WO2000000170A1 - Hair shampoo and conditioner system - Google Patents

Abstract

A shampoo and conditioner system comprising: (a) a shampoo composition optionally comprising a silicone material and wherein the shampoo composition provides a Silicone Deposition Value of 50 or less as measured by the Silicone Deposition Value Technical Method; (b) a conditioner composition; comprising a quaternary ammonium compound wherein the system has a Volume Index Value of 50 or greater as measured by the Volume Technical Test Method and a Detangling Value of 90 or greater as measured by the Detangling Technical Test Method. The shampoo and conditioner system of the present invention provides excellent cleansing and hair detangling with the additional benefits of leaving the hair feeling clean and providing improved volume.

Description

Hair Shampoo and Conditioner System

Technical Field

The present invention relates to a hair shampoo and conditioner system.

Background ofthe Invention

Scalp hair becomes soiled due to its contact with the surrounding environment and from sebum secreted from the hair follicles. The build-up of sebum and environmental soiling can cause the hair to have a dirty or greasy feel, and an unattractive appearance. In order to ameliorate these effects, it is necessary to shampoo the hair regularly.

Shampooing the hair removes excess sebum and other environmental soiling. However, the shampooing process has disadvantages in that the hair is left in a wet, tangled and generally unmanageable state. Shampooing can also result in the hair becoming dry and frizzy, and a loss of lustre, due to removal of natural oils or other hair moisturizing materials. After shampooing, the hair can also suffer from a loss of "softness" perceived by the user upon drying. The hair can also suffer from increased levels of static upon drying after shampooing. This can interfere with combing and can result in fly-away hair.

A variety of approaches have been developed to condition the hair. These range from post-shampooing hair rinses, to leave-on hair conditioners, to the inclusion of hair conditioning components in shampoos. There are several advantages for providing hair conditioning components such as silicones in shampoos. First of all many consumers prefer the ease and convenience of a shampoo which includes conditioners. An additional advantage of conditioning shampoo compositions is that such compositions provide a good in-use wet hair feel compared to shampoos which do not contain conditioning ingredients. A substantial proportion of consumers however prefer the more conventional conditioner formulations which are applied to the hair as a separate step from shampooing, usually subsequent to shampooing. These hair conditioners typically are formulated as a thickened product, such as a gel or cream, for ease of dispensing and application to the hair. Consumers who have fine or straight hair may ideally prefer conditioners which provide increased hair volume versus what is achievable from today's marketed conditioners at the same time as providing conditioning/detangling benefits. Many conventional conditioning compositions based on fatty alcohols and many conditioning shampoos relying upon conditioning ingredients such as silicones, although effective at providing a detangling benefit, cause a decrease in hair volume post-conditioning in dry hair. It would therefore be desirable to provide a shampooing and conditioning system which minimized decrease in dry hair volume following conditioning.

It would be even more desirable to provide a shampoo and conditioner system wherein the system provides good in-use wet hair feel, a wet clean feel on rinsing and post rinsing, dry clean feel, good wet detangling and which minimizes volume loss typically experienced with conditioning shampoo and conditioner systems.

As mentioned above, shampoo compositions containing conditioning materials provide good in-use wet hair feel characteristics, such as smooth, soft and silky hair feel. However, as also mentioned above such compositions generally also provide a significant reduction in dry hair volume versus typical unconditioned dry hair. In addition, as mentioned above conventional conditioner compositions based on fatty alcohols generally provide a significant reduction in hair volume post conditioning. Conventional conditioner compositions based on fatty alcohols can also suffer from the disadvantage of leaving the hair feeling greasy both during rinsing and post rinsing. Therefore, although it would be possible to use a conventional conditioning shampoo in combination with a conventional conditioner to provide good in-use feel and good detangling, such a system would lead to a large reduction in dry hair volume versus typical unconditioned dry hair and may also leave the hair feeling greasy.

It has now surprisingly been found that a shampoo and conditioner system wherein the shampoo provides zero or low levels of silicone deposition and wherein the conditioner system is not based on fatty alcohols but based on certain quaternary ammonium compounds, provides a good in-use wet feel on shampooing, a good clean feel on rinsing and post rinsing, good dry clean feel, together with excellent wet detangling and minimized dry hair volume loss typically experienced with conventional shampoo and conditioner systems. Summary ofthe Invention

According to the present invention there is provided a shampoo and conditioner system comprising:

(a) a shampoo composition optionally comprising a silicone material and wherein the shampoo composition provides a Silicone Deposition Index Value of 50 or less as measured by the Silicone Deposition Index Value Technical Test Method;

(b) a conditioner composition;

wherein the system has a Volume Index Value of 20 or greater as measured by the Volume Index Technical Test Method and a Detangling Index Value of 90 or greater as measured by the Detangling Index Technical Test Method.

The shampoo and conditioner system of the present invention provides excellent in-use wet feel, excellent clean feel during rinsing and post-rinsing, good dry clean feel and excellent wet detangling, in addition to minimizing dry hair volume loss versus conventional shampoo and conditioner systems.

The levels, concentrations and ratios herein are by weight of the cleansing composition, unless otherwise specified. Surfactant chain lengths are also on a weight average chain length basis, unless otherwise specified.

Detailed Description ofthe Invention

The shampoo and conditioner system herein comprises a shampoo composition and a conditioner composition. The shampoo composition optionally comprises a silicone material. In addition, the shampoo composition provides a Silicone Deposition Index Value of 50 or less as measured by the Silicone Deposition Test Method described hereinbelow. The system has a Volume Index Value of 20 or greater as measured by the Volume Index Technical Test Method described hereinbelow and a Detangling Index Value of 90 or greater as measured by the Detangling Index Technical Test Method described hereinbelow. Shampoo composition

Any silicone containing shampoo composition suitable for use for cleansing hair can be used herein provided that it provides a Silicone Deposition Value for the shampoo composition of 50 or less, preferably 25 or less, more preferably 20 or less, as measured by the Silicone Deposition Technical Test Method, and provided that when used with a conditioner, the shampoo and conditioner system provides a Volume Index Value of 20 or greater as measured by the Volume Index Technical Test Method described hereinbelow and a Detangling Index Value of 90 or greater as measured by the Detangling Index Technical Test Method described hereinbelow.

Shampoo composition

The shampoo compositions used herein comprise a suitable surfactant system.

Surfactant System

The surfactant system of the present invention is preferably present in the shampoo compositions at an active level of from about 4% to about 30%, more preferably from about 4% to about 25%, even more preferably from about 5% to about 20%. It should be recognized , however, that the concentration of the surfactant system may vary with the cleaning or lather performance desired, the surfactants incorporated into the surfactant system, the desired product concentration, the presence of other components in the composition, and other factors well known in the art.

The surfactant system of the present invention comprises primary detersive surfactants selected from the group consisting of anionic surfactants, amphoteric surfactants and mixtures thereof as well as additional detersive surfactants selected from the group consisting of nonionic surfactants, cationic surfactants or mixtures thereof. The purpose ofthe detersive surfactant is to provide cleaning performance to the composition.

Amphoteric surfactant components useful in the present composition include those known to be useful in personal cleansing compositions, and which, preferably, contain a group that is anionic at the pH of the compositions of the present invention. The active concentration of such surfactant components in the surfactant system of the present invention preferably ranges from about 0.5 % to about 20%, more preferably from about 1% to about 15%, and most preferably from about 2% to about 10% by weight of the surfactant system. Examples of amphoteric surfactants suitable for use in the composition herein are described in U.S. Patents 5,104,646 (Bolich Jr. et al.), U.S. Patent 5,106,609 (Bolich Jr. et al.), which descriptions are incorporated herein by reference. Examples of amphoteric detersive 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, sodium lauroamphoacetate, 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.

Other amphoterics, sometimes classified as zwitterionics, such as betaines can also be used in the present invention. Such zwitterionics are considered as amphoterics in the present invention where the zwitterionic has an attached group that is anionic at the pH of the composition. Examples of betaines useful herein include the high alkyl betaines, such as coco dimethyl carboxymethyl betaine, cocoamidopropyl betaine, cocobetaine, lauryl amidopropyl betaine, oleyl 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(CH ) radical is attached to the nitrogen atom of the betaine are also useful in this invention. Most preferred for use herein is cocoamidopropyl betaine.

Suitable anionic surfactants include alkyl sulfate, alkyl ethoxylated sulfate, or a mixture thereof. These materials have the respective formulae (I) ROSO3M and (II) RO(C2H_iO)_xSO3M, wherein R is alkyl or alkenyl of from about 8 to about 30 carbon atoms, x is 1 to 10, and M is H or a salt-forming cation such as ammonium, alkanolamine containing C1-C3 alkyl groups such as triethanolamine, and monovalent and polyvalent metals such as the alkaline and alkaline earth metals. Preferred metals include sodium, potassium, magnesium, and calcium. The cation M, of the anionic surfactant should preferably be chosen such that the anionic surfactant component is water soluble. Solubility of anionic surfactants, in general, will depend upon the particular anionic surfactants and cations chosen. As an aid to determining appropriate mixtures of anionic surfactants, the anionic surfactants should be chosen such that the Krafft temperature is about 15°C or less, preferably about 10°C or less, more preferably about 0°C or less. It is also preferred that the anionic surfactant be soluble in the composition hereof.

Preferably, R has from about 10 to about 18 carbon atoms in both the alkyl and alkyl ethoxylated sulfates. The alkyl ethoxy lated sulfates are typically made as condensation products of ethylene oxide and monohydric alcohols having from about 8 to about 24 carbon atoms. The alcohols can be derived from fats, e.g., coconut oil, palm kernel oil, or tallow, or can be synthetic. Such alcohols are preferably reacted with about 1 to about 10, more preferably from about 1 to about 4, most preferably from about 2 to about 3.5, molar proportions of ethylene oxide and the resulting mixture of molecular species having, for example, an average of 3 moles of ethylene oxide per mole of alcohol, is sulfated and neutralized.

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

The sulfate surfactant is preferably comprised of a combination of ethoxylated and nonethoxylated sulfates. Alkyl sulfates can provide excellent cleaning and lather performance. Alkyl ethoxylated sulfates can provide excellent cleaning performance.

Other suitable anionic detersive surfactants include, but are not limited to water-soluble salts of organic, sulfuric acid reaction products of the general formula [R1-SO3-M] where R\ is selected from the group consisting of a straight or branched chain, saturated aliphatic hydrocarbon radical having from about 8 to about 24, preferably about 10 to about 18, carbon atoms; and M is a cation such as ammonium, alkanolamines, such as triethanolamine, monovalent metals, such as sodium and potassium, and polyvalent metal cations, such as magnesium, and calcium. The cation M, of the anionic detersive surfactant should be chosen such that the detersive surfactant component is water soluble. Solubility will depend upon the particular anionic detersive surfactants and cations chosen. Examples of such detersive surfactants are the salts of an organic sulfuric acid reaction product of a hydrocarbon ofthe methane series, including iso-, neo- , and n-paraffins, having about 8 to about 24 carbon atoms, preferably about 10 to about 18 carbon atoms and a sulfonating agent, e.g., SO3, H2SO4, obtained according to known sulfonation methods, including bleaching and hydrolysis. Preferred are alkali metal and ammonium sulfonated CJO-18 n-paraffins.

Another class of anionic detersive surfactants suitable for use in 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 or palm kernal oil; sodium, ammonium, tetraethylammonium or potassium salts of fatty acid amides of methyl tauride in which the fatty acids, for example, are derived from coconut oil or palm kernal oil. Other similar anionic surfactants are described in U.S. Patent 2,486,921; U.S. Patent 2,486,922; and U.S. Patent 2,396,278, which descriptions are incorporated herein by reference.

Other anionic detersive surfactants suitable for use in the present invention are the succinnates, examples of which include disodium N-octadecylsulfosuccinnate; disodium lauryl sulfosuccinate; diammonium lauryl sulfosuccinate; tetrasodium N-(l,2- dicarboxyethyl)-N-octadecylsulfosuccinnate; diamyl ester of sodium sulfosuccinic acid; dihexyl ester of sodium sulfosuccinic acid; dioctyl esters of sodium sulfosuccinic acid.

Other suitable anionic detersive surfactants include alkyl glyceryl ether sulfonate surfactants (also referred to herein as an "AGS" surfactant), derivatives thereof and salts thereof. These AGS surfactants are derived from an alkyl glyceryl ether containing a sulfonate or sulfonate salt group. These compounds generally can be described as an alkyl monoether of glycerol that also contains a sulfonate group.

These AGS surfactants can be described as generally conforming to the following structures: ROCH₂CHCH₂SO₃-X⁺

OH

HOCH2CHCH₂SO₃-X⁺

OR

wherein R is a saturated or unsaturated straight chain, branched chain, or cyclic alkyl group having from about 10 to about 18 carbon atoms, preferably from about 11 to about 16 carbon atoms, and most preferably from about 12 to about 14 carbon atoms, and X is a cation selected from the group consisting of ammonium; mono-alkylsubstituted ammonium; di-alkylsubstituted ammonium; tri-alkylsubstituted ammonium; tetra- alkylsubstituted ammonium; alkali metal; alkaline metal; and mixtures thereof. More preferably, the alkyl radicals, R in the above formulas, are saturated and straight chain.

Without being limited by theory, it is believed that the distribution of alkyl chain lengths in the AGS surfactant has some effect on the character of the overall cleansing composition. A satisfactory distribution can be achieved in a commercially practicable way by using fatty alcohols derived from coconut oil and tallow. An equivalent distribution of alkyl chain lengths can be achieved using other starting materials. In the preparation of the coconut fatty alcohols used to provide the alkyl group of the AGS, preferably the middle cut of the coconut oil is taken. The higher boiling cut can be retained with the middle cut coconut oils if desired. In the preparation of the tallow fatty alcohols, a hydrogenation step is included to insure that they are substantially saturated.

The preferred AGS compounds are those where the alkyl group is derived from at least about 50% from alcohols of about 10 to about 18 carbons, having mainly monoglyceryl radicals present, with less than about 30% of diglyceryl radicals present. The AGS used in the Examples described below contains about 15% of diglyceryl ether sulfonates, and is preferred because of the ease of manufacturing this material. The term "AGS" is intended to include monoglyceryl, diglyceryl, and traces of the higher glyceryl compounds. Small amounts, that is less than about 3% total, of triglyceryl ether sulfonates and tetraglyceryl ether sulfonates can be present. Also included are AGS's derived from glyceryl ethers having branched or mixed branched and straight chain lengths that emulate the straight chain lengths. The AGS surfactants useful in the present invention are more fully described in U.S. Patent No. 2,979,465, to Parran et al., issued April 11, 1961; U.S. Patent No. 3,179,599, to Eaton et al., issued April 20, 1965; British Patent No. 848,224, published Sept. 14, 1960; British Patent No. 791,415, published March 5, 1958; U.S. Patent No. 5,322,643, to Schwartz et al., issued June 21, 1994; and U.S. Patent No. 5,084,212, to Farris et al. issued Jan. 28, 1992; which are all hereby incorporated herein by reference in their entirety. These references also disclose various cleansing products in which the AGS surfactant of this invention can be used.

