WO2003094872A1

WO2003094872A1 - Hair conditioning compositions

Info

Publication number: WO2003094872A1
Application number: PCT/EP2003/003722
Authority: WO
Inventors: Emmanuel Paul Jos Marie Everaert; Anand Ramchandra Mahadeshwar; Ruby Loo Bick Tan-Walker; Stephen Lee Wire
Original assignee: Hindustan Lever Ltd; Unilever NV
Current assignee: Hindustan Unilever Ltd; Unilever NV
Priority date: 2002-05-13
Filing date: 2003-04-09
Publication date: 2003-11-20
Anticipated expiration: 2004-11-13
Also published as: GB0210936D0; AR039797A1; AU2003221567A1

Abstract

Hair conditioning compositions comprising an aqueous phase, a cleansing surfactant or a conditioning surfactant and discrete, dispersed droplets of a conditioning blend, characterised in that the droplets of the conditioning blend comprise both a non-silicone oil and an oil-dispersible cationic surfactant within the same droplets where the weight ratio of oil-dispersible surfactant to non-silicone oil is from 1:8 to 8:1. The compositions are used for conditioning and reducing the volume of dried hair.

Description

- 1

HAIR CONDITIONING COMPOSITIONS

Technical Field

The invention is concerned with leave-on or rinse off hair conditioning compositions. Particularly, it is concerned with rinse-off compositions such as shampoos or conditioners which are applied to the, hair then largely rinsed off the hair a short time after application.

The invention is more particularly concerned with improvements to hair conditioning from such compositions which comprise particles or droplets of non-silicone oils.

Background to the Invention

Compositions which provide a combination of cleansing and conditioning to the hair are well know in the art. Such compositions typically comprise one or more surfactants and one or more conditioning agents. The purpose of the conditioning agent is to make the hair easier to comb when wet and more manageable when dry, e.g. less static and flyaway. Typically, these conditioning agents are either water- insoluble oily materials or cationic materials.

Shampoo compositions which provide a combination of cleansing and conditioning to the hair are also known in the art. Such shampoo compositions typically comprise one or more surfactants for shampooing or cleansing purposes and one or more conditioning agents. Amongst the most popular oily materials used in conditioning products are silicone polymers, present in the shampoo as emulsion droplets. Conditioning is achieved by the silicone being deposited onto the hair resulting in the formation of a film. Whilst the silicone film gives excellent conditioning, for example wet comb properties, the repeated use of compositions containing silicones can lead to a build up of silicone and undesirable affects such as a heavy, oily feel to the hair. This can lead to the perception by the user that their hair is not clean.

Another class of conditioning agents used in hair treatment compositions is non-silicone water-insoluble oily materials. Such oily materials have been used to a far lesser degree than silicone oils. Although non-silicone oils (such as triglycerides, mineral oils and ester oils) provide softness and connote a clean feel to the consumer when applied from rinse-off compositions, the conditioning effects they provide (ease of combing and improved manageability) are inadequate compared to silicone-based conditioning oils.

Thus, there is a need to improve the conditioning effects obtained from rinse-off conditioning compositions containing non-silicone oils while maintaining the beneficial, clean- feel, effects of the non-silicone oils.

Additionally, it is desirable for some consumers to obtain reduced volume of hair after drying. Many consumers blow dry their hair with heated-air hair dryers while brushing in order to reduce the volume of the hair when dry. There is a need to provide low volume hair after drying without the need to employ a hot-air hair dryer. Such a process is also known in the art as de-fluffing.

US 3,808,311 discloses a hair conditioning shampoo comprising an oil from the group consisting of mineral oil, vegetable oil, animal oil and synthetic oil. In this patent, it is specified that the oil must be dissolved in the composition such that it forms a single phase liquid shampoo .

WO 93/08787 discloses hair conditioning shampoo compositions comprising, in an aqueous carrier, a dispersed insoluble non-volatile nonionic silicone hair conditioning component, a water soluble hair conditioning cationic polymer, an anionic surfactant and an organic, non-volatile, water- insoluble liquid selected from the group consisting of hydrocarbon oils, fatty esters and mixtures thereof.

US 4,183,917 discloses hair conditioner compositions in the form of oil-in-water emulsion comprising a high molecular synthetic oil with a molecular weight of 1,500, a cationic surface active agent, a nonionic surface active agent and water. The composition may also include a liquid ester oil as optional component .

Surprisingly, it has now been found that the incorporation into rinse-off conditioning compositions of droplets or particles of non-silicone oils blended with certain cationic surfactants leads to improved hair conditioning from the oils without the loss of other benefits associated with the oils. Moreover, it has also been found that such compositions lead to reduced volume of hair after drying.

Summary of the Invention

In a first aspect, the invention is concerned with a hair conditioning composition comprising; i) an aqueous phase, ii) a surfactant selected from the group consisting of anionic, amphoteric and zwitterionic cleansing surfactants and cationic conditioning surfactants and iii) discrete, dispersed droplets of a conditioning blend, wherein the droplets of the conditioning blend comprise both a non-silicone oil and an oil- dispersible cationic surfactant within the same droplets and wherein the weight ratio of oil- dispersible surfactant to non-silicone oil is from 1:5 to 5:1.

Detailed Description of the Invention

In order for the compositions to remain physically stable after preparation, it is highly preferred if the components comprising the droplets of the conditioning blend are water- insoluble. By water- insoluble is meant a solubility in water (to form a homogeneous aqueous solution) at 25 °C of 0.1% or less by weight. Conditioning Blend

The conditioning blend of the compositions according to the invention is provided as a single blend which is added to the composition during manufacture. This single blend may simply be in the form of a water-insoluble liquid blend, which can be added to the composition during manufacture.

However, it is preferred that the conditioning blend is in the form of an aqueous emulsion which is added to the composition during manufacture. Pre- formed aqueous emulsions of conditioning blend may have advantages in that they themselves may be easier to handle or process than the "raw" ingredients comprising the conditioning blend.

In any event, when added to the hair treatment composition, the conditioning blend becomes the internal phase of an emulsion which itself constitutes the hair treatment composition, and which preferably has a water-based continuous phase.

A further feature of the invention is that the conditioning blend present in the composition, when added as an already homogenised mixture, will be present in the hair treatment composition as a homogeneous mixture of cationic surfactant and non-silicone oil. That is, each conditioning blend droplet in the composition will have essentially the same composition and will comprise a mixture of the two essential components: cationic surfactant and non-silicone conditioning oil, which together make up the conditioning blend component of the composition. Typically, the mixture of the non-silicone conditioning oil and the cationic surfactant will be a single phase solution, wherein the two essential components are miscible with each other, but alternatively, it may be an intimate blend of two phases, but contained within common droplets. This is what is meant by the statement that the cationic surfactant is oil- dispersible. It is preferred if the oil and the cationic surfactant are mutually soluble to form a single phase when blended.

