WO2012139944A2

WO2012139944A2 - Hair care composition

Info

Publication number: WO2012139944A2
Application number: PCT/EP2012/056156
Authority: WO
Inventors: Nicholas John Ainger; Stephen Norman Batchelor; Neil Stephen Burnham; Robert George Riley
Original assignee: Unilever Plc; Unilever N.V.; Hindustan Unilever Limited
Priority date: 2011-04-13
Filing date: 2012-04-04
Publication date: 2012-10-18
Also published as: WO2012139944A3; AR085975A1

Abstract

A kit for colouring hair comprising: (i) a composition comprising a mixture of metal ion Fe(ll), Fe(lll) and Cu(ll) and/or complex where the wt fraction of Cu/Fe is from 0.1 to 5; and (ii) a second composition comprising from 0.05 to 10wt% of the total composition of a polyphenol comprising gallic acid or C₁ - C₆ chain esters thereof.

Description

Hair Care Composition

The present invention relates to kits and methods for colouring hair. Background

Polyphenol compound mordanted with metal ions have been known to dye human hair for many years. EP0327345 (Beechams) discloses a metal shampoo, polyphenol conditioner systems.

Two part colouring systems in which one part comprises a metal salt are disclosed in WO2010/135237 (Advance Cosmetic Technologies), WO/2007/130777, WO 2000/29036 (Henkel).

However, there remains the need for a colourant that can be used routinely and which delivers an effective level of colouring to hair. Furthermore, it is often desired to introduce red/mahogany shades into blue-blacks, because this better reflects the natural shade of human hair. Surprisingly, we have found this may be achieved by mixing low levels Cu(ll) with Fe(ll) or Fe(lll), whilst maintaining a high depth of shade,.

Description of the Invention

Accordingly the present invention provides a kit for colouring hair comprising (i) a composition comprising a mixture of metal ion Fe(ll), Fe(lll) and Cu(ll) and/or complex where the weight fraction of Cu/Fe is from 0.1 to 5; and (ii) a second composition comprising from 0.05 wt% to 10 wt% of the total composition of a polyphenol comprising gallic acid or short chain Ci to C6 esters thereof. Also described is a method of colouring hair comprising the steps of applying to hair sequentially in any order the composition described above.

Detailed Description of the Invention Unless stated otherwise the wt% quoted in this specification relate to the wt% in each composition of the kit and not the total level of ingredient within the kit.

Metal Salt/Complex Compositions of the invention comprise Fe and Cu ion in the form of a salt and/or complex.

The total level of metal ion within the kit is from 0.01 wt% to 5 wt% more preferably 0.2 to 3 wt%.

The weight fraction of Cu/Fe is from 0.1 to 5, preferably from preferably from 0.6 to 3, more preferably from 0.5 to 2.

Preferably, the metal ion resides only in the one composition of the kit, and in this instance the above levels relate to one composition.

Preferably, the Cu/Fe containing composition further comprises a cleansing surfactant. The level of metal ion in the formulation may be determined by quantitative elemental analysis.

For the avoidance of doubt, if the formulation contains 2 wt% of the complex

With molecular weight of 446.14, then it will contain 55.84/446.14^*2 = 0.25 wt% of Fe(ll) (2 decimal places). If the formulation contained 1 wt% of the salt FeC then the it will contain 55.84/126.75^*1 = 0.44 wt% of Fe(ll) (2 decimal places).

It is preferable if Fe(ll) is one of the metal ions present.

The metal ion is present as a salt or as a complex with a ligand. Simple salts include sulphates and halides, for instance Fe(ll)S0₄ and mixed salts, for instance Fe(ll) ammonium sulphate. It is preferred is the metal is present as a complex with a ligand.

In the context of this invention a ligand is a molecule that contains more than one organic group, preferably 2 to 4 groups, most preferably 2 groups, that coordinate with the metal ion. Groups for co-ordinating with the metal ion are COO^", OH, ketones, esters, primary amines, secondary amines and tertiary amines, more preferably COO^", tertiary amines and OH, most preferably COO^" and OH. introduce a reddish hue to the hair with hue angles close to 0 (360) when the wt fraction of Cu/Fe is less than 5, preferably less than 2. This is achieved whilst maintaining the Polyphenols are not permitted as multidentate ligands. The ligand-metal complex may be pre-formed before addition to the composition for example Iron (II) gluconate, iron (II) glutamate. The ligand metal complex may be formed in the composition by the addition of an iron salt and the ligand, for example FeC and sodium lactate. Preferably the mole ratio of metal ion to ligand is from 1 : 1 to 1 :4, more preferably 1 : 1 .5 to 1 :2.5.

