WO2012119811A2

WO2012119811A2 - Composition

Info

Publication number: WO2012119811A2
Application number: PCT/EP2012/051262
Authority: WO
Inventors: Stephen Norman Batchelor
Original assignee: Hindustan Unilever Ltd; Unilever NV
Current assignee: Hindustan Unilever Ltd; Unilever NV
Priority date: 2011-03-10
Filing date: 2012-01-26
Publication date: 2012-09-13
Anticipated expiration: 2013-09-10
Also published as: AR085707A1; WO2012119811A3

Abstract

A kit for colouring hair comprising at least two parts; iii) a first composition comprising an oxidizing agent; iv) a second composition comprising an alkalinity agent, in which the first composition and/or the second composition and/or an additional third composition comprises a polymer dye comprising a positively charged polymer covalently bound to a negatively charged reactive dye.

Description

COMPOSITION

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

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.

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. US 4 228 259 (L'Oreal) discloses a dye for keratinic material comprises a water- soluble cationic polymer.

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 WO 201 1/1 13680 discloses hair dye

compositions comprising a positively charged polymer covalently bound to a negatively charged reactive dye. Despite the prior art there remains a need for improved hair dye compositions, that increases the deposition of dye-polymer to hair. Description of the Invention

The present invention provides a kit for colouring hair comprising at least two parts; i) a first composition comprising an oxidising agent;

ii) a second composition comprising an alkalinity agent,

in which the first composition and/or the second composition and/or an additional third composition further comprises a polymer dye comprising a positively charged polymer covalently bound to a negatively charged reactive dye.

In a second aspect the invention provides a method for dying hair comprising the steps of applying to the hair the compositions within the kit as described in any one of the previous claims.

Detailed description of the invention

Dye Polymer

The composition of the invention comprises a polymer dye comprising a positively charged polymer covalently bound to a negatively charged reactive dye.

A hydrolysed reactive dye is one in which the reactive groups has reacted with the hydroxide anion, HO^", rather than the polymer. A reactive dye that has two reactive groups, where one reactive group has reacted with the polymer to form a covalent bond and one reactive group has reacted with HO^", is not classed as a hydrolysed reactive dye in the context of the invention. Equally a reactive dye that has three reactive groups where one or two reactive groups have reacted with the polymer to form covalent bonds and one or two reactive groups have reacted with HO^", is not classed as a hydrolysed reactive dye in the context of the reaction.

A hydrolysed dye has no covalent bond to the polymer.

The composition of the invention preferably comprise less than 100ppm of hydrolysed reactive dye per l OOOOppm of dye polymer, more preferably less than 50ppm, most preferably less than 5ppm. Most preferably hydrolysed reactive dyes are not present in the composition. Such dyes may be removed by dialysis or careful control of the reactions conditions.

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.

The total kit comprises from 0.2 to 10wt% of dye polymer, most preferably from 0.5 to 3wt% of the dye polymer. The dye polymer may be present in one or more than one parts of the kit, however it is preferable if the dye polymer is only present in one part of the kit.

Reactive dye Reactive dyes are described in Industrial Dyes (K. Hunger ed, Wiley VCH 2003). Many Reactive dyes are listed in the colour index (Society of Dyers and Colourists and American Association of Textile Chemists and Colorists).

Reactive groups are preferably selected from heterocyclic reactive groups and, a sulfooxyethylsulfonyl reactive group (-SO₂CH₂CH₂OSO₃Na), which is converts to a vinylsulfone in alkali. The heterocyclic reactive groups are preferably nitrogen contains aromatic rings bound to a halogen or an ammonium group or a quaternary ammonium group, which react with NH₂ or NH groups of the polymers to form a covalent bonds. The halogen is preferred, most preferably CI or F.

Preferably, the reactive dye comprises a reactive group selected from

dichlorotriazinyl, difluorochloropynmidine, monofluorotrazinyl, dichloroquinoxahne, vinylsulfone, difluorotriazine, monochlorotriazinyl, bromoacrlyamide and

trichloropyrimidine.

The reactive group may be linked to the dye chromophore via an alkyl spacer for example: dye-NH-CH₂CH₂-reactive group.