One method for preparing compositions according to the invention is to first prepare a liquid blend comprising the non-silicone conditioning oil and the oil-dispersible cationic surfactant. This blend can then be added along with the other components comprising the hair treatment composition, followed by suitable high shear mixing of the composition in order to ensure that the blend is dispersed as droplets of a suitable size.

However it is preferred if the liquid blend is first formed into an aqueous emulsion prior to incorporation into the hair treatment composition. Thus another aspect of the invention is a method for incorporating droplets of a conditioning blend comprising both a non-silicone oil and an oil-dispersible cationic surfactant, into a hair treatment composition, comprising the steps of; i) forming an intimate, non-aqueous blend comprising the non-silicone oil and the oil dispersible cationic surfactant, ii) preparing an aqueous emulsion comprising droplets comprising both a non-silicone oil and a oil- dispersible cationic surfactant in the same droplets and

iii) mixing said aqueous emulsion with the hair treatment composition.

Suitable emulsifiers for use in the preparation of the aqueous emulsion are well known in the art and include anionic, cationic, zwitterionic, amphoteric and nonionic surfactants, and mixtures thereof.

Examples of anionic surfactants used as emulsifiers for the conditioning blend are alkylarylsulphonates, e.g., sodium dodecylbenzene sulphonate, alkyl sulphates e.g., sodium lauryl sulphate, alkyl ether sulphates, e.g., sodium lauryl ether sulphate nEO, where n is from 1 to 20 alkylphenol ether sulphates, e.g., octylphenol ether sulphate nEO where n is from 1 to 20, and sulphosuccinates, e.g., sodium dioctylsulphosuccinate .

Examples of nonionic surfactants used as emulsifiers are alkylphenol ethoxylates, e.g., nonylphenol ethoxylate nEO, where n is from 1 to 50 and alcohol ethoxylates, e.g., lauryl alcohol nEO, where n is from 1 to 50, ester ethoxylates, e.g., polyoxyethylene monostearate where the number of oxyethylene units is from 1 to 30. It is preferred if the emulsifier is blended into the conditioning blend prior to the formation of the aqueous emulsion of the mixture droplets.

It is most preferred if the oil-dispersible cationic surfactant itself is used as the emulsifier.

A preferred process for preparing oil-in-water emulsions of the conditioning blend droplets which can then be incorporated into the hair treatment compositions involves use of a mixer. Depending upon the viscosities of components, a suitable mixer should be chosen so as to provide sufficient shear to give the required final particle size of the emulsion. Examples of suitable benchtop mixers spanning the range of necessary shear are Heidolph RZR2100, Silverson L4R, Ystral X10/20-750 and Rannie Mini-Lab 7.30VH high pressure homogeniser. Other mixers of similar specification are well known to those skilled in the art and can also be used in this application. Equally it is possible to manufacture oil-in-water emulsions of this description on larger scale mixers which offer similar shear regimes to those described above.

The required amounts of the oil-dispersible cationic surfactant and non-silicone conditioning oil are combined under shear to produce a uniform mixture. To this mixture a suitable emulsifier system is added slowly with further shear. Examples of suitable emulsifier systems for this application are given above. As is well known to those skilled in the art, the emulsifier system can be used to help to control the final particle size of the emulsion. When the addition of the emulsifier is complete, the aqueous portion of the emulsion is added slowly with the required level of shear so as to produce an emulsion with the desired particle size.

Optionally the aqueous phase of the emulsion contains a polymeric thickening agent to prevent phase separation of the emulsion after preparation. Preferred thickening agents are cross-linked polyacrylates, cellulosic polymers or derivatives of cellulosic polymers.

Preferably the emulsification is carried out at a temperature at which both the oil-dispersible cationic surfactant and the non-silicone oil are liquids. Suitable non-silicone oils for the invention oils have a slip melting point (measured according to AOCS Cc 3-25) of 50 °C or less. Preferably the non-silicone oil has a slip melting point of 40°C or less, more preferably 30°C or less, most preferably 20°C or less.

Preferably, the mixer is also capable of having the temperature of mixing controlled, e.g. it comprises a jacket through which a heat transfer fluid can be circulated.

When the conditioning blend is used in compositions such as shampoos or shower gels which additionally comprise a cleansing surfactant, it is preferred if the D₃₍₂ average particle diameter of the conditioning blend droplets in the emulsion and also in the final composition is 15 micrometres or less, more preferably 7 micrometres or less, and yet more preferably 4 micrometres or less. Suitably, the average particle size of the conditioning blend droplets in the emulsion and also in the final composition is 0.02 micrometres or greater, preferably 0.05 micrometres or greater. A smaller conditioning blend droplet size within the preferred ranges enables a more uniform distribution of conditioning blend onto the hair for the same amount of silicone in the composition.

Conditioning blend particle size may be measured by means of a laser light scattering technique, for example using a 2600D Particle Sizer from Malvern Instruments.

When the compositions according to the invention are in the form of shampoos or shower gels which additionally comprise a cleansing surfactant, it is also preferred if a cationic deposition formula is included in the composition. Such cationic conditioning polymers are described in detail below.

A suitable weight ratio of oil-dispersible cationic surfactant to non-silicone conditioning oil contained within the conditioning blend droplets is from 1:8 to 8:1. Preferably, the weight ratio is from 1:5 to 5:1, more preferably from 1:3 to 3:1.

The total amount of conditioning blend present in hair conditioning compositions according to the invention from 0.1% to 20% by weight of the composition, preferably from 0.5% to 10%, more preferably from, 1% to 7% Non-Silicone Oil

A non-silicone oil is an essential component of the conditioning blend droplets. Suitable non-silicone oils are selected from hydrocarbon oils, ester oils and mixtures thereof .

Hydrocarbon oils

Suitable hydrocarbon oils include cyclic hydrocarbons, straight chain aliphatic hydrocarbons (saturated or unsaturated) , and branched chain aliphatic hydrocarbons (saturated or unsaturated) . Straight chain (linear) hydrocarbon oils will typically contain from 6 to 16 carbon atoms, preferably from 8 up to 14 carbon atoms. Branched chain hydrocarbon oils can and typically may contain higher numbers of carbon atoms, e.g. from 6 up to 40 carbon atoms, preferably from 8 up to 18 carbon atoms.

