WO2012119810A2

WO2012119810A2 - Composition

Info

Publication number: WO2012119810A2
Application number: PCT/EP2012/051256
Authority: WO
Inventors: Stephen Norman Batchelor
Original assignee: Unilever Plc; Unilever N.V.; Hindustan Unilever Limited
Priority date: 2011-03-10
Filing date: 2012-01-26
Publication date: 2012-09-13
Also published as: BR112013022596A2; WO2012119810A3; EP2683353A2; CN103415279A

Abstract

Hair dye composition comprising a polymer dye, the polymer dye comprising a positively charged polymer covalently bound to a negatively charged reactive dye in which the reactive dye is a bis-azo dye of the structure (I) in which the A ring is substituted by at least one heterocyclic reactive group and/or a sulphonate group.

Description

COMPOSITION

The present invention relates to a hair care composition comprising a polymer dye and a method for dying the hair.

Background

US 4 182 612 (Gillette) discloses polyethylenimine cationic polymers covalently linked to dyes for the colouration of hair. The dyes used do not carry negatively charged substituents that can produce dark shades.

FR 2 456 764 (L'Oreal) discloses quaternary amine polymer linked to dyes for the colouration of hair. The dyes used do not carry negatively charged substituents that can produce dark shades.

WO2008/009579 (Ciba) and WO2009/090121 to WO2009/090125 (BASF) disclose cationic dyes covalently linked to polymers for the colouration of hair.

Co-pending Unilever application WO201 1 /1 13680 discloses hair dye compositions comprising a positively charged polymer covalently bound to a negatively charged reactive dye. However the specific reactive dyes of the present invention are not disclosed.

Despite the prior art there remains a need for improved hair dye compositions that provide a dark blue shade to human hair. Dark blue shades are used in hair dyeing as the basis for dark black and brown shades. Description of the Invention

The present invention relates to a hair dye composition comprising a polymer dye, the polymer dye comprising a positively charged polymer covalently bound to a negatively charged reactive dye in which the reactive dye is a bis-azo dye of the structure:

in which the A ring is substituted by at least one heterocyclic reactive group and/or a sulphonate group .

In a second aspect there is provided a method for dying hair by applying to the hair a composition according to the first aspect of the invention. In a third aspect the invention relates to the use of the above described polymer for colouring the hair.

Detailed description of the invention Dye Polymer

Compositions of the invention comprise a dye polymer as defined in claim 1

A hydrolysed reactive dye is one in which the reactive groups have reacted with the hydroxide anion, HO^", rather than the polymer. Preferably, the composition contains less than 10Oppm of hydrolysed reactive dye, more preferably less than 5ppm per10 OOOppm of dye polymer present. Most preferably, hydrolysed reactive dyes are not present in the composition. Such dyes may be removed by dialysis.

Hydrolysed reactive dyes are not covalently bound to the polymer. A reactive dye that has two reactive groups, where one has reacted with the polymer to form a covalently bond and one has reacted with HO^", is not classed as a hydrolysed dye in the context of the invention.

Reactive Dye

The reactive dye of the polymer used in the invention is a blue bis-azo dye of the form:

Wherein the A ring is substituted by a heterocyclic reactive group and optionally a sulphonate group and the B ring is optionally substituted by groups selected from a heterocyclic reactive group, a sulfooxyethylsulfonyl reactive group, and a sulphonate group.

Preferably, the B ring is substituted by a heterocyclic reactive group.

The heterocyclic reactive groups are preferably nitrogen contains aromatic rings bound to a halogen or a quaternary ammonium group, most preferably CI or F, which react with NH₂ or NH groups of the polymers to form a covalent bonds. More preferred heterocylic reactive groups are dichlorotriazinyl, difluorochloropyrimidine, monofluorotrazinyl, monofluorochlorotrazinyl, dichloroquinoxahne, difluorotriazine, monochlorotnazinyl, and trichloropyrimidine.

Es ecially preferred heterocylic reactive groups are

Wherein Ri is selected from H or alkyl, preferably H.

X is selected from F or CI

When X = CI, Z₁ is selected from -CI, -NR₂R₃, -OR₂, -S0₃Na

When X=F, Z is selected from -NR₂R₃ R₂ and R₃ are independently selected from H, alkyl and aryl groups. Aryl groups are preferably phenyl and are preferably substituted by -S0₃Na or - S0₂CH₂CH₂OS0₃Na. Alkyl groups are preferably methyl or ethyl.