Preferably, the metal ion is in the form of a salt and/or complex that is soluble in aqueous solution at the pH of the formulation. Most preferably the metal ion in the form of a salt and/or complex has a solubility in demineralised water at the pH of the formulation of greater than 0.1 g/L.

The ability of a ligand to complex with a metal ion, Mⁿ⁺, may be defined by its pMⁿ⁺ value, wherein pMⁿ⁺ = -log₁₀[Mⁿ⁺]_free and the ligand concentration is 10^"5 mol/L and the total metal ion concentration is 10^"6 mol/L and [Mⁿ⁺]f_ree is the molar concentration of uncomplexed metal ions. Preferably, the ligand used has a lower pMⁿ⁺, than gallic acid. Preferably, the pMⁿ⁺ are greater than 8 more preferably greater than 10. pMⁿ⁺ values are most preferably measured at pH=4 in de-mineralised water, with the chloride salt of the metal ion, most preferably ferric chloride.

Polyamino carboxylic acids are preferably present at weight % levels of less than 1 /30th of the main ligand, preferably they are absent from the shampoo. A polyamino carboxylic acid is a compound containing two or more amines

connected through carbon atoms to two or more carboxylic acid groups.

2,2',2",2"'-(Ethane-1 ,2-diyldinitrilo)tetraacetic acid is a polyamino carboxylic acid.

Diethylene triamine pentaacetic acid is a polyamino carboxylic acid.

Ethylenediamine-N,N'-disuccinic acid is a polyamino carboxylic acid. Most preferably the ligands are selected from gluconate, tartrate, ascorbate, citrate and lactate. Particularly preferred are gluconate, lactate or ascorbate.

Particularly preferred are iron (II) gluconate, copper (II) gluconate and iron(ll) lactate, iron (II) tartrate, most preferably iron (II) gluconate and copper (II) gluconate.

Preferably, the metal is a composition which further comprises a cleansing surfactant, such as a shampoo composition. More preferably the metal is only in the shampoo composition.

Polyphenol

At least one composition within the kit comprise a polyphenol comprising gallic acid or Ci - Ce ester thereof. It is preferable if the polyphenol is selected from gallic acid, methyl gallate, ethyl gallate and propyl gallate, particularly preferred is gallic acid and propyl gallate, most preferred is propyl gallate.

The polyphenol containing composition is preferably an aqueous polyphenol solution.

The total polyphenol level within the kit is preferably from 0.05 wt% to 10 wt%, more preferably 0.1 wt% to 5 wt%, most preferably from 0.2 wt% to 2 wt%.

Preferably, the polyphenol resides only in the one composition of the kit, and in this instance the above levels relate to that one composition.

Wherein the aqueous polyphenol solution has a pH preferably of 2 to 7 measured using a calibrated pH meter, more preferably 3 to 6. To avoid oxidation of the polyphenols by air it is preferred that the composition is stored in an airtight container, preferably a bottle closed with an air tight cap.

The aqueous polyphenol solution contains water, preferably as the dominate ingredient. Auxiliary ingredients may be present for example to increase the viscosity, perfume and help solubilise the polyphenol. Solubilising ingredients include organic solvents and surfactants., however organic solvent are preferably absent. Preferably, the water used to formulate all compositions has a French hardness of from 0 to 36 degrees, more preferably 0 to 24 degrees, most preferably from 0 to 2 degrees.

Preferably, the water used to formulate all compositions contains less than 1 ppm of chlorine based bleaching agents such as chlorine dioxide or hypochlorite. Most preferably less than 50ppb .

The polyphenol is preferably not in the same composition as the metal ions. Preferably, the polyphenol is not in a composition with a detersive surfactant (a shampoo). It is preferable if the polyphenol is in a conditioning composition more preferably a pre-treatment or post treatment, most preferably a conditioning post treatment. Particularly preferred are rinse-off conditioners, for use after the shampoo process.