Still other suitable anionic detersive surfactants include olefin sulfonates having about 10 to about 24 carbon atoms. The term "olefin sulfonates" is used herein to mean compounds which can be produced by the sulfonation of alpha-olefins by means of uncomplexed sulfur trioxide, followed by neutralization of the acid reaction mixture in conditions such that any sulfones which have been formed in the reaction are hydrolyzed to give the corresponding hydroxy-alkanesulfonates. The sulfur trioxide can be liquid or gaseous, and is usually, but not necessarily, diluted by inert diluents, for example by liquid SO₂, chlorinated hydrocarbons, etc., when used in the liquid form, or by air, nitrogen, gaseous SO₂, etc., when used in the gaseous form.

The alpha-olefins from which the olefin sulfonates are derived are mono-olefins having about 10 to about 24 carbon atoms, preferably about 12 to about 16 carbon atoms. Preferably, they are straight chain olefins.

In addition to the true alkene sulfonates and a proportion of hydroxy-alkanesulfonates, the olefin sulfonates can contain minor amounts of other materials, such as alkene disulfonates depending upon the reaction conditions, proportion of reactants, the nature of the starting olefins and impurities in the olefin stock and side reactions during the sulfonation process.

A specific alpha-olefin sulfonate mixture ofthe above type is described more fully in the U.S. Patent 3,332,880, which description is incorporated herein by reference. Another class of anionic detersive surfactants suitable for use in the present invention are the beta-alkyloxy alkane sulfonates. These compounds have the following formula:

where R! is a straight chain alkyl group having from about 6 to about 20 carbon atoms, R2 is a lower alkyl group preferably having from about 1 to about 3 carbon atoms, and M is a water-soluble cation as hereinbefore described.

Preferred additional anionic detersive surfactants for use in the present invention include alkyl glyceryl ether sulfonate, ammonium lauryl sulfate, ammonium laureth sulfate, triethylamine lauryl sulfate, triethylamine laureth sulfate, triethanolamine lauryl sulfate, triethanolamine laureth sulfate, monoethanolamine lauryl sulfate, monoethanolamine laureth sulfate, diethanolamine lauryl sulfate, diethanolamine laureth sulfate, lauric monoglyceride sodium sulfate, sodium lauryl sulfate, sodium laureth sulfate, potassium lauryl sulfate, potassium laureth sulfate, sodium lauryl sarcosinate, sodium lauroyl sarcosinate, lauryl sarcosine, cocoyl sarcosine, ammonium cocoyl sulfate, ammonium lauroyl sulfate, sodium cocoyl sulfate, sodium lauroyl sulfate, potassium cocoyl sulfate, potassium lauryl sulfate, triethanolamine lauryl sulfate, triethanolamine lauryl sulfate, monoethanolamine cocoyl sulfate, monoethanolamine lauryl sulfate, sodium tridecyl benzene sulfonate, sodium dodecyl benzene sulfonate, and combinations thereof.

In the shampoo compositions herein, a preferred combination of surfactants is ammonium lauryl sulfate and ammonium laureth-3 sulfate in a weight ratio of from about 3:1 to about 1 :3, preferably from about 2:1 to about 1:2, respectively. Another preferred combination of surfactants is alkyl glyceryl sulphonate and ammonium lauryl sulphate in a weight ratio of from about 4:1 to about 1 :4, preferably from about 3:1 to about 1 :3, respectively.

The anionic detersive surfactants are preferably present in the surfactant system of the present invention at total active concentration level of from about 3% to about 30%, preferably from about 4% to about 20%, most preferably from about 6% to about 17%.

Another class of anionic surfactants is fatty acid soaps. Though useful to the present invention, high concentrations of these surfactants in the presence of hard water tend to result in significant buildup on the hair and skin, adversely affecting cleansing and hair and skin feel. Accordingly, if added to the compositions of the present invention, the level ofthe fatty acid soaps is preferably incorporated at concentration levels of less than about 3%, more preferably less than about 1%.

The surfactant system of the present invention may also include nonionic surfactants, cationic surfactants, and combinations thereof. Suitable classes of nonionic surfactants include:

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 12 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. The alkyl substituent in such compounds may be derived from polymerized propylene, diisobutylene, octane, or nonane, for example.

2. Those derived from the condensation of ethylene oxide with the product resulting from the reaction of propylene oxide and ethylene diamine products which may be varied in composition depending upon the balance between the hydrophobic and hydrophilic elements which is desired. For example, compounds containing from about 40% to about 80% polyoxyethylene by weight and having a molecular weight of from about 5,000 to about 11,000 resulting from the reaction of ethylene oxide groups with a hydrophobic base constituted of the reaction product of ethylene diamine and excess propylene oxide, said base having a molecular weight of the order of about 2,500 to about 3,000, are satisfactory.

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

4. Long chain tertiary amine oxides corresponding to the following general formula:

R1 R2R3 N→O wherein Rj contains an alkyl, alkenyl or monohydroxy alkyl radical of from about 8 to about 18 carbon atoms, from 0 to about 10 ethylene oxide moieties, and from 0 to about 1 glyceryl moiety, and R₂ and R3 contain from about 1 to about 3 carbon atoms and from 0 to about 1 hydroxy group, e.g., methyl, ethyl, propyl, hydroxyethyl, or hydroxypropyl radicals. The arrow in the formula is a conventional representation of a semipolar bond. Examples of amine oxides suitable for use in this invention include dimethyl- dodecylamine oxide, oleyldi(2-hydroxyethyl) amine oxide, dimethyloctylamine oxide, dimethyl-decylamine oxide, dimethyl- tetradecylamine oxide, 3,6,9-trioxaheptadecyldiethylamine oxide, di(2- hydroxyethyl)-tetradecylamine oxide, 2-dodecoxyethyldimethylamine oxide, 3 -dodecoxy-2-hydroxypropyldi(3 -hydroxypropyl) amine oxide, dimethylhexadecylamine oxide.

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

RR'R' →O wherein R contains an alkyl, alkenyl or monohydroxyalkyl radical ranging from about 8 to about 18 carbon atoms in chain length, from 0 to about 10 ethylene oxide moieties and from 0 to about 1 glyceryl moiety and R' and R" are each alkyl or monohydroxyalkyl groups containing from about 1 to about 3 carbon atoms. The arrow in the formula is a conventional representation of a semipolar bond. Examples of suitable phosphine oxides are: dodecyldimethylphosphine oxide, tetradecyldimethylphosphine oxide, tetradecylmethylethylphosphine oxide, 3,6,9,- trioxaoctadecyldimethylphosphine oxide, cetyldimethylphosphine oxide, 3- dodecoxy-2-hydroxypropyldi(2-hydroxyethyl) phosphine oxide, stearyldimethylphosphine oxide, cetylethylpropylphosphine oxide, oleyldiethylphosphine oxide, dodecyldiethylphosphine oxide, tetradecyldiethylphosphine oxide, dodecyldipropylphosphine oxide, dodecyldi(hydroxymethyl)phosphine oxide, dodecyldi(2- hydroxyethyl)phosphine oxide, tetradecylmethyl-2-hydroxypropylphosphine oxide, oleydimethylphosphine oxide, 2-hydroxydodecyldimethylphosphine oxide.

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. Examples include: octadecyl methyl sulfoxide, 2-ketotridecyl methyl sulfoxide, 3,6,9,-trixaoctadecyl 2-hydroxyethyl sulfoxide, dodecyl methyl sulfoxide, oleyl 3 -hydroxypropyl sulfoxide, tetradecyl methyl sulfoxide, 3- methoxytridecyl methyl sulfoxide, 3-hydroxytridecyl methyl sulfoxide, 3- hydroxy-4-dodecoxybutyl methyl sulfoxide.

Polyalkylene oxide modified dimethylpolysiloxanes, also known as dimethicone copolyols. These materials include the polyalkylene oxide modified dimethylpolysiloxanes ofthe 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. Dimethicone copolyols among those useful herein are disclosed in the following patent documents, all incorporated by reference herein: U.S. Patent 4,122,029, Gee et al., issued Oct. 24, 1978; U.S. Patent 4,265,878, Keil, issued May 5, 1981; and U.S. Patent 4,421,769, Dixon et al., issued Dec. 20, 1983. Commercially available dimethicone copolyols, useful herein, include Silwet Surface Active Copolymers (manufactured by the Union Carbide Corporation); Dow Corning Silicone Surfactants (manufactured by the Dow Corning Corporation); Silicone Copolymer F-754 (manufactured by SWS Silicones Corp.); and Rhodorsil 70646 Fluid (manufactured by Rhone Poulenc, Inc.).

Cationic surfactants are also useful in compositions ofthe present invention and typically 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 1989); 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. If included in the compositions of the present invention, the cationic surfactant must not interfere with the in-use performance and end-benefits ofthe hair cleansing composition.

Among the quaternary ammonium-containing cationic surfactant materials useful herein are those ofthe 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.

Other quaternary ammonium salts useful herein have the formula:

C+X+:

Rj - N -(CH ) - N 2 X

1 ^l 1

¹ 3 "6 wherein R1 is an aliphatic group having from about 16 to about 22 carbon atoms, R , R3, R4, R5, and R are selected from hydrogen and alkyl having from about 1 to about 4 carbon atoms, and X is an ion selected from halogen, acetate, phosphate, nitrate and alkyl sulfate radicals. Such quaternary ammonium salts include tallow propane diammonium dichloride.

Preferred quaternary ammonium salts include monoalkyltrimethylammonium chlorides and dialkyldimethylammonium chlorides and trialkyl methyl ammonium chlorides, wherein at least one ofthe alkyl groups have from about 12 to about 22 carbon atoms and are derived from long-chain fatty acids, such as hydrogenated tallow fatty acid (tallow fatty acids yield quaternary compounds wherein the long chain alkyl groups are predominately from 16 to 18 carbon atoms). Examples of quaternary ammonium salts useful in the present invention include stearyl trimethyl ammonium chloride, ditallowdimethyl ammonium chloride, ditallowdimethyl ammonium methyl sulfate, dihexadecyl dimethyl ammonium chloride, di(hydrogenated tallow) dimethyl ammonium chloride, dioctadecyl dimethyl ammonium chloride, dieicosyl dimethyl ammonium chloride, didocosyl dimethyl ammonium chloride, di(hydrogenated tallow) dimethyl ammonium acetate, dihexadecyl dimethyl ammonium chloride, dihexadecyl dimethyl ammonium acetate, ditallow dipropyl ammonium phosphate, ditallow dimethyl ammonium nitrate, di(coconutalkyl) dimethyl ammonium chloride, and stearyl dimethyl benzyl ammonium chloride, ditallow dimethyl ammonium chloride, dicetyl dimethyl ammonium chloride, stearyl dimethyl benzyl ammonium chloride and cetyl trimethyl ammonium chloride are preferred quaternary ammonium salts useful herein. Di- (hydrogenated tallow) dimethyl ammonium chloride and tricetyl methyl ammonium chloride are particularly preferred quaternary ammonium salts. These materials also provide anti-static benefits to shampoo embodiments ofthe present invention.

Other surfactants known in the art for use in hair cleansing products may be used in the surfactant system ofthe present invention, provided that the surfactant is also chemically and physically compatible with the essential components of the present invention, or does not otherwise unduly impair product performance, aesthetics or stability. Preferred for use in the surfactant system of the present invention are anionic and/or amphoteric surfactants.

Though useful to the compositions of the present invention, nonionic or cationic surfactants tend to reduce the lathering properties of shampoo compositions. To maintain adequate lathering profiles, nonionic or cationic surfactants are preferably present at low concentrations. Generally, the surfactant system of the present invention will contain less than 3%, more preferably less than 1% of the nonionic and cationic surfactant. Silicone conditioning agent

The compositions of the present invention may optionally include silicone conditioning components. The silicone components can be intermixed into aqueous hair cleansing compositions, forming an emulsified, discontinuous silicone phase. The silicone can also be in the form of a solubilized phase or a microemulsion. The silicone conditioning component will comprise a silicone fluid conditioning agent such as a silicone fluid and can also comprise other ingredients, such as a silicone resin to enhance silicone fluid deposition efficiency or enhance glossiness of the hair (especially when high refractive index (e.g. above about 1.46) silicone conditioning agents are used (e.g. highly phenylated silicones). Preferably the silicone is non-volatile, however volatile silicones are not excluded from use herein.

As used herein, "nonvolatile" refers to silicone material with little or no significant vapor pressure under ambient conditions, as is understood by those in the art. Boiling point under one atmosphere (atm) will preferably be at least about 250°C, more preferably at least about 275°C, most preferably at least about 300°C. Vapor pressure is preferably about 0.2mm Hg at 25°C or less, preferably about 0.1mm Hg at 25°C or less.

The silicone conditioning agent phase may comprise volatile silicone, nonvolatile silicone, or mixtures thereof. Typically, if volatile silicones are present, it will be incidental to their use as a solvent or carrier for commercially available forms of nonvolatile silicone materials ingredients, such as silicone gums and resins.

The silicone conditioning agents for use in the compositions of the present invention preferably have a viscosity of from about 20 to about 2,000,000 centistokes, more preferably from about 1,000 to about 1,800,000 centistokes, even more preferably from about 10,000 to about 1,500,000 centistokes, most preferably from about 30,000 to about 1,000,000 centistokes, at 25°C. The viscosity can be measured by means of a glass capillary viscometer as set forth in Dow Corning Corporate Test Method CTM0004, July 20, 1970.

Silicone fluid for use in the present compositions include silicone oils which are flowable silicone materials with a viscosity of less than 1 ,000,000 centistokes, preferably between about 5 and 1,000,000 centistokes, more preferably between about 10 and about 600,000 centistokes, more preferably between about 10 and about 500,000 centistokes, most preferably between 10 and 350,000 centistokes at 25°C. Suitable silicone oils include polyalkyl siloxanes, polyaryl siloxanes, polyalkylaryl siloxanes, polyether siloxane copolymers, and mixtures thereof. Other insoluble, nonvolatile silicone fluids having conditioning properties can also be used.

Silicone oils for use in the composition include polyalkyl or polyaryl siloxanes which conform to following formula:

where R is aliphatic, preferably alkyl or alkenyl, or aryl, R can be substituted or unsubstituted, and x is an integer from 1 to about 8,000. Suitable unsubstituted R groups include alkoxy, aryloxy, alkaryl, arylalkyl, arylalkenyl, alkamino, and ether-substituted, hydroxy 1-substituted, and halogen-substituted aliphatic and aryl groups. Suitable R groups also include cationic amines and quaternary ammonium groups.

The aliphatic or aryl groups substituted on the siloxane chain may have any structure as long as the resulting silicones remain fluid at room temperature, are hydrophobic, are neither irritating, toxic nor otherwise harmful when applied to the hair, are compatible with the other components of the herein described hair cleansing compositions, are chemically stable under normal use and storage conditions, are insoluble in the compositions of the present invention, and are capable of being deposited on and, of conditioning, the hair.

The two R groups on the silicon atom of each monomeric silicone unit may represent the same group or different groups. Preferably, the two R groups represent the same group.