Preferably, the heterocylic reactive group is bound at the meta position on the A and B ring.

The phenyl groups may be further substituted with suitable uncharged organic groups, preferably with a molecular weight lower than 200. Preferred groups include -CH₃, -C₂H₅, and -OCH_3.

The alkyl groups may be further substituted with suitable uncharged organic groups, preferably with a molecular weight lower than 200. Preferred groups include -CH₃, -C₂H₅, -OH, -OCH₃, -OC₂H₄OH. Most preferred heterocylic reactive groups are selected from

and H H Where n=1 or 2, preferably 1 .

Preferably, the reactive dye contains more than one reactive group, preferably two or three. Polymer

The polymer comprises a free -SH, -OH, -NH or -NH₂ group for reaction with the dye. More preferably, the polymer contains at least one -NH or -NH₂ group, most preferably at least five -NH or -NH₂ group.

When polyamine is referred to as being covalently bound to a reactive dye one skilled in the art will understand that the reactive group is no longer present in the dye polymer. This is exemplified below for three reactive groups:

O O H₂N— polymer ₀ NHpolymer

II H₂ H₂ II II H₂ I

-S— C— C— OS0₃Na dye— S— C=CH₂ *- dye— S— C— CH₂

II alkali II H alkali \\

o o o

Preferably, the polymers have an overall cationic charged at pH 5.0. Preferably, the polymer comprises quaternary amine groups or tertiary amines.

Examples of such polymers are polyethyleneimine, polypropylene- imine, polyvinylamine; polyvinylimine, aminosilcone.

Preferably, the polymer, before reaction with the dye, has a weight averaged molecular weight of from 500 to 1000 000, preferably from 800 to 60 000, most preferably from 800 to 2500.

The molecular weights are determined by dynamic light scattering using a Zetasizer Nano (Malvern).

Preferably, the polymer is a polyamine. Preferably, the polyamine is selected from polyethyleneimine, polypropylene- imine, polyvinylamine, and polyvinylimine.

Polyamines are polyalkyl amines and are generally linear or branched. The polyamine comprises primary, secondary or tertiary amines or a mixture thereof. Preferably, the polyamine comprises ethylene alkyl groups and the polymer is formed by ring opening polymerisation of ethyleneimine to provide polyethyleneimine (PEI). PEI is most preferred.

Alternatively, the polyamines are alkoxylated to provide alkoxylated PEI's, for example ethoxylated polyethyleneimine (EPEI). In this regard, a single or a number of amine functions are reacted with one or more alkylene oxide groups to form a polyalkylene oxide side chain. The alkylene oxide can be a homopolymer (for example ethylene oxide) or a random or block copolymer. The PEI's suitable for use in the composition of the invention can have the general formula: (-NHCH2CH2-)_X[-N(CH2CH2NH2)CH2CH2-I_y wherein x is an integer from about 1 to about 120000, preferably from about 10 to about 20000, more preferably from about 20 to about 10000 and y is an integer from about 1 to about 60000, preferably from about 10 to about 30000, more preferably from about 20 to about 12000. Specific examples of polyethylene imines are PEI-300, PEI-500, PEI 600, PEI- 700, PEI- 800, PEI-1000, PEI-1500, PEI-1800, PEI-2000, PEI-2500, PEI-5000, PEI-10000, PEI-25000, PEI 50000 and PEI-70000, wherein the integer represents the number average molecular weight of the polymer. PEI's which are designated as such are available through Aldrich.

When the PEI alkoxylated, most preferably ethoxylated, the PEI is partially alkoxylated so that at least one NH₂ or NH is available for reaction with the reactive dye, preferably at least one NH₂. The preferred degree of alkoxylation is from 0.2 to 50% of the primary and secondary amines are alkoxylated.

An example of a PEI structure is

Composition Unless specified otherwise, all wt% values quoted hereinafter are percentages by weight based on total weight of the hair treatment composition.

Preferably, the composition comprises from 0.2 to 10 wt%, most preferably from 0.5 to 3 wt% of the dye polymer.

Preferably, the composition has a pH of from 4 to 1 1 , more preferably from 8 to 10 most preferably from 8.5 to 9.5.

The pH may be controlled by the use of common buffers and/or alakli's such as NaOH, NH₄OH and/or acid such as HCI.

