WO2011113675A2

WO2011113675A2 - Method of treating hair

Info

Publication number: WO2011113675A2
Application number: PCT/EP2011/052733
Authority: WO
Inventors: Stephen Norman Batchelor; Jayne Michelle Bird; Wei Chen; Qingsheng Tao; Jinfang Wang
Original assignee: Hindustan Unilever Ltd; Unilever NV
Current assignee: Hindustan Unilever Ltd; Unilever NV
Priority date: 2010-03-19
Filing date: 2011-02-24
Publication date: 2011-09-22
Anticipated expiration: 2012-09-19
Also published as: EA201290925A1; PH12012501848A1; WO2011113250A1; WO2011113676A2; EP2547321A2; AU2011229416A1; JP2013522256A; AU2011229417A1; WO2011113675A3; TW201138853A; WO2011113249A1; EP2547319A2; TW201138892A; CN102844020A; WO2011113676A3; BR112012023598A2; JP2013522255A; EA201290934A1; PH12012501847A1; AR080760A1

Abstract

A method for colouring hair, comprising the step of applying to the hair a composition comprising a dye polymer in which the dye polymer is obtainable by the reaction of a NH₂ group directly and covalently bound to an aromatic ring of a dye i) with a reactive group of a monomeric compound ii) in which the reactive group is selected from the group consisting of isocyanate; oxazolone; ester and epoxide, followed by polymerising the resulting dye monomer to form a dye polymer iii).

Description

Method of Treating Hair

The present invention relates to a method for dying the hair. Numerous cationic polymeric dyes have been disclosed for use as a colorant for human hair, for example in US 4,228,259; US 4,182,612 or FR 2 456 764, WO2008/009579 and WO2009/090121 to WO2009/090125.

Zollinger in Color Chemistry (Wiley-VCH 2003) discloses that several million different coloured compounds have been synthesized. A large number of dyes contain NH₂ groups covalently bound to an aromatic ring of the dye.

However there remains the need for dyes containing NH₂ groups covalently bound to an aromatic ring of the dye to be linked to polymers. Such polymeric dyes can be used to colour the hair.

Description of the invention

The present invention relates to a method for colouring hair, comprising the step of applying to the hair a composition comprising a dye polymer in which the dye polymer is obtainable preferably obtained by the reaction of a NH₂ group directly and covalently bound to an aromatic ring of a dye i) with a reactive group of a monomeric compound ii) in which the reactive group is selected from the group consisting of isocyanate; oxazolone; epoxide; ester, and anhydride, followed by polymerising the resulting dye monomer to form a dye polymer iii). The resulting dye monomer is then polymerised with other suitable monomers to form the dye- polymer. DETAILED DESCRIPTION OF THE INVENTION

Dye Monomer The NH₂ group of a dye is reacted with a monomer containing a reactive group selected from: isocyanate; oxazolone ester and epoxide. Preferably the reactive group of the monomer is an epoxide.

Preferred reactions to form the dye monomer are described below:

Reaction (a): epoxides

The ring-opening reaction of epoxide group with amine can be accelerated by some acidic catalysts.

Reaction (b): oxazolone

Reaction (c)isocynate

H₂N— dye O

H II H

Z— N=C=0 Z— N— C— N— dye Reaction (d): ester

O

H

dye— NH₂ + RO— C— Z dye— N

Where R is H, alkyl, aryl Examples of suitable R groups include

Wherein Z is an organic group containing an unsaturated carbon, carbon double bond. Preferably Z is an acrylate or a styrene, more preferable Z is an acrylate. Preferred monomers for reaction with the dye are glycidyl acrylate, 2-glycidyl methacrylate, 2-vinyl-4,4-dimethyl-5-oxazolone, vinyl isocyanate, 2- isocyanatoethyl methacrylate, N-methacryloxysuccinimide.

Dye description

Examples of dyes are described in Industrial Dyes (K. Hunger ed, Wiley VCH 2003 and in the colour index (Society of Dyers and Colourists and American

Association of Textile Chemists and Colorists). The dye must contain an NH₂ group covalently bound to an aromatic ring of the dye. Preferably the NH₂ is covalently bound to an aromatic ring of the dye, wherein the aromatic ring is in conjugation with the chromophore of the dye. The dye preferably contains the moiety

within the aromatic ring structure of the dye. Preferred dyes include:

Violet

Preferably the dye does not contain reactive groups or polymerisable double bonds. A dye containing a reactive groups is made up of a chromophore which is linked to a reactive group that undergoes addition or substitution reactions with - OH, -SH and -NH₂ groups to form covalent bonds. 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, for example,

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

trichloropyrimidine.

