporated herein by reference. Included are ethylene glycol esters of fatty acids having from about 16 to about 22 carbon atoms. Preferred are the ethylene glycol stearates, both mono and distearate, but particularly the distearate containing less than about 7% of the mono stearate. Other crystalline suspending agents found useful are alkanol amides of fatty acids, having from about 16 to about 22 carbon atoms, preferably about 16 to 18 carbon atoms. Preferred alkanol amides are stearic monoethanolamide, stearic diethanoiamide, stearic monoisopropanolamide and stearic monoethanolamide stearate. Other long chain acyl derivatives include long chain esters of long chain fatty acids (e.g., stearyl stearate, cetyl palmitate, etc.); glyceryl esters (e.g., glyceryl distearate and poly(2-8)glyceryl distearate) and long chain esters of long chain alkanol amides (e.g., stearamide DEA distearate, stearamide MEA stearate).

Still other suitable suspending agents are alkyl (C16-C22) dimethyl amine oxides such as stearyl dimethyl amine oxide. If the compositions contain an amine oxide or a long chain acyl derivative as a surfactant, the suspending function could also be provided by such surfactant and additional suspending agent may not be needed if the level of those materials are at least the minimum level given below. Other crystalline long chain acyl derivatives that can be used include N,N-dihydrocarbyl amido benzoic acid and soluble salts thereof (e.g., Na and K salts), particularly N.N-di(hydrogenated) C-|6. C-|8 and tallow amido benzoic acid species of this family, which are commercially available from Stepan Company (Northfield, Illinois, USA). The long chain acyl derivative materials, when utilized as the suspending agent, are typically present in pourable, liquid formulations at a level of from about 0.1 % to about 5.0%, preferably from about 0.5% to about 3.0%. The suspending agent serves to assist in suspending the silicone material and may give pearlescence to the product. Mixtures of suspending agents are also suitable for use in the compositions of this invention.

Another type of suspending agent that can be used is xanthan gum. Compositions utilizing xanthan gum as a suspending agent for a silicone hair conditioning component are described in U.S. Patent 4,788,006, Bolich and Williams, issued November 29, 1988, incorporated herein by reference. The gum, when used as the silicone hair conditioning component suspending agent, will typically be present in pourable, liquid formulations at a level of from about 0.3% to about 3%, preferably from about 0.4% to about 1.2% in the compositions of the present invention.

Combinations of long chain acyl derivatives and xanthan gum are disclosed as a suspending agent for silicone hair conditioners in U.S. Patent 4,704,272, Oh et al., issued November 3, 1987, incorporated herein by reference, and may also be used in the present compositions.

Other thickening agents include, for example, acrylates/C^<ιo-C30 acrylate crosspolymers.

A preferred type of product formulation of the present invention is a shampoo containing from about 1 % to about 35%, preferably from about 5% to about 30%, more preferably from about 8% to about 25%, most preferably from about 15% to about 22%, by weight, of a detersive surfactant selected from the group consisting of anionic surfactants, amphoteric surfactants, and nonionic surfactants. The preferred shampoos will also contain a suspending agent for suspending the dispersed phases of the polysiloxane hair shine and conditioning agents in the shampoo. Especially preferred are crystalline suspending agents and combinations of crystalline suspending agents with other thickening agents. Suitable anionic, amphoteric, and nonionic surfactants for use as detersive surfactants herein have been described above. Conditioning Agents