Product Format

Shampoo compositions of the invention are generally aqueous, i.e. they have water or an aqueous solution or a lyotropic liquid crystalline phase as their major component. Suitably, the composition will comprise from 50 % to 98%, preferably from 60 % to 90% water by weight based on the total weight of the composition.

It is preferable if the composition comprising the metal salts/complexes is a shampoo composition.

Surfactant Mix

Shampoo compositions of the invention comprise a detersive surfactant,. Anionic Cleansing Surfactant

Shampoo compositions according to the invention may preferably 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, alkyl ether sulphosuccinates, N-alkyl sarcosinates, alkyl phosphates, alkyl ether phosphates, and alkyl ether carboxylic acids and salts thereof, especially their sodium, magnesium, ammonium and mono-, di- and triethanolamine salts. The alkyl and acyl groups generally contain from 8 to 18, preferably from 10 to 16 carbon atoms and may be unsaturated. The alkyl ether sulphates, alkyl ether sulphosuccinates, alkyl ether phosphates and alkyl ether carboxylic acids and salts thereof may contain from 1 to 20 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, sodium lauryl sulphate, sodium lauryl ether sulphate, sodium lauryl ether sulphosuccinate, ammonium lauryl sulphate, ammonium lauryl ether sulphate, sodium dodecylbenzene sulphonate, triethanolamine dodecylbenzene sulphonate, sodium cocoyl isethionate, sodium lauryl isethionate, lauryl ether carboxylic acid and sodium N-lauryl sarcosinate.

Preferred anionic cleansing surfactants are sodium lauryl sulphate, sodium lauryl ether sulphate(n)EO, (where n is from 1 to 3), sodium lauryl ether

sulphosuccinate(n)EO, (where n is from 1 to 3), ammonium lauryl sulphate, ammonium lauryl ether sulphate(n)EO, (where n is from 1 to 3), sodium cocoyl isethionate and lauryl ether carboxylic acid (n) EO (where n is from 10 to 20). Particularly, preferred anionic surfactants are lauryl ether sulphate, most preferred sodium lauryl ether sulfate (SLES) , preferably having from 1 to 3 ethoxy groups.

The level of alkyl ether sulphate is preferably from 0.5 wt% to 25 wt% of the total shampoo composition, more preferably from 3 wt% to 18 wt%, most preferably from 6 wt% to 15 wt% of the total shampoo composition.

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 generally ranges from 0.5 wt% to 45 wt%, more preferably from 1 .5 wt% to 30 wt%.

Nonionc surfactant

Shampoo compositions of the invention preferably comprise from 0 to 50 wt% of the shampoo composition of a nonionic surfactant, preferably from 0 to 20 wt%, more preferably from 0 to 10 wt%.

Nonionic surfactants that can be included in shampoo compositions of the invention include condensation products of aliphatic (Cs - C-is) 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. AlkyI ethoxylates are particularly preferred. Most preferred are alkyl ethoxylates having the formula R-(OCH₂CH₂)nOH, where R is an alkyl chain of C12 to C15, and n is 5 to 9.

Other suitable 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, tAPG 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 about C5 to about C2o- Preferably, R represents a mean alkyl chain length of from about Cs to about C12. Most preferably the value of R lies between about 9.5 and about 10.5. G may be selected from C5 or Ce 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 about 1 to about 10 or more. Preferably, the value of n lies from about 1 .1 to about 2. Most preferably the value of n lies from about 1 .3 to about 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 compositions of the invention include the C-I O-C-I S N-alkyl (Οι-Οβ) 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 C10-C18 N-(3-methoxypropyl) glucamide. Amphoteric/zwitterionic Surfactant

Amphoteric or zwitterionic surfactant can be included in an amount ranging from 0.5 wt% to about 8 wt%, preferably from 1 wt% to 4 wt% of the total shampoo composition. Examples of amphoteric or zwitterionic surfactants include alkyl amine oxides, alkyl betaines, alkyl amidopropyl betaines, alkyl sulphobetaines (sultaines), alkyl glycinates, alkyl carboxyglycinates, alkyl amphoacetates, 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, lauryl betaine, cocamidopropyl betaine and sodium cocoamphoacetate.

A particularly preferred amphoteric or zwitterionic surfactant is cocamidopropyl betaine. Mixtures of any of the foregoing amphoteric or zwitterionic surfactants may also be suitable. Preferred mixtures are those of cocamidopropyl betaine with further amphoteric or zwitterionic surfactants as described above. A preferred further amphoteric or zwitterionic surfactant is sodium cocoamphoacetate.

