WO2011113680A2

WO2011113680A2 - Composition

Info

Publication number: WO2011113680A2
Application number: PCT/EP2011/052841
Authority: WO
Inventors: Stephen Norman Batchelor; Sheng MENG; Andrew Malcolm Murray; Qingsheng Tao; Jinfang Wang
Original assignee: Unilever Plc; Unilever N.V.; Hindustan Unilever Limited
Priority date: 2010-03-19
Filing date: 2011-02-25
Publication date: 2011-09-22
Also published as: EA201290927A1; WO2011113680A3; TW201138848A; BR112012023599A2; JP2013522258A; AU2011229421A1; EP2547320A2; AR080759A1

Abstract

Hair composition comprising a polymer dye, said polymer dye comprising a positively charged polymer and a negatively charged reactive dye and a method for dying hair by applying to the hair a composition comprising a polymer dye, said polymer dye comprising a positively charged polymer and 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.

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.

Despite the prior art there remains a need for improved hair dye compositions.

Accordingly, and in a first aspect, the present invention provides a composition according to claim 1 .

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

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, polyvinylannine; polyvinylinnine, aminosilcone, cationic modified starch and cationic modified polyvinylalcohol. Preferably the polymer has a molecular weight of from 500 to 200 000.

Preferably, the polymer is a polyamine. Preferably, the polyamine is selected from polyethyleneimine, polypropylene- imine, polyvinylannine, and polyvinylinnine. 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 ethoxylated to provide 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 2 to about 60000, more preferably from about 3 to about 24000 and y is an integer from about 1 to about 60000, preferably from about 2 to about 30000, more preferably from about 3 to about 12000. Specific examples of polyethylene imines are PEI-3, PEI-7, PEI-15, PEI-30, PEI-45, PEI-100, 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, PEI-70000, PEI-500000, PEI-5000000 and the like, wherein the integer represents the average molecular weight of the polymer. PEI's which are designated as such are available through Aldrich.

Most preferably the PEI, before alkoxylation and/or reaction with a reactive dye, has an average molecular weight of from 800 to 8000.

The PEI is preferably 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.

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).

Preferably, the reactive dye comprises a reactive group selected from

dichlorotriazinyl, difluorochloropyrimidine, monofluorotrazinyl, dichloroquinoxaline, vinylsulfone, difluorotriazine, monochlorotriazinyl, bromoacrlyamide and

trichloropyrimidine.

More preferably, the reactive dye comprises a reactive group selected from monochlorotriazinyl, dichlorotriazinyl, and vinylsulfonyl.

Preferably, the reactive dye comprises a chromophore selected from azo, anthraquinone, phthalocyanine, formazan and triphendioaxazine. More preferably from azo, anthraquinone, phthalocyanine, and triphendioaxazine. Most preferably from azo and anthraquinone. Where the dye is an azo dye it is preferred that the azo dye is not an azo-metal complex dye.

Examples of reactive dyes include reactive black 5, reactive blue 19, reactive red 2, reactive blue 59, 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.

Preferably the dye contains one, two, three or four SOsNa groups, more preferably one or two. This provides a beneficial level of negative charge.

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 176, 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.

Preferably the dye polymer is obtainable by reacting the polymer with 0.1 -20wt% reactive dye, most preferably 1 to 10wt%. Preferably, the composition comprises a peroxide source to allow bleaching and dyeing simultaneously. Suitable peroxide sources include hydrogen peroxide.

Preferably, the composition is a rinse-off hair treatment composition. Preferably the composition comprises from 5 to 35% wt. anionic surfactant.

Suitable anionic surfactants include the alkali-metal alkyl ether sulphates where the alkyl group comprises from 8 to 18 carbon atoms. Preferred anionic

surfactants include sodium lauryl ether sulphate with 1 , 2 or 3 EO groups, preferably 1 EO group.

Preferably, the composition comprises a pearlescer. Suitable pearlescers include ethylene glycol distearate. Preferably, the composition is packaged in a closable bottle.

Preferably, the composition is a shampoo, conditioner or hair treatment

composition. Where the composition is a hair conditioning composition it will comprise a conditioning active such as fatty alcohol or fatty acid or fatty ester or fatty amide, a cationic surfactant or silicone.

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.

EXAMPLES

Example 1 : Polyamine Polymer Synthesis

(i) Synthesis of Polyethylene glycol (PEG) MeO-methyl glycidyl ether

PEG MeO-methyl glycidyl ether was synthesized as shown by the reaction schme.

A slurry of NaH (0.1 mol, 4 g of 60% suspension in mineral oil) rinsed with anhydrous THF twice (2 x 20 ml) was stirred in 100 ml anhydrous THF. A solution of 37.5 g (0.05 mol) of MeO-PEG-OH in 50 ml THF was added dropwise. This mixture was stirred at room temperature for one hour. 39.2 ml of epichlorohydrin in 40 ml THF was added dropwise. Then the mixture was stirred at room temperature over night, followed by 4 h reflux. After neutralising the excess base with acetic acid, active charcoal was added and stirred for 1 hr. After filtrating, the solution was concentrated under reduced pressure and poured into 2 L of petrol ether and the waxy product was dried in vacuum.

