COMPOSITION

The present invention relates to a polymer dye and a method for its use in dying
hair.
Despite the prior art there remains a need for improved hair dying compositions.
Accordingly, and in a first aspect, there is provided a hair care composition
comprising a polymer dye obtainable by polymerizing:
(a) a first dye monomer which has a structure according to Formula I :
Formula I
where Y is selected from -CONH- o -CO 2CH2CH(OH)CH 2-NH-, and Ri is
selected from H, alkyl; aryl; benzyl; halogen; ester; acid amide; and, CN.
(b) a second monomer according to a structure according to Formula I I and
Formula III: selected from
Formula I I
and
Formula III
where X is an organic bridging group covalently connecting the amine to the
alkene moiety of the monomer, preferably X is -CO2(CH 2)n- where n = 1 to 6;
where R5 is selected from: H, alkyl; aryl; benzyl; halogen; ester; acid amide; and,
CN, preferably R5 is CH3 or H; and
where R2, R3, and R4 are independently selected from H or alkyl, preferably at
least two of R2, R3, and R4 are alkyl.
Preferably, Y is -CH 2CH(OH)CH2-NH. Preferably, Ri is selected from H or CH3.
Preferably, n=2. Preferred alkyl groups are C1to C6 branched linear or cyclic,
most preferably CH3 or C2H5. R2 and R3 may be joined to form a 5 or 6 membered
ring.
Preferably, the dye is an organic dye.
Preferably, the dye is selected from the following chromophore classes:
anthraquinone, azo, oxazine, azine, triphenodioxazine, triphenyl methane,
xanthene and phthalocyanin, more preferably azo, anthraquinone and azine
chromophore classes, most preferably azo and anthraquinone, most preferably,
the dye is an anthraquinone.
Preferably, the dye is negative or uncharged at pH 8 . More preferably, the dye is
uncharged at pH 8 .
Preferably monomer (a) is obtainable by reacting an alkene with a dye selected
from the class acid, basic, disperse or solvent dye bearing an NH2 group
covalently bound to an aromatic group of the dye. Examples of such dyes are
listed in the Color Index (Society of Dyers and Colourists and American
Association of Textile Chemists and Colorists ) .
Preferably, the reactions are selected from:
dye— NH2 +
and
Preferred dyes containing -NH 2 groups for such reactions are selected from: 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; 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; disperse
yellow 9; disperse yellow 11; 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 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
group covalent bound to it.
Preferably, monomer (a) comprises from 0.5 to 30 wt%, preferably from 5 to 20
wt% of the polymer.
Preferably, monomer (b) comprises from 5 to 99.5 wt% of the polymer. Most
preferably (b) is dimethyl amino ethyl methacrylate.
Preferably, the composition of the invention comprises uncharged monomer units,
preferably at from 5 to 99% wt% of the polymer. Preferably the monomer units are
selected from acrylates and styrenes. Preferably they are present at 10-30wt%.
Preferably, the composition of the invention is a rinse-off composition. More
preferably, the composition is a shampoo, conditioner or hair dye composition.
Where the composition is a shampoo it preferably comprises from 5 to 50%
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 of the invention has a pH of from 3 to 9, preferably
from 4 to 8 .
Combination of polymer 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 polymer dyes. Preferably the trichromate system contains a
combination of a blue or black polymer dye, a red polymer dye and a yellow
polymer dye.
In a second aspect the present invention provides a method for dyeing hair by
applying to the hair a composition according to any preceding claim.
EXAMPLES
Example 1 Synthesis of dye monomer
Reaction scheme:
1,4-Diaminoanthraquinone (DAQ) was purchased from Aldrich, ( 90% technical
grade) and used as supplied.
The dye monomer was prepared by the reaction of DAQ ( 1,4-Diaminoaquinone)
and Ac (acryloyl chloride) in the presence of sodium dicarbonate. A mixture of
150ml anhydrous THF, 1g DAQ and 0.6g sodium dicarbonate was charged into
250ml three-necked round bottom flask equipped with a condenser, a dropping
funnel, and a magnetic stirring bar. The flask was then maintained at R.T. while
0.38g Ac dissolved in 5ml anhydrous THF was added from the dropping funnel for
3h. The reaction mixture was stirred at 25°C for another 20h. The reaction mixture
was filtered to remove the insoluble solids occurred during the reaction process
20h later, the clear solution was dried by using rotary evaporation pressure
reduced meter, then violet powder was obtained and washed with water for three
times, the powder was completely dried under vacuum at 60°C for 24h. The
structure of DAQ-AC was confirmed using NMR and showed that the reaction had
gone to greater than 88% completion. Consequently greater than 88% of the
anthraquinones contained one NHCOCH=CH2 groups.
Example 2 Synthesis of dye containing polymers
Reaction Scheme:
A solution of 3g dimethyl amino ethyl methacrylate (DMAEMA), 0.03g DAQ-Ac
and 0.06g AIBN in 10ml toluene was charged into a dry N2 gas purged twonecked
tube with a condenser and a magnetic stirring bar. The tube was sealed
and placed in a regulated thermostat bath at 65°C for 24hours. The solution was
precipitated in five-fold excess of petroleum ether for three times after the
reaction, followed by drying under vacuum at 40°C for 24h. The composition of the
co-polymers was regulated via the control of the primary usages of dye monomer
and functional monomer. In the experiments, the amount of dye monomer added
were 10 wt % respectively.
Example 3 Synthesis of dye containing polymers
Analagous reactions to example 1 and 2 were done using acid blue 14 and
methylene violet RAX to produce the following dye polymers.