The compositions hereof may comprise additional conditioning agents, such as cationic surfactants and cationic polymers, organic oils and waxes such as hydrocarbon oils, and fatty acid esters, and alcohols. Suitable cationic polymers include, for example, copolymers of vinyl monomers having cationic amine or quaternary ammonium functionalities with water soluble spacer monomers such as acrylamide, methacrylamide, alkyl and dialkyi acrylamides, alkyl and dialkyi methacrylamides, alkyl acrylate, alkyl methacrylate, vinyl caprolactone, and vinyl pyrrolidone. The alkyl and dialkyi substituted monomers preferable have C^-Cy alkyl groups, more preferably C--C₃ alkyl groups. Other suitable spacer monomers include vinyl esters, vinyl alcohol (made by hydrolysis of polyvinyl acetate), maleic anhydride, propylene glycol and ethylene glycol. Other cationic polymers include cationic-modified polysaccharides, such as cationic ammonium modified cellulose. A variety of cationic surfactants are generally described above. Especially preferred are di(C-|2^_Cl8. especially C^Q-C^ ) alkyl and alkenyl, dimethyl ammonium salts (especially chloride salts). Hair Setting Polymers

The compositions hereof can contain film forming polymers, i.e. adhesive polymers, to aid in styling or setting the hair.

Exemplary hair setting polymers include polyvinylpyrrolidone (PVP), particularly poly N-vinyl pyrrolidone, copolymers of PVP and methylmetharylate, copolymers of PVP and vinyl acetate (VA), and polyvinyl alcohol (PVA).

Exemplary hair setting polymers also include copolymers of VA and crotonic acid, copolymers of methylvinylether and maleic hemiesters (e.g. maleic ethyl ester and maleic butyl ester), hydroxypropyl cellulose, hydroxypropyl guar gum, polystyrene sulfonate salts, polyacrylic polymers such as polymers and copolymers of acrylic acid and methacrylic acid, co- and ter- polymers of acrylic acid and/or methacylic acid with acrylamide and/or vinyl pyrrolidone such as terpolymers of vinyl pyrrolidone/methyl methacrylate/methacrylic, terpolymers of vinyl pyrrolidone/ethylmethacrylate/methacrylic acid, terpolymers of t-butyl acrylamide/ethyl acrylate/acrylic acid, and terpolymers of VA/crotonic acid/vinyl neodecanoate.

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

Polymeric hair setting polymers also include amphoteric polymers. One class of amphoteric polymers that can be used are acrylic resins with both cationic and carboxylic groups. Examples include terpolymers of octyl and acrylamide/acrylic acid/ butylaminoethyl methacrylate, copolymers of acrylic acid/betaine methacrylate, and copolymers of octylacrylamide/acrylates. Silicone-containing adhesive copolymers can also be used as hair setting polymers, such as those containing polysiloxane-containing monomers and non-polysiloxane-containing monomers, wherein the polymer has a weight average molecular weight of at least about 20,000, and comprises from about 1 % to about 50%, by weight, of the poly¬ siloxane-containing monomers.

The silicone-containing polymers can comprise an organic backbone, especially a carbon backbone such as a vinyl polymeric backbone, with a polydimethylsiloxane macromer having a weight average molecular weight of at least about 500, preferably from about 1 ,000 to about 100,000, more preferably from about 2,000 to about 50,000, most preferably about 5,000 to about 20,000, grafted to the backbone. Organic backbones contemplated include those that are derived from polyme zable, ethylenically unsaturated monomers. These include vinyl monomers, and other condensation monomers (e.g., those that polymerize to form polyamides and polyesters) and ring-opening monomers (e.g., ethyl oxazoline and caprolactone).

The preferred polymehzable polysiloxane-containing monomer (C monomer) can be exemplified by the general formula: ^X'^Y>n^Si<^R>3-m^Zm wherein X is a vinyl group copolymerizabie with the A and B monomers;

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

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

0 or 1 ; and m is an integer from 1 to 3.

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

Suitable polymers are also disclosed in EPO Application

90307528.1 , published as EPO Application 0408 311 A2 on January 11 ,

1991 , Hayama, et al., U.S. Patent 5,061 ,481 , issued October 29, 1991 , Suzuki et al., U.S. Patent 5,106,609, Bolich et al., issued April 21 , 1992,

U.S. Patent 5,100,658, Bolich et al., issued March 31 , 1992, U.S. Patent

5,100,657, Ansher-Jackson, et al., issued March 31 , 1992, and U.S.