Preferred alkyl and alkenyl substituents are C1-C5 alkyls and alkenyls, more preferably from C1-C4, most preferably from Cι-C₂. 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, tri-halogenated (preferably fluoro) alkyl groups such as -Rl-C(F)3, wherein R! is Ci -C3 alkyl. Examples of such polysiloxanes include polymethyl -3,3,3 trifluoropropylsiloxane.

Suitable R groups include methyl, ethyl, propyl, phenyl, methylphenyl and phenylmethyl. The preferred silicones are poly dimethyl siloxane, polydiethylsiloxane, and polymethylphenylsiloxane. Polydimethylsiloxane is especially preferred. Other suitable R groups include methyl, methoxy, ethoxy, propoxy, and aryloxy. The three R groups on the end caps ofthe silicone may also represent the same or different groups.

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

The polyalkylaryl siloxane fluids that may be used, also include, for example, polymethylphenylsiloxanes. These siloxanes are available, for example, from the General Electric Company as SF 1075 methyl phenyl fluid or from Dow Corning as 556 Cosmetic Grade Fluid.

The polyether siloxane copolymers that may be used include, for example, a polypropylene oxide modified polydimethylsiloxane (e.g., Dow Corning DC-1248) although ethylene oxide or mixtures of ethylene oxide and propylene oxide may also be used. For insoluble silicones the ethylene oxide and polypropylene oxide level must be sufficiently low to prevent solubility in water and the composition hereof.

Other suitable silicone fluids for use in the silicone conditioning agents are insoluble silicone gums. These gums are polyorganosiloxane materials having a viscosity at 25°C of greater than or equal to 1,000,000 centistokes. Silicone gums are described in U.S. Patent 4,152,416; Noll and Walter, Chemistry and Technology of Silicones. New York: Academic Press 1968; and in General Electric Silicone Rubber Product Data Sheets SE 30, SE 33, SE 54 and SE 76, all of which are incorporated herein by reference. The silicone gums will typically have a mass molecular weight in excess of about 200,000, generally between about 200,000 and about 1,000,000, specific examples of which include polydimethylsiloxane, (polydimethylsiloxane) (methylvinylsiloxane) copolymer, poly(dimethylsiloxane) (diphenyl siloxane)(methylvinylsiloxane) copolymer and mixtures thereof.

The silicone conditioning agent can also comprise a mixture of polydimethylsiloxane gum (viscosity greater than about 1,000,000 centistokes) and polydimethylsiloxane oil (viscosity from about 10 to about 100,000 centistokes), wherein the ratio of gum to fluid is from about 30:70 to about 70:30, preferably from about 40:60 to about 60:40.

References disclosing examples of some suitable silicone fluids for use in the personal cleansing compositions include U.S. Patent 2,826,551, U.S. Patent 3,964,500, U.S. Patent 4,364,837, British Patent 849,433, and Silicon Compounds, Petrarch Systems, Inc. (1984), all of which are incorporated herein by reference.

Silicone resins can be included in the silicone conditioning agent. These resins are highly crosslinked polymeric siloxane systems. The crosslinking is introduced through the incorporation of trifunctional and tetrafunctional silanes with monofunctional or difunctional, or both, silanes during manufacture of the silicone resin. As is well understood in the art, the degree of crosslinking that is required in order to result in a silicone resin will vary according to the specific silane units incorporated into the silicone resin. In general, silicone materials which have a sufficient level of trifunctional and tetrafunctional siloxane monomer units (and hence, a sufficient level of crosslinking) such that they dry down to a rigid, or hard, film are considered to be silicone resins. The ratio of oxygen atoms to silicon atoms is indicative of the level of crosslinking in a particular silicone material. Silicone materials which have at least about 1.1 oxygen atoms per silicon atom will generally be silicone resins herein. Preferably, the ratio of oxygen:silicon atoms is at least about 1.2:1.0. Silanes used in the manufacture of silicone resins include monomethyl-, dimethyl-, trimethyl-, monophenyl-, diphenyl-, methylphenyl-, monovinyl-, and methylvinyl-chlorosilanes, and tetrachlorosilane, with the methyl-substituted silanes being most commonly utilized. Preferred resins are offered by General Electric as GE SS4230 and SS4267. Commercially available silicone resins will generally be supplied in a dissolved form in a low viscosity volatile or nonvolatile silicone fluid. The silicone resins for use herein should be supplied and incorporated into the present compositions in such dissolved form, as will be readily apparent to those skilled in the art. 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, 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 (0^3)3 SiO 5; D denotes the difunctional unit (CH3)₂SiO; T denotes the trifunctional unit (CH3)SiOι 5; and Q denotes the quadri- or tetra-functional unit SiO . 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 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, MDT and MDTQ resins. Thus, the preferred silicone substituent is methyl. Especially preferred are MQ resins wherein the M:Q ratio is from about 0.5:1.0 to about 1.5:1.0 and the average molecular weight ofthe resin is from about 1000 to about 10,000.

The weight ratio of the nonvolatile silicone fluid, having refractive index below 1.46, to the silicone resin component, when used, is preferably from about 4:1 to about 400:1, preferably this ratio is from about 9:1 to about 200:1, more preferably from about 19:1 to about 100:1. Insofar as the silicone resin forms a part of the same phase in the compositions hereof as the silicone fluid, i.e. the conditioning active, the sum of the fluid and resin should be included in determining the level of silicone conditioning agent in the composition. The number average particle size of the optional silicone component can vary widely without limitation and will depend on the formulation and/or the desired characteristics. Number average particle sizes preferred for use in the present invention will typically range from about 10 nanometers to about 100 microns, more preferably from about 30 nanometers to about 20 microns. As discussed above, the silicone can also be solubilized.

Nonionic or Anionic Water- Soluble Polymer

Another optional component of the present invention is a nonionic or anionic water- soluble polymer. Suitable nonionic polymers include such water soluble polymers as cellulose ethers (e.g., hydroxybutyl methylcellulose, hydroxypropylcellulose, hydroxypropyl methylcellulose, ethylhydroxy ethylcellulose and hydroxyethylcellulose), propylene glycol alginates, polyacrylamide, poly(ethylene oxide), polyvinyl alcohol, polyvinylpyrrolidone, hydroxypropyl guar gum, locust bean gum, amylose, hydroxyethyl amylose, starch and starch derivatives and mixtures thereof. Preferred nonionic polymers include hydroxyethyl cellulose, polyethylene oxide, polyvinyl pyrrolidone, polyvinyl alcohol, polyacrylamide, hydroxypropyl cellulose, ethylhydroxyethyl cellulose, dextran, polypropyleneoxide and hydroxypropyl guar.

Suitable anionic water-soluble polymers include carboxymethyl cellulose, carrageenan, xanthum gum polystyrene sulfonate, gum agar, gum ghatti, gum karaya, pectins, alginate salts, as well as poly(acrylic acid) and acrylic or methacrylic acid derivatives such as the alkali metal and ammonium salts of acrylic acid, methacrylic acid. Mixtures of the above anionic water-soluble polymers may also be used.

These polymeric compositions may be homopolymers or they may be copolymers or terpolymers with other copolymerizing monomers known in the art. Examples of copolymerizing monomers known in the art include but are not limited to ethylene, propylene, isobutylene, styrene, polystyrene, alphamethylstyrene, vinyl acetate, vinyl formate, alkyl ethers, acrylonitrile, methacrylonitrile, vinyl chloride, vinylidene chloride, the alkyl acrylates, the alkylmethacrylates, the alkyl fumarates, the alkyl maleates, and other olefinic monomers copolymerizable therewith as long as the resulting polymers are water soluble and phase separate in the compositions of this invention. Copolymers of anionic and nonionic monomers such as acrylic acid and methacrylic acid with acrylamide, methacrylamide, the N-alkyl substituted amides, the N-aminoalkylamides, the corresponding N-alkylaminoalkyl substituted amides, the aminoalkyl acrylates, the aminoalkyl methacrylamides, and the N-alkyl substituted aminoalkyl esters of either acrylic or methacrylic acids.

Preferred anionic polymers include polyacrylic acid; sodium carboxy methyl cellulose; polyacrylates; polymethyl acrylate; polysulphates such as polyvinyl sulfate, polystyrene sulfonate, polyphosphates, sodium dextran sulfate, alginate salts and pectate

When combined with the aqueous surfactant system and phase separation initiator, described below, the water-soluble nonionic or anionic polymer separates to form aqueous droplets suspended in a continuous aqueous phase. The number average particle size ofthe polymer droplets can be from 0.1 microns to about 10,000 microns, preferably from about 1.0 micron to about 5000 microns, most preferably from about 5 microns to about 1000 microns.

Most preferred for use in the present invention are ethyl hydroxyethyl cellulose, hydroxyethyl cellulose, hydroxypropyl guar and polystyrene sulfonate.

The herein described polymers are preferably present at a concentration level of from above about 0.05% to below 1.0%, more preferably from about 0.15% to about 0.75%, most preferably from about 0.15% to about 0.5%.

Another optional ingredient of the shampoos herein is an "amphiphile" as used herein, means, generally, substances which contain both hydrophilic and hydrophobic (lipophilic) groups. Amphiphiles preferred for use in the present invention are those which generally do not form micelles or liquid crystal phases and include, but are not limited to: amides of fatty acids; fatty alcohols; fatty esters, glycol mono- and di- esters of fatty acids; glyceryl esters.

Amides, including alkanol amides, are the condensation products of fatty acids with primary and secondary amines or alkanolamines to yield products ofthe general formula:

O

II _/X

RC-N ^X wherein RCO is a fatty acid radical and R is Cg_₂o; X is an alkyl, aromatic or alkanol (CHR'CH₂OH wherein R' is H or Cι _₆ alkyl); Y is H, alkyl, alkanol or X. Suitable amides include, but are not limited to , cocamide, lauramide, oleamide and stearamide. Suitable alkanolamides include, but are not limited to, cocamide DEA, cocamide MEA, cocamide MIPA, isostearamide DEA, isostearamide MEA, isostearamide MIPA, lanolinamide DEA, lauramide DEA, lauramide MEA, lauramide MIPA, linoleamide DEA, linoleamide MEA, linoleamide MIPA, myristamide DEA, myristamide MEA, myristamide MIPA, Oleamide DEA, Oleamide MEA, Oleamide MIPA, palmamide DEA, palmamide MEA, palmamide MIPA, palmitamide DEA, palmitamide MEA, palm kernelamide DEA, palm kernelamide MEA, palm kernelamide MIPA, peanutamide MEA, peanutamide MIPA, soyamide DEA, stearamide DEA, stearamide MEA, stearamide MIPA, tallamide DEA, tallowamide DEA, tallowamide MEA, undecylenamide DEA, undecylenamide MEA. The condensation reaction may be carried out with free fatty acids or with all types of esters ofthe fatty acids, such as fats and oils, and particularly methyl esters. The reaction conditions and the raw material sources determine the blend of materials in the end product and the nature of any impurities.

Fatty alcohols are higher molecular weight, nonvolatile, primary alcohols having the general formula:

RCH ₂OH wherein R is a Cg_₂o alkyl. They can be produced from natural fats and oils by reduction of the fatty acid COOH- grouping to the hydroxyl function. Alternatively, identical or similarly structured fatty alcohols can be produced according to conventional synthetic methods known in the art. Suitable fatty alcohols include, but are not limited to, behenyl alcohol, Cg.\ \ alcohols, Cj2-13 alcohols, Cι₂-15 alcohols, Cι₂_i 6 alcohols, C14.15 alcohols, caprylic alcohol, cetearyl alcohol, coconut alcohol, decyl alcohol, isocetyl alcohol, isostearyl alcohol, lauryl alcohol, oleyl alcohol, palm kernel alcohol, stearyl alcohol, cetyl alcohol, tallow alcohol, tridecyl alcohol or myristyl alcohol.

Glyceryl esters comprise a subgroup of esters which are primarily fatty acid mono- and di-glycerides or triglycerides modified by reaction with other alcohols and the like. Preferred glyceryl esters are mono and diglycerides. Suitable glyceryl esters and derivatives thereof include, but are not limited to, acetylated hydrogenated tallow glyceride, glyceryl behenate, glyceryl caprate, glyceryl caprylate, glyceryl caprylate/caprate, glyceryl dilaurate, glyceryl dioleate, glyceryl erucate, glyceryl hydroxystearate, glyceryl isostearate, glyceryl lanolate, glyceryl laurate, glyceryl linoleate, glyceryl oleate, glyceryl stearate, glyceryl myristate, glyceryl distearate and mixtures thereof, Also useful as amphiphiles in the present invention are long chain glycol esters or mixtures thereof. Included are ethylene glycol esters of fatty acids having from about 8 to about 22 carbon atoms. Fatty esters of the formula RCO-OR' also act as suitable amphiphiles in the compositions ofthe present invention, where one of R and R' is a Cg. ₂₂ alkyl and the other is a Ci .3 alkyl.

The amphiphiles of the present invention may also encompass a variety of surface active compounds such as nonionic and cationic surfactants.

Amphiphiles preferred for use herein include cocamide MEA, cetyl alcohol and stearyl alcohol.

The amphiphiles of the present invention are preferably present in the hair cleansing compositions at levels of from 0 to about 4%. preferably from about 0.5% to about 2%.

Suitable electrolytes include mono-, di- and trivalent inorganic salts as well as organic salts. Surfactant salts themselves are not included in the present electrolyte definition but other salts are. Suitable salts include, but are not limited to, phosphates, sulfates, nitrates, citrates and halides. The counter ions of such salts can be, but are not limited to, sodium, potassium, ammonium, magnesium or other mono-, di and tri valent cation. Electrolytes most preferred for use in the compositions of the present invention include sodium chloride, ammonium chloride, sodium citrate, sodium sulfate and magnesium sulfate. The amount of the electrolyte used will generally depend on the amount of the amphiphile incorporated, but may be used at concentration levels of from about 0.1% to about 4%, preferably from about 0.2% to about 3%.

The shampoo composition may further comprise a polyalkylene glycol to improve lather performance. Concentration ofthe polyalkylene glycol in the shampoo composition may range from about 0.01%) to about 5%, preferably from about 0.05% to about 3%, and more preferably from about 0.1% to about 2%, by weight ofthe composition.

The optional polyalkylene glycols are characterized by the general formula:

H(OCH₂CH)_n— OH R wherein R is selected from the group consisting of H, methyl, and mixtures thereof. When R is H, these materials are polymers of ethylene oxide, which are also known as polyethylene oxides, polyoxyethylenes, and polyethylene glycols. When R is methyl, these materials are polymers of propylene oxide, which are also known as polypropylene oxides, polyoxypropylenes, and polypropylene glycols. When R is methyl, it is also understood that various positional isomers ofthe resulting polymers can exist.

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

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

Other useful polymers include the polypropylene glycols and mixed polyethylene/polypropylene glycols.