Dyes are organic molecules that have an absorption coefficient of greater than 4000, preferably greater than 10 000 mol^"1 L cm^"1 at any wavelength in the range 400-700nm. Molar absorption coefficients are preferably measured in an organic solvent, preferably propan-2-ol, using a 1 , 5 or 10 cm cell. The dye is preferably selected from organic dyes selected from the following chromophore classes: Aminoketone, anthraquinone, azo, oxazine, azine, triphenodioxazine, triphenyl methane, naphthalimide, xanthene and

phthalocyanin, more preferably azo, anthraquinone, naphthalimide and azine chromophore classes, most preferably azo and anthraquinone. The dye of preference is an anthraquinone.

The dye may be cationic, anionically, or uncharged. Examples of uncharged dyes are found in the disperse dye category. Examples of anionic charged dyes are found in the acid and direct dye category. Examples of cationic charged dyes are found in the basic dye category. The dye is preferably uncharged or has an anionic charge. Most preferably the dye is an anionic charged dye.

Preferred dyes containing -NH₂ groups covalently bound to an aromatic ring of the dye, are: acid violet 1 ; acid violet 3; acid violet 6; acid violet 1 1 ; acid violet 13; acid violet 14; acid violet 19; acid violet 20; acid violet 36; acid violet 36:1 ; acid violet 41 ; acid violet 42; acid violet 43; acid violet 50; acid violet 51 ; acid violet 63; acid violet 48; acid blue 25; acid blue 40; acid blue 40:1 ; acid blue 41 ; acid blue 45; acid blue 47; acid blue 49; acid blue 51 ; acid blue 53; acid blue 56; acid blue 61 ; acid blue 61 :1 ; acid blue 62; acid blue 69; acid blue 78; acid blue 81 :1 ; acid blue 92; acid blue 96; acid blue 108; acid blue 1 1 1 ; acid blue 215; acid blue 230; acid blue 277; acid blue 344; acid blue 1 17; acid blue 124; acid blue 129; acid blue 129:1 ; acid blue 138; acid blue 145; direct violet 99; direct violet 5; direct violet 72; direct violet 16; direct violet 78; direct violet 77; direct violet 83; food black 2; direct blue 33; direct blue 41 ; direct blue 22; direct blue 71 ; direct blue 72; direct blue 74; direct blue 75; direct blue 82; direct blue 96; direct blue 1 10; direct blue 1 1 1 ; direct blue 120; direct blue 120:1 ; direct blue 121 ; direct blue 122; direct blue 123; direct blue 124; direct blue 126; direct blue 127; direct blue 128; direct blue 129; direct blue 130; direct blue 132; direct blue 133; direct blue 135; direct blue 138; direct blue 140; direct blue 145; direct blue 148; direct blue 149; direct blue 159; direct blue 162; direct blue 163; food black 2; food black 1 wherein the acid amide group is replaced by NH₂; Basic Violet 2; Basic Violet 5; Basic Violet 12; Basic Violet 14; Basic Violet 8; Basic Blue 12; Basic Blue 16; Basic Blue 17; Basic Blue 47; Basic Blue 99; disperse blue 1 ; disperse blue 5; disperse blue 6; disperse blue 9; disperse blue 1 1 ; disperse blue 19; disperse blue 20; disperse blue 28; disperse blue 40; disperse blue 56; disperse blue 60;

disperse blue 81 ; disperse blue 83; disperse blue 87; disperse blue 104; disperse blue 1 18; disperse violet 1 ; disperse violet 4, disperse violet 8, disperse violet 17, disperse violet 26; disperse violet 28; solvent violet 26; solvent blue 12; solvent blue 13; solvent blue 18; solvent blue 68; solvent blue 76; disperse red 4; disperse red 1 1 ; disperse red 15; disperse red 31 ; disperse red 53; disperse red 55;

disperse red 60; disperse red 63; disperse red 86; disperse red 91 ; disperse red 92; basic red 2; basic red 3; basic red 4; basic red 5; basic red 6; basic red 9; basic red 30; disperse yellow 9; disperse yellow 1 1 ; basic yellow 5; basic yellow 6; basic yellow 7; basic yellow 9; basic brown 1 ; basic brown 2; basic brown 4; basic brown 5; basic brown 17; disperse orange 3; disperse orange 3:1 ; disperse orange 6; disperse orange 1 1 ; disperse green 2; acid red 33; acid red 30; acid red 34; acid yellow 7; acid yellow 9; acid yellow 66; acid green 20; acid green 33; acid brown 4; acid brown 9; disperse black 9; disperse black 3 disperse black 4; disperse black 7 and acid black 1 .

Further preferred dyes are selected from mono-azo dyes which contain a phenyl group directly attached to the azo group, wherein the phenyl group has an NH₂ groups covalent bound to it.