(ii) Synthesis of PEG modified PEI (2K)

EPEI polymer were synthesized by mixing PEG MeO-methyl glycidyl ether with PEI in methanol and refluxing for 4 days. The viscous product was obtained after dialysis in water and lyophilisation.

Example 2: Dye-polymer Synthesis

0.5g of the polyethylene imine polymer of example 1 , 0.1 g Na₂CO3 and 0.1 g of reactive dye were mixed together in 35ml of demineralised water and heated at 65°C for 5 hours. Following the reaction the product was dialyzed against water (COMW=3500) for 72 hours. Water was then removed by rotary evaporation. The resultant polymer was dried in vacuum.

The following polymer was synthesized

(P1 ) PEG750-PEI2000 0.1 Og Reactive Blue 4 (RB4)

Where the integer after PEG and PEI represent the average molecular weight. Example 3: cationic polyvinylalcohol and reactive dye synthesis

Cationic modified polyvinyl alcohol from Lauren Pan (1g) was dissolved in 100ml deionised water with 0.07g Reactive Blue 4 and 0.03g Reactive Red 2, and 0.5g Na₂COs to produce polymer P2. The solution was then heated to 60°C for 6h. The product was dialyzed against water (COMW=12'000) for 72 hours. Water was then removed by rotary evaporation and final sample was dried in vacuum. Example 4: Dyeing Performance

A 1 wt% solution of the dye polymers was made in demineralised water. A 3 by 10cm knitted woollen swatch (sheep) was place into the dye-polymer solution and agitated for 20seconds, removed and dried. The colour of the wool was assessed by measuring the reflectance of the swatch using a reflectomer and expressing the colour as CIE L^*a^*b^* values and as a ΔΕ value relative to an undyed control. The swatch was then rinsed in water for 30 seconds under a running tap, dried and the colour re-measured. The swatch was then washed in shampoo, rinsed, dried and re-measured. The results are shown below

- experiment not done

C^* is a comparative example of a neutral polymer (hydroxyethyl cellulose) with reactive dyes) synthesised as follows 0.5g of hydroxyethylcellulose, 0.5g Na₂CO3 and 0.05g of reactive dye (0.040g Reactive Blue 4 and 0.01 Og Reactive Red 2) were mixed together in 100ml of demineralised water and heated at 60°C for 5 hours. Following the reaction the product was dialyzed against water

(COMW= 12000) for 72 hours. Water was then removed by rotary evaporation. The resultant polymer was dried in vacuum.

The shampoo used was of the following formula: 20wt% Sodium lauryl ether sulphate; 5.3wt% cocoamidopropyl betaine; 6.5wt% Mirasheen A-220 (ex Rhodia) which is a mix of Glycol Distearate, Ammonium Laureth Sulfate, Amonium Lauryl Sulfate, Cocamide MEA, Ammonium Xylene Sulfonate; remainder minors and water. Example 5

The following are compositions made by standard processes.

Shampoo

Conditioner

Ingredient Wt%

Water To 100

Lactic acid 0.38

Methyl parahydroxybenzoate 0.2

Stearyl alcohol 5

Behenyltrimmonium chloride 0.87

LexamineS-13 (100%TAS) 1 .25

Silicone emulsion 2.5

Perfume 0.5

Dye-polymer 2 The dye-polymer was a 1 :1 :1 mixture of 3 dye polymers, all based on PEI, polyethylene imine Aldrich CAS[25987-06-8], Mn = 1800.

Polymer A: PEI reacted with 2.5wt% of reactive black 5

Polymer B: PEI reacted with 2.5wt% reactive yellow 176

Polymer C: PEI reacted 2.5wt% with reactive red 239

Claims

1 . Hair care connposition comprising a polymer dye, said polymer dye

comprising a positively charged polymer covalently bound to a negatively charged reactive dye.

2. Composition according to claim 1 wherein the dye is covalently bound to the polymer.

3. Composition according to any preceding claim comprising from 0.01 to 10wt% dye polymer, more preferably from 0.1 to 2% by weight of the composition.

4. Composition according to any preceding claim comprising from 2 to 30% wt. surfactant.

5. Composition according to any preceding claim comprising a pearlescer.

6. Composition according to any preceding claim wherein the reactive dye comprises a reactive group selected from dichlorotriazinyl,

difluorochloropyrimidine, monofluorotrazinyl, dichloroquinoxaline, vinylsulfone, difluorotriazine, monochlorotriazinyl, bromoacrlyamide and trichloropyrimidine.

7. Composition according to any preceding claim wherein the reactive dye comprises a chromophore selected from azo, anthraquinone,

phthalocyanine, formazan and triphendioaxazine. More preferably from azo, anthraquinone, phthalocyanine, and triphendioaxazine. Most preferably from azo and anthraquinone.

8. Composition according to any preceding claim wherein the pH is from 4 to 9, preferably from 5 to 8.

9. Method for dying hair by applying to the hair a composition comprising a polymer dye, said polymer dye comprising a positively charged polymer and a negatively charged reactive dye.