Note: Descriptions are shown in the official language in which they were submitted.
CA 02428173 2005-04-06
Hair Conditioning Compositions Comprising Aminofunctional
Polysiloxanes
Technical Field of the Invention
The present invention relates to hair conditioning
compositions and in particular hair colouring compositions
comprising hair conditioning agents.
Background of the Invention
The alteration of the colour of hair by the application
of hair dyes is well known.
In order to provide the consumer with the hair colour
and intensity of shade desired, a very complex chemical
process is utilised. The hair dyeing molecules are typically
produced from the reaction of at least one oxidative
colouring agent with an oxidising agent which are formed in
situ on the hair of consumers and typically in an aggressive
environment at ca pH 10 and in the presence of alkalising
agent. Moreover this process is repeated regularly by the
consumer in order maintain the desired hair colour and
intensity of the hair colour shade and ensure continual,
even coverage of the hair including coverage of new hair
growth.
The manufacturer of such products is also required to
work within a large number of constraints. Since these
products are being placed in direct contact with the
consumers' skin and potentially accidental contact with the
eye or ingestion (for example) can occur during the dyeing
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process, the formulation must meet rigorous safety
requirements and not cause any allergic reaction. In
addition to meeting these requirements, the products must
also be optically and olfactory pleasing to the consumer and
meet certain physical parameters in order to ensure that the
product can be easily applied to the hair by the consumer to
provide the desired effect, without unintentional staining
on the consumers clothes, skin or other objects.
The chemistry involved in the hair dyeing process may
result in some damage to the hair which is permanent.
Damaging effects include tangling, brittleness and dryness.
Consequently there is a need to provide the hair dye
composition or hair dyeing kit with a conditioning component
in order to combat this damage and improve at least the
consumers' perception of the condition of the hair;
immediately after the hair dyeing process and the on-going
condition of the hair during the post dyeing washing cycle
until the next hair dyeing cycle.
The use of conditioning compositions is well known in
the art and are incorporated as part of conventional shampoo
and conditioning regimes as well as in so called two-in-one
shampoo conditioners. Their use in hair dyeing kits is also
well known. Typically they are provided in a sachet for use
in the final rinse, after dyeing is completed. These
conditioners such as amino silicones as described for
example in US 4 563 347, EP 275 707 and W099/49836 usually
provide an acceptable immediate improved feel of the hair to
the consumer. However, this conditioning benefit is not
durable over a number of hair washing cycles such that the
consumer becomes dissatisfied with the condition of the hair
during the course of the post dyeing cycle.
Unfortunately durable conditioning cannot be achieved
by simply increasing the levels of conditioning material in
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the composition. In fact, if excessive conditioner is
applied, the initial feel of the hair becomes heavy and
greasy which is completely unacceptable to the consumer.
Moreover if the conditioning material is such that it
is sustained on the hair during the post dyeing wash cycle
such that it is still present on the hair at the start of
the next colouring cycle, the performance of the dyeing
process cannot be predicted and may be detrimentally
effected. Such ja result is equally undesirable for the
consumer.
Progress has however been made in the field of durable
hair conditioning materials and in particular compounds such
as amodimethicone have been identified as delivering
improved durable conditioning benefits.
It has further been taught in the art for example in
W099/49836 to utilise microemulsions of organosiloxanes in
order to improve the conditioning effect.
However, there is still a need to provide durable
conditioning materials for use in hair dye compositions
which have the required initial deposition and retention
over time without any greasy feel negatives after the
initial application and which do not negatively affect the
performance of the next hair dyeing cycle.
There is also a need to provide a hair dye composition
which does not necessarily require a separate post hair
dyeing conditioning step .
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Summary of the Invention
An object of the present invention is to provide
hair conditioning compositions and their use in hair
colouring compositions. In accordance with an aspect of
the present invention, there is provided a hair care
composition comprising an aminofunctional polysiloxane
according to the formula: R3_ZQZSiO [A] Xl [B] Y[C] cSi4zR3-a
wherein; A represents R2SiO, B represents RQSiO and C
represents R3_ZQZ [A]XZSiORi, wherein R is an alkyl group of
1 to 5 carbons, a phenyl group, an alkoxy group or an
hydroxy group and at least 50% of said R groups are
methyl, R' is R or Q or RZ , R2 is R3 -zQz [Al X3 , Q is an amine
functional group of the formula -R3Z, wherein R3 is a
divalent alkylene radical of 3 to 6 carbons, preferably
trimethylene, pentamethylene, -CH2CHCH3CH21 or -CH2CH2-
CHCH3 CHZ - , Z i s -N ( R4 ) 2, -NR4 ( CHZ ) nN ( R4 ) 2, N+ ( R4 ) 3A-, -
NR4 (CH2) n or N+ (R' ) 3A-, R' is an H atom or alkyl group of 1
to 20 carbon atoms or phenyl or benzyl, A is F-, C1-, Br-,
I- and wherein: t is from 0 to 3, xl from 1 to 3000, xZ is
from 0 to 3000, x3 is from 0 to 3000, xi + xa + x3 is from
to 3000, y is from 0 to 100, z is from 0 to 1, n is
from 2 to 6, and wherein said aminofunctional
polysiloxane has an average effective particle size as
defined herein of greater than 2 micrometers to 50
micrometers.
In accordance with another aspect of the invention,
there is provided a hair colouring composition comprising
at least one oxidative dye and comprising an
aminofunctional polysiloxane according to the formula
R3-ZQZSiO [A] x1 [B] Y[C] tSiQZR3-Z wherein A is R2SiO, B is
RQSiO, C is R,-ZQZ [Al xaSiORl and R is a methyl or hydroxy
or methoxy group and at least 50% of said R groups are
methyl, Rl is R or Q, Q is an amine functional group of
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CA 02428173 2005-04-06
the formula -R3Z, wherein R3 is propyl or isobutyl, Z is
NH2 or NHCH2CH2NH2, N+ (R4) 3A", -NR4 (CH2)õ or N` (R4) 3A-, A is F-
, C1-, Br-, I- and wherein t is from 0 to 2, xl is from 10
to 400, x2 is from 22 to 124, xl + x2 is from 10 to 400, y
is from 0 to 9 when z=1, and y is from 1 to 9 when z=0
such that said composition has (1) an initial average
Combing Index Value on wet hair of 1 or more, preferably
of 1.05 as measured according to the Combing Test Method
defined herein, (2) an initial average Sensory Index
value of 0.95 or more, preferably of 0.98 or more as
measured according to the sensory test method defined
herein, (3) a final average Combing Index Value on wet
hair after 18 washes as measured by the Combing test
Method of 1 or more, preferably of 1.01 or more and (4) a
final average Sensory Index value after 18 washes as
measured according to the sensory test method of 0.95 or
more, preferably of 0.98 or more.