The total amount of surfactant (including any co-surfactant, and/or any emulsifier) in a shampoo composition of the invention is generally from 1 % to 50%, preferably from 0.5 % to 40%, more preferably from 1 .5 to 30% by total weight surfactant based on the total weight of the composition.

Further Ingredients Cationic Polymers Cationic polymers are preferred ingredients in a shampoo composition of the invention for enhancing performance.

Suitable cationic polymers may be homopolymers which are cationically substituted or may be formed from two or more types of monomers. The weight average (M_w) molecular weight of the polymers will generally be between 100 000 and 2 million daltons. The polymers will have cationic nitrogen containing groups such as quaternary ammonium or protonated amino groups, or a mixture thereof. If the molecular weight of the polymer is too low, then the conditioning effect is poor. If too high, then there may be problems of high extensional viscosity leading to stringiness of the composition when it is poured.

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 polymers having a cationic charge density in the required range, which is generally from 0.2 to 3.0 meq/gm. The cationic charge density of the polymer is suitably determined via the Kjeldahl method as described in the US

Pharmacopoeia under chemical tests for nitrogen determination.

Suitable cationic polymers include, for example, copolymers of vinyl monomers having cationic amine or quaternary ammonium functionalities with water soluble spacer monomers such as (meth)acrylamide, alkyi and dialkyi (meth)acrylamides, alkyi (meth)acrylate, vinyl caprolactone and vinyl pyrrolidine. The alkyi and dialkyi substituted monomers preferably have C1 -C7 alkyi groups, more preferably C1 -3 alkyi 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 polymers can comprise mixtures of monomer units derived from amine- and/or quaternary ammonium-substituted monomer and/or compatible spacer monomers.

Suitable cationic polymers include, for example: cationic diallyl quaternary ammonium-containing polymers including, for example, dimethyldiallylammonium chloride homopolymer and copolymers of acrylamide and dimethyldiallylammonium chloride, referred to in the industry (CTFA) as Polyquaternium 6 and Polyquaternium 7, respectively; mineral acid salts of amino-alkyl esters of homo-and co-polymers of unsaturated carboxylic acids having from 3 to 5 carbon atoms, (as described in U.S. Patent 4,009,256); cationic polyacrylamides(as described in W095/2231 1 ). Other cationic polymers that can be used include cationic polysaccharide polymers, such as cationic cellulose derivatives, cationic starch derivatives, and cationic guar gum derivatives.

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

A-O-[R-N⁺(R¹)(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 group, or combination thereof. R¹, R² and R³ independently represent alkyl, aryl, alkylaryl, arylalkyl, alkoxyalkyl, or alkoxyaryl groups, each group containing up to about 18 carbon atoms. The total number of carbon atoms for each cationic moiety (i.e., the sum of carbon atoms in R¹, R² and R³) is preferably about 20 or less, and X is an anionic counterion.

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 the Amerchol Corporation, for instance 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 hydroxypropyltrimethylammonium chloride (commercially available from Rhodia in their JAGUAR trademark series). Examples of such materials are JAGUAR C13S, JAGUAR C14, JAGUAR C15, JAGUAR C17 and JAGUAR C16 Jaguar CHT and JAGUAR C162. Mixtures of any of the above cationic polymers may be used.

Cationic polymer will generally be present in a shampoo composition of the invention at levels of from 0.01 to 5%, preferably from 0.03 to 1 %, more preferably from 0.05 to 0.5% by total weight of cationic polymer based on the total weight of the composition.

Suspending Agent

Preferably, an aqueous shampoo composition of the invention further comprises a suspending agent. 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, since these impart pearlescence to the composition. 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 941 and Carbopol 980. An example of a suitable copolymer of a carboxylic acid containing monomer and acrylic acid esters is Carbopol 1342. All Carbopol (trademark) materials are available from Lubrizol.