Preferably the dye monomer is not

Dye Polymer Description

The dye polymer is formed by polymerization of the dye monomer, preferably with suitable co-monomer.

Preferably the dye-polymer contains 0.1 to 30 Molar% dye units, more preferably 1 to 15 Molar% dye monomers units, most preferably 2 to 10 Molar%.

Preferably the polymeric compound within the dye polymer is covalently bound to 1 to 100 dye molecules. More preferably 1 to 40 dye molecules. Most preferably 1 to 10 dye molecules.

Apart from the charge on the dye, the polymer may contain cationic and anionic charged groups.

For polymers which carry cationic groups on the co-monomers the dye is preferably uncharged or anionic charged.

For polymers which carry cationic groups on the co-monomer the dye is preferably uncharged or anionic charged.

Examples of uncharged dyes are found in the disperse dye category. Examples of anionic charged dyes are found in the acid and direct dye category. Examples of cationic charged dyes are found in the basic dye category.

For polymer which carry anionic groups on the co-monomers the dye is preferably cationic or anionic charges.

Co-monomers may be selected from any suitable alkenes, acrylates and styrenes are particularly preferred. Suitable co-monomers include diethylanninoethylnnethacrylate, dimethylaminopropyl metacryannide, methyl vinylether, methacrylic acid, 2-acrylamido-2-methyl-1 -propanesulfonic acid, 2- hydroxyethyl acrylate; 2-hydroxyethyl methacrylate dimethylaminoethyl methacrylate, methyl methacrylate, methyl acrylate, hydroxyethyl methacrylate, ethyl methacrylate, ethyl acrylate, hydroxyethyl acrylate, butyl methacrylate, butyl acrylate, acrylamide, t-butyl methacrylate, t-butyl acrylate, sodium 4- vinylbenzenesulphonate, styrene, benyl methacrylate, acrylic acid, vinyl acetate, vinyl pyridine, sodium acrylate, diethylaminoethyl methacrylate (preferred), 4- vinylphenol, methacrylic acid, acrylonitrile, 4-vinyl-9H-carbazole, sodium methacrylate, 4,4-dimethyl-2-vinyloxazol-5(4H)-one, 4,4-dimethyl-2-(prop-1 -en-2- yl)oxazol-5(4H)-one, vinyl pyrrolidone, 4-pentenoic acid, ethyl 2-cyanoacrylate, stearyl acrylate, glycosyloxyethyl methacryrlate, methyl ether methacrylate, poly(ethylene glycol) ethyl ether methacrylate, poly(ethylene glycol) methyl ether methacrylate, isopropyl methacrylate, 2-hydroxypropyl methacrylate, 2- isocyanatoethyl methacrylate, 2-(methylthio)ethyl methacrylate, 2-aminoethyl methacrylate hydrochloride (preferred), furfuryl methacrylate, cyclohexyl methacrylate, 2,2,2-trifluoroethyl methacrylate, tetrahydrofurfuryl methacrylate, hexyl methacrylate, 3-chloro-2-hydroxypropyl methacrylate, N- isopropylacrylamide, Ν,Ν-dimethylacrlyamide, 2-ethylhexyl methacrylate, 2- (dimethylamino)ethyl methacrylamide, potassium 3-sulphopropyl methacrylate , potassium 5-methyl-4-oxohex-5-ene-1 -sulphonate, 2-butoxyethyl methacrylate, 2- (t-butylamino)ethyl methacrylate, 2-acrlamido-2-methyl-1 -propanesulphonic acid, 4-vinylbenzoic acid, N-(6-aminopyridin-2-yl)acrylamide, N-(3-aminophenyl) acrylamide, 2-acrylamido pyridine, 4-vinylphenylboronic acid, itaconic acid, 2- aminoethyl methacrylate, and methylvinyl ether.

The monomers within the polymer may be arranged in any suitable manner. For example as alternating copolymers possess regularly alternating monomer residues; Periodic copolymers have monomer residue types arranged in a repeating sequence; Random copolymers have a random sequence of monomer residue types; Statistical copolymers have monomer residues arranged according to a known statistical rule; Block copolymers have two or more homopolymer subunits linked by covalent bonds. Most preferably the polymer is a random copolymer. The polymer should have a molecular weight 2000 and greater.

Preferred ranges are from 2000 to 500 000, more preferred ranges are from 2000 to 20 000. In this context the molecular weight is the number average molecular weight. This is the ordinary arithmetic mean of the molecular weights of the individual macromolecules. It is determined by measuring the molecular weight of j polymer molecules, summing the weights, and dividing by j. Molecular weights are determined by Gel Permeations Chromatography.