Suspending Agents

The shampoo compositions of the present invention may further comprise a suspending agent at concentrations effective for suspending the preferred silicone conditioning agent, or other water-insoluble material, in dispersed form in the shampoo compositions. Such concentrations range from about 0.1 % to about 10%, preferably from about 0.3% to about 5.0%, by weight ofthe shampoo compositions. Optional suspending agents include crystalline suspending agents which can be categorized as acyl derivatives, long chain amine oxides, and mixtures thereof, concentrations of which range from about 0.1% to about 5.0%, preferably from about 0.5%) to about 3.0%), by weight ofthe shampoo compositions. These suspending agents are described in U.S. Patent 4,741,855, which description is incorporated herein by reference. These preferred suspending agents include ethylene glycol esters of fatty acids preferably having from about 16 to about 22 carbon atoms. More preferred are the ethylene glycol stearates, both mono and distearate, but particularly the distearate containing less than about 7% of the mono stearate. Other suitable suspending agents include alkanol amides of fatty acids, preferably having from about 16 to about 22 carbon atoms, more preferably about 16 to 18 carbon atoms, preferred examples of which include stearic monoethanolamide, stearic diethanolamide, stearic monoisopropanolamide and stearic monoethanolamide stearate. Other long chain acyl derivatives include long chain esters of long chain fatty acids (e.g., stearyl stearate, cetyl palmitate, etc.); glyceryl esters (e.g., glyceryl distearate) and long chain esters of long chain alkanol amides (e.g., stearamide diethanolamide distearate, stearamide monoethanolamide stearate). Long chain acyl derivatives, ethylene glycol esters of long chain carboxylic acids, long chain amine oxides, and alkanol amides of long chain carboxylic acids in addition to the preferred materials listed above may be used as suspending agents. For example, it is contemplated that suspending agents with long chain hydrocarbyls having Cg-C₂₂ chains may be used.

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

Examples of suitable long chain amine oxides for use as suspending agents include alkyl (Ci 6-C₂₂) dimethyl amine oxides, e.g., stearyl dimethyl amine oxide

Other suitable suspending agents include xanthan gum at concentrations ranging from about 0.3%) to about 3%, preferably from about 0.4% to about 1.2%, by weight of the shampoo compositions. The use of xanthan gum as a suspending agent in silicone containing shampoo compositions is described, for example, in U.S. Patent 4,788,006, which description is incorporated herein by reference. Combinations of long chain acyl derivatives and xanthan gum may also be used as a suspending agent in the shampoo compositions. Such combinations are described in U.S. Patent 4,704,272, which description is incorporated herein by reference.

Other suitable suspending agents include carboxy vinyl polymers. Preferred among these polymers are the copolymers of acrylic acid crosslinked with polyallylsucrose as described in U.S. Patent 2,798,053, which description is incorporated herein by reference. Examples of these polymers include Carbopol 934, 940, 941, and 956, available from B. F. Goodrich Company .

Other suitable suspending agents include primary amines having a fatty alkyl moiety having at least about 16 carbon atoms, examples of which include palmitamine or stearamine, and secondary amines having two fatty alkyl moieties each having at least about 12 carbon atoms, examples of which include dipalmitoylamine or di(hydrogenated tallow)amine. Still other suitable suspending agents include di(hydrogenated tallow)phthalic acid amide, and crosslinked maleic anhydride-methyl vinyl ether copolymer.

Other suitable suspending agents may be used in the shampoo compositions, including those that can impart a gel-like viscosity to the composition, such as water soluble or colloidally water soluble polymers like cellulose ethers (e.g., methylcellulose, hydroxybutyl methylcellulose, hyroxypropylcellulose, hydroxypropyl methylcellulose, hydroxyethyl ethylcellulose and hydroxyethylcellulose), guar gum, polyvinyl alcohol, polyvinyl pyrrolidone, hydroxypropyl guar gum, starch and starch derivatives, and other thickeners, viscosity modifiers, gelling agents, etc. Mixtures of these materials can also be used.

Other Optional Components

The shampoo compositions of the present invention may further comprise one or more optional components known for use in shampoo compositions, provided that the optional components are physically and chemically compatible with the essential component described herein, or do not otherwise unduly impair product stability, aesthetics or performance. Concentrations of such optional components typically range from about 0.001%) to about 30% by weight ofthe shampoo compositions.

Optional components include anti static agents, cationic conditioning polymers such as polyquaterinum-10, dyes, organic solvents or diluents, emollient oils (such as polyisobutylene, mineral oil, petrolatum and isocetyl stearyl stearate), pearlescent aids, foam boosters, pediculocides, pH adjusting agents, perfumes, preservatives, proteins, antioxidants; chelators and sequestrants; and aesthetic components such as fragrances, colorings, essential oils, skin sensates, astringents, skin soothing agents, skin healing agents and the like, nonlimiting examples of these aesthetic components include panthenol and derivatives (e.g. ethyl panthenol), pantothenic acid and its derivatives, clove oil, menthol, camphor, eucalyptus oil, eugenol, menthyl lactate, witch hazel distillate, allantoin, bisabalol, dipotassium glycyrrhizinate and the like, suspending agents, styling polymers, sunscreens, thickeners, vitamins and derivatives thereof (e.g., ascorbic acid, vitamin E, tocopheryl acetate, retinoic acid, retinol, retinoids, and the like), and viscosity adjusting agents. This list of optional components is not meant to be exclusive, and other optional components can be used.

The shampoo compositions ofthe present invention are aqueous systems which comprise an aqueous carrier, typically water. The exact level of water will vary with the levels of the remaining components present. Generally, the shampoo compositions of the present invention comprise from about 20% to about 95%, preferably from about 50% to about 92%, and more preferably from about 60% to about 90% water.

Conditioning Composition

The conditioning composition herein can be any conditioning composition suitable for use in conditioning hair provided that the shampoo and conditioning system provides a Volume Index Value of 20 or greater as measured by the Volume Index Technical Test Method and a Detangling Index Value of 90 or greater as measured by the Detangling Index Technical Test Method.

Conditioning compositions hereof are characterized by not having the same surfactant system of shampoos (anionic and/or amphoteric cleansing surfactants). The conditioning composition herein comprises one or more conditioning agents preferably in a level of from about 1% to about 25%, preferably from about 5% to about 20%, more preferably from about 5% to about 15%, by weight of the conditioning composition.

Suitable conditioning agents for use herein include, but are not limited to, quaternary ammonium conditioning agents, such as ester substituted quaternary ammonium compounds, amide substituted quaternary ammonium compounds and alkyl substituted quaternary ammonium compounds such as those quaternary ammonium compounds disclosed in US-A-5,610,187 (Witco) incorporated herein by reference, mixed amide/ester substitituted quaternary ammonium compounds such as those disclosed in EP-A-682935 (Kao) incorporated herein by reference and protonated amines. Preferred for use herein are ester substituted quaternary ammonium compounds such as those disclosed in WO98/03619 and WO98/47991 incorporated herein by reference.

Preferred ester substituted quaternary ammonium compounds for use herein may be defined as the Diester Quaternary Ammonium actives (DEQA) selected from compounds having the formula:

[RC(O)OC₂H₄]_nN⁺(Rl)_m X- wherein each R in a compound is a C6-C₂₂ hydrocarbyl group, preferably having an IV from about 70 to about 140 based upon the IV of the equivalent fatty acid with the cis/trans ratio preferably being as described hereinafter, n is a number from 1 to three on the weight average in any mixture of compounds, each R! in a compound is a Ci .3 alkyl or hydroxy alkyl group, the total of n and the number of R^ groups that are hydroxyethyl groups equaling 3, n+m equaling 4, and X is a hair conditioner compatible anion, preferably methyl sulfate. Preferably the cis:trans isomer ratio of the fatty acid (of the C18:l component) is at least about 1 :1, preferably about 2:1, more preferably 3:1, and even more preferably about 4:1, or higher.

The level of conditioning agent containing polyunsaturated alkylene groups is preferably at least about 3% by weight of the total conditioning agent present and the conditioning agent preferably comprises a mixture of monoester and diester. The compound, or mixtures of compounds, have (a) either a Hunter "L" transmission of at least about 85, typically from about 85 to about 95, preferably from about 90 to about 95, more preferably above about 95, if possible, (b) only low, relatively non-dectectable levels, at the conditions of use, of odorous compounds selected from the group consisting of: isopropyl acetate; 2,2'-ethylidenebis(oxy)bispropane; 1,3,5- trioxane; and/or short chain fatty acid (4-12, especially 6-10, carbon atoms) esters, especially methyl esters; or (c) preferably, both.

The Hunter L transmission is measured by (1) mixing the conditioning active with solvent at a level of about 10% of active, to assure clarity, the preferred solvent being ethoxylated (one mole EO) 2,2,4-trimethyl-l,3-pentanediol and (2) measuring the L color value against distilled water with a Hunter ColorQUEST® colorimeter made by Hunter Associates Laboratory, Reston, Virginia.

The level of odorant is defined by measuring the level of odorant in a headspace over a sample of the conditioning active (about 92% active). Chromatograms are generated using 200 mL of head space sample over about 2 grams of sample. The head space sample is trapped on to a solid absorbent and thermally desorbed onto a column directly via cryofocussing at about -100°C. The identifications of materials is based on the peaks in the chromatograms. Some impurities identified are related to the solvent used in the quaternization process, (e.g., ethanol and isopropanol). The ethoxy and methoxy ethers are typically sweet in odor. There are C -Cg methyl esters found in the current commercial samples, but not in the typical conditioner actives of this invention. These esters contribute to the perceived poorer odor of the current commercial samples. The level of each odorant found in a typical commercial sample is as follows:

Approximate concentration of head space impurities

Chemical Identification Gas phase concentration (nε/L)

Commercial sample Typical invention sample

Isopropyl acetate 6 < 1

1,3,5-trioxane 61 5

2,2'-ethylidenebis(oxy)- 244 < 1 bispropane

C6 methyl ester 10 < 1

C8 Methyl ester 9 < 1

CIO Methyl ester 4 < 1

The acceptable level of each odorant is as follows: isopropyl acetate should be less than about 5, preferably less than about 3, and more preferably less than about 2, nanograms per liter (ηg/L.); 2,2'-ethylidenebis(oxy)bispropane should be less than about 200, preferably less than about 100, more preferably less than about 10, and even more preferably less than about 5, nanograms per liter (ηg/L.); 1,3,5-trioxane should be less than about 50, preferably less than about 20, more preferably less than about 10, and even more preferably less than about 7, nanograms per liter (ηg/L.); and/or each short chain fatty acid (4-12, especially 6-10, carbon atoms) ester, especially methyl esters should be less than about 4, preferably less than about 3, and more preferably less than about 2, nanograms per liter (ηg/L.).

The elimination of color and odor materials can either be accomplished after formation of the compound, or, preferably, by selection of the reactants and the reaction conditions. Preferably, the reactants are selected to have good odor and color. For example, it is possible to obtain fatty acids, or their esters, for sources of the long fatty acyl group, that have good color and odor and which have extremely low levels of short chain (C_ι._ι ₂, especially Cβ-io) f^atty ^acyl groups. Also, the reactants can be cleaned up prior to use. For example, the fatty acid reactant can be double or triple distilled to remove color and odor causing bodies and remove short chain fatty acids. Additionally, the color ofthe triethanolamine reactant needs to be controlled to a low color level (e.g. a color reading of about 20 or less on the APHA scale). The degree of clean up required is dependent on the level of use and the presence of other ingredients. For example, adding a dye can cover up some colors. However, for clear and/or light colored products, the color must be almost non-detectable. This is especially true for higher levels of active, e.g., from about 8% to about 75%), preferably from about 13% to about 60%), more preferably from about 18%> to about 40%, of the conditioner active by weight of the composition. Similarly, the odor can be covered up by higher levels of perfume, but at the higher levels of conditioner active there is a relatively high cost associated with such an approach, especially in terms of having to compromise the odor quality. Odor quality can be further improved by use of ethanol as the quaternization reaction solvent.

Preferred biodegradable hair conditioning compounds comprise quaternary ammonium salt, the quatemized ammonium salt being a quatemized product of condensation between: a)-a fraction of saturated or unsaturated, linear or branched fatty acids, or of derivatives of said acids, said fatty acids or derivatives each possessing a hydrocarbon chain in which the number of atoms is between 5 and 21, and b)-triethanolamine, characterized in that said condensation product has an acid value, measured by titration of the condensation product with a standard KOH solution against a phenolphthalein indicator, of less than about 6.5. The acid value is preferably less than or equal to about 5, more preferably less than about 3. Indeed, the lower the AV, the better softness performance is obtained.

The acid value is determined by titration of the condensation product with a standard KOH solution against a phenolphthalein indicator according to ISO#53402. The AV is expressed as mg KOH/g ofthe condensation product.

For optimum conditioning benefit, it is preferred that the reactants are present in a molar ratio of fatty acid fraction to triethanolamine of from about 1 :1 to about 2.5:1, preferably from about 1.8:1 to 2.2:1.

Preferred cationic, preferably biodegradable quaternary, ammonium hair conditioning compounds can contain the group -(O)CR which is derived from animal fats, unsaturated, and polyunsaturated, fatty acids, e.g., oleic acid, and/or partially hydrogenated fatty acids, derived from vegetable oils and/or partially hydrogenated vegetable oils, such as, canola oil, safflower oil, peanut oil, sunflower oil, com oil, soybean oil, tall oil, rice bran oil, etc. Non-limiting examples of fatty acids (FA) have the following approximate distributions:

Fatty Acyl Group

FA¹ FA2 FA³ FA⁴ FA⁵

C12 trace trace 0 0 0

C14 3 3 0 0 0

C16 4 4 5 5 5

C18 0 0 5 6 6

C14:l 3 3 0 0 0

C16.1 11 7 0 0 3

C18:l 74 73 71 68 67

C18:2 4 8 8 11 11

C18:3 0 1 1 2 2

C20:l 0 0 2 2 2

C20 and up 0 0 2 0 0

Unknowns 0 0 6 6 7

Total 99 99 100 100 102

IV 86-90 88-95 99 100 95 cis/trans (C 18:1) 20-30 20-30 4 5 5

TPU 4 9 10 13 13

TPU is the percentage of polyunsaturates present.

Mixtures of fatty acids, and mixtures of F As that are derived from different fatty acids can be used, and are preferred. Nonlimiting examples of FA's that can be blended, to form FA's of this invention are as follows: Fatty Acyl Group FA° ] FA'

C14 0 1

C16 11 25

C18 4 20

C14:l 0 0

C16:l 1 0

C18:l 27 45

C18:2 50 6

C18:3 7 0

Unknowns 0 3

Total 100 100

IV 125-138 56 cis/trans (C 18:1) Not Available 7

TPU 57 6

FA6 is prepared from a soy bean fatty acid, and YP is prepared from a slightly hydrogenated tallow fatty acid.

The more preferred essential hair conditioning actives containing an effective amount of molecules containing two ester linked hydrophobic groups [RC(CO)O-], said actives being referred to hereinafter as "DEQA's", are those that are prepared as a single DEQA from blends of all the different fatty acids that are represented (total fatty acid blend), rather than from blends of mixtures of separate finished DEQA's that are prepared from different portions ofthe total fatty acid blend.