Patent 5,104,646, Bolich et al., issued April 14, 1992, all of which are incorporated by reference herein. Preferred of these polymers are copolymers comprising t-butyl acrylate and/or t-butyl methacrylate with vinyl monomers having polydimethylsiloxane macromers covalently attached thereto. Other Optional Ingredients

The compositions herein can contain a variety of other optional components suitable for rendering such compositions more cosmetically or aesthetically acceptable or to provide them with additional usage benefits. Such conventional optional ingredients are well-known to those skilled in the art, e.g., pearlescent aids, such as mica, mother of pearl, ethylene glycol distearate preservatives, such as benzyl alcohol, methyl paraben, propyl paraben and imidazolidinyl urea; viscosity modifiers, such as a diethanolamide of a long chain fatty acid (e.g., PEG 3 lauric diethanolamide), cocomonoethanol amide; sodium chloride; sodium sul- fate; polyvinyl alcohol; pH adjusting agents, such as citric acid, sodium citrate, succinic acid, phosphoric acid, sodium hydroxide, sodium car¬ bonate; salts, in general, such as potassium acetate and sodium chloride; coloring agents, such as any of the FD&C or D&C dyes; anti- dandruff agents, such as zinc pyrithione, selenium sulfide, coal tar, salicylic acid, etc.;hair oxidizing (bleaching) agents, such as hydrogen peroxide, perborate and persulfate salts; hair reducing agents, such as the thioglycolates; perfumes; sequestering agents, such as disodium ethylenediamine tetra-acetate; and polymer plasticizing agents, such as glycerin, disobutyl adipate, butyl stearate, and propylene glycol. Such optional ingredients generally are used individually at levels of from about 0.01 % to about 10.0%, preferably from about 0.05% to about 5.0%, of the composition.

The pH of the present compositions generally will be between about 3 and about 9, preferably between about 4 and about 8. The hair care compositions of the present invention can be made using conventional formulation and mixing techniques, as set forth below.

Method of Use The hair care compositions of the present invention are used in conventional ways to provide the conditioning and shine benefits of the present invention. Such method of use depends upon the type of composition employed. The compositions may be applied to dry hair or hair that has been wetted or dampened with water. An effective amount of the product to provide conditioning and shine is applied to the hair. The product may be applied to the hair via any means effective, such as by spraying, pouring, applying with the hands, and the like, and may be further worked into the hair with the hands or a hair styling implement (e.g., a brush and/or comb). The composition may be left on the hair or rinsed off. Shampoos and hair rinses are preferably applied to wet or dampened hair, and subsequently rinsed off. sprays, mousses, gels, and tonics may be applied to wet or dry hair, and are generally left on the hair. After application to the hair, the hair is generally styled or dried. Alternately, especially for sprays, the hair may be styled prior to application of the composition. By "effective amount" is meant an amount sufficient to provide hair shine and conditioning benefits. In general, from about 0.1g to about 60g will be applied to the hair, although amounts outside this range may be effective depending upon the length and amount of the users hair, the type of hair and amount of shine and conditioning desired, the particular product formulations, and whether excess product is applied by the user.

Experimental The following procedure is used to determine Glossmeter Specular Reflectance.

A collagen solution is prepared by dissolving 10.0g of gelatin (175 bloom) in 83.0g DRO (double reverse osmosis) water at 155°C , with stirring. Next, 0.05g propylparaben is dissolved in the gelatin solution. Next, 4.5g 1M NaOH is added, followed by 3.0g of Ceraphyl GA-D (a mixture of 10-15% soy bean oil and 85-90% maleated soy bean oil available from VanDyk Inc., Belleville, NJ, USA) to form a stable, white emulsion. Next, 1.2g of lactic acid is stirred into the emulsion, referred hereinafter as Solution A.

A 3.0%, by weight, formaldehyde in water solution, Solution B, is prepared and contained separately from Solution A.

Ceramic tiles, approximately 7.3cm x 7.3cm in size having a black glazed top and an average peak height ("roughness") of 5.0 -7.0 microns (can be measured with a Rodenstock RM600-2D/3-D Measuring Station (Rodenstock Meterology, Munich, W. Germany)) are prepared and coated with the collagen on their top surfaces. Glossmeter Specular Reflectance of the collagen-coated tile should be from 8.0 - 12.0%.

Specular reflectance of the collagen-coated tile is measured utilizing a glossmeter, such as a BYK-Gardner "micro-gloss" glossmeter. Specular reflection measurements are made as described in ASTM Method D 523 at an angle of incidence of 60°. Specular reflectance measured this way is referred to herein as "Glossmeter Specular Reflectance." The tiles can be prepared as follows. Syringe A is filled with 3.0cc of Solution A. Syringe B is filled with 0.2cc of Solution B. Syringe B contents are emptied onto the top surface of a tile. Syringe A contents are emptied onto the top of Solution B, on the top surface of the tile. The solutions are mixed for five seconds and spread uniformly on the top surface of the tile with a spatula. At 30 seconds after mixing, a 1.0 inch inside diameter metal ring is placed on the top surface of the tile. The collagen film is allowed to dry for eight hours. The metal ring is removed. The roughness of the collagen coated surface of the tile should be from 3.0 to 5.0 microns.

A polysiloxane hair shine agent or polysiloxane-containing hair shine component is prepared, as previously described, at a 1.00% concentration in a compatible diluent. Any spreading agents or other additives in the shine agent phase of the product should be present at a weight ratio corresponding to that found in this phase of the composition. A syringe is used to deposit 0.05cc of the mixture at the center of the area encompassed by the ring on the surface of the collagen-coated tile. The mixture is allowed to dry. Glossmeter Specular Reflectance is measured.

EXAMPLES The following examples further illustrate preferred embodiments within the scope of the present invention. The examples are given solely for the purposes of illustration and are not be construed as limitations of the present invention as many variations of the invention are possible without departing from its spirit and scope.

PREMIX EXAMPLES 1-9 The following are a variety of exemplary polysiloxane hair conditioning agent dispersions useful in the present invention. These premixes can be used in a variety hair care compositions containing other cosmetically or pharmaceutically active ingredients, carrier ingredients, or other ingredients.

Component (Weioht%) Ex. 1 Ex. 2 Ex. 3

Pentaphenyl Trimethyl Trisiloxane (l ) 57.00 0.00 98.00

Methylphenyl Diphenyl Siloxane Copolymer (2) 38.00 0.00 0.00 Diphenyl Dimethyl Siloxane Copolymer (3) 0 0..0000 90.00 0.00 MQ Silicone Resin/Volatile Cyclomethicone (4) 5.00 10.00 0.00 Fluorosurfactant (5) 0.00 0.00 2.00

Component (Weioht%) Ex. 4 Ex. 5 Ex. 6 Pentaphenyl Trimethyl Trisiloxane (1 ) 99.00 75.00 59.00 Methylphenyl Diphenyl Siloxane Copolymer (2) 0.00 0.00 29.00

Diphenyl Dimethyl Siloxane Copolymer (3) 0 0..0000 0.00 0.00 MQ Silicone Resin/Volatile

Cyclomethicone (4) 0.00 25.00 10.00 Fluorosurfactant (5) 1.00 0.00 2.00

1. Dow Corning 705, Dow Corning

2. PS162, Huls

3. SF1265, General Electric

4. SS4230, General Electric Silicone Products Division (50%/50% of polytrimethyl hydrosilylsilicate/decamethylcyclopentasiloxane)

5. FC-171 Fluorad, 3M

Component (Weight⁰/.) Ex. 7 Ex. 8 Ex. 9

Ammonium Lauryl Sulfate(6) 40.50 0.00 20.00

Ammonium Laureth(3) Sulfate(7) 0.00 60.00 0.00

Diphenyl Dimethyl Siloxane(8) 40.50 0.00 70.00

Pentaphenyl Siloxane (9) 0.00 25.00 0.00

MQ Silicone Resin/Nonvolatile

Dimethicone(IO) 17.50 13.50 8.00

Sodium Chloride 1.50 1.50 1.00

6. 28%, by weight, active in aqueous solution

7. 28%, by weight, active in aqueous solution 8. SF 1265, General Electric Silicone Products Division