The present invention relates to a hair care
composition comprising an amino functional polysiloxane
as defined hereinafter having an average particle size of
from greater than 2 micrometers to 50 micrometers which
provides improved conditioning particularly when utilised
in combination with a hair colouring composition.
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Detailed Description of the Invention
As used herein the hair treated may be "living" i.e. on
a living body or may be 'non-living' i.e. in a wig,
hairpiece or other aggregation of non-living fibres, such as
those used in textiles and fabrics. Mammalian, preferably
human hair is preferred. However wool, fur and other melanin
containing fibres are suitable substrates for the
compositions according to'the present invention.
The hair care composition according to the present
invention comprises at least one or a mixture of an amino
functional polysiloxane compound having the formula:
R3_ZQZSiO [A] Xl [B] 1, [C] tSi%R3_Z
wherein; A represents R2SiO, B represents RQSiO and C
represents R3_ZQz [A] X2SiOR1, wherein
R is an alkyl group of 1 to 5 carbons wherein at least 50%
of said R groups are methyl, preferably R is a methyl,
ethyl, propyl, isopropyl, butyl or isobutyl, a phenyl group,
an alkoxy group or an hydroxy group and R' is R or Q or Rz,R2
is R3_ZQZ [A] X3 wherein, Q is an amine functional group of the
formula -R3Z, R3 is a divalent alkylene radical of 3 to 6
carbons, preferably trimethylene, pentamethylene, -
CH2CHCH3CH2-, or-CH2CH2CHCH3CH2-, Z is -N (R4) 21 -NR4 (CH2) nN (R4) 2,
, -N+(R4) 3A-, -NRg (CH2) n N* (Rg) 3A", preferably a monovalent radical
including at least 1 amine; unsubstituted amine radical -
NHz, alkyl substituted amine radicals such as -NHCH3 or -
NHCH2CH2CH2CH3; aminoalkyl substituted amine radicals such as
-NHCH2CH2NH2 , -NH ( CH2 ) 6NH2 and -NHCH2CH2N ( CH3 ) 2 ; diaminoalkyl
substituted amine radicals such as -N (CH2CH2CH2NH2) 2 -
N(CHaCHzCH2N (CH3) 2) 2, R4 is an H atom or alkyl group of 1 to 20
carbon atoms or phenyl or benzyl, A- is F", C1-, Br-, I-, and
wherein :t is from 0 to 3,x.1 is from 1 to 3000,x2 is from 0
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to 3000,x3" is from 0 to 3000,x,. + xz + x3 is from 10 to
3000,y is from 0 to 100, preferably y is 0 when z=1 and
preferably y is from 1 to 100 when z=0, z is from 0 to 1,
and n is from 2 to 6.
More preferably R is a methyl or hydroxy or methoxy
group, most preferably methyl and at least 50% of R groups
are methyl. R' is R or Q, most preferably R, ~Q is an amine
functional group of the formula - R3Z, R3 is propyl or
isobutyl and Z is NH2 or NHCH2CH2NH2 and wherein t is from 0
to 2, most preferably 0, xl is from 10 to 400, x2 is from 22
to 124, xl + x2 is from 10 to 400, y is from 0 to 9 when z=1,
and y is from 1 to 9 when z=0.
It has now been found that the particle size of the
aminofunctional polysiloxane in the hair care composition
plays a critical role in the performance of the composition,
particularly when utilised as,part of a hair dyeing regime.
Accordingly it has now been surprisingly found that
compositions comprising aminofunctional polysiloxanes
according to the formula described herein above, having an
average effective particle size of from greater than 2
micrometers to 50 micrometers, preferably from 5 micrometers
to 40 micrometers, more preferably from 10 micrometers to 30
micrometers, most preferably from 15 micrometers to 20
micrometers provides a hair care conditioning composition
which not only provides the desired initial conditioning as
determined by the Combing technical test Methods and the
Sensory Technical Test Method described hereinafter but
which is also maintained over a number of hair washing
cycles.
The term average effective particle size as used herein
refers to the average size of individual discrete particles
of amino functional polysiloxanes as defined herein and
discrete particles comprising an aminofunctional
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polysiloxane and a polycation or cationic polymers. Whilst
not being bound by theory such particles have been referred
to as coascervates and form discrete particles consisting
localised concentrations of the amino functionalised
silicone that are associated with the hydrophobic
environment of the polycation or cationic polymers. Examples
of suitable cationic polymers include cationic cellulose
(polyquaternium 10) and hydrophobically modified cationic
cellulose (i.e. Amerchol's quatrisoft LM200), cationic guar
(guar hydroxypropyltrimonium chloride), merquatTM 100
(polyquaternium 6), Merquat 550 (polyquaternium 7), Luviquat
(polyquaternium-16) and GafquatTm755N (polyquaternium 11).
The effective particle size can be determined by
standard microscopy method as detailed hereinafter in the
test methods.
It has also been found that a number of other factors
may be selected to beneficially influence the performance of
the aminofunctional polysiloxane, such as molecular weight,
viscosity, degree of curability, degree of silicone
branching (i.e. the number of T and T' groups), the amine
type, the linker type and the charge density to molecular
weight of nitrogen.
Preferably, the viscosity of the aminofunctional
polysiloxane should be selected such that it is in a range
of from lOcps to 3000cps, preferably from 100 to 500cps.
whilst not being bound by theory it is believed that
viscosity is proportional to polymer molecular weight and
inversely proportional to the degree of branching.
Viscosity will impact spreading on hair and ease .of
processing in the composition. Thus molecular weight also
influences both of these important parameters.
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The molecular weight of said aminofunctional
polysiloxane is preferably from 1000 to 50000, more
preferably from 1500 to 35000. The ratio of charge density
to molecluar weight of nitrogen is preferably from 190 to
3000.
Whilst not intending to be bound by theory it is
believed that increasing the charge density, to a point,
provides more affinity for negatively charged, damaged hair,
thus improving substantivity and durability through the
colour cycle. If charge density is too high, the surfactancy
of the silicone is increased to a point where wash-off is
achieved too easily and durability thus reduced.
According to the present invention, the hair care
composition comprises from 0.1% to 10%, preferably from 0.5%
to 5%, most preferably from 1% to 3% by weight of the total
composition applied to the hair of the amino functional
polysiloxane compound.
It has further been found that the compositions
according to the present invention when utilised in
conjunction with a hair colouring composition provide, not
only the desired initial conditioning as determined by the
Combing Technical Test Methods and the Sensory Technical
Test Method described hereinafter but also provide
conditioning which is also maintained over a number of hair
washing cycles.