A preferred hydrocarbon oil is light mineral oil. Mineral oils are clear oily liquids obtained from petroleum oil, from which waxes have been removed, and the more volatile fractions removed by distillation. The fraction distilling between 250°C to 300°C is termed mineral oil, and it consists of a mixture of hydrocarbons, in which the number of carbon atoms per hydrocarbon molecule generally ranges from Cio to

C₄₀. Mineral oil may be characterised in terms of its viscosity, where light mineral oil is relatively less viscous than heavy mineral oil, and these terms are defined more specifically in the U.S. Pharmacopoeia, 22nd revision, p. 899 (1990) . A commercially available example of a suitable light mineral oil for use in the invention is

Sirius M40 (carbon chain length C₁₀-C₂₈ mainly C12-C20/

-3 -1 viscosity 4.3 x 10 Pa . s at 25°C and shear rate 21 sec ), available from Silkolene.

Other hydrocarbon oils that may be used in the invention include relatively lower molecular weight hydrocarbons including linear saturated hydrocarbons such a tetradecane, hexadecane, and octadecane, cyclic hydrocarbons such as dioctylcyclohexane (e.g. CETIOL S from Henkel), branched chain hydrocarbons (e.g. ISOPAR L and ISOPAR V from Exxon Corp . ) .

The oil may be volatile or non-volatile. An example of a suitable volatile mineral oil is Permethyl 101A.

The hydrocarbon oil may be present in the conditioning blend of the invention as a single material or as a blend with other non-silicone oils.

Ester Oils

By ester oils is meant the esters formed between alcohols and long chain carboxylic acids such as C₆-C₃₀ carboxylic acids. The carboxylic acids may be linear or branched, saturated or unsaturated or contain hydrophilic groups such as hydroxyl . Suitable alcohols forming the ester oils include, but are not limited to, ethylene glycol, propylene glycol, glycerol, sorbitol, pentaerithrytol and the various sugars such as sucrose, glucose, fructose and dipentaerythritol . There may be only one long-chain acid bonded to the alcohol by an ester link, or several.

Preferred ester oils are mono-, di- and tri- esters of glycerol. Particularly preferred are triglycerides (i.e. tri-esters of glycerol and carboxylic acids) .

Preferred glyceride fatty esters are derived from carboxylic acids of carbon chain length ranging from Cβ to C₂₄, more preferably C₁₀ to C₂₂- most preferably C12 to Cis ■

A variety of these types of materials are present in vegetable and animal fats and oils, such as camellia oil, coconut oil, castor oil, safflower oil, sunflower oil, peanut oil, cottonseed oil, corn oil, olive oil, cod liver oil, almond oil, avocado oil, palm oil, sesame oil, lanolin and soybean oil . These have various ranges of carbon chain lengths depending on the source, typically between 12 to 18 carbon atoms. Synthetic oils include trimyristin, triolein, tristearin and glyceryl dilaurate. Vegetable derived glyceride fatty esters are particularly preferred, and specific examples of preferred materials for inclusion in hair oils of the invention as sources of glyceride fatty esters include almond oil, castor oil, coconut oil, sesame oil, sunflower oil and soybean oil. Coconut oil, sunflower oil, castor oil and mixtures thereof are particularly preferred.

The glyceride fatty ester may be present in conditioning blends of the invention as a single material or as a blend.

Oil-dispersible Cationic Surfactant

The droplets of conditioning blend comprise an oil- dispersible cationic surfactant as an essential component. Suitable cationic surfactants are selected from the group consisting of monoalkyl trimethyl quaternary ammonium salts, dialkyl dimethyl quaternary ammonium salts, hydrocarbyl ester quaternary ammonium salts, imidazolinium salts, pyrimidinium salts, benzoimidazolium salts and mixtures thereof .

Examples of suitable cationic surfactants are those corresponding to the general formula :

[N(Rι) (R₂) (R₃) ( ₄)] (X)

in which Ri, R , R₃ , and R₄ are independently selected from

(a) an aliphatic group of from 1 to 22 carbon atoms, or (b) an aromatic, alkoxy, polyoxyalkylene, alkylamido, hydroxyalkyl , aryl or alkylaryl group having up to 22 carbon atoms; and X is a salt-forming anion such as those selected from halogen, (e.g. chloride, bromide), acetate, citrate, lactate, glycolate, phosphate nitrate, sulphate, and alkylsulphate radicals. The aliphatic groups can contain, in addition to carbon and hydrogen atoms, ether linkages, and other groups such as amino groups. The longer chain aliphatic groups, e.g., those of 10 carbons, or higher, can be saturated or unsaturated.

Preferred cationic surfactants for conditioning blends of the present invention are monoalkyl trimethyl, dialkyl dimethyl and hydrocarbyl ester quaternary ammonium compounds in which the hydrocarbyl chain length is Cio to C₂₂. more preferably Cχ₆ to C₂₂- For the hydrocarbyl ester compounds, preferably the other substituents on the quaternary nitrogen are further Cχo to C₂₂ hydrocarbyl ester, hydroxyethyl or methyl groups .

Examples of suitable cationic surfactants include: cetyltrimethylammonium chloride, behenyltrimethylammonium chloride, cetylpyridinium chloride, tetramethylammonium chloride, tetraethylammonium chloride, octyltrimethylammonium chloride, dodecyltrimethylammonium chloride, hexadecyltrimethylammonium chloride, octyldimethylbenzylammonium chloride, decyldimethylbenzylammonium chloride, stearyldimethylbenzylammonium chloride , didodecyldimethylammonium chloride , dioctadecyldimethylammonium chloride, tallowtrimethylammonium chloride, cocotrimethylammonium chloride, PEG-2 oleylammonium chloride and salts of these where the chloride is replaced by halogen, (e.g. , bromide or iodide), acetate, citrate, lactate, glycolate, phosphate nitrate, sulphate, or alkylsulphate. Other suitable counter-ions include fluoride, perchlorate, hexafluorophosphate, tetrafluoroborate or tetraphenylborate . Further suitable cationic surfactants include those materials having the CTFA designations Quaternium-5, Quaternium-31 and Quaternium-18. Mixtures of any of the foregoing materials may also be suitable.