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

Mixtures of any of the above suspending agents may be used. Preferred is a mixture of cross-linked polymer of acrylic acid and crystalline long chain acyl derivative. Suspending agent will generally be present in a shampoo composition of the invention at levels of from 0.1 to 10%, preferably from 0.5 to 6%, more preferably from 0.9 to 4% by total weight of suspending agent based on the total weight of the composition. Preferably, the shampoo composition has a pH of 2 to 8 measured using a calibrated pH meter, more preferably from 3 to 6.5 Product form

To avoid oxidation of the metal by air it is preferred that the shampoo is stored in an air tight container such as a bottle closed with an air tight cap.

Conditioning Agents

Silicone Conditioning Agents The compositions of the invention can contain, emulsified droplets of a silicone conditioning agent, for enhancing conditioning performance. Silicone conditioning agents may be present in the shampoo or conditioner.

Suitable silicones include polydiorganosiloxanes, in particular

polydimethylsiloxanes which have the CTFA designation dimethicone. Also suitable for use compositions of the invention (particularly shampoos and conditioners) are polydimethyl siloxanes having hydroxyl end groups, which have the CTFA designation dimethiconol. Also suitable for use in compositions of the invention are silicone gums having a slight degree of cross-linking, as are described for example in WO 96/31 188.

The viscosity of the emulsified silicone itself (not the emulsion or the final hair conditioning composition) is typically at least 10,000 est at 25 °C the viscosity of the silicone itself is preferably at least 60,000 est, most preferably at least 500,000 est, ideally at least 1 ,000,000 est. Preferably the viscosity does not exceed 10⁹ est for ease of formulation.

Emulsified silicones for use in the shampoo compositions of the invention will typically have an average silicone droplet size in the composition of less than 30, preferably less than 20, more preferably less than 10 μηι, ideally from 0.01 to 1 μΓΠ . Silicone emulsions having an average silicone droplet size of < 0.15 μηι are generally termed microemulsions.

Emulsified silicones for use in the conditioner compositions of the invention will typically have an size in the composition of less than 30, preferably less than 20, more preferably less than 15. Preferably, the average silicone droplet is greater than 0.5 μηι , more preferably greater than 1 μηι , ideally from 2 to 8 μηι.

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

Examples of suitable pre-formed emulsions include Xiameter MEM 1785 and microemulsion DC2-1865 available from Dow Corning. These are emulsions /microemulsions of dimethiconol. Cross-linked silicone gums are also available in a pre-emulsified form, which is advantageous for ease of formulation.

A further preferred class of silicones for inclusion in shampoos and conditioners of the invention are amino functional silicones. By "amino functional silicone" is meant a silicone containing at least one primary, secondary or tertiary amine group, or a quaternary ammonium group. Examples of suitable amino functional silicones include: polysiloxanes having the CTFA designation "amodimethicone", Specific examples of amino functional silicones suitable for use in the invention are the aminosilicone oils DC2-8220, DC2-8166 and DC2-8566 (all ex Dow Corning).

Suitable quaternary silicone polymers are described in EP-A-0 530 974. A preferred quaternary silicone polymer is K3474, ex Goldschmidt.

Also suitable are emulsions of amino functional silicone oils with non ionic and/or cationic surfactant. Pre-formed emulsions of amino functional silicone are also available from suppliers of silicone oils such as Dow Corning and General Electric. Specific examples include DC939 Cationic Emulsion and the non-ionic emulsions DC2- 7224, DC2-8467, DC2-8177 and DC2-8154 (all ex Dow Corning).

With some shampoos it is preferred to use a combination of amino and non amino functional silicones.

The total amount of silicone is preferably from 0.01 to 10 %wt of the total composition more preferably from 0.1 to 5 wt%, most preferably 0.5 to 3 wt% is a suitable level, especially for a shampoo composition.

(ii) Non-silicone Oily Conditioning Components Compositions according to the present invention may also comprise a dispersed, non-volatile, water-insoluble oily conditioning agent. Preferably such non-silicone conditioning oily conditioning agents are present in conditioner compositions.

By "insoluble" is meant that the material is not soluble in water (distilled or equivalent) at a concentration of 0.1 % (w/w), at 25°C.

Suitable oily or fatty materials are selected from hydrocarbon oils, fatty esters and mixtures thereof. Straight chain hydrocarbon oils will preferably contain from about 12 to about 30 carbon atoms. Also suitable are polymeric hydrocarbons of alkenyl monomers, such as C2-C6 alkenyl monomers.