Combination of polymeric dyes may be used to achieve a wide colour palette. For colouration of hair a palette of three or more polymeric dyes is preferable, particularly preferred is a palette of three polymeric dyes. It is most effective to use dye-polymer mixtures containing a red dye-polymer, a yellow dye-polymer and a blue dye polymer. Variation of the fractions of blue, yellow, and red in the mixture enables many colours to be reached, for example black, and brown.

The level of polymeric dye within the composition is preferably from 0.001 to 5wt% of the total composition, more preferably from 0.01 to 1 wt% most preferably from 0.04 to 0.4wt%.

Preferably, the method of the invention comprises a rinse-off step. Preferably the method of the invention comprises applying the dye compositions directly to dry hair or wet hair.

Preferably the application temperature is from 18 to 38 °C. Preferably, the composition is a shampoo, conditioner or hair dye composition. Where the composition is a shampoo it preferably comprises from 5 to 50wt% of the total composition of a cleansing surfactant. Preferably, the cleansing surfactant comprises anionic and amphoteric surfactant. Where the composition is a conditioning composition it preferably comprises a conditioning active such as fatty alcohols, fatty acids, fatty amides and fatty esters, silicones, cationic surfactants etc. Preferably the composition contains a perfume. Preferably the perfume is present at 0.001 to 5wt% of the total composition. Preferably, the composition of the invention has a pH of from 3 to 9, preferably from 4 to 8.

Preferably the composition contains greater than 40wt% of the total composition of water. Preferably the composition is a liquid and the viscosity of the liquid is greater than 4 centipoise at 293K. Viscosity is measured using a falling ball

viscometer, with Stokes' law used to calculate the viscosity of the fluid.

The invention is hereby illustrated by the following non-limiting Examples:

Examples

Example 1

The dye monomer was synthesised by heating 1 g of the anthraquinone dye with 0.5ml of the epoxide monomer for 3 hours in 20 ml of acetic acid. Following reaction the dye-monomer was purified and 0.15g of its polymerised with 3 g of co-monomer in tetrahydrofuran as shown below.

The polymer was coded P1

CH₃

H₂C=C

I ©

The reaction was repeated using C02CH2CH₂N(CI-l3)3 _as the co-monomer

CH₃

H₂C=C

I ©

and a 65:30 mix of C0₂CH2CH₂N(CH3)3 with a polyethylene glycol (M_n=300) acrylate. The polymers were code P2 and P3 respectively.

Example 2: Hair Dyeing Performance A 0.04 wt% solution of the dye polymers was made in demineralised water. A blonde human hair swatch (weight=1 .4g) was placed in 7ml of the dye-polymer solution and agitated for 60 seconds, removed and dried. The colour of the hair 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 60 seconds under a running tap, dried and the colour remeasured. The swatch was then washed in 0.5g/L Sodium lauryl ether sulphate (3 ethoxy group) surfactant solution for 60 seconds, rinsed in demineralised water, dried and remeasured. The results are summarised below.

Human hair

The results demonstrate the successful colouring of hair. Washing and rinsing of hair increases the dispersion and evenness of dye across the hair switch, resulting in a ΔΕ value.

Claims

A method according to claim 1 in which the reactive group of the monomeric compound ii) is an epoxide.

A method according to any preceding claim in which the dye i) has anionic charge.

4. A method according to any preceding claim in which the dye monomer is not

5. A method for colouring hair according to any preceding claim, comprising the step of applying to the hair a composition comprising a dye polymer in which the dye polymer is obtained by the reaction of a NH₂ group directly and covalently bound to an aromatic ring of a dye i) with a reactive group of a monomeric compound ii) in which the reactive group is selected from the group consisting of isocyanate; oxazolone; ester and epoxide, followed by polymerising the resulting dye monomer to form a dye polymer iii).

6. A method according to any preceding claim in which the dye polymer is present in the composition at a level from preferably 0.001 to 5wt% of the total composition.

7. A method according to claim 5 in which the dye polymer is present in an aqueous solution at a level from 0.04 to 0.4wt% of the total composition.

8. A method according to any preceding claim in which the composition

comprises a mixture of three or more polymeric dyes.

9. A method according to any preceding claim in which the dye i) is selected from the azo, anthraquinone, naphthalimide or azine chromophore classes.

10. A method according to any claim 9 in which the dye i)is selected from the anthraquinone chromophore class.

1 1 . A method according to any preceding claim in which the dye polymer

comprises 1 to 10 dye molecules i) covalently bound to a polymeric backbone.

12. A method according to any preceding claim in which the dye-polymer

comprises 1 to 15 Molar% dye monomers units 0.1 to 30 Molar% dye units.

13. A method according to any preceding claim in which the method further comprises rinsing the hair after application of the composition comprising dye.