Other suitable surfactants for use as the oil-dispersible cationic surfactant in the conditioning blend of the invention include imidazolinium salts (formula 1) , pyrimidinium salts (formula 2) , benzoimidazolium salts

(formula 3) and mixtures thereof. In these compounds, a fatty acid alkyl chain is linked to the quaternary nitrogen head group by an amide linkage

Formula 1 :

In formula 1 the CH₃ group is bonded to either of the nitrogen atoms in the ring. Formula 2 :

Formula 3

Formulae 1 to 3 represent the cation of the salt. Suitable anions can be selected from the group consisting of halogen, (e.g. , bromide, chloride iodide), acetate, citrate, lactate, glycolate, phosphate nitrate, sulphate, alkylsulphate, fluoride perchlorate, hexafluorophasphate, tetrafluoroborate or tetraphenylborate . A particularly preferred anion is sulphate .

In formulae 1 to 3 Ri is selected from methyl, ethyl or propyl . R₂ is an alkyl chain (branched or straight, saturated or unsaturated) comprising from 10 to 22 carbon atoms

A particularly preferred selection for the oil-dispersible cationic surfactant is a mixture of (a) a di- Cio to C₂₂ alkyl dimethyl quaternary ammonium salt with (b) a Cio to C₂₂ hydrocarbyl ester quaternary ammonium salt, wherein the ratio of (a) to (b) is from 4:1 to 1:2. By Cio to C₂₂ hydrocarbyl ester quaternary ammonium salt is meant a quaternary ammonium salt wherein at least one hydrocarbyl group (i.e. saturated or unsaturated) comprising 10 to 22 carbon atoms is attached to the quaternary nitrogen via an ester linkage. Particularly suitable are quaternary nitrogen salts (such as methosulphate or methochloride) derived from compounds which are mono- di- or tri-esters of

Cio to C₂₂ saturated or unsaturated fatty acids and triethanolamine .

Hair Conditioning Compositions

Hair treatment compositions according to the invention may suitably take the form of shampoos, conditioners, sprays, mousses, oils, styling products, hair colouring products or lotions. Preferred hair treatment composition forms are shampoos, conditioners and mousses.

Shampoo Compositions

A particularly preferred hair conditioning composition in accordance with the invention is a shampoo composition or a shower gel composition.

Such a shampoo composition will comprise one or more cleansing surfactants which are cosmetically acceptable and suitable for topical application to the hair. Further surfactants may be present as an additional ingredient if sufficient for cleansing purposes is not provided by the emulsifier for the water-insoluble oily component. It is preferred that shampoo compositions of the invention comprise at least one further surfactant (in addition to that used as emulsifying agent for the water- insoluble oily component) to provide a cleansing benefit. Suitable cleansing surfactants, which may be used singularly or in combination, are selected from anionic, amphoteric and zwitterionic surfactants, and mixtures thereof. The cleansing surfactant may be the same surfactant as the emulsifier, or may be different.

For stability reasons, it is preferred if the pH of shampoo compositions according to the invention are from 3 to 7.5, preferably from 3.5 to 5.5.

Anionic Cleansing Surfactant

Shampoo compositions according to the invention will typically comprise one or more anionic cleansing surfactants which are cosmetically acceptable and suitable for topical application to the hair.

Examples of suitable anionic cleansing surfactants are the alkyl sulphates, alkyl ether sulphates, alkaryl sulphonates, alkanoyl isethionates, alkyl succinates, alkyl sulphosuccinates, N-alkyl sarcosinates, alkyl phosphates, alkyl ether phosphates, alkyl ether carboxylates, and alpha- olefin sulphonates, especially their sodium, magnesium, ammonium and mono-, di- and triethanolamine salts. The alkyl and acyl groups generally contain from 8 to 18 carbon atoms and may be unsaturated. The alkyl ether sulphates, alkyl ether phosphates and alkyl ether carboxylates may contain from 1 to 10 ethylene oxide or propylene oxide units per molecule. Typical anionic cleansing surfactants for use in shampoo compositions of the invention include sodium oleyl succinate, ammonium lauryl sulphosuccinate, ammonium lauryl sulphate, sodium dodecylbenzene sulphonate, triethanolamine dodecylbenzene sulphonate, sodium cocoyl isethionate, sodium lauryl isethionate and sodium N-lauryl sarcosinate. The most preferred anionic surfactants are sodium lauryl sulphate, sodium lauryl ether sulphate (n) EO, (where n ranges from 1 to 3) , ammonium lauryl sulphate and ammonium lauryl ether sulphate (n) EO, (where n ranges from 1 to 3) .

Mixtures of any of the foregoing anionic cleansing surfactants may also be suitable.

The total amount of anionic cleansing surfactant in shampoo compositions of the invention is generally from 5 to 30, preferably from 6 to 20, more preferably from 8 to 16 percent by weight.

Co-surfactant

The shampoo composition can optionally include co- surfactants, to help impart aesthetic, physical or cleansing properties to the composition.

A preferred example is an amphoteric or zwitterionic surfactant, which can be included in an amount ranging from 0 to 8, preferably from 1 to 4 percent by weight of the composition. Examples of amphoteric and zwitterionic surfactants include alkyl amine oxides, alkyl betaines, alkyl amidopropyl betaines, alkyl sulphobetaines (sultaines) , alkyl glycinates, alkyl carboxyglycinates, alkyl amphopropionates, alkylamphoglycinates, alkyl amidopropyl hydroxysultaines, acyl taurates and acyl glutamates, wherein the alkyl and acyl groups have from 8 to 19 carbon atoms. Typical amphoteric and zwitterionic surfactants for use in shampoos of the invention include lauryl amine oxide, cocodimethyl sulphopropyl betaine and preferably lauryl betaine, cocamidopropyl betaine and sodium cocamphopropionate .

Another preferred example is a nonionic surfactant, which can be included in an amount ranging from 0 to 8, preferably from 2 to 5 percent by weight of the composition.

For example, representative nonionic surfactants that can be included in shampoo compositions of the invention include condensation products of aliphatic (Cs - Ciβ) primary or secondary linear or branched chain alcohols or phenols with alkylene oxides, usually ethylene oxide and generally having from 6 to 30 ethylene oxide groups.

Other representative nonionic surfactants include mono- or di-alkyl alkanolamides . Examples include coco mono- or di- ethanolamide and coco mono-isopropanolamide .

Further nonionic surfactants which can be included in shampoo compositions of the invention are the alkyl polyglycosides (APGs) . Typically, the APG is one which comprises an alkyl group connected (optionally via a bridging group) to a block of one or more glycosyl groups. Preferred APGs are defined by the following formula:

RO - (G)_n

wherein R is a branched or straight chain alkyl group which may be saturated or unsaturated and G is a saccharide group.