Specific examples of suitable hydrocarbon oils include paraffin oil, mineral oil, saturated and unsaturated dodecane, saturated and unsaturated tridecane, saturated and unsaturated tetradecane, saturated and unsaturated pentadecane, saturated and unsaturated hexadecane, and mixtures thereof. Branched-chain isomers of these compounds, as well as of higher chain length hydrocarbons, can also be used.

Suitable fatty esters are characterised by having at least 10 carbon atoms, and include esters with hydrocarbyl chains derived from fatty acids or alcohols,

Monocarboxylic acid esters include esters of alcohols and/or acids of the formula R'COOR in which R' and R independently denote alkyl or alkenyl radicals and the sum of carbon atoms in R' and R is at least 10, preferably at least 20. Di- and trialkyl and alkenyl esters of carboxylic acids can also be used.

Particularly preferred fatty esters are mono-, di- and triglycerides, more

specifically the mono-, di-, and tri-esters of glycerol and long chain carboxylic acids such as C1-C22 carboxylic acids. Preferred materials include cocoa butter, palm stearin, sunflower oil, soyabean oil and coconut oil.

The oily or fatty material is suitably present at a level of from 0.05 wt% to 10 wt%, preferably from 0.2 wt% to 5 wt%, more preferably from about 0.5 wt% to 3 wt%.

Cationic conditioning surfactants

Conditioner compositions will typically comprise one or more conditioning surfactants which are cosmetically acceptable and suitable for topical application to the hair. Suitable conditioning surfactants include those selected from cationic surfactants, used singly or in admixture. Preferably, the cationic surfactants have the formula N⁺R¹R²R³R⁴ wherein R¹, R², R³ and R⁴ are independently (Ci to C₃₀) alkyl or benzyl. Preferably, one, two or three of R¹, R², R³ and R⁴ are independently (C₄ to C30) alkyl and the other R¹, R², R³ and R⁴ group or groups are (C-i-Ce) alkyl or benzyl. More preferably, one or two of R¹, R², R³ and R⁴ are independently (C6 to C30) alkyl and the other R¹ , R², R³ and R⁴ groups are (Ο-ι-Οβ) alkyl or benzyl groups. Optionally, the alkyl groups may comprise one or more ester (-OCO- or - COO-) and/or ether (-O-) linkages within the alkyl chain. Alkyl groups may optionally be substituted with one or more hydroxyl groups. Alkyl groups may be straight chain or branched and, for alkyl groups having 3 or more carbon atoms, cyclic. The alkyl groups may be saturated or may contain one or more carbon- carbon double bonds (e.g. oleyl). Alkyl groups are optionally ethoxylated on the alkyl chain with one or more ethyleneoxy groups. Suitable cationic surfactants for use in conditioner compositions according to the invention 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, dihydrogenated tallow dimethyl ammonium chloride (eg, Arquad 2HT/75 from Akzo Nobel), cocotrimethylammonium chloride, PEG-2-oleammonium chloride and the corresponding hydroxides thereof. 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 conditioners according to the invention is cetyltrimethylammonium chloride, available commercially, for example as GENAMIN CTAC, ex Hoechst Celanese. Another particularly useful cationic surfactant for use in conditioners according to the invention is

behenyltrimethylammonium chloride, available commercially, for example as GENAMIN KDMP, ex Clariant. Another example of a class of suitable cationic surfactants for use in the invention, either alone or together with one or more other cationic surfactants, is a

combination of (i) and (ii) below:

(i) an amidoamine corresponding to the general formula (I):

R¹CO

(ii) in which R¹ is a hydrocarbyl chain having 10 or more carbon atoms, R² and R³ are independently selected from hydrocarbyl chains of from 1 to 10 carbon atoms, and m is an integer from 1 to about 10; and

(iii) an acid. As used herein, the term hydrocarbyl chain means an alkyl or alkenyl chain.

Preferred amidoamine compounds are those corresponding to formula (I) in which

R¹ is a hydrocarbyl residue having from about 1 1 to about 24 carbon atoms, R² and R³ are each independently hydrocarbyl residues, preferably alkyl groups, having from 1 to about 4 carbon atoms, and m is an integer from 1 to about 4.

Preferably, R² and R³ are methyl or ethyl groups. Preferably, m is 2 or 3, i.e. an ethylene or propylene group.