9. Dow Corning 705 Fluid, Dow Corning Corp.

10. SS4267, General Electric Silicone Products Division

(50%/50% of polytrimethyl hydrosilylsilicate/dimethylpolysiloxane, 300-700 centipoise, 25°C)

The premixes are prepared by blending all the components with agitation for about 1/2 hour at room temperature, to form a stable dispersion or emulsion.

The exemplary hair care compositions below can be made utilizing any of premix Examples 1-9, above (hereafter referred to as "Shine Premix Examples").

PREMIX EXAMPLES 10-13

Component (Weioht% . Ex. 10 Ex.11 Ex. 12 Ex. 13

Ammonium Lauryl Sulfate(12) 49.00 40.00 45.00 0.00 Ammonium Laureth(3) Sulfate(13) 0.00 30.00 0.00 0.00 Dimethicone(14) 49.00 0.00 43.00 90.00

Dimethicone Copolyol(15) 0.00 0.00 10.00 10.00 Cetyl Dimethicone(16) 0.00 28.00 0.00 0.00 Sodium Chloride 2.00 2.00 2.00 0.00

12. 28%, by weight, active in aqueous solution

13. 28%, by weight, active in aqueous solution

14. 40/60 weight ratio of dimethicone gum (SE 76, General Electric

Silicone Products Division) and dimethicone fluid (350 centipoise)

15. DC-190, Dow Corning Corp. 16. Abil Wax WS08, Goldschmidt

The premixes are prepared by blending all of the components with agitation for about 1/2 hour at room temperature, to form a stable dispersion or emulsion. The exemplary hair care compositions which follow can be made utilizing any of premix Examples 10-12, above (hereinafter referred to as "Conditioning Premix Examples").

EXAMPLES Nil The following are hair spray compositions representative of the present invention.

Component Example 3 (Weight %)

1 JL Hi

Conditioning Premix 2.5 2.5 2.5 Shine Premix 2.0 2.0 2.0

Diisobutyl adipate 0.7 — —

Potassium Hydroxide

Solution (45% cone) 1.0 1.0 1.0

Perfume 0.2 0.2 0.2

Water (DRO) -q.s. to 100%-

The Conditioning and Shine Premixes, plasticizer, if applicable, potassium hydroxide, and water are combined with mixing. The perfume is then added with mixing. The product can be packaged in conventional nonaerosol pump spray containers and compressed air pump spray aerosol containers.

The composition is made by mixing the above components together in a conventional manner. EXAMPLE IV

The following is a shampoo composition representative of the present invention.

Component Weight %

Ammonium Lauryl Sulfate 4.00 Ammonium Laureth Sulfate 12.00

Ammonium Xylene Sulfonate 1.50

Ethylene Glycol Distearate 2.00

Cocomonoethanol Amide 2.00

Tricetyl Methyl Ammonium Chloride 0.50 Cetyl Alcohol 0.42

Stearyl Alcohol 0.18

Conditioning Premix 1.50

Shine Premix 1.50

Preservative 0.03 Fragrance 1.20

Water (DRO) q.s.

Ammonium lauryl sulfate and citric acid are added to the distilled water at about 15 C. The mixture is heated to from 70 C. to 80 C. The cocamide MEA and glycol distearate are added at this point. The ammonium laureth-3 sulfate, cetyl alcohol, stearyl alcohol conditioning premix, and shine premix are blended at from 70 C to 90 C. This mixture is added to the batch following the ethylene glycol distearate. The preservative is then added. The batch is mixed for 5 minutes then cooled to room temperature (15 C to 25 C). The fragrance is added, then the batch is milled under high shear for at least 5 minutes using conventional milling apparatus.

