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 4,1 82,612 or FR 2 456 764,
WO2008/009579 and WO2009/0901 2 1 to WO2009/0901 25.
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 liked 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 obtained more preferably obtained by the reaction of i)a NH2 group
directly and covalently bound to an aromatic ring of a dye with ii)a reactive group
of a polymeric compound; in which the reactive group is selected from the group
consisting of isocyanate; oxazolone; epoxide; ester, and anhydride.
Detailed Description of the Invention
REACTION DESCRIPTION
The dye-polymer for use with the method of the invention is formed by the step of
reaction a reactive polymer with the NH2 group of a dye, the NH group being
directly covalently bound to an aromatic ring of the dye. The reactive polymer has
a group for reacting with the NH2, the group selected from: isocyanate; oxazolone;
epoxide; ester, and anhydride, preferably epoxide or anhydride, most preferably
anhydride. Of the ester classes, activated esters are preferred.
Suitable post-polymerization modifications of reactive polymers for use with the
invention are described in detail in Gauthier, M.A., Gibson, M.I., and Klok H-A.,
Angew. Chem. Int. Ed 2009 48, 48058.
Preferably the reactions are selected from:
Reaction (a): ester and anhydrides
Where R is H, alkyl, aryl or selected so that the COOR group forms an anhydride.
Examples of suitable R groups include . Z is
a polymer.
Most preferably the reaction is of the form
dye NH
Non-limiting examples of polymers formed by such reactions are:
dye— NH
Catalysts may be used to accelerate the reactions.
Such reactions are discussed in Macromolecules 1994, 27, 7 12 1-7126.
Reaction (b): epoxides
Non-limiting Examples of polymers formed by such reactions are:
Reaction (c): oxazolone and isocynate
Reaction with oxazolone and isocynate are exemplified below
— ye
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 -NH 2 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 -NH 2 groups covalently bound to an aromatic ring of
the dye, are: acid violet 1; acid violet 3; acid violet 6; acid violet 11; acid violet 13;
acid violet 14; acid violet 19; acid violet 20; acid violet 36; acid violet 36:1 ; acid
violet 4 1; acid violet 42; acid violet 43; acid violet 50; acid violet 5 1; acid violet 63;
acid violet 48; acid blue 25; acid blue 40; acid blue 40:1 ; acid blue 4 1; acid blue
45; acid blue 47; acid blue 49; acid blue 5 1; acid blue 53; acid blue 56; acid
blue 6 1; acid blue 6 1:1 ; acid blue 62; acid blue 69; acid blue 78; acid blue 8 1:1 ;
acid blue 92; acid blue 96; acid blue 108; acid blue 111; acid blue 2 15; acid
blue 230; acid blue 277; acid blue 344; acid blue 117; 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 4 1; direct blue 22; direct blue 7 1; direct
blue 72; direct blue 74; direct blue 75; direct blue 82; direct blue 96; direct blue
110; direct blue 111; direct blue 120; direct blue 120:1 ; direct blue 12 1; 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 11; disperse blue 19; disperse blue
20; disperse blue 28; disperse blue 40; disperse blue 56; disperse blue 60;
disperse blue 8 1; disperse blue 83; disperse blue 87; disperse blue 104; disperse
blue 118; 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 11; disperse red 15; disperse red 3 1; disperse red 53; disperse red 55;
disperse red 60; disperse red 63; disperse red 86; disperse red 9 1; 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 11; 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 11; 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.
REACTIVE POLYMER DESCRIPTION
The reactive polymer may be synthesised by polymerisation of the monomers,
preferably the monomers are alkenes. Preferably 2-80 mol%, more preferably 5-
55 mol%. of the monomer are selected from monomers which contain or form
isocyanate; oxazolone; epoxide; ester, or anhydride groups on polymerisation.
Preferred Suitable monomers include maleic anhydride, glycidyl acrylate, 2-
glycidyl methacrylate, 2-vinyl-4,4-dimethyl-5-oxazolone, vinyl isocyanate, 2-
Isocyanatoethyl methacrylate, N-methacryloxysuccinimide,.