R may represent a mean alkyl chain length of from C₅ to C₂₀- Preferably R represents a mean alkyl chain length of from Cβ to C ₂. Most preferably the value of R lies between 9.5 and

10.5. G may be selected from C₅ or Q monosaccharide residues, and is preferably a glucoside. G may be selected from the group comprising glucose, xylose, lactose, fructose, mannose and derivatives thereof. Preferably G is glucose.

The degree of polymerisation, n, may have a value of from 1 to 10 or more. Preferably, the value of n is 1.1 to 2. Most preferably the value of n is from 1.3 to 1.5.

Suitable alkyl polyglycosides for use in the invention are commercially available and include for example those materials identified as: Oramix NS10 ex Seppic; Plantaren 1200 and Plantaren 2000 ex Henkel .

Other sugar-derived nonionic surfactants which can be included in shampoo compositions of the invention include the

Cιo~^ci₈ N-alkyl (Ci-Cβ) polyhydroxy fatty acid amides, such as the C₁₂-C₁₈ N-methyl glucamides, as described for example in

WO 92 06154 and US 5 194 639, and the N-alkoxy polyhydroxy fatty acid amides, such as Cio-Ciβ N- (3-methoxypropyl) glucamide .

The shampoo composition can also optionally include one or more cationic co-surfactants included in an amount ranging from 0.01 to 10, more preferably from 0.05 to 5, most preferably from 0.05 to 2 percent by weight of the composition. Useful cationic surfactants are described hereinbelow in relation to conditioner compositions.

The total amount of surfactant (including any co-surfactant , and/or any emulsifier) in shampoo compositions of the invention is generally from 5 to 50, preferably from 5 to 30, more preferably from 10 to 25 percent by weight of the composition.

Cationic Polymer

A cationic polymer is a preferred ingredient in shampoo compositions of the invention, for enhancing conditioning performance of the shampoo.

The cationic polymer may be a homopolymer or be formed from two or more types of monomers. The molecular weight of the polymer will generally be between 5 000 and 10 000 000, typically at least 10 000 and preferably from 100 000 to 2 000 000. The polymers will have cationic nitrogen containing groups such as quaternary ammonium or protonated amino groups, or a mixture thereof.

The cationic nitrogen-containing group will generally be present as a substituent on a fraction of the total monomer units of the cationic polymer. Thus when the polymer is not a homopolymer it can contain spacer non-cationic monomer units. Such polymers are described in the CTFA Cosmetic Ingredient Directory, 3rd edition. The ratio of the cationic to non-cationic monomer units is selected to give a polymer having a cationic charge density in the required range.

Suitable cationic conditioning polymers include, for example, copolymers of vinyl monomers having cationic amine or quaternary ammonium functionalities with water soluble spacer monomers such as (meth) acrylamide, alkyl and dialkyl (meth) acrylamides, alkyl (meth) acrylate, vinyl caprolactone and vinyl pyrrolidine. The alkyl and dialkyl substituted monomers preferably have C1-C7 alkyl groups, more preferably Cl-3 alkyl groups. Other suitable spacers include vinyl esters, vinyl alcohol, maleic anhydride, propylene glycol and ethylene glycol .

The cationic amines can be primary, secondary or tertiary amines, depending upon the particular species and the pH of the composition. In general secondary and tertiary amines, especially tertiary, are preferred.

Amine substituted vinyl monomers and amines can be polymerized in the amine form and then converted to ammonium by quaternization. The cationic conditioning polymers can comprise mixtures of monomer units derived from amine- and/or quaternary ammonium-substituted monomer and/or compatible spacer monomers .

Suitable cationic conditioning polymers include, for example :

copolymers of 1-vinyl -2 -pyrrolidine and 1-vinyl -3- methyl -imidazolium salt (e.g. chloride salt), referred to in the industry by the Cosmetic, Toiletry, and Fragrance Association, (CTFA) as Polyquaternium-16. This material is commercially available from BASF Wyandotte Corp. (Parsippany, NJ, USA) under the LUVIQUAT tradename (e.g. LUVIQUAT FC 370);

copolymers of l-vinyl-2-pyrrolidine and dimethylaminoethyl methacrylate, referred to in the industry (CTFA) as Polyquaternium-11. This material is available commercially from Gaf Corporation (Wayne, NJ,

USA) under the GAFQUAT tradename (e.g., GAFQUAT 755N) ;

cationic diallyl quaternary ammonium-containing polymers including, for example, dimethyldiallyammonium chloride homopolymer and copolymers of acrylamide and dimethyldiallylammonium chloride, referred to in the industry (CTFA) as Polyquaternium 6 and Polyquaternium 7, respectively;

- mineral acid salts of amino-alkyl esters of homo-and copolymers of unsaturated carboxylic acids having from 3 to 5 carbon atoms, (as described in U.S. Patent 4,009,256) ;

cationic polyacrylamides (as described in W095/22311) .

Other cationic conditioning polymers that can be used include cationic polysaccharide polymers, such as cationic cellulose derivatives, cationic starch derivatives, and cationic guar gum derivatives. Suitably, such cationic polysaccharide polymers have a charge density from 0.1 to 4 meq/g.

Cationic polysaccharide polymers suitable for use in compositions of the invention include those of the formula:

A-O- [R-N⁺(R^X) (R²) (R³)X^"] ,

wherein: A is an anhydroglucose residual group, such as a starch or cellulose anhydroglucose residual . R is an alkylene, oxyalkylene, polyoxyalkylene, or hydroxyalkylene

1 2 3 group, or combination thereof. R , R and R independently represent alkyl, aryl, alkylaryl, arylalkyl, alkoxyalkyl, or alkoxyaryl groups, each group containing up to 18 carbon atoms. The total number of carbon atoms for each cationic

1 2 3 moiety (i.e., the sum of carbon atoms in R , R and R ) is preferably 20 or less, and X is an anionic counterion.

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

Other suitable cationic polysaccharide polymers include quaternary nitrogen-containing cellulose ethers (e.g. as described in U.S. Patent 3,962,418), and copolymers of etherified cellulose and starch (e.g. as described in U.S. Patent 3,958,581).

A particularly suitable type of cationic polysaccharide polymer that can be used is a cationic guar gum derivative, such as guar hydroxypropyltrimonium chloride (commercially available from Rhone-Poulenc in their JAGUAR trademark series) .