Especially 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.

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.

Preferably, the reactive dye comprises a chromophore selected from azo, anthraquinone, phthalocyanine, formazan and triphendioaxazine.

Where the dye is an azo dye it is preferred that the azo dye is not an azo-metal complex dye. Preferably the reaction of the polyamine and the reactive dye to form the dye polymers, takes place in water at alkaline pH, preferable pH=10 to 1 1 .5, at temperature of 40-100°C for 1 to 3 hours after the dye is added to the solution. Thereafter the solution is cooled to room temperature and neutralised to pH=7 within 1 to 2 hours. The level of polyamine in the reaction solution is preferable from 2 to 50wt%, more preferably from 5 to 20wt%. These conditions minimise the production of hydrolysed dye. Examples of reactive dyes include reactive black 5, reactive blue 19, reactive red 2, reactive blue 171 , reactive blue 269, reactive blue 1 1 , reactive yellow 17, reactive, reactive orange 4, reactive orange 16, reactive green 19, reactive brown 2, reactive brown 50.

Reactive blue dyes are preferably selected from anthraquinone, mono azo, bis- azo, triphenodioxazine, and phthalocyanine, more preferably anthraquinone, bis- azo, and triphenodioxazine, most preferably bis-azo and triphenodioxazine.

A preferred blue bis-azo dye is of the form

Where one or both of the A and B rings are substituted by a reactive group. The A and B rings may be further substituted by sulphonate groups (SOsNa). The A and B rings may be further substituted with suitable uncharged organic groups, preferably with a molecular weight lower than 200. Preferred uncharged organic groups are -CH₃, -C2H5, and -OCH3_. A preferred blue anthraquinone dye is of the form

Where the C ring is substituted by a reactive group. The dye may be further substituted with sulphonate groups (SOsNa) and suitable uncharged organic groups, preferably with a molecular weight lower than 200. Preferred uncharged organic groups are-CH₃, -C2H5, and -OCH3.

A preferred blue triphenodioxazine dye is of the form

Where the D and E rings are substituted by a reactive groups. Preferably the D and E rings are further substituted by sulphonate groups (SOsNa).

Examples of reactive blue dyes are reactive blue 2, reactive blue 4, reactive blue 5, reactive blue 7, reactive blue 15, reactive blue 19, reactive blue 27, reactive blue 29, reactive blue 49, reactive blue 50, reactive blue 74, reactive blue 94, reactive blue 246, reactive blue 247, reactive blue 247, reactive blue 166, reactive blue 109, reactive blue 187, reactive blue 213, reactive blue 225, reactive blue 238, reactive blue 256. Further structures are exemplified below:

Reactive Red dyes are preferably selected from mono-azo and bis-azo dyes. A preferred reactive red azo dye is of the form

Where the F ring is optionally extended to form a naphthyl group and is optionally substituted by groups selected from sulphonate groups (SOsNa) and a reactive group.

G is selected from a reactive group, H, or alky group. A reactive group must be present on the dye.

Examples of reactive red dyes are reactive red 2, reactive red 3, reactive red 4, reactive red 8, reactive red 9, reactive red 12, reactive red 13, reactive red 17, reactive red 22 .reactive red 24, reactive red 29, reactive red 33 reactive red 139, reactive red 198 and reactive red 141 .

Reactive yellow and orange dyes are preferably selected from mono-azo dyes. Examples of reactive yellow and orange dyes are reactive yellow 1 , reactive yellow 2, reactive yellow 3, reactive yellow 16, reactive yellow 17, reactive yellow 25 , reactive yellow 39, reactive orange 107, reactive yellow 176 and reactive yellow 135.

Combination of reactive dyes may be used to obtain a wide colour palette with use of a limited number of dyes. Preferably, a trichromate system consisting of a mixture of three reactive dyes. Preferably, the trichromate system contains a combination of a reactive blue or a reactive black dye, a reactive red and a reactive yellow dye. For example reactive black 5, reactive yellow 176 and reactive red 239; reactive blue 171 , reactive yellow 176 and reactive red 141 .

Preferably, each polymer molecule should be covalently bound to at least one dye molecule, preferably more than two.