It is preferred that at least a majority of the fatty acyl groups are unsaturated, e.g., from about 50% to 100%, preferably from about 55%> to about 95%), more preferably from about 60% to about 90%>, and that the total level of active containing polyunsaturated fatty acyl groups (TPU) be preferably from about 3% to about 30%. The cis/trans ratio for the unsaturated fatty acyl groups is usually important, with the cis/trans ratio being from about 1:1 to about 50:1, the minimum being about 1 :1, preferably at least 3:1, and more preferably from about 4:1 to about 20:1. (As used herein, the "percent of conditioner active" containing a given R group is the same as the percentage of that same R group is to the total R groups used to form all ofthe conditioner actives.)

The unsaturated, including the preferred polyunsaturated, fatty acyl and/or alkylene groups, discussed hereinbefore and hereinafter, surprisingly provide effective conditioning, but also provide better rewetting characteristics, good antistatic characteristics, and especially, superior recovery after freezing and thawing. The highly unsaturated materials are also easier to formulate into concentrated premixes that maintain their low viscosity and are therefore easier to process, e.g., pump, mixing, etc. These highly unsaturated materials (total level of active containing polyunsaturated fatty acyl groups (TPU) being typically from about 3% to about 30%), with only the low amount of solvent that normally is associated with such materials, i.e., from about 5% to about 20%, preferably from about 8% to about 25%), more preferably from about 10%> to about 20%, weight of the total conditioner/solvent mixture, are also easier to formulate into concentrated, stable compositions of the present invention, even at ambient temperatures. This ability to process the actives at low temperatures is especially important for the polyunsaturated groups, since it mimimizes degradation. Additional protection against degradation can be provided when the compounds and conditioning compositions contain effective antioxidants, chelants, and/or reducing agents, as disclosed hereinafter.

It will be understood that substituents R and R can optionally be substituted with various groups such as alkoxyl or hydroxyl groups, and can be straight, or branched so long as the R groups maintain their basically hydrophobic character.

A preferred long chain DEQA is the DEQA prepared from sources containing high levels of polyunsaturation, i.e., N,N-di(acyl-oxyethyl)-N,N- methylhydroxyethylammonium methyl sulfate, where the acyl is derived from fatty acids containing sufficient polyunsaturation, e.g., mixtures of tallow fatty acids and soybean fatty acids. Another preferred long chain DEQA is the dioleyl (nominally) DEQA, i.e., DEQA in which N,N-di(oleoyl-oxyethyl)-N,N-methylhydroxyethylammonium methyl sulfate is the major ingredient. Preferred sources of fatty acids for such DEQAs are vegetable oils, and/or partially hydrogenated vegetable oils, with high contents of unsaturated, e.g., oleoyl groups.

As used herein, when the DEQA diester (n=2) is specified, it can include the monoester (n=T) and/or triester (n=3) that are present. Preferably, at least about 30%> of the DEQA is in the diester form, and from 0% to about 30%> can be DEQA monoester, e.g., there are three R! group. The overall ratios of diester quat to monoester quat are from about 2.5:1 to about 1 :1, preferably from about 2.3:1 to about 1.3:1. The level of monoester present can be controlled in manufacturing the DEQA by varying the ratio of fatty acid, or fatty acyl source, to triethanolamine. The overall ratios of diester quat to triester quat are from about 10:1 to about 1.5:1, preferably from about 5:1 to about 2.8:1.

The above compounds, used as the essential biodegradable quatemized ester-amine conditioning material in the practice of this invention, can be prepared using standard reaction chemistry. In one synthesis of a di-ester variation of DTDMAC, an amine ofthe formula N(CH₂CH₂OH)3 is esterified, preferably at two hydroxyl groups, with an acid chloride of the formula RC(O)Cl, to form an amine which can be made cationic by acidification (one R is H) to be one type of conditioner, or then quatemized with an alkyl halide, R*X, to yield the desired reaction product (wherein R and R' are as defined hereinbefore). However, it will be appreciated by those skilled in the chemical arts that this reaction sequence allows a broad selection of agents to be prepared.

In preferred DEQA conditioner actives, each R is a hydrocarbyl, or substituted hydrocarbyl, group, preferably, alkyl, monounsaturated alkenyl, and polyunsaturated alkenyl groups, with the conditioner active containing polyunsaturated alkenyl groups being preferably at least about 3%, more preferably at least about 5%, more preferably at least about 10%, and even more preferably at least about 15%>, by weight of the total conditoner active present; the actives preferably containing mixtures of R groups, especially within the individual molecules.

In preferred quaternary ammonium compounds, and especially in the DEQAs, RC(O)O is derived from unsaturated fatty acid, e.g., oleic acid, and/or fatty acids and/or partially hydrogenated fatty acids, derived from animal fats, vegetable oils and/or partially hydrogenated vegetable oils, such as: canola oil; safflower oil; peanut oil; sunflower oil; soybean oil; com oil; tall oil; rice bran oil; etc.] [As used herein, similar biodegradable actives containing ester linkages are referred to as "DEQA", which includes both diester, triester, and monoester compounds containing from one to three, preferably two, long chain hydrophobic groups. These actives have the characteristic that they can be processed by conventional mixing means at ambient temperature, at least in the presence of about 15%) of solvent C. as disclosed hereinbefore.

The DEQAs herein can also contain a low level of fatty acid, which can be from unreacted starting material used to form the DEQA and/or as a by-product of any partial degradation (hydrolysis) of the conditioner active in the finished composition. It is preferred that the level of free fatty acid be low, preferably below about 15%, more preferably below about 10%, and even more preferably below about 5%>, by weight ofthe conditioner active.

The above compounds, used as the quatemized ester-amine conditioning active in the practice of this invention, can be prepared using standard reaction chemistry. In one synthesis of a di-ester variation of DTDMAC, an amine of the formula RN(CH CH₂OH)₂ is esterified at both hydroxyl groups with an acid chloride of the formula R*C(O)Cl, then quatemized with an alkyl halide, RX, to yield the desired reaction product (wherein R and R¹ are as defined hereinbefore). However, it will be appreciated by those skilled in the chemical arts that this reaction sequence allows a broad selection of agents to be prepared.

The actives of the present invention are preferably prepared by a process wherein a chelant, preferably a diethylenetriaminepentaacetate (DTP A) and/or an ethylene diamine- N,N -disuccinate (EDDS) is added to the process. Also, preferably, antioxidants are added to the fatty acid immediately after distillation and/or fractionation and/or during the esterification reactions and/or prior to, or during, the quatemization reaction, and/or post-added to the finished conditioner active. The resulting conditioner active has reduced discoloration and malodor associated therewith. The typical process comprises the steps of: a) providing a source of triglyceride and reacting the source of triglyceride to form a mixture of fatty acids and/or fatty acid esters; b) using the mixture formed from step (a) to react under esterification conditions with triethanolamine; c) quaternizing, if desired, the mixture of fatty acid esters formed from step (b) by reacting the mixture under quaternizing conditions with a quaternizing agent of the formula R^X wherein R^ is defined as in step (b) and X is a conditioner compatible anion, preferably selected from the group consisting of chloride, bromide, methylsulfate, ethylsulfate, sulfate, and nitrate thereby forming a quaternary hair conditioning active, the methyl sulfate and ethyl sulfate being highly preferred, wherein at least step (c) is carried out in the presence of a chelating agent selected from the group consisting of diethylenetriaminepentaacetic acid, ethylenediamine-N,N'-disuccinnic acid and mixtures thereof.

The step of reacting the source of triglyceride can further include reacting in the presence of the chelating agent step (b) can further include the presence of the chelating agent.

The total amount of added chelating agent is preferably within the range of from about 10 ppm to about 5,000 ppm, more preferably within the range of from about 100 ppm to about 2500 ppm by weight of the formed active. The source of triglyceride is preferably selected from the group consisting of animal fats, vegetable oils, partially hydrogenated vegetable oils, and mixtures thereof. More preferably, the vegetable oil or partially hydrogenated vegetable oil is selected from the group consisting of canola oil, partially hydrogenated canola oil, safflower oil, partially hydrogenated safflower oil, peanut oil, partially hydrogenated peanut oil, sunflower oil, partially hydrogenated sunflower oil, com oil, partially hydrogenated com oil, soybean oil, partially hydrogenated soybean oil, tall oil, partially hydrogenated tall oil, rice bran oil, partially hydrogenated rice bran oil, and mixtures thereof. Most preferably, the source of triglyceride is canola oil, partially hydrogenated canola oil, and mixtures thereof. The process can also include the step of adding from about 0.01% to about 2% by weight of the composition of an antioxidant compound to any or all of steps (a), (b) or (c).

The above processes produce a hair conditioner active with reduced coloration and malodor.

The DEQA actives described hereinabove can contain a low level ofthe fatty acids which can be unreacted starting material and/or by-product of any partial degradation, e.g., hydrolysis, of the actives in the finished compositions. It is preferred that the level of free fatty acid be low, preferably below about 10%>, more preferably below about 5%, by weight ofthe active.

Another suitable conditioning agent for use herein is a protonated amine, derived from amines having the formula NR3 wherein each R is independently selected from C1-C4 alkyl or Cg-C₂ alkyl, provided that at least one ofthe R groups is Cg-C₂₂ alkyl.

Particularly preferred conditioning actives and their methods of preparation are disclosed in US Application No. 60/044719 and WO98/47991.

A commercially available diester quaternary ammonium compound for use herein has the tradename Tetranyl Co-40 and is supplied by Kao. The INCI name for this material is Dioleylethyl Hydroxyethylmonium methosulfate.

A particularly preferred conditioning active for use herein is "SC3" which is prepared according to the method below.

Detailed Synthesis of new conditioning active "SC3"

Step 1, fatty alcohol compound synthesis: A mixture of about 1,200 grams of the hydrogenated oil from Synthesis Example F (see below)and about 200 grams of the hydrogenated oil from Synthesis Example A (see below) is hydrolyzed three times with about 250°C steam at about 600 psig for about 2.5 hours at a ratio of steam:oil of about

1.2 (by weight). An aqueous solution containing the glycerine which had split off is removed. The resulting mixture of fatty acids is vacuum distilled for a total of about 150 minutes, in which the pot temperature rose gradually from about 200°C to about 238°C and the head temperature rose gradually from about 175°C to about 197°C. Vacuum of about 0.3-0.6 mm is maintained.

The fatty acids product of the vacuum distillation has an Iodine Value of about 99.1, an amine value (AV) of about 197.6 and a saponification value (SAP) of about 198.6.

step 2 -Esterification:

About 571 grams of Canola fatty acid with an IV of about 100 and an Acid Value of about 196 as made according to the above Fatty Acid Compound Synthesis is added into the reactor, the reactor is flushed with N₂ and about 149 grams of triethanolamine is added under agitation. The molar ratio of fatty acid to triethanol amine is of about 1.875:1. The mixture is heated above about 150° C and the pressure is reduced to remove the water of condensation. The reaction is prolonged until an Acid Value of about 3 is reached.

Step 3VOuatemization:

To the about 698 grammes of the product of condensation, about 122 grams of dimethylsulfate is added under continuous agitation. The reaction mixture is kept above about 50° C and the reaction is followed by verifying the residual amine value. About 820 grams of conditioner compound ofthe invention is obtained.

The quatemized material is optionally diluted with e.g. about 15%) of an approximately 50:50 ethanol/ hexyleneglycol, preferably more hexylene glycol than ethanol, mixture which lowers the melting point of the material thereby providing a better ease in the handling ofthe material.

Other Fatty Acid and hair Conditioner Synthesis Examples

Fatty Acid Compound Synthesis Example A

About 1,300 grams of food grade (refined, bleached, degummed) canola oil and approximately 6.5 grams of a commercial nickel hydrogenation catalyst (Engelhard, "N-

545"®) corresponding to approximately 0.13 wt.% Ni, are placed in a hydrogenation reactor which is equipped with stirrer. The reactor is sealed and evacuated. The contents are heated to about 170°C and hydrogen is fed into the reactor. Stirring at about 450 rpm is maintained throughout the reaction. After about 10 minutes the temperature in the reactor is about 191°C and the hydrogen pressure is about 11 psig. The temperature is held at about 190°C. After about 127 minutes from when the hydrogen feed began, the hydrogen pressure is about 10 psig. A sample ofthe reaction mass is drawn and found to have an Iodine Value of about 78 and a cis:trans ratio of about 1.098. After another about 20 minutes at about 190°C, the hydrogen pressure is about 9.8 psig. The hydrogen feed is discontinued and the reactor contents cooled with stirring. The final reaction product has an Iodine Value of about 74.5 and a cis:trans ratio of about 1.35.

The product that forms in the reactor is removed and filtered. It has a cloud point of about 22.2°C. The chain length distributions of the acyl substituents on the sample taken at about 127 minutes, and of the final product, are determined to be as shown in Table 1 in which "sat." means saturated, and "mono" and "di" means monounsaturated and diunsaturated, respectively.

TABLE 1

Approximate Percent (mol.^')

Chain length Sample @ 127 min. Product

C14-sat. 0.1 0.1

C16-sat. 4.7 4.6

C16-mono. 0.4 0.4

C18-sat. 8.9 13.25

C18-mono. 77.0 73.8

C18-di. 4.5 3.1

C20-sat. 0.7 0.75

C-20-mono. 2.1 2.0

Other 1.6 2.0

Fatty Acid Compound Synthesis Ex ample B

About 1,300 grams of food grade canola oil and about 5.2 grams of Engelhard "N-545"® nickel hydrogenation catalyst are placed in a hydrogenation reactor which is equipped with a stirrer. The reactor is sealed and evacuated. The contents are heated to about 175°C and hydrogen is fed into the reactor. Stirring is maintained at about 450 rpm throughout the course of reaction. After about 5 minutes the temperature in the reactor is about 190°C and the hydrogen pressure is about 7 psig. The temperature is held at about 190°C. After about 125 minutes from the start of the hydrogen feed, the hydrogen pressure is about 7 psig. A sample of the reaction mass is drawn and found to have an Iodine Value of about 85.4. After another about 20 minutes at about 190°C, the hydrogen pressure is about 6 psig. The hydrogen feed is discontinued and the reactor contents cooled with stirring. The final reaction product has an Iodine Value of about 80. The product that forms in the reactor is removed and filtered. It has a cloud point of about 18.6°C.

Fatty Acid Compound Synthesis Example C About 1,300 grams of food grade canola oil and about 2.9 grams of Engelhard "N-545"® nickel hydrogenation catalyst are placed in a hydrogenation reactor which is equipped with a stirrer. The reactor is sealed and evacuated. The contents are heated to about 180°C and hydrogen is fed into the reactor. Stirring is maintained at about 450 rpm throughout the course of the reaction. After about 5 minutes the temperature in the reactor is about 192°C and the hydrogen pressure is about 10 psig. The temperature is held at about 190 +3°C. After about 105 minutes from the start ofthe hydrogen feed, the hydrogen pressure is about 10 psig. A sample ofthe reaction mass is drawn and found to have an Iodine Value of about 85.5. After another about 20 minutes at about 190°C, the hydrogen pressure is about 10 psig. The hydrogen feed is discontinued and the reactor contents cooled with stirring. The final reaction product has an Iodine Value of about 82.4. The product that forms in the reactor is removed and filtered. It has a cloud point of about 17.2°C.