Accordingly, another aspect of the present invention
relates to the provision of a hair colouring composition
comprising an aminofunctional polysiloxane according to the
formula
R3_ZQZSiO [A] ,l [B] Y[C] tSiQZR3_Z
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wherein A is RaSiO, B is RQSiO, C is C R3-ZQZ [A] XzSiOR' and R
is a methyl or hydroxy or methoxy group and at least 50% of
said R groups are methyl,R' is R or. Q, Q is an amine
functional group of the formula - R3Z, R3 is propyl or
i sobutyl , Z is NH2 or NHCHzCHZNH,, N"( R ) 3A" , -NR" ( CH, )õ or
N' (R') 3A', A is F-, Cl-, Br-, I-
and wherein;
t is from 0 to 2, x, is from 10 to 400, xais from 22 to 124,
xl + xZ, is from 10 to 400, y is from 0 to 9 when z=1, y is
from 1 to 9 when z =0;
such that said composition has an initial average Combing
Index Value on wet hair of 1 or more, preferably of 1.05,
most preferably of 1.08 or more as measured by the Combing
Technical Test Method as defined herein, an initial average
Sensory Index value of 0.95 or more, preferably of 0.98 or
more, most preferably of 1 or more, a final average Combing
index Value on wet hair after 18 washes as measured by the
Combing Test Method of 1 or more, preferably of 1.01 or
more, most preferably of 1.02 or, more and a final average
Sensory Index value after 18 washes of 0.95 or more,
preferably of 0.98 or , most preferably of 1 or more as
defined herein. -
According to the present invention the Combing Index value
and the Sensory Index value are determined by the test
methods described herein after the results of which are
applied to the following equations:
Combing Index value =
[{Ease of De-Tangling}Sample}/[{Ease of De-Tangling) Virgin]
+[{Ease of Combing] Test}/ [Fase of Combing] Virgin} / 2
Sensory Index value =
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{[No Residue] Test / [No Residue] Virgin + [Not Greasy]
Test / [Not Greasy] Virgin + [Not Coated] Test /[Not
Coated] Virgin} / 3
Hair colouring agents
The composition according to the present application
finds particular utility in hair colouring compositions
especially oxidative hair colourants wherein the hair is
subjected to a particularly aggressive environment.
Oxidative Hair colouring agents
A preferred hair colouring agent for use herein is an
oxidative hair colouring agent. The concentration of each
oxidative hair colouring agent in the colouring compositions
according to the present invention is preferably from about
0.0001% to about 5% by weight. The exact amount is dependant
upon the end shade required. Typically blond shades comprise
from 0.0001o to 1.00%, red shades comprise 0.0010% to 4%,
brown shades comprise 0.0100o to 4.00% and black shades
comprise 0.100 to 4.00% by weight of the total composition
on the hair.
Any oxidative hair colouring agent can be used in the
compositions herein. Typically, but without intending to be
limited thereby, oxidative hair colouring agents, consist
essentially of at least two components, which are
collectively referred to as dye forming intermediates (or
precursors). Dye forming intermediates can react in the
presence of a suitable oxidant to form a coloured molecule.
The dye forming intermediates used in oxidative hair
colorants include: aromatic diamines, aminophenols, various
heterocycles, phenols, napthols and their various
derivatives. These dye forming intermediates can be broadly
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classified as; primary intermediates and secondary
intermediates. Primary intermediates, which are also known
as oxidative dye precursors, are chemical compounds which
become activated upon oxidation and can then react with each
other and/or with couplers to form coloured dye complexes.
The secondary intermediates, also known as colour modifiers
or couplers, are generally colourless molecules which can
form colours in the presence of activated precursors/primary
intermediates, and are used with other intermediates to
generate specific colour effects or to stabilise the colour.
Primary intermediates suitable for use in the
compositions and processes herein include: aromatic
diamines, polyhydric phenols, amino phenols and derivatives
of these aromatic compounds (e.g., N-substituted derivatives
of the amines, and ethers of the phenols) . Such primary
intermediates are generally colourless molecules prior to
oxidation.
While not wishing to be bound by any particular theory
it is proposed herein that the process by which colour is
generated from these primary intermediates and secondary
coupler compounds generally includes a stepwise sequence
whereby the primary intermediate can become activated (by
oxidation), and then enjoins with a coupler to give a
dimeric, conjugated coloured species, which in turn can
enjoin with another 'activated' primary intermediate to
produce a trimeric conjugated coloured molecule.
Oxidative Dye Precursors
In general terms, Qxidative dye primary intermediates
include those monomeric materials which, on oxidation, form
oligomers or polymers having extended conjugated systems of
electrons in their molecular structure. Because of the new
electronic structure, the resultant oligomers and polymers
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exhibit a shift in their electronic spectra to the visible
range and appear coloured. For example, oxidative primary
intermediates capable of forming coloured polymers include
materials such as aniline, which has a single functional
group and which, on oxidation, forms a series of conjugated
imines and quinoid dimers, trimers, etc. ranging in colour
from green to black. Compounds such as p-phenylenediamine,
which has two functional groups, are capable of oxidative
polymerization to yield higher molecular weight coloured
materials having extended conjugated electron systems.
Oxidative dyes known in the art can be used in the
compositions according to the present invention. A
representative list of primary intermediates and secondary
couplers suitable for use herein is found in Sagarin,
"Cosmetic Science and Technology"," Interscience, Special
Ed. Vol. 2 pages 308 to 310. It is to be understood that the
primary intermediates detailed below are only by way of
example and are not intended to limit the compositions and
processes herein.
The typical aromatic diamines, polyhydric phenols,
amino phenols, and derivatives thereof, described above as
primary intermediates can also have additional substituents
on the aromatic ring, e.g. halogen, aldehyde, carboxylic
acid, nitro, sulfonic acid and substituted and unsubstituted
hydrocarbon groups, as well as additional substituents on
the amino nitrogen and on the phenolic oxygen, e.g.
substituted and unsubstituted alkyl and aryl groups.
Examples of suitable aromatic diamines, amino phenols,
polyhydric phenols and derivatives thereof, respectively,
are compounds havin.g the general formulas (I), (II) and
(III) below:
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Rl-N-R2
ITNR3R4
1( R5
OR
Rl N-R2
TN-R3R4 HX
Y R5
wherein Y is hydrogen, halogen, (e.g. fluorine, chlorine,
bromine or iodine), nitro, amino, hydroxyl,
O
11
-CH
-COOM or -SO3M (where M is hydrogen or an alkali or alkaline
earth metal, ammonium, or substituted ammonium wherein one
or more hydrogens on the ammonium ion is replaced with a 1
to 3 carbon atom alkyl or hydroxyalkyl radical), wherein Rl,
R2, R3 and R4 are the same or different from each other and
are selected from the group consisting of hydrogen, CZ to C4
alkyl or alkenyl and C6 to Cg aryl, alkaryl or aralkyl, and
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R5 is hydrogen, Cl to C4 unsubstituted or substituted alkyl
or alkenyl wherein the substituents are selected from those
designated as Y,= above, or C6 to Cg unsubstituted or
substituted aryl, alkaryl or aralkyl wherein the
substituents are selected from those defined as Y, above.
Since the precursors of formula (I) are amines, they can be
used herein in the form of peroxide-compatible salts,, as
noted, wherein X represents peroxide-compatible anions of
the type herein before detailed. The general formula of the
salt indicated is to be understood to encompass those salts
having mono-, di-, and tri-negative anions.
Specific examples of formula (I) compounds are: o-
phenylenediamine, m-phenylenediamine, p-phenylenediamine, 2-
chloro-p-phenylenediamine, 2-iodo-p-phenylenediamine, 4-
nitro-o-phenylenediamine, 2-nitro-p-phenylenediamine, 1,3,5-
triaminobenzene, 2-hydroxy-p-phenylenediamine, 2,4-
diaminobenzoic acid, sodium 2,4-diaminobenzoate, calcium di-
2,4-diaminobenzoate, ammonium 2,4-diaminobenzoate,
trimethylammonium 2,4-, diaminobenzoate, tri-(2-
hydroxyethyl)ammonium 2,4-diaminobenzoate,' 2,4-
diaminobenzaldehyde carbonate, 2,4-diaminobenzensulfonic
acid, potassium 2,4-diaminobenzenesulfonate, N,N-
diisopropyl-p-, phenylenediamine bicarbonate, N,N-dimethyl-
p-phenylenediamine, N-ethyl-N'-(2-propenyl)-p-
phenylenediamine, N-phenyl-p-phenylenediamine, N-phenyl-N-
benzyl-p-phenylenediamine, N-ethyl-N'-(3-ethylphenyl)-p-
phenylenediamine, 2,4-toluenediamine, 2-ethyl-p-
phenylenediamine, 2-(2-bromoethyl)-p-phenylenediamine, 2-
phenyl-p-phenylenediamine laurate, 4-(2,5-
diaminophenyl)benzaldehyde, 2-benzyl-p-phenylenediamine
acetate, 2-(4-nitrobenzyl)-p-phenylenediamine, 2-(4-
methylphenyl)-p-phenylenediamine, 2-(2,5-diaminophenyl)-5-
methylbenzoic acid, methoxyparaphenylenediamine, dimethyl-p-
phenylenediamine, 2,5-dimethylpara-phenylenediamine, 2-
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methyl-5-methoxy-para-phenylenediamine, 2,6-methyl-5-
methoxy-para-phenylenediamine, 3-methyl-4-amino-N,N-
diethylaniline, N,N-bis(S-hydroxyethyl)-para-
phenylenediamine, 3-methyl-4-amino-N,N-bis(S-
hydroxyethyl)aniline, 3-chloro-4-amino-N,N-bis(i3-
hydroxyethyl)aniline, 4-amino-N-ethyl-N-
(carbamethyl)aniline, 3-methyl-4-amino-N-ethyl-N-
(carbamethyl)aniline, 4-amino-N-ethyl-(S-
piperidonoethyl)aniline, 3-methyl-4-amino-N-ethyl-(i3-
piperidonoethyl)aniline, 4-amino-N-ethyl-N-(f3-
morpholinoethyl)aniline, 3-methyl-4-amino-N-ethyl-N-(i3-
morpholinoethyl)aniline, 4-amino-N-ethyl-N-(i3-
acetylaminoethyl)aniline, 4-amino-N-(i3-methoxyethyl)
aniline, 3-methyl-4-amino-N-ethyl-N-(Z-acetylaminoethyl)
aniline, 4-amino-N-ethyl-N-(9-mesylaminoethyl) aniline, 3-
methyl-4-amino-N-ethyl-N-(Z-mesylaminoethyl) aniline, 4-
amino-N-ethyl-N-(S-sulphoethyl) aniline, 3-methyl-4-amino-N-
ethyl-N-(i3-sulphoethyl) aniline, N-(4-amino-
phenyl)morpholine, N-(4-aminophenyl)piperidine, 2,3-
dimethyl-p-phenylenediamine, isopropyl-p-phenylene-diamine,
N,N-bis-(.2-hydroxyethyl)-p-phenylenediamine sulphate.
Compounds having the general structure (II) are as
follows:
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?R6
/
R5 l` \J N R1 R2
1 (TTl
Y
OR
R6
R N' R1 R2 HX
Y
where X and Y are the same as in formula (I), R1 and R2 can
be the same or different from each other and are the same as
in formula (I), R5 is the same as in formula (I) and R6 is
hydrogen or Cl to C4 substituted or unsubstituted alkyl or
alkenyl wherein the substituents are selected from those
defined as Y in formula (I).
Specific examples of formula (II) compounds are:
o-aminophenol, m-aminophenol, p-aminophenol, 2-iodo-p-
aminophenol, 2-nitro-p-aminophenol, 3,4-dihydroxy-aniline,
3,4-diaminophenol, chloroacetate, 2-hydroxy-4-aminobenzoic
acid, 2-hydroxy-4-aminobenzaldehyde, 3-amino-4-
hydroxybenzenesulfonic acid, N,N-diisopropyl-p-aminophenol,
N-methyl-N-(1-propenyl)-p-aminophenol, N-phenyl-N-benzyl-p-
aminophenol sulphate, N-methyl-N-(3-ethylphenyl)-p-
aminophenol, 2-nitro-5-ethyl-p-amino-phenol, 2-nitro-5-(2-
bromoethyl)-p-aminophenol, (2-hydroxy-5-
aminophenyl)acetaldehyde, 2-methyl-p-amino-phenol, (2-
hydroxy-5-aminophenyl)acetic acid, 3-(2-hydroxy-5-
aminophenyl)-1-propene, 3-(2-hydroxy-5-aminophenyl)-2-
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chloro-l-propene, 2-phenyl-p-aminophenol palmitate, 2-(4-
nitrophenyl)-p-aminophenol, 2-benzyl-p-aminophenol, 2-(4-
chlorobenzyl-p-aminophenol perchlorate, 2-(4-methylphenyl)-
p-aminophenol, 2-(2-amino-4-methylphenyl)-p-aminophenol, p-
methoxyaniline, 2-bromoethyl-4-aminophenyl ether phosphate,
2-nitroethyl-4-aminophenyl ether bromide, 2-aminoethyl-4-
aminophenyl ether , 2-hydroxyethyl-4-aminophenyl ether, (4-
aminophenoxy)acetaldehyde, (4-aminophenoxy) acetic acid, (4-
aminophenoxy)methanesulfonic acid, 1-propenyl-4-aminophenyl
ether isobutyrate, (2-chloro)-1-propenyl-4-aminophenyl
ether, (2 -nitro) -1-propenyl-4-aminophenyl ether, (2-amino)-
propenyl-4-aminophenyl ether, (2-hydroxy)-1-propenyl-4-
aminophenyl ether, N-methyl-p-aminophenol, 3-methyl-4-
aminophenol, 2-chloro-4-aminophenol, 3-chloro-4-aminophenol,
2,6-dimethyl-4-aminophenol, 3,5-dimethyl-4-aminophenol, 2,3-
dimethyl-4-aminophenol, 2,5-dimethyl-4-aminophenol, 2-
hydroxymethyl
-4-aminophenol, 3-hydroxymethyl-4-aminophenol, 2,6-dichloro-
4-aminophenol, 2,6-dibromo-4-aminophenol and 2-bromo-4-
aminophenol.
R6
R5 I-OR6 (TTi)
Y
Specific examples of formula (III) compounds are:
o-hydroxyphenol (catechol), m-hydroxyphenol (resorcinol), p-
hydroxyphenol (hydroquinone), 4-methoxyphenol, 2-
methoxyphenol, 4-(2-chloroethoxy) phenol, 4-(2-propenoxy)
phenol, 4-(3-chloro-2-propenoxy) phenol, 2-chloro-4-
hydroxyphenol (2-chlorohydroquinone), 2-nitro-4-
hydroxyphenol(2-nitrohydroquinone), 2-amino-4-hydroxyphenol,
1,2,3-trihydroxybenzene (pyrogallol), 2,4-
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dihydroxybenzaldehyde, 3,4-dihydoxybenzoic acid, 2,4-
dihydroxybenzenesulfonic acid, 3-ethyl-4-hydroxyphenol, 3-
(2-nitroethyl)-4-hydroxyphenol, 3-(2-propenyl)-4-
hydroxyphenol, 3-(3-chloro-2-propenyl)-4-hydroxyphenol, 2-
phenyl-4-hydroxyphenol, 2-(4-chlorophenyl)-4-hydroxyphenol,
2-benzyl-4-hydroxyphenol, 2-(2-nitrophenyl)-4-hydroxyphenol,
2-(2-methylphenyl)-4-hydroxyphenol, 2-(2-methyl-4-
chlorophenyl)-4-hydroxyphenol, 3-methoxy-4-hydroxy-
benzaldehyde, 2-methoxy-4-(l-propenyl)phenol, 4-hydroxy-3-
methoxy-cinnamic acid, 2,5-dimethoxyaniline, 2-
methylresorcinol, alpha napthol and salts thereof. Secondary
coupling compounds which are suitable for inclusion in the
colouring compositions and processes herein before described
include certain aromatic amines and phenols and derivatives
thereof which do not produce colour singly, but which modify
the colour, shade or intensity of the colours developed by
the primary oxidised dye intermediates. Certain aromatic
amines and phenolic compounds, and derivatives thereof,
including some aromatic diamines and polyhydric phenols of
the types described by formulasl (I), (Ia), (Ib), (II) and
( I I I) above, but which are well known in the art not to be
suitable primary intermediates, are suitable as couplers
herein. Polyhydric alcohols are also suitable for use as
couplers herein.
The aromatic amines and phenols and derivatives
described above as couplers can also have additional
substituents on the aromatic ring, e.g., halogen, aldehyde,
carboxylic acid, nitro, sulfonyl and substituted and
unsubstituted by hydrocarbon groups, as well as additional
substituents on the amino nitrogen, or phenolic oxygen, e.g.
substituted and unsubstituted alkyl and aryl groups. Again,
peroxide-compatible salts thereof are suitable for use
herein.
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Examples of aromatic amines, phenols and derivatives
thereof are compounds of the general formulas (IV) and (V)
below:
Rl - N-R2
R7-I - -Z (T(Il
OR
RlN-R2
R7-I = -Z HX
wherein Z is hydrogen, C1 and C3 alkyl, halogen (e.g.
fluorine, chlorine, bromine or iodine) nitro,
O
11
-CH
-COOM or SO3M, (where M is hydrogen or an alkali or alkaline
earth metal, ammonium or substituted ammonium wherein one or
more hydrogen atoms on the ammonium ion is replaced with 1
to 3 carbon atom alkyl or hydroxyalkyl radical), wherein R1
and R2 are the same or different and are selected from the
group consisting of hydrogen, C1 to C4 alkyl or alkenyl and
C6 to Cg aryl, alkaryl or aralkyl and R7 is hydrogen, C1 to
C4 unsubstituted or substituted alkyl or alkenyl wherein the
substituents are selected from those designated as Z above
or C6 to C9 unsubstituted or substituted aryl, alkaryl or
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aralkyl wherein the substituents are selected from those
defined as Z above and wherein X is as defined in formula
(I) =
Specific examples of formula (IV) compounds are:
aniline, p-chloroaniline, p-fluoroaniline, p-nitroaniline,
p-aminobenzaldehyde, p-aminobenzoic acid, sodium-p-
aminobenzoate, lithium-p-aminobenzoate, calcium di-p-
aminobenzoate, ammonium-p-aminobenzoate, trimethylammonium-
p-aminobenzoate, tri(2-hydroxyethyl)-p-aminobenzoate, p-
aminobenzenesulfonic acid, potassium p-
aminobenzenesulfonate, N-methylaniline, N-propyl-N-
phenylaniline, N-methyl-N-2-propenylaniline, N-
benzylaniline, N-(2-ethylphenyl)aniline, 4-methylaniline, 4-
(2-bromoethyl) aniline, 2- (2-nitroethyl) aniline, (4-
aminophenyl)acetaldehyde, (4-aminophenyl) acetic acid, 4-(2-
propenyl) aniline acetate, 4- (3-bromo-2-propenyl) aniline, 4-
phenylaniline chloroacetate, 4- (3-chlorophenyl) aniline, 4-
benzylaniline, 4-(4-iodobenzyl)aniline, 4-(3-
ethylphenyl)aniline, 4-(2-chloro-4-ethylphenyl)aniline.
P8
R7 I'Z
wherein Z and R7 are defined as in formula (IV) and R8 is
hydrogen or Cl to C4 substituted or unsubstituted alkyl or
alkenyl wherein the substituents are selected from those
defined as Z in formula (IV).
Specific examples of formula (V) compounds are:
phenol, p-chlorophenol, p-nitrophenol, p-
hydroxybenzaldehyde, p-hydroxybenzoic acid, p-
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hydroxybenzenesulfonic acid, ethylphenyl ether, 2-
chloroethylphenyl ether, 2-nitroethylphenyl ether,
phenoxyacetaldehyde, phenoxyacetic acid, 3-phenoxy-l-
propene, 3-phenoxy-2-nitro-l-propene, 3-phenoxy-2-bromo-l-
propene, 4-propylphenol, 4-(3-bromopropyl)phenol, 2-(2-
nitroethyl)phenol, (4-hydroxyphenyl)acetaldehyde, (4-
hydroxyphenyl)acetic acid, 4-(2-propenyl)phenol, 4-
phenylphenol, 4-benzylphenol, 4-(3-fluoro-2-propenyl)phenol,
4-(4-chlorobenzyl)phenol, 4-(3-ethylphenyl)phenol, 4-(2-
chloro-3-ethylphenyl)phenol, 2,5-xylenol, 2,5-
diaminopyridine, 2-hydroxy-5-aminopyridine, 2-amino-3-
hydroxy pyridine, tetraaminopyrimindine, 1,2,4-
trihydroxybenzene, 1,2,4-trihydroxy-5-(C1-C6-alkyl)benzene,
1,2,3-trihydroxybenzene, 4-aminoresorcinol, 1,2-
dihydroxybenzene, 2-amino-1,4-dihydroxybenzene, 2-amino-4-
methoxy-phenol, 2,4-diaminophenol, 3-methoxy-l,2-dihydroxy-
benzene, 1,4-dihydroxy-2-(N,N-diethylamino)-benzene, 2,5-
diamino-4-methoxy-l-hydroxybenzene, 4,6-dimethoxy-3-amino-l-
hydroxybenzene, 2,6-dimethyl-4-[N-(p-hydroxyphenyl)amino]-1-
hydroxybenzene, 1,5-diamino-2-methyl-4-[N-(p-
hydroxyphenyl)amino]benzene and salts thereof.
Additional primary intermediates suitable for use
herein include catechol species and in particular catechol
"dopa" species which includes dopa itself as well as
homologs, analogs and derivatives of DOPA. Examples of
suitable cachetol species include cysteinyl dopa, alpha
alkyl dopa having 1 to 4 , preferably 1 to 2 carbon atoms in
the alkyl group, epinephrine and dopa alkyl esters having 1
to 6 , preferably 1 to 2 carbon atoms in the alkyl group.
In general suitable catechols are represented by
formula (VI) below:
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Rr~~ OH
R2 L I fVTI
.
R3 OH
wherein Rl, R2 and R3, which may be the same or different,
are electron donor or acceptor substituents selected from
H, lower (C1-C6) alkyl, OH, OR, COOR, NHCOR, CN, COOH,
Halogen, NO2, CF3, SO3H or NR4R5, with the proviso that only
one of the Rl, R2 or R3 can be CN, COOH, halogen, NO2, CF3
or SO3H: R4 and R5, which may be the same or different, are
H, lower (Cl-C6) alkyl or substituted lower (C1-C6) alkyl in
which the substituent may be OH, OR, NHCOR6, NHCONH2, NHCO2R
6, NHCSNH2, CN, COOH, SO3H, SO2NR6, SO2R6 or CO2R6; R6 is
lower (C1-C6) alkyl, lower (CZ-C6) hydroxyalkyl phenyl
linked to the nitrogen by an alkylene chain, phenyl or
substituted phenyl with the substituent defined as R1, and R
is C2-C6 alkyl or Cl-C6 hydroxyalkyl.
Also included herein are oxidative hair colouring
agents of the formula:
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O O
Rj'~~ N, R
H
wherein: Rl = substituted or unsubstituted benzene ring,
tertiary-butyl, etc.; R = substituted or unsubstituted
benzene ring and the formula:
R
0 N
I
RJ
wherein R = aminoalkyl, amidoalkyl, aminobenzene
(substituted or unsubstituted), amidobenzene (substituted or
unsubstituted), alkyl, substituted or unsubstituted benzene
ring ; Ri = substituted or unsubstituted benzene ring.
The primary intermediates can be used herein alone or
in combination with other primary intermediates, and one or
more can be used in combination with one or more couplers.
The choice of primary intermediates and couplers will be
determined by the colour, shade and intensity of coloration
which is desired. There are nineteen preferred primary
intermediates and couplers which can be used herein, singly
or in combination, to provide dyes having a variety of
shades ranging from ash blonde to black; these are:
pyrogallol, resorcinol, p-toluenediamine, p-
phenylenediamine, o-phenylenediamine, m-phenylenediamine, o-
aminophenol, p-aminophenol, 4-amino-2-nitrophenol, nitro-p-
phenylenediamine, N-phenyl-p-phenylenediamine, m-
aminophenol, 2-amino-3-hydroxypyridine, l-napthol, N,N bis
(2-hydroxyethyl)p-phenylenediamine,. 4-amino-2-
hydroxytoluene, 1,5-dihydroxynapthalene, 2-methyl resorcinol
and 2,4-diaminoanisole. These can be used in the molecular
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form or in the form of peroxide-compatible salts, as
detailed above.
For example low intensity colours such as natural blond
to light brown hair shades generally comprise from about
0.001o to about 5%, preferably from about 0.1% to about 20,
more preferably from about 0.2% to about lo by weight of
colouring composition of total oxidative dyeing agents and
may be achieved by the combination of primary intermediates
such as 1,4-diamino-benzene, 2,5-diamino toluene, 2,5-
diamino-anisole, 4-aminophenol, 2,5-diamino-benzyl alcohol
and 2-(2',5'-diamino)phenyl-ethanol with couplers such as
resorcinol, 2-methyl resorcinol or 4-chloro resorcinol.
Similarly combination of the above primary
intermediates with couplers, such as, 5-amino-2-methyl
phenol and 1,3-diamino-benzene derivatives such as 2,4-
diamino-anisole at levels of from about 0.5% to about 1% of
total dyeing agents can lead to medium intensity red
colours. High intensity colours such as blue to blue-violet
hair shades can be produced by the combination of the above
primary intermediates with couplers such as 1,3-diamino-
benzene or its derivatives such as 2,5-diamino-toluene at
levels of from about 1% to about 6% by weight of composition
of total dyeing agents. Black hair colours can be obtained
by combining the aforementioned primary intermediates with
couplers such as 1,3-diaminobenzene or its derivatives.
Non-oxidative and other hair colouring agents
The hair colouring compositions of the present
invention may, in addition to or instead of an oxidative
hair colouring agent, include non-oxidative and other dye
materials. Optional non-oxidative and other dyes suitable
for use in the hair colouring compositions and processes
according to the present invention include both semi-
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permanent, temporary and other dyes. Non-oxidative dyes as
defined herein include the so-called 'direct action dyes',
metallic dyes, metal chelate dyes, fibre reactive dyes and
other synthetic and natural dyes. Various types of non-
oxidative dyes are detailed in: 'Chemical and Physical
Behaviour of Human Hair' 3rd Ed. by Clarence Robbins (pp250-
259); 'The Chemistry and Manufacture of Cosmetics'. Volume
IV. 2nd Ed. Maison G. De Navarre at chapter 45 by G.S. Kass
(pp841-920); 'cosmetics: Science and Technology' 2nd Ed.,
Vol. II Balsam Sagarin, Chapter 23 by F.E. Wall (pp 279-
343); 'The Science of Hair Care' edited by C. Zviak, Chapter
7 (pp 235-261) and .'Hair Dyes', J.C. Johnson, Noyes Data
Corp., Park Ridge, U.S.A. (1973), (pp 3-91 and 113-139).
Direct action dyes which do not require an oxidative
effect in order to develop the colour, are also designated
hair tints and have long been known in the art. They are
usually applied to the hair in a base matrix which includes
surfactant material. Direct action dyes include nitro dyes
such as the derivatives of nitroamino benzene or
nitroaminophenol; disperse dyes such as nitroaryl amines,
aminoanthraquinones or azo dyes; anthraquinone dyes,
naphthoquinone dyes; basic dyes such as Acridine Orange C.I.
46005. In the case of direct dyes, these are preferably used
in combination with an oxidative hair colouring agent in the
compositions herein.
Nitrodyes are added to dyeing compositions to enhance
colour of colorant and to add suitable aesthetic colour to
the dye mixture prior to application. Further examples of
direct action dyes include the Arianor dyes basic brown 17,
C.I.(colour index) - no. 12,251; basic red 76, C.I. -
12,245; basic brown 16, C.I. - 12,250; basic yellow 57, C.I.
- 12,719 and basic blue 99, C.I. - 56,059 and further direct
action dyes such as acid yellow 1, C.I. - 10,316 (D&C yellow
no.7); acid yellow 9, C.I. - 13,015; basic violet C.I. -
CA 02428173 2003-05-05
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45,170; disperse yellow 3, C.I. - 11,855; basic yellow 57,
C.I. - 12,719; disperse yellow 1, C.I. - 10,345; basic
violet 1, C.I. - 42,535, basic violet 3, C.I. - 42,555;
greenish blue, C.I. - 42090 (FD&C Blue no.1); yellowish red,
C.I.-14700 (FD&C red no.4); yellow, C.I.19140 (FD&C yellow
no5); yellowish orange, C.I.15985 (FD&C yellow no.6); bluish
green, C.I.42053 (FD&C green no.3); yellowish red, C.I.16035
(FD&C red no.40) ; bluish green, C.I.61570 (D&C green no.3) ;
orange, C.I.45370 (D&C orange no.5); red, C.I.15850 (D&C red
no.6); bluish red, C.I.15850(D&C red no.7); slight bluish
red, C.I.45380(D&C red no.22); bluish red, C.I.45410(D&C
red no.28); bluish red, C.I.73360(D&C red no.30); reddish
purple, C.I.17200(D&C red no.33); dirty blue red,
C.I.15880(D&C red no.34); bright yellow red, C.I.12085(D&C
red no.36); bright orange, C.I.15510(D&C orange no.4);
greenish yellow, C.I.47005(D&C yellow no.10); bluish green,
C.I.59040(D&C green no.8); bluish violet, C.I.60730(Ext. D&C
violet no.2); greenish yellow, C.I.10316(Ext. D&C yellow
no.7).
Fibre reactive dyes include the Procion (RTM),
Drimarene (RTM), Cibacron (RTM), Levafix (RTM) and Remazol
(RTM) dyes available from ICI, Sandoz, Ciba-Geigy, Bayer and
Hoechst respectively.
Natural dyes and vegetable dyes as defined herein
include henna (Lawsonia alba), camomile (Matricaria
chamomila or Anthemis nobilis), indigo, logwood and walnut
hull extract.
Temporary hair dyes, or hair colouring rinses, are
generally comprised of dye molecules which are too large to
diffuse into the hair shaft and which act on the exterior of
the hair. They are usually-applied via a leave-in procedure
in which the dye solution is allowed to dry on the hair
surface. As such these dyes are typically less resistant to
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the effects of washing and cleaning the hair with surface
active agents and are washed off of the hair with relative
ease. Any temporary hair dye may suitably be used in the
compositions of the invention and examples of preferred
temporary hair dyes are illustrated below. Temporary dyes
are preferably used together with an oxidative colouring
agent in the composition herein.
N CH3 H NH2
N=N
SO CH
3 3 S03CH3
O OH
Violet Red
SO3H CH3
N=N &S03CH3
S03H
O OH
Yellow Blue-Violet
Semi-permanent hair dyes are dyes which are generally
smaller in size and effect to temporary hair rinses but are
generally larger than permanent (oxidative) dyes. Typically,
semi-permanent dyes act in a similar manner to oxidative
dyes in that they have the potential to diffuse into the
hair shaft. However, semi-permanent dyes are generally
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smaller in size than the aforementioned conjugated oxidative
dye molecules and as such are pre-disposed to gradual
diffusion out of the hair again. Simple hair washing and
cleaning action will encourage this process and in general
semi-permanent dyes are largely washed out of the hair after
about 5 to 8 washes. Any semi-permanent dye system may be
suitably used in the compositions of the present invention.
Suitable semi-permanent dyes for use in the compositions of
the present invention are HC Blue 2, HC Yellow 4, HC Red 3,
Disperse Violet 4, Disperse Black 9, HC Blue 7, HC Yellow 2,
Disperse Blue 3, Disperse violet 1 and mixtures thereof.
Examples of semi-permanent dyes are illustrated below:
H, N'C2H4OH *HN N02 NH 2
(C2H4OH)2 0 NH2
N
BlueBlue
H
NH2 N-N
NH2 N(C2H40H)2
NH2
YellowYellow
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H~,' N'C2H4OH NO 2 H
NO2
\ I \ \
NH2
NO2
RedRed
Typical semi-permanent dye systems incorporate mixtures
of both large and small colour molecules. As the size of the
hair is not uniform from root to tip the small molecules
will diffuse both at the root and tip, but will not be
retained within the tip, while the larger molecules will be
generally only be able to diffuse into the ends of the hair.
This combination of dye molecule size is used to help give
consistent colour results from the root to the tip of the
hair both during the initial dyeing process and during
subsequent washing.
Oxidising Agents
The hair colouring compositions herein preferably
comprise at least one oxidising agent, which may be an
inorganic or organic oxidising agent. The oxidising agent is
preferably present in the colouring composition at a level
of from about 0.01o to about 10%, preferably from about
0.01% to about 6%, more preferably from about 1% to about 4%
by weight of the composition.
Inorganic Oxidising Agents
A preferred oxidising agent for use herein is an
inorganic peroxygen oxidising agent. The inorganic peroxygen
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oxidising agent should be safe and effective for use,in the
compositions herein. Preferably, ' the inorganic peroxygen
oxidising agents suitable for use herein will be soluble in
the compositions according'to the present invention when in
liquid form or in the form intended to be used. Preferably,
inorganic peroxygen oxidising agents suitable for use herein
will be water-soluble. Water soluble oxidising agents as
defined herein means agents which have a solubility to the
extent of about 10g in 1000ml of deionised water at 25 C
("Chemistry" C. E. Mortimer. 5th Edn. p277).