Examples are JAGUAR C13S, which has a low degree of substitution of the cationic groups and high viscosity. JAGUAR C15, having a moderate degree of substitution and a low viscosity, JAGUAR C17 (high degree of substitution, high viscosity), JAGUAR C16, which is a hydroxypropylated cationic guar derivative containing a low level of substituent groups as well as cationic quaternary ammonium groups, and JAGUAR 162 which is a high transparency, medium viscosity guar having a low degree of substitution. Preferably the cationic conditioning polymer is selected from cationic cellulose and cationic guar derivatives. Particularly preferred cationic polymers are JAGUAR C13S, JAGUAR C15, JAGUAR C17 and JAGUAR C16 and JAGUAR C162.

The cationic conditioning polymer will generally be present in compositions of the invention at levels of from 0.01 to 5, preferably from 0.05 to 1, more preferably from 0.08 to 0.5 percent by weight of the composition.

Conditioner Compositions

Compositions in accordance with the invention may also be formulated as conditioners for the treatment of hair (typically after shampooing) and subsequent rinsing.

Conditioning Surfactant

Such a conditioner will comprise one or more conditioning surfactants which are cosmetically acceptable and suitable for topical application to the hair.

Suitable conditioning surfactants are selected from cationic surfactants, used singly or in admixture.

For the sake of clarity, it must be emphasised that any cationic surfactant used as a conditioning surfactant is in addition to the oil-dispersible cationic surfactant which is an essential component in the conditioning blend of compositions according to the invention. Cationic surfactants useful in compositions of the invention contain amino or quaternary ammonium hydrophilic moieties which are positively charged when dissolved in the aqueous composition of the present invention.

Examples of suitable cationic surfactants are those corresponding to the general formula:

[N(Rι) (R₂) ⁽R₃ ⁾ (R₄ ⁾]^{+ (}X)^~

in which Ri, R₂, R₃, and R₄ are independently selected from

(a) an aliphatic group of from 1 to 22 carbon atoms, or (b) an aromatic, alkoxy, polyoxyalkylene, alkylamido, hydroxyalkyl, aryl or alkylaryl group having up to 22 carbon atoms; and X is a salt-forming anion such as those selected from halogen, (e.g. chloride, bromide), acetate, citrate, lactate, glycolate, phosphate nitrate, sulphate, and alkylsulphate radicals.

The aliphatic groups can contain, in addition to carbon and hydrogen atoms, ether linkages, and other groups such as amino groups. The longer chain aliphatic groups, e.g., those of 12 carbons, or higher, can be saturated or unsaturated.

The most preferred cationic surfactants for conditioner compositions of the present invention are monoalkyl quaternary ammonium compounds in which the alkyl chain length is C16 to C22.

Examples of suitable cationic surfactants include: cetyltrimethylammonium chloride, behenyltrimethylammonium chloride, cetylpyridinium chloride, tetramethylammonium chloride, tetraethylammonium chloride, octyltrimethylammonium chloride, dodecyltrimethylammonium chloride, hexadecyltrimethylammonium chloride, octyldimethylbenzylammonium chloride, decyldimethylbenzylammonium chloride, stearyldimethylbenzylammonium chloride, didodecyldimethylammonium chloride, dioctadecyldimethylammonium chloride, tallowtrimethylammonium chloride, cocotrimethylammonium chloride, PEG-2 oleylammonium chloride and salts of these where the chloride is replaced by halogen, (e.g. , bromide), acetate, citrate, lactate, glycolate, phosphate nitrate, sulphate, or alkylsulphate. Further suitable cationic surfactants include those materials having the CTFA designations Quaternium-5, Quaternium-31 and Quaternium-18. Mixtures of any of the foregoing materials may also be suitable. A particularly useful cationic surfactant for use in hair conditioners of the invention is cetyltrimethylammonium chloride, available commercially, for example as GENAMIN CTAC, ex Hoechst Celanese.

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

Particularly useful are amido substituted tertiary fatty amines. Such amines, useful herein, include stearamidopropyldimethylamine , stearamidopropyidiethylamine , stearamidoethyldiethylamine, stearamidoethyldimethylamine , palmitamidopropyld imethylamine , palmitamidopropyldiethylamine , palmitamidoethyldiethylamine , palmitamidoethyldimethylamine, behenamidopropyldimethylamine, behenamidopropyldiethylamine, behenamidoethyldiethylamine, behenamidoethyldimethylamine, arachidamidopropyldimethylamine, arachid amidopropyldiethylamine, arachidamidoethyldiethylamine , arachidamidoethyldimethylamine, diethylaminoethylstearamide . Also useful are; dimethylstearamine, dimethylsoyamine, soyamine, myristylamine, tridecylamine, ethylstearylamine, N- tallowpropane diamine, ethoxylated (with 5 moles of ethylene oxide) stearylamine, dihydroxyethylstearylamine, and arachidyl behenylamine. These amines are typically used in combination with an acid to provide the cationic species. The preferred acid useful herein includes L- glutamic acid, lactic acid, hydrochloric acid, malic acid, succinic acid, acetic acid, fumaric acid, tartaric acid, citric acid, L- glutamic hydrochloride, and mixtures thereof; more preferably L-glutamic acid, lactic acid, citric acid. Cationic amine surfactants included among those useful in the present invention are disclosed in U.S. Patent 4,275,055 to Nachtigal, et al . , issued June 23, 1981.

The molar ratio of protonatable amines to H from the acid is preferably from 1:0.3 to 1:1.2, and more preferably from 1:0.5 to 1:1.1. In the conditioners of the invention, the level of cationic surfactant is preferably from 0.01 to 10, more preferably 0.05 to 5, most preferably 0.1 to 2 percent by weight of the total composition.

Fatty Materials

Conditioner compositions of the invention preferably additionally comprise fatty materials. The combined use of fatty materials and cationic surfactants in conditioning compositions is believed to be especially advantageous, because this leads to the formation of a lamellar phase, in which the cationic surfactant is dispersed.

By "fatty material" is meant a fatty alcohol, an alkoxylated fatty alcohol, a fatty acid or a mixture thereof.

Preferably, the alkyl chain of the fatty material is full saturated.

Representative fatty materials comprise from 8 to 22 carbon atoms, more preferably 16 to 22. Examples of suitable fatty alcohols include cetyl alcohol, stearyl alcohol and mixtures thereof. The use of these materials is also advantageous in that they contribute to the overall conditioning properties of compositions of the invention.

Alkoxylated, (e.g. ethoxylated or propoxylated) fatty alcohols having from 12 to 18 carbon atoms in the alkyl chain can be used in place of, or in addition to, the fatty alcohols themselves. Suitable examples include ethylene glycol cetyl ether, polyoxyethylene (2) stearyl ether, polyoxyethylene (4) cetyl ether, and mixtures thereof.