Fatty Acid Compound Synthesis Example D About 1,300 grams of food grade canola oil and about 1.4 grams of Engelhard "N-545"® nickel hydrogenation catalyst are placed in a hydrogenation reactor which is equipped with a stirrer. The reactor is sealed and evacuated. The contents are heated to about 180°C and hydrogen is fed into the reactor. After about 5 minutes the temperature in the reactor is about 191°C and the hydrogen pressure is about 10 psig. The temperature is held at about 190 +3°C. After about 100 minutes from the start of the hydrogen feed, the hydrogen pressure is about 10 psig. A sample ofthe reaction mass is drawn and found to have an Iodine Value of about 95.4. After another about 20 minutes at about 190°C, the hydrogen pressure is about 10 psig. The hydrogen feed is discontinued and the reactor contents cooled with stirring. The final reaction product had an Iodine Value of about 2.3. The product that forms in the reactor is removed and filtered. It has a cloud point of about 34°C. Fatty Acid Compound Synthesis Example E About 1,300 grams of food grade canola oil and about 1.3 grams of Engelhard "N-545"® nickel hydrogenation catalyst are placed in a hydrogenation reactor which is equipped with a stirrer. The reactor is sealed and evacuated. The contents are heated to about 190°C and hydrogen is fed into the reactor to a hydrogen pressure of about 5 psig. After about 3 hours from the start of the hydrogen feed, a sample of the reaction mass is drawn and found to have an iodine value of about 98. The hydrogenation is interrupted, another about 0.7 grams of the same catalyst is added, and the reaction conditions are reestablished at about 190°C for another about 1 hour. The hydrogen feed is then discontinued and the reactor contents cooled with stirring. The final reaction product had an Iodine Value of about 89.9. The product that forms in the reactor is removed and filtered. It has a cloud point of about 16°C.

Fatty Acid Compound Synthesis Example F About 1,300 grams of food grade canola oil and about 2.0 grams of Engelhard "N-545"® nickel hydrogenation catalyst are placed in a hydrogenation reactor which is equipped with a stirrer. The reactor is sealed and evacuated. The contents are heated to about 190°C and hydrogen is fed into the reactor to a hydrogen pressure of about 5 psig. Stirring is maintained at about 420 rpm throughout the course of reaction ofthe hydrogen feed. After about 130 minutes from the start of the hydrogen feed, the hydrogen feed is discontinued and the reactor contents cooled with stirring. The final reaction product had an Iodine Value of about 96.4. The product that forms in the reactor is removed and filtered. It has a cloud point of about 11.2°C.

Synthesis Example of conditioning compound 1 (SCI) lVEsterification:

About 489 grams of partly hydrogenated tallow fatty acid with an IV of about 45 and an Acid Value of about 206, commercially available under the tradename Distal 51 and sold by Witco Corporation, is added into the reactor, the reactor is flushed with N₂ and about 149 grams of triethanolamine is added under agitation. The molar ratio of fatty acid to triethanol amine is of about 1.8:1. The mixture is heated above about 150° C and the pressure is reduced to remove the water of condensation. The reaction is prolonged until an Acid Value of about 5 is reached. 2)-Quaternization:

To about 627 grams of the product of condensation, about 122 grams of dimethylsulfate is added under continuous agitation. The reaction mixture is kept above about 50° C and the reaction is followed by verifying the residual amine value. 749 grams of conditioner compound ofthe invention is obtained.

The quatemized material is optionally diluted with e.g. about 15% of ethanol which lowers the melting point of the material thereby providing a better handling of the material.

Synthesis Example of conditioning compound 2 (SC2 l)-Esterifιcation:

About 504 grams of oleic fatty acid with an IV of about 90 and an Acid Value of about 198, commercially available under the tradename Emersol 233 and sold by Henkel Corporation, is added into the reactor, the reactor is flushed with N₂ and about 149 grams of triethanolamine is added under agitation. The molar ratio of fatty acid to triethanol amine is about 1.8:1. The mixture is heated above about 150° C and the pressure is reduced to remove the water of condensation. The reaction is prolonged until an Acid Value of about 2 is reached.

2>Quaternization:

To the about 629 grams of the product of condensation, about 122 grams of dimethylsulfate is added under continuous agitation. The reaction mixture is kept above about 50° C and the reaction is followed by verifying the residual amine value. About 751 grams of conditioner compound ofthe invention is obtained.

The quatemized material is optionally diluted with e.g. about 8%> of ethanol which lower the melting point of the material thereby providing a better ease in the handling ofthe material.

Synthesis Example of Hair Conditioner compound 4 (804 1 VEsterification:

About 457 grams of Canola fatty acid with an IV of about 100 and an Acid Value of about 196, as made according to Fatty Acid Compound Synthesis Example G, is added into the reactor, the reactor is flushed with N2 and about 149 grams of triethanolamine is added under agitation. The molar ratio of fatty acid to triethanol amine is about 1.6:1. The mixture is heated above about 150° C and the pressure is reduced to remove the water of condensation. The reaction is prolonged until an Acid Value of about 1 is reached.

2 -Ouatemization:

To the about 582 grams of the product of condensation, about 122 grams of dimethylsulfate is added under continuous agitation. The reaction mixture is kept above about 50° C and the reaction is followed by verifying the residual amine value. 704 grams of conditioner compound ofthe invention is obtained.

The quatemized material is optionally diluted with e.g. about 8% of ethanol which lower the melting point of the material thereby providing a better ease in the handling ofthe material.

The above synthesized compounds have a Hunter L transmission of about 90 and the following levels of odorants in ηg/L: Isopropyl acetate < about 1, typically non- detectable; 1,3,5-trioxane about 5.3; 2,2'-ethylidenebis(oxy)-bispropane < about 1, typically non-detectable; C6 methyl ester < about 1 , typically non-detectable; C8 Methyl ester < about 1, typically non-detectable; and CIO Methyl ester < about 1, typically non- detectable.

The above synthesized conditioner compound are also exemplified below in the non-limiting hair conditioning composition examples. Abbreviations used in the Examples

In the compositions, the abbreviated component identification have the following meanings:

SCI : Hair Conditioner compound as made according to Synthesis Example of conditioner compound 1 SC2 : Hair Conditioner compound as made according to Synthesis Example of conditioner compound 2 SC3 : Hair Conditioner compound as made according to Synthesis Example of conditioner compound 3 SC4 : Hair Conditioner compound as made according to Synthesis Example of conditioner compound 4 TMPD : 2,2,4-trimethyl-l,3-pentanediol

CHDM : 1 ,4 cyclohexanedimethanol The conditioning compositions herein can comprise an aqueous dispersion of the conditioning active. An optional but preferred component from the viewpoint of improving stability and clarity of the conditioning compositions herein is a principal solvent system.

Principal Solvent System

The conditioning compositions ofthe present invention may comprise a principal solvent system in addition to water. This is particularly the case when formulating liquid, clear hair conditioning compositions. When employed, the principal solvent preferably comprises less than about 40%>, preferably from about 5% to about 35%>, more preferably from about 5% to about 20%>, and even more preferably from about 5%> to about 15%, by weight of the composition. The principal solvent is selected to minimize solvent odor impact in the composition and to provide a low viscosity to the final composition. For example, isopropyl alcohol is not very effective and has a strong odor. n-Propyl alcohol is more effective, but also has a distinct odor. Several butyl alcohols also have odors but can be used for effective clarity/stability, especially when used as part of a principal solvent system to minimize their odor. The alcohols are also selected for optimum low temperature stability, that is they are able to form compositions that are liquid with acceptable low viscosities and translucent, preferably clear, down to about 40°F (about 4.4°C) and are able to recover after storage down to about 20°F (about 6.7°C).

Suitable solvents for use herein can be selected based upon their octanol/water partition coefficient (P). Octanol/water partition coefficient of a principal solvent is the ratio between its equilibrium concentration in octanol and in water. The partition coefficients of the principal solvent ingredients of this invention are conveniently given in the form of their logarithm to the base 10, logP.

The logP of many ingredients has been reported; for example, the Pomona92 database, available from Daylight Chemical Information Systems, Inc. (Daylight CIS), Irvine, California, contains many, along with citations to the original literature. However, the logP values are most conveniently calculated by the "CLOGP" program, also available from Daylight CIS. This program also lists experimental logP values when they are available in the Pomona92 database. The "calculated logP" (ClogP) is determined by the fragment approach of Hansch and Leo (cf, A. Leo, in Comprehensive Medicinal Chemistry, Vol. 4, C. Hansch, P. G. Sammens, J. B. Taylor and C. A. Ramsden, Eds., p. 295, Pergamon Press, 1990, incorporated herein by reference). The fragment approach is based on the chemical structure of each ingredient, and takes into account the numbers and types of atoms, the atom connectivity, and chemical bonding. These ClogP values, which are the most reliable and widely used estimates for this physicochemical property, are preferably used instead of the experimental logP values in the selection of the principal solvent ingredients which are useful in the present invention. Other methods that can be used to compute ClogP include, e.g., Crippen's fragmentation method as disclosed in J. Chem. Inf. Comput. Sci., 27, 21 (1987); Viswanadhan's fragmentation method as disclose in J. Chem. Inf. Comput. Sci., 29, 163 (1989); and Broto's method as disclosed in Eur. J. Med. Chem. - Chim. Theor., 19, 71 (1984). The principal solvents herein are selected from those having a ClogP of from about 0.15 to about 0.64, preferably from about 0.25 to about 0.62, and more preferably from about 0.40 to about 0.60, said principal solvent preferably being at least somewhat asymmetric, and preferably having a melting, or solidification, point that allows it to be liquid at, or near room temperature. Solvents that have a low molecular weight and are biodegradable are also desirable for some purposes. The more assymetric solvents appear to be very desirable, whereas the highly symmetrical solvents such as 1,7- heptanediol, or 1 ,4-bis(hydroxymethyl) cyclohexane, which have a center of symmetry, appear to be unable to provide the essential clear compositions when used alone, even though their ClogP values fall in the preferred range.

Operable principal solvents are disclosed and listed below which have ClogP values which fall within the requisite range. These include mono-ols, C6 diols, C7 diols, octanediol isomers, butanediol derivatives, trimethylpentanediol isomers, ethylmethylpentanediol isomers, propyl pentanediol isomers, dimethylhexanediol isomers, ethylhexanediol isomers, methylheptanediol isomers, octanediol isomers, nonanediol isomers, alkyl glyceryl ethers, di(hydroxy alkyl) ethers, and aryl glyceryl ethers, aromatic glyceryl ethers, alicyclic diols and derivatives, C3C7 diol alkoxylated derivatives, aromatic diols, and unsaturated diols. Particularly preferred principal solvents include hexanediols such as 1 ,2-Hexanediol and 2-Ethyl-l,3-hexanediol and pentanediols such as 2,2,4-Trimethyl- 1,3 -pentanediol. These principal solvents are all disclosed in copending U.S. Patent application numbers 08/621,019; 08/620,627; 08/620,767; 08/620,513; 08/621,285; 08/621,299; 08/621,298; 08/620,626; 08/620,625; 08/620,772; 08/621,281; 08/620,514; and 08/620,958, all filed March 22, 1996 and all having the title "CONCENTRATED, STABLE, PREFERABLY CLEAR, FABRIC SOFTENING COMPOSITION", and WO98/47991, the disclosures of which are all herein incorporated by reference. Especially preferred for use in the hair conditioning compositions herein is 1,2- hexanediol.

In addition to a principal solvent, the conditioning compositions of the present invention optionally comprise from about 0.1% to about 10%, preferably from about 1% to about 5%, more preferably from about 2% to about 4%, by weight of the composition of water soluble organic solvent which does not have the ClogP value of the principal solvent. The water soluble organic solvent is preferably mixed with the conditioning active to help provide a low viscosity for ease of processing, e.g., pumping and/or mixing, even at ambient temperatures, and to improve clarity and stability ofthe composition.

The organic solvent is preferably water soluble solvent, e.g., ethanol; isopropanol; 1,2-propanediol; 1,3-propanediol; propylene carbonate, butylene glycol, etc., preferably 1,3-butylene glycol.

The hair conditioning compositions herein can also comprise a wide variety of additional ingredients which are known for use in conventional hair conditioning compositions, non-limiting examples of which are given below.

Emollients

The conditioning compositions herein may contain one or more emollients.

The conditioning compositions herein comprise an emollient selected from polyethylene glycol derivatives of glyceride, polypropylene and polyethylene glycol ethers of glucose and polypropylene glycol ethers of fatty alcohol, and mixtures thereof, preferably a water-soluble emollient. The compositions preferably comprise from about 0.1% to about 10%), preferably 0.1%> to about 5%>, by weight, ofthe emollient.

Polyethylene glycol derivatives of glycerides

Suitable polyethylene glycol derivatives of glycerides include any polyethylene glycol derivative of glycerides which are water-soluble and which are suitable for use in a hair conditioning composition. Suitable polyethylene glycol derivatives of glycerides for use herein include derivatives of mono-, di- and tri-glycerides and mixtures thereof. One class of polyethylene glycol derivatives of glycerides suitable herein are poly ethylenegly col glyceryl fatty esters having the formula (1):

O il

RCOCH₂CH (OH) CH₂ (OCH₂CH₂ ) _nOH

wherein n, the degree of ethoxylation, is from about 4 to about 200, preferably from about 5 to about 100, more preferably from about 6 to about 80, and wherein R comprises an aliphatic radical having from about 5 to about 25 carbon atoms, preferably from about 7 to about 20 carbon atoms.

Suitable polyethylene glycol derivatives of glycerides include PEG-20 almond glycerides, PEG-60 almond glycerides, PEG-11 avocado glycerides, PEG-6 capric/caprylic glycerides, PEG-8 capric/caprylic glycerides, PEG-20 com glycerides, PEG-60 com glycerides, PEG-60 evening primose glycerides, PEG-7 glyceryl cocoate, PEG-30 glyceryl cocoate, PEG-40 glyceryl cocoate, PEG-78 glyceryl cocoate, PEG-80 glyceryl cocoate, PEG- 12 glyceryl dioleate, PEG- 15 glyceryl isostearate, PEG-20 glyceryl isostearate, PEG-30 glyceryl isostearate, PEG-75 cocoa butter glycerides, PEG- 20 hydrogenated palm oil glycerides, PEG-70 mango glycerides, PEG- 13 mink glycerides, PEG-75 shorea butter glycerides, PEG- 10 olive glycerides, PEG- 12 palm kemal glycerides, PEG-45 palm kernal glycerides, PEG-8 glyceryl laurate and PEG-30 glyceryl laurate. Mixtures of polyethylene glycol derivatives of glycerides can also be used herein.

Preferred for use herein is a polyethylene glycol derivative of sunflower oil commerically available from Floratech under the tradename Florasun PEG- 10.

Polyalkylene glycol ether of a glucose

Suitable polyalkylene glycol ethers of glucose for use herein include any water-soluble polyalkylene glycol ether of glucose suitable for use in a hair conditioning composition. Preferred herein are polyethylene glycol ether and polypropylene glycol ethers of glucose. Suitable examples include PPG- 10 methylglucose ether, PPG-20 methyl glucose ether, Methyl Gluceth-20 and Methyl Gluceth-10. Mixtures of polyalkylene glycol ethers of glucose can also be used herein. Polypropylene glycol ether of fatty alcohol

Suitable polypropylene glycol ethers of fatty alcohol for use herein include any water- soluble polypropylene glycol ether of fatty alcohol suitable for use in a hair conditioning composition. Suitable examples include PPG-2 myristyl ether propionate. Mixtures of polypropylene glycol ethers of fatty alcohols can also be used herein.

Most preferred for use in the compositions herein is a polyethylene glycol ether of a glyceride.

The conditioning compositions herein may contain one or more monohydric fatty alcohols. Suitable fatty alcohols for use herein are fatty alcohols having a melting point of 30°C or lower being preferably selected from unsaturated straight chain fatty alcohols, saturated branched chain fatty alcohols, saturated Cg-Cι straight chain alcohols, and mixtures thereof. When present the fatty alcohol is preferably used at a level of from about 0.1%) to about 10%, by weight, preferably from about 0.1 %> to about 5%>, more preferably from about 0.25% to about 1%.

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

Preferably, the unsaturated straight chain fatty alcohols will have an aliphatic chain size of from Cι ₂-C_{2 j} more preferably from Cι₂-Cι g, most preferably from Ci _β-Ci g. Especially preferred alcohols of this type include oleyl alcohol and palmitoleic alcohol.

The branched chain alcohols will typically have aliphatic chain sizes of from Cι₂-C₂₂, preferably Ci4-C o, more preferably Ci g-Ci . Exemplary branched chain alcohols for use herein include isostearyl alcohol, octyl dodecanol, and octyl decanol.

Examples of saturated Cg-Cι straight chain alcohols include octyl alcohol, caprylic alcohol, decyl alcohol, and lauryl alcohol. The present compositions are preferably limited to levels of fatty alcohols, such as cetyl alcohol and stearyl alcohol, of no more than about 5%>, preferably no more than about 1%), more preferably 0%, by weight ofthe composition.

The conditioning compositions herein may also comprise from about 0.1 %> to about 10%), by weight, preferably from about 0.2% to about 5%>, more preferably from about 0.5% to about 3%, of a polymer of ethylene oxide, propylene oxide, and mixtures thereof, having the general formula:

H(OCH₂CH)_n— OH R wherein R is selected from the group consisting of H, methyl, and mixtures thereof; and n has an average value of from about 2,000 to about 14,000, preferably from about 5,000 to about 9,000, more preferably from about 6,000 to about 8,000. When R is H, these materials are polymers of ethylene oxide, which are also known as polyethylene oxides, polyoxyethylenes, and polyethylene glycols. When R is methyl, these materials are polymers of propylene oxide, which are also known as polypropylene oxides, polyoxypropylenes, and polypropylene glycols. When R is methyl, it is also understood that various positional isomers of the resulting polymers can exist. In the above structure, n has an average value of from about 2,000 to about 14,000, preferably from about 5,000 to about 9,000, more preferably from about 6,000 to about 8,000.

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

Other useful polymers include the polypropylene glycols and mixed polyethylene/polypropylene glycols. The compositions herein can comprise conditioning agents in addition to the quaternary ammonium conditioning agents described hereinabove. Suitable conditioning agents include cationic surfactants, cationic polymers, nonvolatile silicones, nonvolatile hydrocarbons, saturated C14 to C₂₂ straight chain fatty alcohols, nonvolatile hydrocarbon esters, and mixtures thereof. Suitable conditioning agents are disclosed in WO95/20939 which is incorporated herein by reference.

Other Components

A wide variety of additional ingredients can be formulated into the present conditioning compositions. These include hair-hold polymers, detersive surfactants such as anionic, nonionic, amphoteric, and zwitterionic surfactants, additional viscosity modifying agents and suspending agents such as xanthan gum, guar gum, hydroxypropyl guar, hydroxyethyl cellulose, methyl cellulose, hydroxyethylcellulose, starch and starch derivatives; insoluble and soluble silicones such as dimethicone copolyol, viscosity modifiers such as methanolamides of long chain fatty acids such as cocomonoethanol amide; crystalline suspending agents; pearlescent aids such as ethylene glycol distearate; preservatives such as benzyl alcohol, methyl paraben, propyl paraben and imidazolidinyl urea; polyvinyl alcohol; ethyl alcohol; anti-dandruff agents such as climbazole, octopirox, ZPT; antimicrobials such as triclosan and triclocarban; anti-lice compounds such as pyrethrin; pH adjusting agents, such as citric acid, sodium citrate, succinic acid, phosphoric acid, sodium hydroxide, sodium carbonate; salts, in general, such as potassium acetate and sodium chloride; coloring agents, such as any of the FD&C or D&C dyes; hair oxidizing (bleaching) agents, such as hydrogen peroxide, 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 from about 0.01%> to about 10.0%, preferably from about 0.05% to about 5.0% by weight ofthe composition.

The conditioning compositions of the present invention can be formulated in a wide variety of product forms, including but not limited to creams, gels, aerosol or non-aerosol foams, mousses and sprays. Mousses, foams and sprays can be formulated with propellants such as propane, butane, pentane, dimethylether, hydrofluorocarbon, CO2, N2O, or without specifically added propellants (using air as the propellant in a pump spray or pump foamer package). METHOD OF USE

The shampoo and conditioning system of the present invention may be used in a conventional manner for cleansing and conditioning human hair. An effective amount of the shampoo composition, typically from about 1 gram to about 50 grams, preferably from about 1 gram to about 20 grams, is applied to the hair. Preferably the hair has been wetted with water before application of the shampoo composition. Application of the shampoo typically includes working the composition through the hair, generally with the hands and fingers, to generate a lather. The shampoo composition is then rinsed from the hair with water. An effective amount of the conditioner composition, typically from about 1 gram to about 50 grams, preferably from about 1 gram to about 20 grams, is then applied to the hair. Application of the conditioner typically includes working the composition through the hair, generally with the hands and fingers, or with a suitable implement such as a comb or brush. The conditioner composition is then rinsed from the hair with water.

The preferred method for cleansing and conditioning the hair therefore comprises the steps of:

(a) wetting the hair with water,

(b) applying an effective amount ofthe shampoo composition to the hair,

(c) shampooing the hair with the composition, i.e. working the composition in contact with the hair and into a lather, and

(d) rinsing the composition from the hair using water,

(e) applying an effective amount ofthe conditioning composition to the hair,

(f) working the conditioning composition into the hair with hands and fingers or with a suitable implement,

(g) rinsing the conditioning composition from the hair using water.

These steps can be repeated as many times as desired to achieve the cleansing and conditioning benefit sought.

In an alternative method herein the conditioner can be left on the hair instead of being rinsed out. The shampoo and conditioner system herein can be provided as a kit wherein the kit comprises (a) shampoo and (b) conditioner, wherein the shampoo optionally comprises a silicone material and wherein the shampoo composition provides a Silicone Deposition Value of less than 50 as measured by the Silicone Deposition Value Test Method, and wherein the shampoo and conditioner system has a Volume Index of 20 or greater as measured by the Volume Index Technical Test Method and a Detangling Value of 90 or greater as measured by the Detangling Index Technical Test Method.

The present invention also relates to kits comprising a shampoo and means for facilitating the use of the shampoo with a conditioner, wherein the shampoo optionally comprises a silicone material and wherein the shampoo provides a Silicone Deposition Value of less than 50 as measured by the Silicone Deposition Value Test Method, and wherein the shampoo and conditioner system has a Volume Index of 20 or greater as measured by the Volume Index Technical Test Method and a Detangling Value of 90 or greater as measured by the Detangling Index Technical Test Method.

The present invention further relates to kits comprising a conditioner and means for facilitating use of the conditioner with a shampoo, wherein the shampoo optionally comprises a silicone material and wherein the shampoo composition provides a Silicone Deposition Value of less than 50 as measured by the Silicone Deposition Value Test Method, and wherein the shampoo and conditioner system has a Volume Index of 20 or greater as measured by the Volume Index Technical Test Method and a Detangling Value of 90 or greater as measured by the Detangling Index Technical Test Method.

As used herein the term "means for facilitating the use of the shampoo with a conditioner" means anything which suggests or recommends the use of the shampoo together with a specified conditioner, such as printed instructions for use either on the shampoo packaging or otherwise, advertising material, and the like. The specified conditioner, for example, may be a conditioner having the same tradename as the shampoo provided in the kit, e.g. Pantene or Vidal Sassoon.

As used herein the term "means for facilitating the use of the conditioner with a shampoo" means anything which suggests or recommends the use of the conditioner together with a specified shampoo, such as printed instructions for use either on the shampoo packaging or otherwise, advertising material, and the like. The specified shampoo, for example, may be a shampoo having the same tradename as the conditioner provided in the kit, e.g. Pantene or Vidal Sassoon.

As mentioned above, the shampoo and conditioner system of the present invention must provide a Detangling Index Value on wet hair of 90 or greater, preferably 95 or greater, more preferably 100 or greater, as measured by the Detangling Index Technical Test Method described hereinbelow and Volume Index Value of 20 or greater, preferably 25 or greater, more preferably 50 or greater, as measured by the Volume Index Technical Test Method described hereinbelow.

Detangling Technical Test Method

The hair switches used in this test method are medium brown virgin hair, weighing 4 grams and being 8 inches in length. Ten of these hair switches are treated per shampoo and conditioner system as follows.

Treatment of switches with shampoo only (herein denoted as standard surfactant solution

I)

The switch is hung above a sink and thoroughly wetted with water at 100°F and 1.5 gpm pressure and 8-15grains water hardness where in the test methods 1 grain is equivalent to 17.1ppm of calcium and/or magnesium ions. (The same water hardness is used throughout the experiment). Excess water is squeezed out of the switch. 0.4cc of the shampoo product to be tested is applied evenly down the switch and milked into the switch for 30 seconds. The switch is then rinsed with water at 100°F for 30 seconds. Excess water is squeezed out ofthe switch. Another 0.4cc of shampoo is applied evenly down the switch and is worked into the shampoo, this time while tangling the switch for 30 seconds. The switch is rinsed with water for 60 seconds. Excess water is squeezed out of the switch. 0.4cc of conditioner is applied evenly down the switch and is worked into the switch for 30 seconds. The switch is rinsed with 100°F water for 30 seconds. Excess water is squeezed out ofthe switch.

Treatment of switches with shampoo and conditioner system

The shampoo is applied as described above. Following this, 0.4ml of conditioner is applied evenly down the switch and is worked into the switch for 30 seconds. The switch is then rinsed with water at 100°F for 30 seconds. Excess water is squeezed out of the switch.

Detangling Measurements

The equipment for measuring detangling comprises a computer (IBM compatible, 286 or less), a load cell on a frame, signal box and matador No. 4 saw cut combs (one per product). The signal box allows the forces on the transducer to be recorded by the computer. A schematic diagram of the operational set-up is shown in the diagram below:

The hair switch is secured in a transducer clamp. The hair is then combed out using a different comb for each product. Combing is started at the bottom of the switch, working up the switch, gently teasing out the tangles. It is important not to force the comb or hold the switch. When the switch is fully combed the signal box is then switched off and the switch removed.

The test must include two controls:

Low control: Standard Surfactant Solution 1

High Control: Standard Surfactant Solution + Pantene Pro-V conditioner for Nourishing

Conditioner for Dry/Permed/Damaged Hair Standard Surfactant Solution 1

A mixture of purified water, ammonium laureth-3 sulfate (34%> w/w; 25%) active) and ammonium lauryl sulfate (17% w/w; 25% active) is stirred and heated to 74°C (+/- 3°C). During the heating process the following materials are added; monosodium phosphate (0.84% w/w), disodium phosphate (0.19%) w/w) and tetrasodium ethylenediaminae tetraacetic acid (0.05%) w/w). Each of these materials is added separately, with sufficient time being allowed between additions to ensure adequate dispersion. Once the temperature of the mixture reaches 74°C (+/- 3°C), cocamide MEA (3.5% w/w; 94% active) is added. The resultant mixture is then stirred for 10 minutes and allowed to cool. Finally DMDM hydantoin (0.033% w/w; 55%> active) is added, when the mixture reaches a temperature of below 38°C.

A mean of the combing force is calculated for each treatment (Dettreatment) and these means are tested for significance using standard statistical tests.

The means are then converted into the Detangling Index using the values ofthe high and low controls (Eq. 1)

Detangling Index = 100 x Dettregtrngnt - Dethigh control (Eq 1.)

De low control - Dethigh control

Example:

Detangling Force (High Control) = 3398

Detangling Force (Low Control) = 4855

Detangling Force (Treatement A) = 4125

From Eq. 1 :

Detangling index (Treatment A) = 100*(4125-3398)/(4855-3398)

= 50

Volume Technical Test Method

This test method makes use of a "ring volume" method which measures forces developed in the process of pulling a hair switch through a ring.

Equipment Needed (see figure 1)

Mini-Instron MN-55 tensile tester with Merlin Profiler software (1)

Instron load cell, 5N maximum capacity with a cross-head adapter (2)

String with small clip (3)

Special stage for ring volume measurements (4)

Set of aluminium or Teflon templates for ring volume measurements (5)

20cm x 8g round hair switches, medium brown hair, not chemically treated (6)

For each test, 3 hair switches per shampoo and conditioner treatment are used. All hair switches are wetted with 0 grain water hardness and then a 12%) ammonium lauryl sulphate solution is applied to strip the hair of soil (O.lg product per 1 g hair, lather for 30 seconds, rinse for 30 seconds again in 0 grains water hardness, O.lg product per lg of hair, lather for 30 seconds, rinse for 60 seconds). The same washing conditions should be used throughout the test (including water temperature, water flow rate, water hardness). The wet hair switch is combed through to remove tangles and flattened between two fingers by squeezing out excess water. A uniform flat "rectangular" shape should be achieved for all hair switches.

The switches are left to dry naturally in a controlled environment room which should stay constant throughout the test method (25°C, 50% relative humidity). The wet switches are hung freely and vertically on a rack and without any obvious distortion of shape. When the switches are partially dried (approximately 2 hours after starting the drying procedure), all the hair switches are combed through 3 times. The switches are then allowed to dry fully, preferably overnight.

The load cell is assembled on the cross-head of the Mini Instron tester. Any load cells are removed from the base ofthe tester. The string is assembled with the clip on the load cell. The ring volume stage is assembled with a template with a 35mm diameter hole. The Mini Instron tester is switched on and the transducer is allowed to equilibrate. The computer is switched on and the Merlin Profiler software is downloaded. Merlin Profiler software is commercially available from the Instron Corporation]. The conditions outlined in the test profile are as follows (Pulling Speed - 4mm/sec, number of repetitions is 3 per switch).

The cross-head of the Mini Instron tester is set into the starting position. This position should ensure that the switch does not touch the bottom of the stage and there is sufficient travelling distance for performing the experiment, and the gauge length reset to zero.