Product Form

Compositions of the present invention are formulated into hair colouring compositions which may take a variety of forms, including, for example, mousses, gels, lotions, creams, sprays and tonics. These product forms are well known in the art.

The preferred product is a lotion, cream, spray, aerosol mousse or gel. To improve the feel of the hair, the composition is preferably a hair conditioning composition containing a conditioning active such as a cationic surfactant or silicone, fatty alcohol, fatty acid, fatty ester, fatty amide or mixtures thereof. Cationic Surfactant

If present 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 C₃o) 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 (Ο-ι-Οβ) alkyl or benzyl. More preferably, one or two of R¹, R², R³ and R⁴ are independently (Ce to C30) alkyl and the other R¹, R², R³ and R⁴ groups are (C1-C6) 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 (eg, 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):

R1 CONH(CH2)mN(R2)R3 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

(ii) 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 compositions 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. Silicones

The compositions of the invention can contain, emulsified droplets of a silicone conditioning agent, for enhancing conditioning performance. 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 micron, ideally from 0.01 to 1 micron. Silicone emulsions having an average silicone droplet size of £ 0.15 micron 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 micron, more preferably greater than 1 micron, ideally from 2 to 8 micron.

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). Non-Silicone Oils

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

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

Compositions 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 to 10%, preferably from 0.1 % to 8%, more preferably from 0.2 % to 7 %, most preferably from 0.3 % to 6 % 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.

Cationic Polymers

Cationic polymers may be present in the formulation.

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 the composition 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% by total weight of cationic polymer based on the total weight of the composition. Other Optional Ingredients

A composition of the invention may contain from 0.01 to 2 wt% of the total composition of other ingredients for enhancing performance and/or consumer acceptability. Such ingredients include fragrance, dyes and pigments, pH adjusting agents, pearlescers or opacifiers, viscosity modifiers, preservatives, and natural hair nutrients such as botanicals, fruit extracts, sugar derivatives and amino acids. Preferably, the composition is a rinse off hair treatment composition. A rinse off composition is applied hair preferably wet hair, and left on the hair for up to I hour, preferably left on the hair for up to 30 minutes before it is removed by rinsing.

To provide further colours the dye-polymers is preferably mixed with analagous dye-polymer made with reactive red or reactive yellow dyes. Preferably, the reactive red or reactive yellow dyes are mono-azo or bis-azo compounds.

Alternatively the reactive red and yellow dyes may be attached to the same polymer backbone as the bis-azo reactive dye. For the avoidance of doubt, in the text "a" means one or more.

The invention will now be further illustrated by the following, non-limiting

Examples. Experimental

Preparation of dye polymer

The bis-azo reactive blue dye of formula:

was reacted with branched polyethyleneimine (Mw=2000) and branched polyethyleneimine (Mw = 750 000), where Mw is the weight Average Molecular Weight. No hydrolysed dye could be detected by Thin Layer Chromatography.

The following polymers were made

Table 1

The wt% dye on polymer was calculated from the UV-VIS absorption of the dye- polymer, using an extinction coefficient of 50 000 L mol^"1 cm^"1 for the dye.

Colouring of hair

A 1 .4g human bleached blond hair truss was placed in a 1 .4g aqueous solution of the dye polymer and agitated for 60 seconds. The aqueous solution contained 1 .4wt% of the dye-polymer. The truss was removed, rinsed in demineralised water for 60 seconds, dried and the colour measured using a reflectometer and expressed as the CIE L^*a^*b^* values.

The L^* values are shown below

Table 2 L^*

Control (no dye treatment) 63

DP1 32

DP2 24

DP3 38

The dye polymers effective dye the hair giving large decreases in L^* The polymer with lower Mw gives more colour. Table 3

Trade / Common Name INCI % w/w

Cocamidopropyl Betaine Cocamidopropyl Betaine 25

Plantacare 818 UP Coco Glucoside 7

Glycerine Glycerin 1

Antil 127 PEG-120 Methyl Glucose 2

Dioleate

EDTA Disodium EDTA 0.05

Merquat 550 PR Polyquaternium-7 0.5

Jaguar C162 Hydroxypropyl Guar 0.25

Hydroxyprorpyltrimonium

Chloride

Ammonia 880 Ammonia q.s (to pH=9)