The level of fatty alcohol material in conditioners of the invention is suitably from 0.01 to 15, preferably from 0.1 to 10, and more preferably from 0.1 to 5 percent by weight of the composition. The weight ratio of cationic surfactant to fatty alcohol is suitably from 10:1 to 1:10, preferably from 4:1 to 1:8, optimally from 1:1 to 1:7, for example 1:3.

Conditioner compositions of the invention can also contain a cationic polymer. Suitable cationic polymers are described hereinabove in relation to shampoo compositions.

Suspending Agents

In a preferred embodiment, the hair conditioning composition, especially if it is a shampoo composition, further comprises from 0.1 to 5 percent by weight of the composition of a suspending agent for the coated particles. Suitable suspending agents are selected from polyacrylic acids, cross-linked polymers of acrylic acid, copolymers of acrylic acid with a hydrophobic monomer, copolymers of carboxylic acid-containing monomers and acrylic esters, cross-linked copolymers of acrylic acid and acrylate esters, heteropolysaccharide gums and crystalline long chain acyl derivatives. The long chain acyl derivative is desirably selected from ethylene glycol stearate, alkanolamides of fatty acids having from 16 to 22 carbon atoms and mixtures thereof. Ethylene glycol distearate and polyethylene glycol 3 distearate are preferred long chain acyl derivatives. Polyacrylic acid is available commercially as Carbopol 420, Carbopol 488 or Carbopol 493. Polymers of acrylic acid cross-linked with a polyfunctional agent may also be used, they are available commercially as Carbopol 910, Carbopol 934, Carbopol 940, Carbopol 941 and Carbopol 980. An example of a suitable copolymer of a carboxylic acid containing a monomer and acrylic acid esters is Carbopol 1342. All Carbopol (trade mark) materials are available from Goodrich.

Suitable cross- linked polymers of acrylic acid and acrylate esters are Pemulen TR1 or Pemulen TR2. A suitable heteropolysaccharide gum is xanthan gum, for example that available as Kelzan mu.

Other conditioning ingredients

In addition to the conditioning blend in accordance with the invention, compositions according to the invention may optionally include other silicone or non-silicone conditioning agents. These may be incorporated into the conditioning blend of the invention, or added separately.

Mousses

Hair treatment compositions in accordance with the invention may also take the form of aerosol foams (mousses) in which case a propellant must be included in the composition. This agent is responsible for expelling the other materials from the container and forming the hair mousse character. The propellant gas can be any liquefiable gas conventionally used for aerosol containers. Examples of suitable propellants include dimethyl ether, propane, n-butane and isobutane, used singly or in admixture.

The amount of the propellant gases is governed by normal factors well known in the aerosol art. For hair mousses, the level of propellant is generally from 3 to 30, preferably from 5 to 15 percent by weight of the total composition.

Small additional quantities of surfactant ranging anywhere from 0.1 to 10, preferably from 0.1 to 1 percent by weight of composition, for example 0.3 percent by weight of composition may be present in the hair mousse compositions of the invention. The surfactant may be an anionic, nonionic or cationic emulsifier. Particularly preferred are nonionic emulsifiers which are formed from alkoxylation of hydrophobes such as fatty alcohols, fatty acids and phenols.

Adjuvants

The compositions of the present invention may also contain adjuvants suitable for hair care. Generally such ingredients are included individually at a level of up to 2, preferably up to 1 percent by weight of the total composition.

Among suitable hair care adjuvants, are: (i) natural hair root nutrients, such as amino acids and sugars. Examples of suitable amino acids include arginine, cysteine, glutamine, glutamic acid, isoleucine, leucine, methionine, serine and valine, and/or precursors and derivatives thereof. The amino acids may be added singly, in mixtures, or in the form of peptides, e.g. di- and tripeptides. The amino acids may also be added in the form of a protein hydrolysate, such as a keratin or collagen hydrolysate. Suitable sugars are glucose, dextrose and fructose. These may be added singly or in the form of, e.g. fruit extracts. A particularly preferred combination of natural hair root nutrients for inclusion in compositions of the invention is isoleucine and glucose. A particularly preferred amino acid nutrient is arginine.

(ii) hair fibre benefit agents. Examples are: ceramides, for moisturising the fibre and maintaining cuticle integrity. Ceramides are available by extraction from natural sources, or as synthetic ceramides and pseudoceramides . A preferred ceramide is Ceramide II, ex

Quest. Mixtures of ceramides may also be suitable, such as Ceramides LS, ex Laboratoires Serobiologiques .

Mode of Use

The compositions of the invention are primarily intended for topical application to the hair and/or scalp of a human subject in rinse-off compositions, to improve hair fibre surface properties such as smoothness, softness, manageability, cuticle integrity, and shine. In particular the compositions according to the invention are used to reduce the volume or fluffiness of hair after washing and natural drying as compared to the volume or fluffiness of hair after washing and natural drying without the use of compositions according to the invention.

The invention is further illustrated by reference to the following examples.

Examples

2g of 25 cm long European hair switches were washed in pretroleum ether and rinsed under a tap in demineralised water. Using 4-5 switches per treatment, 0.2 ml of shampoo composition was placed along the length of the switch and agitated for 30 seconds, followed by a rinse in flowing demineralised water for 30 seconds. Again, 0.2 ml of shampoo was placed along the length of the switch and agitated for 30 seconds, followed by a rinse for 1 minute. The switches were combed through whilst suspended vertically from a clamp stand, then further rinsed with a jet of demineralised water to pull all the fibers together and allowed to dry naturally overnight.

Switches treated with conditioner composition were first base washed as above with a control shampoo base (by weight: 16% SLES 2EO, 2% coco amidopropyl betaine, 82% water), then 0.2 mis of conditioner was placed along the length of the switch and agitated for 1 minute followed by a rinse for 1 minute. The switches were combed through whilst suspended vertically from a clamp stand, then rinsed with a water jet to pull all the fibres together and allowed to dry naturally overnight.

Each switch was suspended vertically from a clamp stand and a 2 mW, 632.8nm wavelength Helium-Neon laser shone perpendicular to the untouched, dried switch, approximately 5cm from the bottom of the switch, and the illuminated image recorded onto an optical disc using a 35mm camera.

Image analysis software was then used in order to calculate the radial distribution of the fibres in the switch about the centre line of the switch. This was then used to provide an estimate of the volume of the switch. Broader radial distributions correspond to larger mean volumes.

Table 1 shows shampoo compositions according to the invention (examples 1 and 2) along with comparative examples which are not according to the invention (A,B, C and D) .