Preferred amidoamines useful herein include stearamido-propyldimethylamine, stearamidopropyldiethylamine, stearamidoethyldiethylamine,

stearamidoethyldimethylamine, palmitamidopropyldimethylamine, palmitamidopropyl-diethylamine, palmitamidoethyldiethylamine, palmitamidoethyldimethylamine, behenamidopropyldimethyl-amine,

behenamidopropyldiethylmine, behenamidoethyldiethyl-amine,

behenamidoethyldimethylamine, arachidamidopropyl-dimethylamine,

arachidamidopropyldiethylamine, arachid-amidoethyldiethylamine,

arachidamidoethyldimethylamine, and mixtures thereof.

Particularly preferred amidoamines useful herein are

stearamidopropyldimethylamine, stearamidoethyldiethylamine, and mixtures thereof.

Commercially available amidoamines useful herein include:

stearamidopropyldimethylamine with tradenames LEXAMINE S-13 available from Inolex (Philadelphia Pennsylvania, USA) and AMIDOAMINE MSP available from Nikko (Tokyo, Japan), stearamidoethyldiethylamine with a tradename

AMIDOAMINE S available from Nikko, behenamidopropyldimethylamine with a tradename INCROMINE BB available from Croda (North Humberside, England), and various amidoamines with tradenames SCHERCODINE series available from Scher (Clifton New Jersey, USA).

A protonating acid may be present. Acid may be any organic or mineral acid which is capable of protonating the amidoamine in the conditioner composition. Suitable acids useful herein include hydrochloric acid, acetic acid, tartaric acid, fumaric acid, lactic acid, malic acid, succinic acid, and mixtures thereof.

Preferably, the acid is selected from the group consisting of acetic acid, tartaric acid, hydrochloric acid, fumaric acid, lactic acid and mixtures thereof.

The primary role of the acid is to protonate the amidoamine in the hair treatment composition thus forming a tertiary amine salt (TAS) in situ in the hair treatment composition. The TAS in effect is a non-permanent quaternary ammonium or pseudo-quaternary ammonium cationic surfactant.

Suitably, the acid is included in a sufficient amount to protonate more than 95 mole% (293 K) of the amidoamine present.

In conditioners of the invention, the level of cationic surfactant will generally range from 0.01 % to 10%, more preferably 0.05 % to 7.5%, most preferably 0.1 % to 5% by weight of the composition.

Conditioners of the invention will typically also incorporate a fatty alcohol. The combined use of fatty alcohols 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.

Representative fatty alcohols comprise from 8 to 22 carbon atoms, more preferably 16 to 22. Fatty alcohols are typically compounds containing straight chain alkyl groups. 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.

The level of fatty alcohol in conditioners of the invention will generally range from 0.01 wt% to 10 wt%, preferably from 0.1 wt% to 8 wt%, more preferably from 0.2 wt% to 7 wt%, most preferably from 0.3 wt% to 6 wt% by weight of the

composition. The weight ratio of cationic surfactant to fatty alcohol is suitably from 1 : 1 to 1 : 10, preferably from 1 : 1 .5 to 1 :8, optimally from 1 :2 to 1 :5. If the weight ratio of cationic surfactant to fatty alcohol is too high, this can lead to eye irritancy from the composition. If it is too low, it can make the hair feel squeaky for some consumers. Adjuncts

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

Suitable hair care adjuncts, include amino acids, sugars and ceramides and viscosity modifiers. Method of use

The method of colouring hair comprises the steps of applying to hair sequentially in any order:

(i) a composition comprising a mixture of metal ion Fe(ll), Fe(lll) and

Cu(ll) and/or complex where the wt fraction of Cu/Fe is from 0.1 to 5; and

(ii) a second composition, which comprises from 0.05 wt% to 10wt% of a polyphenol comprising gallic acid or short chain esters thereof Preferably, the compositions of the invention are applied to wet hair, necessitating the step of wetting the hair before application of the compositions of the invention.

Preferably, the method comprises the step of rinsing hair between application of the first composition and the second composition (ii). It is highly preferred if the hair is rinsed after application of both compositions of the invention.

It is preferred if the first composition to be applied is a shampoo composition, a more preferred system is that the first application is a shampoo composition followed by application of a conditioner composition. Further conditioning and/or styling products may be applied as part of the colouring process.

The level of each composition applied to the head of hair is preferably from 5g to 100g.