The reactive polymer may comprise a co-monomer. Preferred co-monomers may
be selected from alkenes, acrylates and styrenes. Suitable co-monomers include
diethylaminoethylmethacrylate, dimethylaminopropyl metacryamide, 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 pyrrol idone, 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, Nisopropylacrylamide,
,-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 preferably has a molecular weight of 2000 and greater.
Preferred ranges are from 2000 to 1 000 000, more preferred ranges are from
5000 to 100 000. 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 polymer molecules, summing the weights, and dividing by j . Molecular
weights are determined by Gel Permeations Chromatography.
In a further embodiment the polymeric compound can comprise a siloxane
polymers with pendant isocyanate; oxazolone; epoxide; ester, or anhydride
groups.
DYE POLYMER DESCRIPTION
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.
Preferably the polymer does not contain a primary amine.
The dye is preferably uncharged or has an anionic charge. Most preferably the
dye is anionic charged. Anionic dyes are particularly preferred when the polymer
carries anionic groups on the co-monomers. Particularly preferred is a dye
polymer having a poly (methyl vinyl ether-alt-maleic anhydride) polymer reacted
with an anionic dye.
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.
Poly (methyl vinyl ether-alt-maleic anhydride) polymers reacted with an anionic
dye are most preferred. Preferably the anionic dye contains 1 or 2 sulphonate
groups, most preferably 1.
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 1wt% 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 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 was 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
Reaction Scheme DAQ.
1g of the polymer (PMVEMA, CAS: 901 - 6-9, Mn=80000, Mw=210000 ex
Aldrich) was mixed with 0.069g acid blue 62 and 0.030 g 1,4-
Diaminoanthraquinone (DAQ) of the dye in 50ml of tetrahydrofuran and heated at
65°C for 8 hours. The resultant polymer was further washed by CHCI3 for three
times to remove the non-reacted dyes and vacuum dried at r.t. over night
thereafter. Finally, the resultant polymer containing non-reacted maleic anhydride
underwent hydrolyzation treatment producing carboxylic acid groups of moderate
acidity. The polymer was coded P .
Example 2
The reaction of example 1 was repeated using the anionic charged dye Acid Blue
1g of the polymer was mixed with 0.1 g of the dye in 50ml of tetrahydrofuran and
heated at 65°C for 8 hours. The resultant dye polymer was precipitate in
petroleum ether and dried in a vacuum. The reaction was conducted twice with
polymers of initial molecular weights (Mw) of 200,000 and 2,000,000 and the
resultant dye polymers coded P2 and P3. Polymers were obtained from ISP
(Gantrez™ AN 119 and An1 69, respectively).
Analagous polymers were created with DAQ and where coded P4 and P5
corresponding to Gantrez™ AN 119 and An1 69, respectively.
Example 3 : 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 place 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 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 above Examples demonstrate that the hair has been coloured.
Claims
1. 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 polymeric compound
ii) in which the reactive group is selected from the group consisting of
isocyanate; oxazolone; epoxide; ester, and anhydride.
2 . A method according to claim 1 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 polymeric compound ii) in which
the reactive group is selected from the group consisting of isocyanate;
oxazolone; epoxide; ester, and anhydride.
3 . A method according to claim 1 or claim 2 in which the reactive group of the
polymeric compound ii) is an epoxide or anhydride group.
4 . A method according to any preceding claim, in which the reactive group of
the polymeric compound ii) is an anhydride group.
5 . A method according to any preceding claim in which the dye i) has an
anionic charge.
6 . A method according to any preceding claim in which the dye polymer is a
poly (methyl vinyl ether-alt-maleic anhydride) polymer reacted with an
anionic dye.
7 . 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.
8 . A method according to claim 7 in which the dye polymer is present in an
aqueous solution at a level from 0.04 to 0.4wt% of the total composition.
9 . A method according to any preceding claim in which the composition
comprises a mixture of three or more polymeric dyes.
10 . A method according to any preceding claim in which the dye i) is selected
from the azo, anthraquinone, naphthalimide or azine chromophore classes.
11. A method according to any claim 10 in which the dye i)is selected from the
anthraquinone chromophore class.
12 . A method according to any preceding claim in which the polymeric
compound ii) within the dye polymer is covalently bound to 1 to 10 dye
molecules i).
13 . A method according to any preceding claim in which the method further
comprises rinsing the hair after application of the composition comprising
dye.