Table 1

All values are percent ingredient by weight at 100% active, SLES 2EO is Sodium lauryl ether sulphate (Empicol ESB70 ex Albright and Wilson) . CAP-B is cocoamidopropyl betaine (Tegobetaine CK ex Goldschmidt) . Jaguar C13-S is guar hydroxypropyl trimonium chloride ex Rhone Poulenc. DC1766 is dimethiconol (polydimethylsiloxane ex Dow Corning with a

2 -1 viscosity of 1000000 mm sec at 25 °C - particle size 800 nm) . Varisoft TA-100 is Distearyldimonium chloride ex Goldschmidt. PK300AM is commercial etylene glycol distearate dispersion ex Cognis and carbopol 980 is a cross- linked polyacrylate .

For Example C, the Soybean oil and Varisoft were added to the composition as separate ingredients. For Examples 1 and 2 the Soybean oil and Varisoft were pre-blended before addition to the composition.

Hair volume results from the shampooed and dried hair switches are shown in table 2.

Table 2

From the data in table 2 it can be seen that the shampoo compositions according to the invention provide lower hair volume than the comparative examples.

Table 3 shows a conditioner composition according to the invention (ex 3) along with a comparative example using silicone (ex E. )

Table 3

All values are percent by weight as 100% active ingredient. For Examples 3 the Soybean oil and Varisoft were pre-blended before addition to the composition.

Table 4 shows the hair volume results for hair switches treated with the conditioners from table 3.

Table 4

A further experiment was carried out with example E, where a hot air dryer was used to dry and de-fluff the switches after treatment with the conditioner. This gave a mean volume of 9.7. Hence the conditioner example according to the invention gives significantly lower volume compared to a conventional silicone conditioner composition, even when hot air drying is used for the control and ambient drying for the composition according to the invention.

Further shampoo compositions were prepared according to the formulations in table 5. Examples F and G are comparative examples with silicone DC1785 (ex Dow Corning - 60% active polydimethylsiloxame emulsion with viscosity 100000 mm²sec^"1 and droplet diameter of 0.5 to 1.0 miicrometres) and sunflower oil as conditioning oil respectively.

Examples 4 and 5 are according to the invention, and comprise droplets of sunflower oil pre-blended with oil- dispersible cationic surfactant. In each of the examples according to the invention, 3% by weight of blended material was present in the shampoo composition.

Table 5

All values are percent by weight as 100% active ingredient. Active ingredients are as described above for the other shampoo examples. Tetranyl AO-1 is a commercial ester guaternary surfactant supplied by Kao Corporation Barcelona. They are blends of mono-, di- and tri-oleoylethyl hydroxyethylmonium methosulfate . AO-1 is 90% active in IPA. All figures are as 100% active by weight in the composition. Shampoos G and 4 were compared in a blind in-homes consumer test with untrained consumers. The participants scored the shampoos for various conditioning attributes on a 0-10 scale, with 10 being the best. The results are indicated in Table 6 Table6

The results show that the incorporation of the cationic surfactant into the conditioning blend improved the conditioning results without the loss of clean feel.

Table 7 shows results for comparison of shampoos F and 5 by a trained panel of assessors.

Table 7

The results from table 7 demonstrate that compositions according to the invention can provide comparable or improved conditioning to a silicone-containing conditioning shampoo while also providing better clean feel.

Claims

1. A hair conditioning composition comprising; i) an aqueous phase, ii) a surfactant selected from the group consisting of anionic, amphoteric and zwitterionic cleansing surfactants and cationic conditioning surfactants and iii) discrete, dispersed droplets of a conditioning blend, wherein the droplets of the conditioning blend comprise both a non-silicone oil and an oil-dispersible cationic surfactant within the same droplets and wherein the weight ratio of oil-dispersible surfactant to non- silicone oil is from 1:8 to 8:1.

2. A composition according to claim 1 wherein the non- silicone oil is selected from the group consisting of hydrocarbon oils, fatty ester oils and mixtures thereof.

3. A composition according to any preceding claim comprising from 0.1% to 20% by weight of the conditioning blend.

4. A composition according to any preceding claim wherein the wherein the ratio of oil-dispersible surfactant to non-silicone oil in the conditioning blend is from 1:5 to 5:1.

5. A composition according to any preceding claim wherein the oil-dispersible cationic surfactant is selected from monoalkyl trimethyl quaternary ammonium salts, dialkyl dimethyl quaternary ammonium salts, hydrocarbyl ester quaternary ammonium salts, alkyl imidazolinium salts, alkyl pyrimidinium salts, alkyl benzoimidazolium salts and mixtures thereof, wherein the alkyl or hydrocarbyl chain has chain length of from 10 to 22 carbon atoms.

6. A composition according to any preceding claim wherein the oil-dispersible cationic surfactant in the conditioning blend comprises a blend of

(a) Cio to C22 dialkyl dimethyl quaternary ammonium salt and

(b) Cio to C22 hydrocarbyl ester quaternary ammonium salt,

wherein the ratio of (a) to (b) is from 4:1 to 1:2.

7. A composition according to any preceding claim which is a shampoo composition comprising at least one cleansing surfactant selected from anionic, nonionic, amphoteric and zwitterionic surfactants and mixtures thereof .

8. A composition according to claim 7 wherein the mean diameter D_{3 # 2} of the conditioning blend droplets is from 0.02 to 15 micrometres.

9. A composition according to claim 8 which comprises a cationic deposition polymer.

10. A composition according to any one of claims 7 to 9 wherein the pH of the composition is from 3 to 6.5.

11. A composition according to any one of claims 1 to 6 which is a hair conditioner composition comprising at least one cationic conditioning surfactant and a fatty material selected from a fatty alcohol, an alkoxylated fatty alcohol and mixtures thereof.

12. A composition according to any preceding claim wherein the composition further comprises a silicone oil .

13. The use of a composition according to any preceding claim for reducing the volume of dried hair.

14. The use of a composition according to any preceding claim for providing hair conditioning combined with a clean feel.

15. A method for incorporating discrete droplets of a conditioning blend comprising both a non-silicone oil and an oil-dispersible cationic surfactant in the same droplets, into a hair treatment composition according to any preceding claim, comprising the steps of;

i) forming an intimate, non-aqueous blend comprising the non-silicone oil and the oil-dispersible cationic surfactant,

ii) preparing an aqueous emulsion comprising droplets comprising both a non-silicone oil and a oil- dispersible cationic surfactant in the same droplets and

iii) mixing said aqueous emulsion with the hair treatment composition.