EXAMPLE V The following is a styling gel composition representative of the present invention.

Component Weight %

Conditioning Premix 1.00

Shine Premix 1.00 Carbopol 9401 0.75

Triethanolamine 1.00

Dye solution 0.05

Perfume 0.10

Laureth-23 0.10 Water (DRO) q.s.

1 cross-linked polyacrylic acid, commercially available from B. F. Goodrich

This batch is made by mixing the listed components together in a conventional manner. EXAMPLE VI

The following is a hair mousse composition representative of the present invention.

Component Weight %

Conditioning Premix 1.50 Shine Premix 1.50

Ethanol 15.00

Cocamine oxide 0.60

Cocamide DEA 0.30

Perfume 0.10 Isobutane 7.00

Water (DRO) q.s.

The composition is made by blending all of the ingredients except isobutane at ambient temperature until well mixed. Aluminum aerosol cans are then filled with 95 parts of this batch, affixed with a valve which is crimped into position, and lastly pressure filled with 5 parts isobutane.

Examples VII-IX The following are conditioning rinse compositions representative of the present invention.

Component Ex. VII Ex. VII Ex. IX

Hydroxethyl Cellulose 0.40 0.20 0.00

Cetyl Hydroxyethylcellulose 0.00 0.40 0.50

Crotein Q 1.00 1.00 1.00

Stearylamidopropyl Dimethyl Amine 1.00 1.00 1.00

Ditallowdimethylammonium Chloride 0.75 0.75 0.75

Glyceryl Monostearate 0.25 0.00 0.00

Dipropylene Glycol lsoceteth-20 Acetate 0.00 0.25 0.25

Cetyl Alcohol 0.90 1.70 1.70

Stearyl Alcohol 0.60 0.00 0.00

Emulsifying Wax 0.50 0.00 0.00

Octyl Methoxy Cinnamate 0.00 1.00 1.00

Conditioning Premix 1.30 0.40 1.80

Shine Premix 1.30 1.80 0.40

Trimethyl silyl amodimethicone (1) 0.00 0.00 0.20

Fragrance 0.30 0.30 0.30

Citric Acid 0.22 0.22 0.22

Preservative 0.03 0.03 0.03

Water (DRO) q.s. q.s. q.s.

1. Dow Corning Q2-8820, Dow Corning

Hydroxyethyl cellulose is added to the water at a temperature of 15 C to 40 C and mixed to disperse the hydroxyethyl cellulose. This mixture is then heated to a temperature of from 60 C to 90 C. Materials listed 2 through 10 (counted from the top of the list) are added to the batch while the temperature is maintained in this range. The mixture is stirred for approximately 10 minutes, then cooled to approximately 50 C. The remaining materials are added at this temperature. The mixture is milled under high shear for approximately 2 minutes using a conventional milling apparatus, then cooled to room temperature. EXAMPLE X - XIV

Additional shampoo formulations of the present invention are exemplified below. Component fwt. %) Ex. X Ex. XI Ex. XII Ex. XIII Ex. XIV

Ammonium Laureth(3)

Sulfate (28% active) 60.20 40.00 54.04 42.86 32.14

Ammonium Lauryl

Sulfate (20% active) 20.00 13.60 0.00 0.00 45.00

Cocamidopropyl Betaine

(30% active) 0.00 0.00 22.22 0.00 0.00

Sodium Lauroyl

Sarcosinate (30% active) 0.00 0.00 0.00 6.67 0.00 Ethylene Glycol Distearate 2.00 2.00 1.50 1.50 2.00 Cocamide MEA 1 0.88 0.88 0.88 0.00 0.88 Diphenyl Dimethyl Siloxane 2 0.50 1.00 0.75 0.25 2.00 Sodium Chloride 0.10- 0.10- 0.02 0.02 0.10-