Sodium Metabisulphite Sodium Metabisulphite 2

Sodim Isoascorbate Sodium Isoascorbate 0.15

Aculyn 88 Acrylates/Steareth-20 4

Methacrylate Crosspolymer

Kathon CG Methylchloroisothiazolinone, 0.07

Methylisothiazolinone

Purified Water Aqua To 100% Trade / Common Name INCI % w/w

Natrasol 250HHR Hydroxyethylcellulose 0.7

Tego Amid S18 Stearamidopropyl 1

Dimethylamine

Lanette 16 Cetyl Alcohol 3

Lanette 0 Cetearyl Alcohol 1 .5

Varisoft EQ 65 Distearoylethyl Dimonium 1

Chloride

DC 200 Dimethicone 2

Cetiol CC Dicaprylyl Carbonate 0.5

Panthenol DL50 Panthenol 0.01

Kathon CG Methylchloroisothiazolinone, 0.07

Methylisothiazolinone

Sodium Hydroxide Sodium Hydroxide q.s. (to pH=9)

Fragrance Parfum 0.3

Purified Water Aqua To 100%

0.1 wt% and 0.5wt% of Dye Polymer were added to the formulations.

The dye-polymer used was 100wt% Reactive blue 171 bound to Lupasol G35 (PEI with Mw=2000 ex BASF).

Claims

1 . Hair dye composition comprising a polymer dye, the polymer dye

comprising a positively charged polymer covalently bound to a negatively charged reactive dye in which the reactive dye is a bis-azo dye of the structure:

in which the A ring is substituted by at least one heterocyclic reactive group and/or a sulphonate group.

Hair dye composition according to claim 1 in which the B ring of the azo dye is substituted by at least one heterocyclic reactive group, and/or a sulfooxyethylsulfonyl reactive group, and/or a sulphonate group.

Hair dye composition according to claim 1 or claim 2 in the B ring is substituted by a heterocyclic reactive group.

Hair dye composition according to any preceding claim in which the heterocylic reactive groups is selected from dichlorotriazinyl,

difluorochloropyrimidine, monofluorotrazinyl, monofluorochlorotrazinyl, dichloroquinoxaline, difluorotriazine, monochlorotriazinyl, and

trichloropyrimidine.

Hair care composition according to any preceding claim in which the heterocylic reactive groups is selected from the following structure:

In which Ri is selected from H or C1 -C6 alkyl, preferably H.; X is selected from F or CI such that when X = CI, Zi is selected from -CI, -NR2R3, -OR2, - SOsNa and hen X=F, Zi is selected from -NR2R3; R2 and R₃ are

independently selected from H, alkyl and aryl groups.

Hair dye composition according to claim 5 in which the aryl groups of Zi are phenyl groups substituted by -SOsNa or -S0₂CH₂CH₂OS0₃Na.

Hair dye composition according to claim 6 in which the substituted aryl groups of Zi are further substituted with the groups selected from -CH₃, -

Hair dye composition according to claim 5 in which the alkyl groups are substituted groups selected from -CH₃, -C₂H₅, -OH, -OCH3, -OC₂H₄OH.

Hair dye composition according to any one of claims 1 to 5 in which the heterocylic reactive groups is selected from

H H and H H in which n=1 . Hair dye composition according to any preceding claim in which the reactive dye contains two or three reactive groups.

1 1 . Hair dye composition according to any preceding claim in which the

composition contains less than 50ppm of hydrolysed reactive dye per l OOOOppm of dye polymer.

12. Hair dye composition according to any preceding claim in which the

positively charged polymer is a polyamine.

13. Hair dye composition according to claim 12 in which the polyamine is

polyethylene imine (PEI).

14. Hair dye composition according to claim 13 in which the polyamine is an ethoxylated polyethyleneimine (EPEI).

15. Hair dye composition according to any preceding claim comprising from from 0.5 to 3% by weight of the total composition of dye polymer. 16. Hair dye composition according to any preceding claim wherein the pH is from 8 to 10.

17. Method for colouring hair by applying to the hair a composition comprising a polymer dye, said polymer dye comprising a positively charged polymer covalently bound to a negatively charged reactive dye in which the reactive dye is a bis-azo dye of the structure:

Use of a polymer dye for colouring the hair, the polymer dye comprising a positively charged polymer covalently bound to a negatively charged reactive dye in which the reactive dye is a bis-azo dye of the structure: