Note: Descriptions are shown in the official language in which they were submitted.
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TITLE: ENZYMATIC FOAM COMPOSITIONS FOR DYEING KERATINOUS FIBRES
FIELD OF THE INVENTION
The present invention relates to enzymatic foam compositions for bleaching or
dyeing keratinous fibres such as hair, fur, hide and wool, a method for dyeing
such
fibres, and the use of a composition containing an oxidation enzyme and a
foaming
agent for dyeing hair and other keratinous fibres.
BACKGROUND OF THE INVENTION
Hair is often dyed to cover grey hair that appears with age. Further, during
the last
few decades, hair dyeing has become more and more popular in the western world
for
purely cosmetic purposes, i.e. the hair is dyed a different colour than its
natural colour in
order to obtain a desired "look".
In general, hair dyeing compositions on the market today can be divided, into
three main
groups:
- temporary hair dyes,
- semi-permanent hair dyes, and
- permanent oxidative hair dyes.
The temporary hair dyes are only intended to change the natural hair colour
for a short
period of time and usually function by depositing dyes on the surface of the
hair. Such hair
dyes are easy to remove with normal shampooing.
When using semi-permanent hair dyes the dyed colour can survive for five or
more
shampooings. This is achieved by using dyes having a high affinity for hair
keratin and
which are able to penetrate into the interior of the hair shaft.
Permanent hair dyes are very resistant to sunlight, shampooing and other hair
treatments and need only be refreshed about once a month as new hair grows
out. With
these dyeing systems, the dyes are created directly in and on the hair. Small
aromatic dye
precursors (e.g, p-phenylene-diamine and o-aminophenol) penetrate deep into
the hair,
where they are oxidised by an oxidising agent to coloured polymeric compounds.
These
coloured compounds are larger than the dye precursors and cannot be washed out
of the
hair.
By including compounds referred to as modifiers for coupiersl in the hair
dyeing
composition, a number of hair colour tints can be obtained. Catechol and
Resorcinol are
examples of such modifiers.
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Traditionally, HZOZ (hydrogen peroxide) has been used as the oxidising agent
(colour
builder), but also as a bleaching agent. Dyeing compositions comprising H202
are often
referred to as "lightening dyes" due to the bleaching effect of H202.
The use of HZOZ in dye compositions has some disadvantages, however, as HZOZ
damages the hair. Further, oxidative dyeing often demands high pH (normally
around pH
9-10), which also inflicts damage on the hair and irritation to the scalp.
Consequently, it is
not recommendable to dye the hair too often with dye compositions comprising
H202.
To overcome the disadvantages of using H202 it has been suggested to use
oxidation
enzymes to replace H2O2.
US patent No. 3,251,742 (Revlon) describes a method for dyeing human hair by
dye
formation in situ. An oxidative enzyme is used for colour formation reactions
at a
substantially neutral pH (pH 7-8.5). Laccases, tyrosinases, polyphenolases and
catacolases
are mentioned as suitable oxidation enzymes.
EP patent No. 0504005 (Perms S.A.) concerns compositions for dyeing hair which
do
not require the presence of H202. The compositions comprise an enzyme capable
of
catalyzing the formation of polymeric dyes and also dye precursors, such as
bases and
couplers, in a buffer solution wherein the pH of the composition is between
6.5 and 8, the
enzyme having an optimal activity in this pH range. Rhizoctonia praficola
lactase and Rhus
vernicifera lactase have a pH-optimum between 6.5 and 8 and can be used to
form the
polymeric dyes according to this patent.
The problem arises, however, when using such oxidation enzymes to dye
keratinous fibrous such as human hair, that oxygen is the limiting factor in
the enzymatic
reaction, since the reaction proceeds relatively quickly, especially for
laccases. This is
especially the case with compositions having a relatively high viscosity, such
as gels and
mousses. As a result, the reaction proceeds extensively at the parts of the
hair lying at
the hair/air interface, since the lactase at the interface has access to an
adequate supply
of oxygen from the air. In contrast, the major portion of the hair lying below
this inter-
face, i.e. between the air and the scalp, does not have access to adequate
oxygen for
the enzymatic oxidation to proceed after exhaustion of oxygen present in the
reaction
media, whereby the reaction proceeds slower (or comes to a complete stop) and
this
part of the hair is dyed relatively little compared to the surface hair
fibres.
Thus, when using oxidative enzymes for dyeing of hair, it would be desirable
to
obtain a more uniform and faster dyeing effect throughout the hair than that
which can
be obtained with the presently available hair dyeing compositions containing
oxidative
enzymes.
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SUMMARY OF THE INVENTION
'The object of the present invention is to provide improved enzyme-based
compositions for bleaching or dyeing of hair and other keratinous fibres, in
particular
compositions which provide the advantages made possible by use of oxidative
enzymes,
e.g. reduced damage to hair, but which at the same time result in an improved
uniformity of the hair dyeing effect.
It has now surprisingly been found that hair dyeing compositions comprising an
oxidation enzyme and a foaming agent result in improved uniformity of the
dyeing effect,
in particular an improved dyeing of the parts of the hair removed from the air
interface.
Such foam compositions of the invention serve to provide oxygen for the
enzymatic
oxidation process to parts of the hair that would otherwise rapidly suffer
from an
insufficient supply of oxygen, thereby ensuring that oxidation can proceed
more
uniformly throughout the hair. As a result, a more uniform hair dyeing is
obtained, with
reduced variation in hair colour intensity between different areas of the
hair.
In a first aspect, the invention thus relates to an enzymatic foam composition
adapted for dyeing of keratinous fibres, comprising 1 ) at least one oxidation
enzyme, 2)
at least one foaming agent, 3) at least one dye precursor and optionally 4) at
least one
modifier.
Another aspect of the invention relates to a method for dyeing keratinous
fibres,
comprising contacting the fibres with the enzymatic foam composition for a
period of
time and under conditions sufficient to permit oxidation of the dye precursor
to a
coloured compound
A further aspect of the invention relates to the use of the enzymatic foam
composition for oxidative dyeing of keratinous fibres, in particular hair,
fur, hide or wool.
BRIEF DESCRIPTION OF THE DRAWING
Figure 1 shows the effect on colour uniformity by dyeing with a foam
formulation
of the invention (See Example 1 ) The first and second columns shows the
Coefficient of
Variance (CV) (determined as 0L'" and DE'") for a dyeing composition
comprising foam
SDS-Betaine-pPD-Laccase; the third and fourth columns show the CV of a dyeing
composition comprising foam SDS-pPDP-Laccase; the fifth and sixth columns
(references) show the CV of a dyeing composition comprising pPD-laccase-water.
Figure 2 shows the effect on colour uniformity by dyeing with a foam
formulation
of the invention (see Example 1 ). The first column shows the Coefficient of
Variance
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(CV) (determined as DL" and DE') for a dyeing composition comprising foam SDS-
Betaine-oAP-Laccase; the second column shows the CV of a dyeing composition
comprises foam SDS-OAP-Laccase; the third column (reference) shows the CV of a
dyeing composition comprising oAP-laccase-water.
Figure 3 shows the effect of hair dyeing using tyrosinase as the oxidation
enzyme.
DETAILED DESCRIPTION OF THE INVENTION
The .composition of the invention comprising 1 ) at least one oxidation enzyme
and
2) at least one foaming agent is in particular a composition adapted for
dyeing keratinous
fibres, e.g. hair, fur, hide or wool. For the dyeing of keratinous fibres, the
composition of
the invention further comprises 3) at least one dye precursor and optionally
4) at least
one modifier. A preferred use of the composition is as a permanent dye for the
dyeing of
human hair.
The oxidation enzyme is an oxidoreductase, i.e. an enzyme classified under the
Enzyme Classification number E.C. 1 (Oxidoreductases) in accordance with the
Recommendations (1992) of the International Union of Biochemistry and
Molecular
Biology (IUBMB)) which catalyses oxidoreduction reactions.
Within the group of oxidoreductases enzymes are preferred which catalyse the
oxidation of a substrate (an electron or hydrogen donor) by acting on oxygen
(02)
andlor a peroxide as the acceptor. Such enzymes include enzymes classified
within the
enzyme classes comprising oxidases, including E.C. 1.1.3. E.C. 1.2.3, E.C.
1.3.3, E.C.
1.4.3, E.C. 1.5.3, E.C. 1.7.3, E.C. 1.8.3 and E.C. 1.9.3, laccases and related
enzymes
in E.C. 1.10.3, and peroxidases in E.C. 1.11.
According to the invention three types of oxidoreductases are specifically
contemplated:
a) Laccases or related enzymes, which act on molecular oxygen and yield water
(H20)
without any need for peroxide (e.g. H202),
b) Oxidases, which act on molecular oxygen (02) and yield peroxide (H20z), and
c) Peroxidases, which act on peroxide (e.g. H202) and yield water (H20).
Also, enzyme systems which comprise a combination of more than one enzyme
from a single group or from different groups among the three types of enzymes
are
contemplated. In the present specification, although reference will often be
made to a
single enzyme for the sake of simplicity, it is to be understood that the
description is
generally applicable to such combinations of more than one enzyme. Further,
although
the invention is generally described in terms of the preferred aspect relating
to the
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dyeing of hair, it is to be understood that the description is generally
applicable to foam
compositions according to the invention adapted for dyeing of other types of
keratinous fibres.
Particularly preferred enzymes are laccases and related enzymes, the term
5 "laccases and related enzymes" including enzymes comprised by the enzyme
classi-
fication E.C. 1.10.3.2 (laccases) and catechol oxidase enzymes comprised by
E.C.
1.10.3.1, bilirubin oxidase enzymes comprised by the enzyme classification
E.C.
1.3.3.5 and mono-phenol mono-oxygenase enzymes comprised by the enzyme
classification E.C. 1.14.99.1. Laccases are multi-copper containing enzymes
that
catalyze the oxidation of phenols and aromatic amines. Laccase-mediated
oxidations
result in the production of aryloxy-radical intermediates from suitable
phenolic
substrates; the ultimate coupling of the intermediates so produced provides a
combination of dimeric, oligomeric, and polymeric reaction products. Certain
reaction
products can be used to form dyes suitable for dyeing hair.
The laccase may be derived from a microorganism, e.g. a fungus or a bacteria,
or a
plant. Preferably, the laccase employed is derived from a fungus. More
preferably, it is
derived from a strain of Polyporus sp., in particular a strain of P. pinsitus
or P.
versicolor, a strain of Myceliophthora sp., e.g. M. thermophila, a strain of
Rhizoctonia
sp., in particular a strain of Rh. praticola or Rh. solani, a strain of
Pyricularia sp, in
particular P. oryzae, or a strain of Scytalidium, such as S. thermophilium.
The laccase
may also be from a plant such as Rhus sp., e.g. Rhus vernicifera,
In specific embodiments of the invention the oxidoreductase is a iaccase such
as a
Polyporus sp. laccase, especially the Pblyporus pinisitus laccase (also called
Trametes
viilosa laccase) described in WO 96/00290 (from Novo Nordisk Biotec Inc.) or a
Myceliophthora sp. laccase, especially the Myceiiophthora thermophila laccase
described in WO 95133836 (from Novo Nordisk Biotech Inc.).
Further, the faccase may be a Scytalidium sp. laccase such as the S.
thermophiiium
laccase described in WO 95/33837 and WO 97/19998 (from Novo Nordisk Biotech
Inc.), the contents of which is incorporated herein by reference, or a
Pyricularia sp.
laccase, such as the Pyricularia oryzae laccase which can be purchased from
SIGMA
under the trade name SIGMA No. L5510, or a Coprinus sp. faccase, such as a C.
cinereus laccase, especially a C. cinereus IFO 301 16 laccase, or a
Rhizoctonia sp.
laccase, such as a Rh. solani laccase, especially the neutral Rh. solani
laccase
described in WO 95/07988 (from Novo Nordisk AIS) having a pH optimum in the
range
of from fi.0 to 8.5.
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The laccase may also be derived from a fungus such as Collybia, Fomes,
Lentinus,
Pleurotus, Aspergillus, Neurospora, Pbdospora, Phlebia, e.g. P. radiata (WO
92/01046),
Coriolus sp., e.g. C. hirsitus (JP 2-238885), or Botrytis.
Bilirubin oxidase may preferably be derived from a strain of Myrothecium sp.,
such
as M. verrucaria.
Oxidases yielding peroxide (H202) are typically used in combination with a
peroxidase to remove or at least reduce the peroxide produced.
Suitable oxidases include glucose oxidase (E.C. 1.1.3.4), hexose oxidase (E.C.
1.1.3.5), L-amino-acid oxidase (E.C. 1.4.3.2), xylitol oxidase, galactose
oxidase (E.C.
1.1.3.9), pyranose oxidase (E.C. 1.1.3.10) and alcohol oxidase (E.C.
1.1.3.131.
If an L-amino acid oxidase is used it may be derived from a Trichoderma sp.
such
as Trichoderma harzianum, such as the L-amino acid oxidase described in WO
94/25574 (from Novo Nordisk A/S), or Trichoderma wide.
A suitable glucose oxidase may originate from Aspergillus sp., such as a
strain of
Aspergillus niger, or from a strain of Cladosporium sp. in particular
Cladosporium
oxysporum.
Hexose oxidases from the red sea-weed Chondrus crispus (commonly known as
Irish moss)(Sullivan and Ikawa, (19731, Biochim. Biophys. Acts, 309, p. 11-22;
ikawa,
(1982), Meth. in Enzymol. 89, Carbohydrate Metabolism Part D, 145-149) oxidise
a
broad spectrum of carbohydrates, such as D-glucose, D-galactose, maltose,
cellobiose,
lactose, D-glucose 6-phosphate, D-mannose, 2-deoxy-D-glucose, 2-deoxy-D-
galactose,
D-fructose, D-glucuronic acid, and D-xylose.
The foaming agent may be present in the form of a single agent or a
combination
of two or more agents. The foaming agent is typically selected from soaps and
ani-
onic, cationic, non-ionic, amphoteric, sugar surfactants andlor zwitterionic
surfactants and mixtures thereof. The foaming agents) may be present at levels
of
from 0.1 °~6 to 15°.6, preferably from 0.2 to 13°~, more
preferably from 0.25 to
10°~, e.g. from 0.5 to 8°.6 by weight of the final composition.
Examples of anionic
surfactants suitable for use as the foaming agent are soaps, e.g. in the form
of alkali
or ethanol amine, isopropanol 2-methyl-2-amino-1,3-propandiol salts of fatty
acids
such as laurate, myristate, palmitate, stearate, isostearate, behenate,
oieate,
linoleate, etc.; fatty alcohol ether sulfates such as sodium lauryl ether
sulfate; fatty
alcohol sulfates such as sodium lauryl sulfate (SLS and SDS); sulfo
succinates, e.g.
dioctyl sodium sulfo succinate; a-olefin sulfonates; alkyl amide ether
sulfates; fatty
acid condensation products; alkyl ether phosphates and monoglyceride sulfates.
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Examples of non-ionic surfactants suitable for use as the foaming agent are
especially the nonionic fatty acids and fatty amines that often are used as
foam
stabilisers, thickeners and boosters, e.g. fatty acid alkanol amides and
dialkanoi
amides and fatty acid alkanol amide polyglycol ethers and fatty amine oxides.
Examples of amphoteric surfactants suitable for use in combination with
anionic
surfactants as the foaming agent are alkyl betaines, alkyl imidazolinium
betaines,
alkyl sulfo betaines, amidoalkyl betaines, N-alkyl-f3-amino propionates, etc.
Examples of foaming agents in the form of sugar surfactants include (a) alkyl-
and/or alkenyloligoglycosides and/or (b) fatty acid-N-
alkylpolyhydroxyalkylamides.
The alkyl- andlor alkenyloligoglycoside (a) may have the formula (I):
R'-O-[G]p (I)
in which R' = a C,,_z2 alkyl and/or alkenyl group, G = a sugar residue with 5
or 6
carbon atoms, and p = 1-10.
The fatty acid-N-alkylpofyhydroxyalkylamide (b) may have the formula:
RICO-N(R3)-[Zl (11)
in which RICO = a C-~.z2 aliphatic acyl residue, R3 = H, alkyl or hydroxyalkyl
with
1-4 carbon atoms, and [Z) = a linear or branched polyhydroxyalkyl residue with
3-12 carbon atoms and 3-10 OH groups.
It also includes a) alkyl and alkenyl oligogfycosides of the formula R'-O-[G]P
and
b) alkali andlor alkali metal salts of C-,2_22 secondary 2,3-alkyl sulphates,
where
R1 = C-;-yy alkyl and/or alkenyl; G = a sugar residue with 5 or 6 carbon
atoms, and
p = 1-10. The weight ratio (I):(11) is preferably 1:99-99:1.
Also included are fatty acid-N-alkyl polyhydroxyalkyl amides; and sugar
surfactants of: saccharose esters, sorbitan esters andfor polysorbates.
A sugar surfactant may also comprise 10-40°~ by weight of alkyl andlor
alkenyl-
oligoglucoside of the formula R'-O-[G)P, 10-40°~ by weight of an alkyl-
and/or
alkenyl-oligoglucoside of the formula R2-O-(G)P and 80-2096 by weight of an
alkyl
ether sulphate of the formula R3-(OCHZCH2)" O-S03M, in which R' = Ce." alkyl
or
alkenyl; (G) = a glucose group.; p = 1-10, preferably 1-3; R2 = C-,2_z2 alkyl
or
alkenyl; R3 = C-&22 alkyl or aikenyl; M = an alkali or alkaline earth metal,
or an
ammonium or alkanolammonium ion, preferably Na or Mg; and n = 1-20, preferably
2-7. Preferably, R2 and R3 are independently a C-,Z_,4 alkyl.
Another example of a sugar surfactant is a polyglycerin fatty acid ester
polyoxyalkylene ether R R' Rz R3 N +-CH(Y)-CH2 O-CHZ-C(CH3)2-C(OH)(H)-C( = O)-
NH-
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CHz-CHz-OH X- (1) where R, R', Rz = C-,_z4 alkyl Or C-e_24 alkenyl; R3 = C-
,_,a
alkylene; X = a monovalent organic or inorganic anion; and Y = OH or H.
A sugar surfactant may also include (A) 1-5 wt. % of a fatty alcohol
polyglycol
ether, 1-5°r6 of a Guerbet alcohol, and 1-5°~ of a polyol
partial ester, (B) 1-5°~ of a
anionic polymer, (C) 15-30°r6 of a fatty alcohol polyglycoi ether
sulphate, (D)
15-30°~6 of an alkyloligoglycoside; and a sulphated product of fatty
acid-N-
alkylpolyhydroxyalkyl amides of the formula R' CO- N(Rz)-Z, where R' CO = C-
e_zz
aliphatic acyl; Rz = H, C-,~ alkyl or C,~ hydroxyalkyl; Z = C-3_12
polyhydroxyalkyl
containing 3-10 hydroxy groups.
Sugar surfactants can also be selected from alkyl oligoglycosides of formula
(I)
and carboxylic acid N-polyhydroxyalkylamides of formula (II):
R'-O(G) (I)
R2 CO-NR3-Z (II)
where R' = optionally hydroxylated C-,_a alkyl; G = a sugar_residue with 5 or
6
carbon atoms; p = 1-10; Rz CO = C-,.a aliphatic acyl; R3 = H, C-,.e alkyl or C-
,.a
hydroxyalkyl; Z = C-3_~p polyhydroxyalkyl containing 3-10 OH groups.
Examples of preferred foaming agents are SDS (sodium dodecyl sulfate), sodium
dodecyl ether sulfate and soaps.
It may also be desired to add other additives that function as stabilisers,
boosters
and thickeners, for example one or more compounds selected from fatty acid
alkanol
amides, dialkanol amides or fatty alkanol amides, polyglycol ethers such as
ethoxylated
lauric acid monoethanol amide, or fatty amine oxides such as alkyl dimethyl
amine oxide.
Compositions of the invention may furthermore include, as a stabiliser, a
water-
soluble polymer capable of stabilising the foam, e.g. one or more of a
cellulose derivative
such as cationized cellulose, hydroxyethyl cellulose, hydroxymethyl cellulose,
hydroxypropytmethyl cellulose, an amphoteric resin, vinylethylether maleate
polymer,
polyvinyl pyrrolidone and acrylic resin alkanol amine.
To obtain dyeing of the keratinous fibres such as hair, the dyeing composition
of
the invention also comprises at least one dye precursor which is converted
into a
coloured compound (i.e. a dye) by the oxidation enzyme. Without being limited
thereto,
the dye precursor may be an aromatic compound belonging to one of three major
che-
mical families: the aromatic diamines, aminophenols (or aminonaphthols) and
the
phenols. Examples of isatin derivative dye precursors can be found in DE
4,314,317-
A1. Further, a number of indole or indoline derivative dye precursors are
disclosed in
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9
WO 94/00100. The dye precursors mentioned in these documents are hereby
incorpo-
rated herein by reference.
Examples of suitable dye precursors include compounds from the group
comprising
p-phenylene-diamine (pPD), p-toluylene-diamine, chloro-p-phenylenediamine, p-
aminophenol, o-aminophenol, 3,4-diaminotoluene, 2,5-diaminotoluene, 2-methyl-
1,4-
diaminobenzene, 4-methyl-o-phenylenediamine, 2-methoxy-p-phenylenediamine, 2-
chloro-1,4-diamino-benzene, 4-amino diphenylamine, 1-amino-4-(3-
methoxyethylamino-
benzene, 1-amino-4-bis-(~i-hydroxyethyl)-aminobenzene, 1-3-diamino-benzene, 2-
methyl-1,3-diamino-benzene, 2,4-diaminotoluene, 2,6-diaminopyridine, 1-hydroxy-
2-
amino-benzene, 1-hydroxy-3-amino-benzene, 1-methyl-2-hydroxy-4-amino-benzene,
1-
methyl-2-hydroxy-4-p-hydroxyethylamino-benzene, 1-hydroxy-4-amino-benzene, 1-
hydroxy-4-methylamino-benzene, 1-methoxy-2,4-diamino-benzene, 1-ethoxy-2,3-
diamino-benzene, 1-~i-hydroxyethyioxy-2,4-diamino-benzene, 3,4-diamino-
benzhydrazide, 3,5-diamino-benzhydrazide, 3-hydroxytyramine and catechin; phen-
azines, such as 4,7-phenazinedicarboxylic acid, 2,7-phenazinedicarboxylic
acid, 2-
phenazinecarboxylic acid, 2,7-diaminophenazine, 2,8-diaminophenazine, 2,7-
diamino-
3,8-dimethoxyphenazine, 2,7-diamino-3-methoxyphenazine, 2,7-diamino 3-
methoxyphenazine, 3-dimethyl 2,8-phenazinediamine, 2,2'-((8-amino-7-methyl-2-
phenazinyl)imino]bis-ethanol, 2,2'-f(8-amino-7-methoxy-2-phenazinyl)iminolbis-
ethanol,
2,2'-[(8-amino-7-chloro-2-phenazinyl)iminolbis-ethanol, 2-f(8-amino-7-methyl-2-
phena-
zinyl)aminol-ethanol, 2,2'-f(8-amino-2-phenazinyl)imino)bis-ethanol, 3-amino-7-
(dimethyiamino)-2,8-dimethyl-5-phenyl-chloride, 9-(diethylamino)-
benzo(a]phenazine-
1,5-diol, N-[8-(diethyiamino)-2-phenazinyll-methanesulfonamide, N-(8-methoxy-2-
phenazinyl)-methanesulfonamide, N,N,N',N'-tetramethyl-2,7-phenazinediamine,
3,7-di-
methyl-2-phenazinamine; p-amino benzoic acids, such as p-amino benzoic acid
ethyl, p-
amino benzoic acid glyceride, p-amino benzoic acid isobutyl, p-dimethylamino
benzoic
acid anvil, p-dimethylamino benzoic acid octyl, p-diethoxyamino benzoic acid
anvil, p-
dipropoxyamino benzoic acid ethyl; acetylsalicylic acid, and isatin
derivatives, such as
2,3-diamino benzoic acid.
Examples of other dye precursors include amino benzoic acid compounds of the
general formula 1
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WO 99!15137 PCT/DK98100406
COR
Z X
(I)
NH2
Y
wherein
R is an amino, a mono - or disubstituted amino or OR', where R' is H, alkyl,
5 alkenyl, alkynyl, halogenalkyl, vitro, benzyl, phenyl or substituted phenyl,
X, Y and Z may each independently be hydrogen, alkyl, alkenyl, alkynyl,
halogenalkyl, vitro, benzyl, phenyl, substituted phenyl, amino, hydroxy or
mercapto with the proviso that at feast one of the groups X, Y and Z is an
amino group or a salt thereof. Compounds where R' is a methyl, ethyl or
10 isopropyl ester are preferred.
In one embodiment, the oxidoreductase is used with the dye precursor directly
to
oxidise it into a coloured compound. The dye precursor may be used alone or in
combination with other dye precursors.
However, it is believed that when using a diamine or an aminophenol as the dye
precursor, at least one of the intermediates in the copolymerisation must be
an ortho-
or para-diamine or art~inophenol. Examples of such are described in US patent
No.
3,251,742 (Revlon), the contents of which are incorporated herein by
reference.
Optionally, the dyeing composition of the invention (especially hair dyeing
compositions) also comprises a modifier (coupler) by means of which a number
of
colour tints can be obtained. Modifiers are normally used in hair dyeing compo-
sitions, as the colours resulting from hair dyeing compositions without a
modifier are
usually unacceptable for most people.
Modifiers are typically m-aromatic diamines, m-aminophenols, polyphenols,
amino naphthalines or naphthols. The modifier (coupler) reacts with the dye
precur
sor in the presence of the oxidative enzyme, converting it into a coloured
compound.
Examples of modifiers (couplers) include m-phenylene-diamine, 2,4-
diaminoanisole, 1-
hydroxynaphthalene(a-naphthol), 1,4-dihydroxybenzene(hydroquinone), 1,5-
dihydroxynapthalene, 1,2-dihydroxybenzene(pyrocatechol), 1,3-dihydroxybenzene
(re-
sorcinol), 1,3-dihydroxy-2-methylbenzene, 1,3-dihydroxy-4-chforobenzene(4-
chlororesorcinol), 1,2,3-trihydroxybenzene, 1,2,4-trihydroxybenzene, 1,2,4-
trihydroxy-
5-methylbenzene, and 1,2,4-trihydroxytoluene.
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11
Compositions according to the invention may in addition contain additives and
excipients commonly used in hair-dyeing compositions and other cosmetic
products,
e.g. humectants, oils, thickening agents, antioxidants, buffers,
preservatives,
fragrances, colours, etc.
In a second aspect, the invention relates to a method for dyeing keratinous
fibres,
in particular hair, fur, hide and wool, using a composition as described
above. The
dyeing method can be conducted with one or more dye precursors and optionally
in
combination with one or more modifiers. The amount of dye precursors) and
other
ingredients used in the composition of the invention for this purpose are in
accordance
with usual commercial amounts. Hair dyeing is typically carried out at or near
room
temperature, preferably around the optimum temperature of the enzyme being
used,
and at a pH in the range of from 3.0 to 9.0, preferably 4.0 to 8.5, especially
6.0 to
8Ø Suitable dye precursors and optional modifiers are described above.
Although it is contemplated that the method of the invention typically will be
performed using a single pre-mixed composition applied to the hair or other
fibres as a
foam comprising the oxidation enzyme, the foaming agent, the dye precursor and
the
optional modifier in order to obtain the most uniform result, it is also
contemplated that
the method may alternatively be performed by mixing two or more separate
compositions and/or ingredients in order to result in the desired foam
composition
containing all of the necessary ingredients.
The invention is further illustrated in the following non-limiting examples.
MATERIALS AND METHODS
Except where otherwise stated, the materials and methods used were the
following.
Materials
Hair:
6" De Meo Virgin Natural White Hair (De Meo Brothers Inc., USA)
Enzvme:
Laccase from Myceliophtora termophilia described in WO 95133837 (available
from
Novo Nordisk Biotech, Inc.1 Dosed as 0.1 mg enzyme per ml of reaction liquid.
Dve precursors:
The dye precursors used were selected from the following:
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12
p-phenylene-diamine (pPD)
o-aminophenol (oAP)
Buffer:
0.1 M borate buffer, pH 7.0 with 60 ppm Ca++
Analytical Eauinment:
Minolta C13200 Chroma Meter
Daylight bulb: .1000 LUX (D65)
Methods
Preparation of foam compositions
Foams are made using foam dispensers or a blender, the foam compositions being
gently blended by stirring during production to avoid foam formation at that
stage. The
following formulations were used:
"Minimal type"
SDS 0.4°r6
Dye precursor 0.5°~6
Buffer up to 100%
The enzyme is added to the formulation as 0.1 mg enzyme protein per ml dye
solution.
"Simple type A "
SDS 2.0~
Betaine phosphate 2.0~6
Dye precursor 05%
Buffer up to 100%
The enzyme is added to the formulationmg enzyme protein per
as 0.1 ml dye
solution
Reference: "still water"
Because foam can only be applied in a maximum amount of about 2.5 g per g of
hair, the precursor concentration in the reference is reduced by 50%:
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Dye precursor 0.25°r6
Buffer up to 100%
The enzyme is added to the formulation as 0.1 mg enzyme protein per ml dye
solution.
A total of 5 ml of reference dye solution is added to the hair (Still water).
Assessment of hair colour
The quantitative colour of the hair wisps is determined on a Minolta CR200
Chroma
Meter using the parameters L* ("0" =black and "100" =white), a* ("-" =green
and
"+"=red) and b* ("-" blue and "+" yellow).
DL*, Da* and ~b* are the delta values of L*, a* and b* respectively compared
to L*,
a* and b* of untreated hair (e. g. DL* = L*"~",, - L*"M,~,~~,w).
DE* is calculated as DE* = sq.root(OL*2 + ~a*Z + Ob*Z) and is an expression
for the
total quantitative colour change.
EXAMPLES
Example 1
Hair dyeing composition comprising laccase formulated as a foam
1 gram hair wisps were dyed with foam formulations (prepared as described
above)
while hanging on a sloped metal plate. The foamed dye solutions were massaged
into the
hair wisps, whereas the reference solution was poured onto the wisps in a 150
ml glass
beaker. 1-2 g of dye formulation was administered on each hair wisp. The
dyeing was
performed for 30 minutes at a temperature of 30°C, two wisps being used
for each
formulation. After administration of the dye formulation, the wisps were hung
on the mount
and placed in a heating cabinet during the dyeing period. The reference was
left untouched.
After dyeing, the wisps were rinsed and washed once and then dried.
The results of dyeing with two different dye precursors using the two foam
formulations mentioned above are shown in the Figures 1 and 2.
Figure 1 shows the effect on colour uniformity by dyeing with a foam
formulation
containing the precursor pPD. The two above-mentioned foam formulations are
each
tested on two hair wisps, the dye uniformity being expressed as the "CV"
(coefficient of
variance) of DE* and DL* after measuring each hair wisp 12 times from tip to
root.
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Figure 1 clearly shows that the colour uniformity is better for the hair wisps
dyed
with the foam formulations. Their CV is significantly lower than for the hair
wisps dyed
in the "still water" reference solution.
The same effect is seen in figure 2, where the dye precursor is oAP. In this
case,
only one hair wisp is shown for each formulation, and again the foam improves
colour
uniformity.
Example 2
Hair dyeing composition comprising tyrosinase formulated as a foam
Materials
Hair: De Meo Virgin Natural White Hair, 1 gram hair wisps.
Enzyme: Tyrosinase from Sigma.
Conc: 0.9 mg e.p/ml formulation (e.p=active enzyme protein)
Dye precursor: p-phenylene-diamine (PPD) or p-toluene-diamine (PTD)
Conc: 0.1 °~6 formulation
Buffer: 0.1 M Borate buffer, pH 7.0 with 60 ppm Ca++
Foam formulation: 0.02 g MiniRiskT"" shampoo per mi formulation
MiniRiskT'" contains 15°r6 SDS
Methods
1) The precursor is dissolved in 0.1 M borate buffer for 15 min. under
stirring.
2) MiniRiskT'", 0.1 M borate buffer and enzyme are mixed gently.
3) The presursor is then added to the formulation and mixed gently.
4) The formulation foam is made using a foam dispenser.
5) The foam is applied in a maximum amount of about 2.5 g per g of hair by
massaging it into the hair wisps.
6) The wisps are hung on a metal plate for 30 minutes at a temperature of
30°C for
dyeing.
7) After 30 minutes the hair is rinsed for 3 minutes, washed with MiniRiskT""
shampoo for 15 sec., then rinsed again and air-dried overnight.
8) After drying the hair color is measured using a Minolta Chroma Meter, an
untreated hair wisp being used as a reference.
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The results are shown in Figure 3, in which it may be seen that hair dyeing is
obtained with tyrosinase when combined with either PPD or PTD as a dye
precursor.
Although the OE value for PPD is somewhat higher than for PTD, it is still at
an
acceptable level, in particular in light of the fact that tyrosinase is
generally not
5 regarded as an enzyme that is suitable for hair colouring purposes. This
example
thus shows that when used according to the present invention, acceptable hair
dyeing may be obtained with tyrosinase.