2.00 2.00 2.00

DMDM Hydantoin ³ 0.20 0.20 0.20 0.20 0.20

Dimethicone ⁴ 0.35 0.15 0.45 1.00 2.00

50/50 Trimethylsiloxysilicate/

Dimethicone 5 0.21 0.42 0.30 0.10 0.84

Disodium Phosphate 0.10- 0.10- 0.00 0.00 0.10-

1.00 1.00 1.00

Ammonium Chloride 0.18 0.18 0.00 0.00 0.18 Ethylene Diamine Tetra

Acetic Acid 0.13 0.13 0.00 0.00 0.13 Sodium Phosphate 0.10- 0.10- 0.00 0.00 0.10-

1.00 1.00 1.00

Sodium Sulfate 0.00 0.00 0.10- 0.10- 0.00 1.50 1.50

Lauryl Alcohol 0.00 0.00 0.21 0.21 0.00 Sodium Hydroxide 0.00 0.00 0.10- 0.10- 0.00 1.00 1.00

Polyquatemium-10 0.02 0.02 0.02 0.00 0.00 Added Water q.s. q.s. q.s. q.s. q.s.

1. Coconut fatty acid monoethanolamide

2. SF 1265, General Electric Silicone Products Division

3. Glydant ™, from Lonza

4. 40/60 weight ratio of dimethicone gum (SE 76, General Electric Silicone Products Division) and dimethicone fluid (350 centipoise, 25° C)

5. SS 4267, General Electric Silicone Products Division The shampoo formulations are prepared as follows. As applicable, premixes are prepared for ethylene glycol distearate, the polysiloxane-containing hair shine component, the polysiloxane- containing hair conditioning component, and the polyquaternium 10. For the premix preparations described below, all percentages are based on the total weight of the particular premix.

In Examples X, XI, and XIV, the ethylene glycol distearate premix is prepared as follows: 72.71 % ammonium laureth (3) sulfate aqueous solution (28% active) and 19.33% added water are mixed and heated to 73° C in a tank. Then 4.00% ethylene glycol distearate, 2.00% cocamide MEA, 0.40% disodium phosphate, 0.36% ammonium chloride, 0.26 % ethylene diamine tetraacetic acid (EDTA), and 0.20% sodium phosphate are sequentially added and mixed in the tank. The mixture is then mixed for an additional 15 minutes, and 0.74% Glydant is finally added with mixing.

In Examples XII and XIII, the ethylene glycol distearate premix is prepared as follows: 88.15% ammonium laureth (3) sulfate aqueous solution (28% active) is heated to 73° C in a tank. Then 6.00% ethylene glycol distearate, 0.40% lauryl alcohol, and 3.50% sodium sulfate are sequentially added to the tank with mixing, and then the mixture is mixed for an additional 15 minutes. 1.50% Glydant is finally added with mixing.

In Examples X, XI, XII, XIII, and XIV, the hair shine component premix is prepared by mixing 40.8% ammonium laureth (3) sulfate (28 % active in aqueous solution), 40.80 % diphenyl dimethyl siloxane, 17.00% of the trimethylsiloxysilicate/dimethicone and 1.40% sodium chloride in a tank for about 30 minutes at ambient temperature.

In Examples X, XI, XII, XIII, and XIV, the hair conditioning premix is prepared by mixing 70.00% dimethicone, 29.00% ammonium laureth(3)sulfate, and 1.00% sodium chloride to a tank at ambient temperature and mixing for about 30 minutes.