To avoid differential build up on multiple treatments, if more than one colour is present, for example a reactive red and a reactive blue, they are preferably bound to the same polymer backbone.

Preferably, the dye polymer is obtainable by reacting the polymer with from 0.1 to 20wt% reactive dye, most preferably from 1 to 10wt%.

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.

The kit of the invention comprises of a least two parts. It is preferable if the parts of the of kit are mixed on the hair or before shortly (10 minutes or less) application to the head. When mixed the pH of the resulting composition is from 6 to 12, preferably from 8 to 10.5 (at 20°C).

The present invention provides a kit for colouring hair comprising at least two parts:

a first part comprising an oxidising agent compsirinig hydrogen peroxide;

a second part comprising an alkalinity agent;

in which the first part and/or the second part and/or an additional third part further comprises a polymer dye comprising a positively charged polymer covalently bound to a negatively charged reactive dye.

One embodiment of the invention provides a kit comprising two parts, the first part comprising hydrogen peroxide/hydrogen peroxide generator and the polymer dye, the second part comprising an alkalinity agent. A second preferred embodiment of the invention comprises a kit comprising two parts, the first part comprising alkalinity agent and the polymer dye, the second part comprising hydrogen peroxide/ hydrogen peroxide generator. A third embodiment comprises a kit of three parts; first part comprising an alkalinity agent, the second part the polymer dye, the third part comprising the hydrogen peroxide/ hydrogen peroxide generator.

It is highly preferred if the hydrogen peroxide/hydrogen peroxide generator is not in the same part as the alkalinity agent.

To improve the feel of the hair, at least one composition within the kit further comprises a conditioning active such as a cationic surfactant or silicone, fatty alcohol, fatty acid, fatty ester, fatty amide or mixtures thereof.

Alkalinity agent

The kit of the invention comprises an alkalinity agent. Suitable alkalinity agents include ammonium hydroxide, ethylamine, dipropylamine, triethylamine and alkanediamines such as 1 ,3- diaminopropane, anhydrous alkaline alkanolamines such as, mono or di- ethanolamine, preferably those which are completely substituted on the amine group such as dimethylaminoethanol, polyalkylene polyamines such as diethylenetriamine or a heterocyclic amine such as mocpholine as well as the hydroxides of alkali metals, such as sodium and potassium hydroxide, hydroxides of alkali earth metals, such as magnesium and calcium hydroxide, basic amino acids such as L-alginine, lysine, oxylysine and histidine and alkanolamines such as dimethylaminoethanol and

aminoalkylpropanediol and mixtures thereof. Also suitable for use herein are compounds that form HC03- by dissociation in water (hereinafter referred to as 'ion forming compounds'). Examples of suitable ion forming compounds are Na2C03, NaHC03, K2C03, (NH4)2C03, NH4HC03, CaC03 and Ca(HC03) and mixtures thereof.

Although the dye polymer may also be used to add alkalinity, an additional alkalinity agent is required.

Ammonium hydroxide is highly preferred.

Oxidizing Agent

The kit comprises an oxidizing agent. The oxidizing agent is preferably in only one composition of the kit. Suitable oxidizing agents include hydrogen peroxide, alkali metal bromate, sodium perborate, urea peroxide, sodium percarbonate, sodium peroxytripolyphosphate, sodium peroxypyrophosphate, sodium peroxyorth ophosphate, sodium silicate/ hydrogen peroxide addition products, sodium sulphate/sodium chloride/ hydrogen peroxide addition products. Hydrogen peroxide and alkali metal bromates are preferred, hydrogen peroxide being particularly preferred. Preferably, the composition comprising the oxidising agent is present as an aqueous solution. The level of oxidising agent within the composition is from 0.1 to 30wt%, preferably from 2 to 10wt%. These levels are particularly relevant with respect to hydrogen peroxide. Preferably the composition comprising hydrogen peroxide has a pH in the range from 2 to 4 at 20°C.