Each hair switch is taken from the rack and combed with strong single strokes 7 times around the hair switch. The switch is passed through the hole in the template and fixed in the clip. The switch is aligned with the load cell by moving the stage. The distance between the template and the switch assembly point is equal for all experiments. The load cell is balanced, and the test method is commenced by activating the moving cross- head.

Under these test conditions three repetitions are carried out on each switch, and three switches are used for every treatment tested [a total of nine readings are therefore obtained for each treatment]. The method is then repeated for all remaining switches.

The hair switches are subsequently treated with shampoo and conditioner products as follows:

Shampoo Only: Apply 0.1 ml product per 1 g hair

Lather 30 seconds, rinse 30 seconds Apply 0.1 ml product per 1 g hair Lather 30 seconds, rinse 60 seconds

Shampoo + Conditioner : Apply shampoo as detailed above Apply 0.1 ml conditioner per 1 g hair

Milk 30 seconds, comb 15 seconds, rinse 30 seconds

The hair switches are then dried vertically on racks under identical conditions as for the stripped switches (25°C, 50% relative humidity, overnight).

Following the drying process, the switches are then tested on the Mini Instron, using the method as outlined above.

Once all the switches are analysed, the pulling work is then calculated for all switches (both stripped and after treatment) over the first 80 mm ofthe switch using the following equation (Eq 1.):

(Eql.) x=D Work (mJ) = J Fdx. x=0

Where :F is the extension load in the load cell when the switch is pulled over a distance x through the ring. D is the length ofthe hair switch used for calculations.

The difference between the pulling force for the treated and initial switches is then calculated for each switch (Eq 2.).

D = Worktreated - orkinitial (Eq 2.)

The differences for each treatment are then combined to produce an average reading per treatment (Dtreatment). These readings are then analysed for significant differences between treatments using standard statistical methods.

The actual pulling work readings are converted into index readings, based on the results obtained for the top and bottom internal controls. In this case the high control is Standard Surfactant Solution 1 described hereinabove in the Detangling Technical Test Method and the low control is Standard Surfactant Solution 1 + Pantene Pro-V Nourishing Conditioner for Dry/Permed/Damaged Hair (Eq 3.)

Volume Index = 100 x Dtreatment - Plow control (Eq 3.)

Dhigh control - Dlow control Example:

Pulling work for switch A (Stripped) 0.5322

Pulling Work for switch A (Treated with Product X)0.7652

Using Eq 2.

D = (0.7652 - 0.5322) = 0.2330 D low control = 0.0890 D high control = 0.4312

Using Eq 3.

Volume Index (Product X) = 100x(0.2330-0.0890)/(0.4312-0.0890) Volume Index (Product X) = 42

Silicone Deposition Technical Test Method

The Silicone Deposition Technical Test Method measures the amount of silicone conditioning ingredients deposited on hair from the shampoo composition.

Treatment of Hair Switches

Three hair switches are treated for each shampoo to be tested. The hair switches used are virgin medium brown hair weighing 2 grams and being 6 inches long. Each hair switch is clamped over a sink. The hair is combed through with fine teeth of new, clean comb. The switch is wetted with water of water hardness 7-9 grains. 0.2ml of test shampoo is applied down the length of the hair switch. Using the thumb and next 2 fingers and alternating hands, the shampoo is lathered evenly from top to bottom ofthe switch for 30 seconds. The switch is rinsed for 30 seconds with water at 38°C using 1.5 gallons of water per minute. The water hardness is 7-9 grains. A further 0.2ml of the same test shampoo is applied down the length of the same hair switch. Again, the shampoo is lathered evenly into the hair from top to bottom for 30 seconds. The switch is rinsed for 60 seconds with water at 38°C, 1.5 gallons per minute, 7-9 grains water hardness. This process is repeated 3 times for each switch. Extraction of Silicone from Hair

A lOmL syringe is placed on a balance which reads to 4 decimal places. Each switch is cut just below the base of the clamp. The hair sample is weighed between 1.6 to 1.8g and placed into respective syringes. The total weight of the syringe plus hair is recorded to 0.00 lg. A syringe tip is attached to each syringe. 6mL of 50/50 (v/v) of methylisobutylketone (MIBK)/toluene solution is added into the syringe. The syringe plunger is inserted gently into the syringe about halfway down the barrel. All the syringes are attached to a mechanical shaker and shaken for 30+/-5 minutes. The syringe tip is removed and the solvent is squeezed into a scintillation vial. The vial is capped.

Atomic Absoφtion Analysis

An Atomic Absoφtion Spectrophotometer with Background Corrector and Wavelength Drive such as a PE Model 1100b (manufactured by Perkin Elmer Coφoration) or equivalent is set up for optimal detection of silica.

Calibration standard solutions of siloxane in 50%/50%> MIBK/toluene are prepared. Stock solutions should be made to approximately 240ppm., 120ppm., 30ppm., lOppm., and 2ppm. The flame of the spectrophotometer is allowed to warm up for 5-10 minutes. The sample of 240ppm standard solution is aspirated. The aspiration rate, fuel flow rate and flame height are adjusted to achieve the maximum signal. The remaining standard solutions are aspirated three times and the readings recorded. The data is fitted to a least squares fit line. The extracted sample solution is aspirated three times and the readings recorded. The ppm of silicone in the extracted sample solution is calculated based on the data and standard least squares fit line. The ppm of the silicone on the hair is calculated using the formula:

ppm silicone on hair = (ppm in extract solution)(6mL')0.833g/mL

(Weight of hair)

The results are indexed against a high control, the high control being US Pert Plus Extra Body for Fine Hair which has a Detangling Index Value of 100. EXAMPLES

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

Preparation

The shampoo and conditioner compositions of the present invention can be prepared by using conventional mixing and formulating techniques.

Shampoo Formulations I and II

Ingredients 11% π/%

Water to i nn

Sodium Alkyl Glyceryl Sulfonate (47%) 0 5.3

Ammonium Lauryl Sulphate (25%>) 24 27.2

Ammonium Laureth-3 Sulphate (25%) 40 0

Ammonium Xylene Sulfonate 1 0

Ethylene Glycol Distearate 1.5 1.5

Cocomonoethanolamide (85%) 0.85 0.85

Cetyl Alcohol 0.65 0.6

Hydroxyethyl Cellulose 0.15 0.2

Dimethicone CF300M¹ 0.5 0

60/40 Dimethicone fluid CF1223¹ 0 0.5

Tetrasodium EDTA 0.1 0.1

Citric Acid (50%) 0.04 0.04

Sodium Citrate 0.45 0.45

Sodium Benzoate 0.25 0.25

Sodium Chloride 1.5 1.5

Glydant 0.25 0.25

Perfume 0.55 0.55

Laureth-4 0.1 0.1

1. Supplied by GE Silicones

Method of Manufacture Examples I and II can be prepared as follows. First a suspending agent premix is made. The water is heated towards the suspending agent melting point. Mixing of the water is started followed by addition of ammonium lauryl sulfate. Next the preservative system is added followed by the amphoteric surfactant. At the melting point of the suspending agent, the sodium chloride and suspending agent is added. The temperature is held constant for 15 minutes. The rapid cooling of the premix using a heat exchanger is started. Cooling is stopped at about 25°C. To the resulting suspending agent premix, ammnoium laureth-3 sulfate is added, followed by the conditioning agent and perfume. The batch is then thinned/thickened as desired. Finally salt and ammnonium xylene sulfonate is added.

Conditioning Compositions III-IX

Foam Spray Mousse Opacifed Gel

Ingredient III/% IV/% V/% VI/%

Tetranyl Co-40 (80% 12.5 3.1 12.5 12.5 active)

1 ,2-Hexanediol 10 10 10 0

Methylparaben 0.2 0.2 0.2 0.2

Propylparaben 0.1 0.1 0.1 0.1

1 ,3 Butylene glycol 2 2 2 2

Perfume 1 1 1 1

Dimethicone copolyol 0.1 0.1 0.1 0.1

Florasun PEG-10² 2 2 2 2

Jaguar HP- 105³ 0 0 0 1

TiO₂ (40% in 1,3-butylene 0 0 0 0.25 glycol)

AP 30 Propellant⁴ 0 4.3

Water -to 100-

Foam Spray Mousse

Ingredient VII/% VIII/% IX/% Tetranyl Co-40 (80% 12.5 3.1 12.5 active) 1,2-Hexanediol 10 10 10

Methylparaben 0.2 0.2 0.2

Propylparaben 0.1 0.1 0.1

1 ,3 Butylene glycol 2 2 2

Perfume 1 1 1

Dimethicone copolyol 0.1 0.1 0.1

Florasun PEG-10² 2 2 2

Jaguar HP-105³ 0 0 0

TiO₂ (40% in 1,3 -butylene 0 0 0 glycol)

AP 30 Propellant⁴ 0 0 4.3

Hexylene Glycol 0.75 0.75 0.75

Ethanol 0.75 0.75 0.75

Water to 100

1. Supplied by Kao

2. Supplied by Floratec

3. Supplied by Rhone Poulenc

4. Mixture of propane, isobutane and n-butane, supplied by BP

5. Supplied by GE Silicones

The conditioners ofthe Examples can be prepared as follows.

Process for preparation of conditioner liquid/gel

The Tetranyl Co-40 and hexanediol are added to the mixing vessel. Agitation is begun slowly. The butylene glycol is added and heated to 40°C. (when hexylene glycol and ethanol are present they are added at 30°C). Agitation is continued and the methyl and propyl paraben is added at 40°C and allowed to dissolve. The composition is then cooled. With agitation the remaining ingredients are added while cooling. The perfume is added at about 25°C. The water is added and mixed until homogeneous. The pH is adjusted to 3.5 with sodium hydroxide.

Process for preparation of foam The resulting liquid is put into a pump foamer package such as AIRSPRAY supplied by Zuiderkade.

Process for preparation of aerosol mousse

To a 150ml aluminium can, 132ml of the above concentrate is added. The can is crimped and a vacuum is drawn. 6g of propellant is added.

Process for preparation of spray

The resulting liquid from the process for preparation of the mousse is put into a suitable spray gel can.

Process for preparation of gel (without hexanediol^')

A premix of the Jaguar and the butylene glycol is made by mixing the two ingredients at room temperature. The Tetranyl Co-40 is added to the mixing vessel and agitation is begun with heating to 40°C. (when hexylene glycol and ethanol are present they are added at this stage but heated to 30°C). Agitation is continued and the methyl and propyl paraben is added at 40°C and allowed to dissolve. The composition is cooled. With agitation, the conditioning ingredients are added, eg. Florasun, Silicone, while cooling. The prefume is added at approximately 25 °C. The Jaguar/Butylene glycol premix is added and mixed until homogeneous. The TiO₂ and water is added and mixed until homogeneous. The pH is adjusted to 3.5 with sodium hydroxide.

Examples X-XI (Pump Foamer Hair Conditioning Compositions^')

Ingredient X/% XI/%

SC3¹ 7.5 7.5

1 ,2-hexanediol 8.0 7.5 hexylene glycol 2.6 2.66

PEG- 10 Sunflower glyceride 0.0 5.0

PEG-20 Glyceryl laurate 4.0 0.0

Dimethicone copolyol 1.0 0.0

PEG-2M 0.6 0.4

PEG-5M 0.4 0.6 Perfume 1 1 Preservative <1 <1 Minors/by products <1 <1 Water » 100 to 100

1. SC3 prepared according to Synthesis Example SC3 hereinabove.

The pH target for the compositions of Example X-Xl is pH 3-4 which is adjusted using sodium hydroxide (32%>/1.0N). The Examples X-XI can be prepared and packaged using conventional techniques such as those used hereinabove in the pump foamer examples.

Either of the shampoos shown in Examples I and II can be used with any of the conditioners shown in Examples III-XI. The shampoo and conditioner systems of the present invention provide excellent cleansing and hair detangling with the additional benefits of leaving the hair feeling clean and providing improved volume.

Claims

What is claimed is:

1. A shampoo and conditioner system comprising:

(a) a shampoo composition optionally comprising a silicone material and wherein the shampoo composition provides a Silicone Deposition Value of less than 50 as measured by the Silicone Deposition Value Technical Test Method;

(b) a conditioner composition;

wherein the system has a Volume Index Value of 20 or greater as measured by the Volume Index Technical Test Method and a Detangling Value of 90 or greater as measured by the Detangling Index Technical Test Method.

2. A shampoo and conditioner system according to Claim 1 wherein the shampoo composition comprises from about 0.1% to about 10% by weight of silicone material.

3. A shampoo and conditioner system according to Claim 1 or 2 wherein the shampoo composition has a Silicone Deposition Value of 25 or less.

4. A shampoo and conditioner system according to any of Claims 1 to 3 wherein the shampoo composition has a Silicone Deposition Value of 20 or less.

5. A shampoo and conditioner system according to any of Claims 1 to 4 wherein the system has a Volume Index Value of 25 or greater.

6. A shampoo and conditioner system according to any of Claims 1 to 5 wherein the system has a Volume Index Value of 50 or greater.

7. A shampoo and conditioner system according to any of Claims 1 to 6 wherein the system has a Detangling Index Value of 95 or greater.

8. A shampoo and conditioner system according to any of Claims 1 to 7 wherein the system has a Detangling Value of 100 or greater.

9. A shampoo and conditioner system according to any of Claims 1 to 8 wherein said conditioner composition is essentially free of silicone.

10. A method of cleansing and conditioning the hair using the shampoo and conditioner system of any of Claims 1 to 8 wherein the method comprises:

(a) wetting the hair with water,

(b) applying an effective amount ofthe shampoo composition to the hair,

(c) rinsing the composition from the hair using water,

(d) applying an effective amount ofthe conditioning composition to the hair, and

(e) rinsing the conditioning composition from the hair using water.

11. A kit comprising a shampoo and conditioner system, the system comprising:

(a) shampoo, and

(b) conditioner

wherein the shampoo optionally comprises a silicone material and wherein the shampoo composition provides a Silicone Deposition Index Value of less than 50 as measured by the Silicone Deposition Value Test Method, and wherein the shampoo and conditioner system has a Volume Index of 20 or greater as measured by the Volume Index Technical Test Method and a Detangling Value of 90 or greater as measured by the Detangling Index Technical Test Method.

12. A kit comprising :

(a) shampoo

(b) means for facilitating use ofthe shampoo with a conditioner;

wherein the shampoo optionally comprises a silicone material and wherein the shampoo provides a Silicone Deposition Index Value of less than 50 as measured by the Silicone Deposition Value Test Method, and wherein the shampoo and conditioner system has a Volume Index of 20 or greater as measured by the Volume Index Technical Test Method and a Detangling Value of 90 or greater as measured by the Detangling Index Technical Test Method.

13. A kit comprising : (a) conditioner

(b) means for facilitating use ofthe conditioner with a shampoo

wherein the shampoo optionally comprises a silicone material and wherein the shampoo composition provides a Silicone Deposition Index Value of less than 50 as measured by the Silicone Deposition Value Test Method, and wherein the shampoo and conditioner system has a Volume Index of 20 or greater as measured by the Volume Index Technical Test Method and a Detangling Value of 90 or greater as measured by the Detangling Index Technical Test Method.