For Examples X and XI only, a polyquaternium 10 premix is prepared by mixing 3.80% polyquaternium 10 and 96.2% water in a tank for about 10 minutes. The shampoo formulations are prepared as follows. The ethylene glycol distearate, polyquaternium 10, hair shine component, and hair conditioning premixes are incorporated into the final mix at the appropriate amounts to provide the indicated level of ethylene glycol distearate, polyquaternium 10, dimethicone, diphenyl dimethyl siloxane, and dimethicone for each of the above shampoo formulations. The EGDS premix is milled with a high shear mill, cooled to 32° C, and added to a mix tank. Any remaining surfactant not accounted for in the premixes is then added to the tank, with mixing. The polyquaternium 10 premix (if applicable), hair shine component premix, and hair conditioning component premix are then added sequentially to the tank and the composition is mixed for about 15 minutes. In Examples X, XI, and XIV, pH is adjusted, as desired, to pH 5.5-6.5 with sodium phosphate, and viscosity is adjusted, as desired, to 2500-5500 centipoise (at 25° C) with sodium chloride. In Examples XII and XIII, pH is adjusted, as desired, to pH 5.5-6.5 with sodium hydroxide, and viscosity is adjusted, as desired, to 2500-5500 centipoise (at 25° C) with sodium sulfate. For all of the these examples, any water not accounted for in the premixes and surfactants is then added, with mixing. The shampoo formulations hereof can provide excellent conditioning to the hair, particularly dry hair conditioning, in combination with improved hair shine.

Claims

WHAT IS CLA.IMED IS:

1. A hair care composition for conditioning and providing shine to the hair, characterized in that said composition comprises:

(a) a dispersed hair conditioning component, comprising from 0.01% to 10%, by weight of the composition, of a nonvolatile, insoluble polysiloxane fluid, said polysiloxane fluid having a viscosity at 25°C of at least 5,000 centipoise, and said hair conditioning component having a refractive index of less than 1.48;

(b) a dispersed hair shine component, comprising from 0.005% to 5%, by weight of the composition, of a nonvolatile, insoluble polysiloxane fluid, said hair shine component having a refractive index of 1.48 or more;

(c) an aqueous carrier suitable for topical application to the hair;

wherein said hair conditioning component and said hair shine component exist in said composition as distinct, discontinuous phases.

2. A hair care composition as in Claim 1 , comprising from 0.1% to 10%, by weight, of a suspending agent for said conditioning agent and shine agent dispersed phases.

3. A hair care composition as in Claim 1 or 2, which is a shampoo further comprising from 1% to 35%, preferably from 8% to 25%, by weight, of a detersive surfactant selected from the group consisting of anionic surfactants, amphoteric surfactants, and nonionic surfactants, and combinations thereof.

4. A hair care composition as in Claim 1 , 2, or 3, wherein said dispersed conditioning agent and shine agent phases have a weight average droplet size of from 0.1 microns to 500 microns, preferably from 2 microns to 250 microns, more preferably from 5 microns to 50 microns.

5. A hair care composition as in Claim 1 , 2, 3, or 4, wherein said conditioning agent has a refractive index of from 1.42 to 1.44 and said shine agent has a refractive index of from 1.50 to 1.70, preferably from 1.50 to 160, more preferably from 1.52 to 1.56.

6. A hair care composition as in Claim 1 , 2, 3, 4, or 5, wherein said polysiloxane of said conditioning agent is polydimethylsiloxane.

7. A hair care composition as in Claim 1 , 2, 3, 4, 5, or 6, wherein said polysiloxane of said shine agent is a polyphenylmethylsiloxane having an average degree of phenyl substitution of at least 50%.

8. A hair care composition as in Claim 1 , 2, 3, 4, 5, 6,or 7 wherein said discontinuous phase of said hair shine agent further comprises a spreading agent for said polysiloxane, said spreading agent is an MQ silicone resin.

9. A method for making a topical hair care composition for providing conditioning and shine to the hair, characterized in that said method comprises the steps of:

(a) providing an aqueous dispersion of a polysiloxane conditioning agent, said polysiloxane conditioning agent having a refractive index of less than 1.48; and an average viscosity at 25°C of at least 5,000 centipoise;

(b) providing an aqueous dispersion of a polysiloxane shine agent, having a refractive index of 1.48 or more;

(c) mixing said dispersion (a) with dispersion (b), wherein said dispersions (a) and (b) exist as distinct discontinuous phases in said composition.

10. A method for providing conditioning and shine to the hair, chacterised in that it comprises applying the composition of Claim 1 , 2, 3, 4, 5, 6, 7, or 8 to the hair.