The pH adjustment to 2 to 4 can be effected by using acidifying agents such as hydrochloric acid, tartaric acid, citric acid, phosphoric acid and carboxylic or sulphonic acids such as ascorbic acid, acetic acid, lactic acid, sulphuric acid, formic acid, ammonium sulphate and sodium dihydrogenphosphate /phosphoric acid, disodium hydrogenphosphate /phosphoric acid, potassium chloride

/hydrochloric acid, potassium dihydrogen phthalate/ hydrochloric acid, sodium citrate / hydrochloric acid, potassium dihydrogen citrate /hydrochloric acid, potassium dihydrogencitrate/ citric acid, sodium citrate / citric acid, sodium tartarate/ tartaric acid, sodium lactate/ lactic acid, sodium acetate/ acetic acid. Phosphoric acid is a preferred agent for buffering hydrogen peroxide solutions.

It is further preferred if the composition comprising the oxidizing agent particularly if it is hydrogen peroxide further comprises a heavy metal sequestrant. Heavy metal ion sequestrants are preferably present at a level of from about 0.005% to about 20%, preferably from about 0.01 % to about 10%, more preferably from about 0.05% to about 2% by weight of the compositions. 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.

Preferably, the composition is a rinse off hair treatment composition. A rinse off composition is applied hair preferably to 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. Method of application

The method of application is to apply the contents of the kit to hair preferably to wet hair.

The compositions of the kit may be added sequentially to the hair but are preferably mixed immediately (within 10 minutes) before application to the hair. The composition is left on the hair for up to 60 minutes, more preferably up to 30 minutes before it is removed by rinsing.

EXAMPLES Example 1 PEI dye-polymers were synthesised by placing 10g of a commercial PEI (Lupasol G35) into 100g of water with 20g of NaCI, to this 4g of Reactive Blue 198 (as received) was added and the solution heated to 50°C for 45 minutes. 20g of soda ash was then added and the solution kept at 50°C for a further 45 minutes and then cooled. HCI was added to the solution to bring it to pH=8.

An aqueous solution containing 0, 1 , 2, 4 and 8wt% of H2O2 at pH=9 was created and 0.7g hair swatches were agitated in 3ml of the solution for 30 minutes, thoroughly rinsed and dried. The hair swatches consisted of 50% black and 50% white hair.

The experiment was repeated with the addition of 1 .5wt% of the PEI-reactive blue 198 polymer to the hair and the CIE L^*a^*b^* values measured using a

reflectometer. The amount of reactive blue - dye polymer deposited to the hair was assessed from the b^* value which measures the blue-yellow colour axis. The results are given in the table below

Lower b value are found with the sample containing H2O2 and dye-polymer, indicating more blue colour on the hair..

Claims

1 . A kit for colouring hair comprising at least two parts;

i) a first composition comprising an oxidizing agent;

ii) a second composition comprising an alkalinity agent,

in which the first composition and/or the second composition and/or an additional third composition comprises a polymer dye comprising a positively charged polymer covalently bound to a negatively charged reactive dye.

2. Hair dye kit according to claim 1 in which the composition comprises less than 5ppm of a hydrolysed reactive dye per l OOOOppm of dye polymer.

3. Hair dye kit according to any preceding claim comprising from 0.2 to 10% by weight of dye polymer within the total kit.

4. Hair dye kit according to any preceding claim wherein the reactive dye of the dye polymer comprises a reactive group selected from dichlorotriazinyl, difluorochloropyrimidine, monofluorotrazinyl, dichloroquinoxaline, vinylsulfone, difluorotriazine, monochlorotriazinyl, bromoacrlyamide and trichloropyrimidine.

5. Hair dye kit according to any preceding claim wherein the reactive dye of the dye polymer comprises a chromophore selected from azo,

anthraquinone, phthalocyanine, formazan and triphendioaxazine.

6. Hair dye kit according to any preceding claim in which the positively

charged polymer is a polyamine.

7. Hair dye kit according to claim 6 in which the polyamine is polyethylene imine (PEI).

8. Hair dye kit according to claim 7 in which the polyamine is an ethoxylated polyethyleneimine (EPEI).

9. Hair dye kit according to any preceding claim in which the oxidising agent is hydrogen peroxide.

10. Method for dying hair comprising the steps of applying to the hair the

compositions within the kit as described in any one of the previous claims.