Preferably, each composition remains on the hair for 5 to 600 seconds, more preferably 10 to 300 seconds. Preferably, the water used to wet and rinse the hair has a French hardness of from 0 to 36 degrees, more preferably 0 to 24 degrees, most preferably from 0 to 2 degrees.

Preferably, the water used to wet and rinse the hair contains less than 1 ppm of chlorine based bleaching agents such as chlorine dioxide or hypochlorite. Most preferably less than 50ppb .

Examples A 0.7g twice bleached platinum blonde hair switch was bathed for 300 seconds in a solution containing 0.5wt% of metal sulphonate and 2wt% of sodium gluconate. The switch was removed and rinsed for 30 seconds before being places in a 0.5wt% solution of polyphenol for 300 seconds, removed rinsed and dried. The colour of the switch was measured using a reflectometer (Color \7) and expressed as the CIE L* and hue angle values. L* measure the depth of shade and the hue angle measures the colour. All water used was demineralised. The metal sulphonate used was selected from mixtures of CuS0₄ and FeS0₄ and the polyphenol from gallic acid and tannic acid. All materials were used as received from Aldrich. The wt% of Cu(ll) and Fe(ll) in the metal bath were calculated from the known weights and purities. The results are shown below. g/L Cu/Fe Gallic acid Tannic acid

(reference)

Cu(ll) Fe(ll) L^* hue L^* hue

0.00 1 .64 0.00 16.5 281 .3 19.3 252.9

0.42 1 .31 0.32 16.2 282.1 22.8 13.0

0.84 0.98 0.85 16.9 283.8 24.7 29.2

1 .25 0.65 1 .92 17.5 286.4 26.4 41 .7

1 .67 0.33 5.1 1 22.4 316.7 30.9 83.6

2.09 0.00 - 39.4 76.0 50.2 99.6

A hue angle of 270 represent blue, 0 (360) is red, 90 is yellow and 180 is

The untreated hair had an L^* of 63.0 and a hue angle of 76.0. Reference treatment with one metal only, are given in italics.

It is desirable to have a dark colour with a red/blue hue, thus a low L^* value and a hue value of 250 to 360. The results above demonstrate that the effect of changing the Cu/Fe ratio is more desirable for gallic acid than tannic acid. Addition of even low levels of Cu to the tannic acid leads to an immediate drop in L^* unlike Gallic acid. Addition of low levels of Cu to tannic acid leads to yellowing of the hair, with the hue angle approaching 90 (yellow). Addition of low levels of Cu to gallic acid adds to the red component.

The desired depth of shade and hue is obtained by a combination of Fe(ll) with Cu(ll). The Cu/Fe wt fraction of 0.85 and 1 .92 with gallic acid, give the best results.

Claims

1 . A kit for colouring hair comprising:

(i) a composition comprising a mixture of metal ion Fe(ll), Fe(lll) and Cu(ll) and/or complex where the weight fraction of Cu/Fe is from 0.1 to 5; and

(ii) a second composition comprising from 0.05 to 10 wt% of the total composition of a polyphenol comprising gallic acid or Ci - C6 chain esters thereof .

2. A kit according to claim 1 in which the composition comprising Cu/Fe, further comprises a detersive surfactant.

3. A kit as claimed in any preceding claim in which the metal complex

comprises a ligand of gluconate, lactate or ascorbate.

4. A kit as claimed in any preceding claim in which the metal salt and/or

complex comprises iron (II) gluconate and copper (II) gluconate.

5. A kit according to any preceding claim in which the polyphenol is selected from gallic acid, methyl gallate, ethyl gallate and propyl gallate.

6. A kit according to any preceding claim in which the polyphenol is propyl gallate.

7. A kit as claimed in any preceding claim in which the weight ratio of Cu/Fe is from 0.6 to 3.

8. A method of colouring hair comprising the steps of applying to hair

sequentially in any order: (i) a composition comprising a mixture of metal ion Fe(ll), Fe(lll) and Cu(ll) and/or complex where the weight fraction of Cu/Fe is from 0.1 to 5; and

(ii) a second composition, which comprises from 0.05 wt% to 10wt% of the total composition of a polyphenol comprising gallic acid or short chain Ci - C6 esters thereof

A method according to claim 8 in which further comprises the step of rinsing hair between application of the fist composition (and the second composition.