Example 3 UV-VIS of dye polymers
The UV-Vis spectra of the dye polymers of example 2 were recorded in
demineralised water at 1g/L dye polymer. The results are given in the table below.
For C 11 1g/L Linear alkyl benzene sulphonate surfactant was added.
* measured at 50% dilution
Example 3 deposition to wool
Bleached knitted wool swatches were agitated in demineralised water for 30
minutes at 293K, to which 20ppm of C7, C 11, C 15 had been added and 40 ppm of
C 19 respectively. The weight ratio of wool to liquor was 1:30. The wool swatches
were removed and dried in the air, then the colour measured using a reflectometer
(UV excluded) and expressed as the CIE L*a*b* values. The results are given in
the table below:-
L* a* b*
Control 86.5 0.1 17.2
C7 78.9 6.5 8.6
C 11 8 1.8 2.9 11.4
C 15 69.6 13.8 0.9
All the dye polymers dyed the wool as shown by changes in the L* , a* and b* to
the control agitated in water alone.
Example 4 deposition to human hair
Human hair swatches were agitated in demineralised water for 30 minutes at
293K, to which 20ppm of C7, C 11, C 15 had been added. The weight ratio of hair
to liquor was 1:30. Grey-brown and blonde hair swatches were used. The hair
swatches were removed and dried in the air, then the colour measured using a
reflectometer (UV excluded) and expressed as the CIE L*a*b* values. The results
are given in the table below and are average of 3 repeats.:-
blonde L* a* b*
Control 86.5 0.1 17.2
C7 78.9 6.5 8.6
C 11 8 1.8 2.9 11.4
C 15 69.6 13.8 0.9
The following dye-polymers were synthesised by polymerisation of the monomers
as listed in the table below:
CH3 20
H2C=C
I ©
C0 2CH2CH 2N(CH3)3
styrene 20
The dye monomers were synthesis by reacting the NH2 group of the
corresponding dye with acryloyl chloride or a s appropriate.
Example 6 : 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 20 seconds, 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 value relative to an undyed control.
The swatch was then rinsed in water for 30 seconds under a running tap, dried
and the colour remeasured. The swatch was then washed in shampoo, rinsed,
dried and re-measured. The results are shown below
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, Cocannide MEA, Ammoniunn Xylene Sulfonate; remainder minors and
water.
Example 7
The following are compositions made by standard processes.
Shampoo
Component %ad %
Sodium Laureth Sulphate 70 17.14
Cocoamidopropyl Betaine 30 5.33
Carbomer 100 0.4
Glycol Distearate 35 4.0
Dimethiconol emulsion 50 4.0
Guar Hydroxypropyl Trimonium 100 0.2
Chloride
Parfum 100% 0.8
DMDM Hydantoin and 3-iodo- 50% 0.2
2propylnylbutyl carbamate
Sodium chloride 100% Vise.
Dye-polymer 100% 0.5
Aqua q.s.to 100
Conditioner
The dye-polymer was a 1:1 :1 mixture of 3 dye polymers, all based on 95wt%
dimethyl amino ethyl methacrylate, with 5wt% dye monomer (a).
Polymer A: dye monomer made by reaction of acroyi chloride with disperse red
55
Polymer B: dye monomer made by reaction of acroyi chloride with disperse yellow
11.
Polymer C: dye monomer made by reaction of acroyi chloride with disperse blue
56.
Analagous formulation were created but with dye monomer made by reaction of
the disperse dye with
CLAIMS
1. Hair composition comprising a polymer dye, said polymer dye obtainable
by polymerizing:
(a) a first dye monomer which has a structure according to Formula I :
Formula I
where Y is selected from -CONH- o -CO 2CH2CH(OH)CH 2-NH-, and Ri is
selected from H, alkyl; aryl; benzyl; halogen; ester; acid amide; and, CN.
(b) a second monomer according to a structure according to Formula I I and
Formula III: selected from
Formula I I
and
Formula
where X is an organic bridging group covalently connecting the amine to
the alkene moiety of the monomer, preferably X is -CO2(CH 2)n- where n =
1 to 6;
where R5 is selected from: H, alkyl; aryl; benzyl; halogen; ester; acid amide;
and, CN, preferably R5 is CH3 or H; and
where R2, R3, and R4 are independently selected from H or alkyl, preferably
at least two of R2, R3, and R4 are alkyl.
Composition according to claim 1 wherein the dye is an organic dye.
Composition according to claim 2 wherein the dye is selected from the
following chromophore classes: anthraquinone, azo, oxazine, azine,
triphenodioxazine, triphenyl methane, xanthene and phthalocyanin, more
preferably azo, anthraquinone and azine chromophore classes, most
preferably azo and anthraquinone, most preferably, the dye is an
anthraquinone.
Composition according to any preceding claim wherein the dye is negative
or uncharged.
Composition according to any preceding claim wherein the dye is
uncharged.
Composition according to any preceding claim wherein monomer (a)
comprises from 0.5 to 30 wt%, preferably from 5 to 20 wt% of the polymer.
7 . Composition according to any preceding claim wherein monomer (b)
comprises from 5 to 99.5 wt% of the polymer.
8 . Composition according to any proceeding claim wherein the polymer also
comprises uncharged monomer units, preferably at from 5 to 94.5% wt% of
the polymer.
9 . Composition according to any preceding claim which is a rinse-off
composition.
10 . Composition according to any preceding claim having a pH of from 3 to 9,
preferably from 4 to 8 .
11. Method for dyeing hair by applying to the hair a composition according to
any preceding claim.