The inorganic peroxygen oxidising agents useful herein
are generally inorganic peroxygen materials capable of
yielding peroxide in an aqueous solution. Inorganic
peroxygen oxidising agents are well known in the art and
include hydrogen peroxide, inorganic alkali metal peroxides
such as sodium periodate, sodium perbromate and sodium
peroxide, and inorganic perhydrate salt oxidising compounds,
such as the alkali metal salts of perborates, percarbonates,
perphosphates, persilicates, persulphates and the like.
These inorganic perhydrate salts may be incorporated as
monohydrates, tetrahydrates etc. Mixtures of two or more of
such inorganic peroxygen oxidising agents can be used if
desired. While alkali metal bromates and iodates are
suitable for use herein the bromates are preferred. Highly
preferred for use in the compositions according to the
present invention is hydrogen peroxide.
In preferred colouring compositions herein the
inorganic peroxygen oxidising agent is present at a level of
from about 0.01% to less than about 6%, preferably from
about 0.01% to about 4%, more preferably from about 1% to
about 4%, more preferably from about 2% to about 3% by
weight of the total composition on hair.
Preformed organic peroxyacid
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The compositions herein may instead or in addition to
the inorganic peroxygen oxidising agent(s), comprise one or
more preformed organic peroxyacid oxidising agents.
Suitable organic peroxyacid oxidising agents for use in
the colouring compositions according to the present
invention have the general formula:
R - C (0) OOH
wherein R is selected from saturated or unsaturated,
substituted or unsubstituted, straight or branched chain,
alkyl, aryl or alkaryl groups with from 1 to 14 carbon
atoms.
A class of organic peroxyacid compounds suitable for
use herein are the amide substituted compounds of the
following general formulae:
-`R2 ~(-OOH
Rl -II -NI II
O R5 0
or
1
Rl N-F RZ ~-OOH
R5 O0
wherein R1 is, a saturated or unsaturated alkyl or alkaryl
group, or an aryl group, having from 1 to 14 carbon atoms, R
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2 is, a saturated or unsaturated alkyl or alkaryl group, or
an aryl group, having from 1 to 14 carbon atoms, and R5 is H
or, a saturated or unsaturated alkyl or alkaryl group, or an
aryl group, having` from 1 to 10 carbon atoms. Amide
substituted organic peroxyacid compounds of this type are
described in EP-A-0,170,386.
Other suitable organic peroxyacid oxidising agents
include peracetic, pernanoic, nonylamidoperoxycaproic acid
(NAPCA), perbenzoic, m-chloroperbenzoic, di-peroxy-
isophthalic, mono-peroxyphthalic, peroxylauric,
hexanesulphonyl peroxy propionic, N,N-phthaloylamino
peroxycaproic, monoper succinic, nonanoyloxybenzoic,
dodecanedioyl-monoperoxybenzoic, nonylamide of peroxyadipic
acid, diacyl and tetraacylperoxides, especially
diperoxydodecanedioic acid, diperoxytetradecanedioic acid
and diperoxyhexadecanedioic acid and derivatives thereof.
Mono- and diperazelaic acid, mono- and diperbrassylic acid
and N-phthaloylaminoperoxicaproic acid and derivatives
thereof are also suitable for use herein.
The preformed organic peroxyacid oxidising agents
should be safe and effective for use in the compositions
herein. Preferably, the preformed organic peroxyacid
oxidising agents suitable for use herein will be soluble in
the compositions used according to the present invention
when in liquid form and in the form intended to be used.
Preferably, organic peroxyacid oxidising agents suitable for
use herein will be water-soluble. Water-soluble preformed
organic peroxyacid oxidising agents as defined herein means
agents which have a solubility to the extent of about lOg in
1000m1 of deionised water at 25 C ("Chemistry" C. E.
Mortimer. 5th Edn. p277).
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The preferred peroxyacid materials suitable for use
herein are selected from peracetic and pernanoic acids and
mixtures thereof.
The preformed organic peroxyacid oxidising agent, where
present, is,preferably present at a level of from about
0.01% to about 8%, more preferably from about 0.1% to about
6%, most preferably from about 0.2% to about 4%, and
especially from about 0.3% to about 3% by weight of the hair
colouring composition.
When both an inorganic peroxygen oxidising agent and a
preformed organic peroxy acid are present in the
compositions herein, the weight ratio of the inorganic
peroxygen oxidising agent to the preformed organic peroxy
acid is preferably in the range of from about 0.0125:1 to
about 500:1, more preferably from about 0.0125:1 to about
50:1. In addition to the inorganic peroxygen oxidising
agents and the preformed organic peroxyacid oxidising agents
suitable for use herein, the compositions according to the
present invention may optionally comprise additional organic
peroxides such as urea peroxide, melamine peroxide and
mixtures thereof. The level of organic peroxide, where
present, is from about 0.01% to about 30, preferably from
about 0.01% to about 2%, more preferably from about 0.1% to
about 1.5% and most preferably from about 0.2% to about 1%
by weight of composition.
Conditioning Agent
The hair care composition according to the present
invention preferably comprises at least one hair
conditioning agent in addition to the aminofunctional
polysiloxane. The conditioning agent herein can be any
conditioning agent suitable for use in conditioning hair.
33
CA 02428173 2006-10-30
The incorporation of an additional conditioning'agent can
further improve the condition of the hair.
The conditioning agent is preferably present at a level
of from about 0.1% to about 25%, preferably from about 1% to
about 20%, more preferably from about 5% to about 20* and
especially from about 5% to about 15%, by weight of the
composition.
Suitable conditioning agents for use herein include,
but are not limited to, cationic surfactants, cationic
polymers, insoluble silicones, non-volatile hydrocarbons,
saturated C14-C22 straight chain fatty alcohols, non-
volatile hydrocarbon esters, and mixtures thereof. Other
suitable conditioning agents are disclosed in WO95/20939 and
W096/32919.
Preferred conditioning agents for use herein include
cationic surfactants, cationic polymers, insoluble silicone
conditioning agents and saturated C14-C22 straight chain
fatty alcohols and mixtures thereof. Especially preferred
for use herein is a mixture of cationic polymer, non-
volatile silicone and C14-C22 straight chain fatty alcohols.
When present, the insoluble silicone conditioning
agents are present at a level of from about 0.1 to 10%,
preferably from about 0.1% to about 5%, more preferably from
about 1* to about 3* by weight of composition. Suitable
insoluble silicones include polyalkyl siloxanes, polyaryl
siloxanes, polyalkylaryl siloxanes, polether siloxane
copolymers, and mixtures thereof. The silicone conditioning
agent will preferably be non-volatile. As used herein the
term "non-volatile" shall mean that the material' has a
boiling point of at least about 260 C, preferably at least
about 275 C, more preferably at least about 300 C. Such
materials exhibit very low or no significant vapour pressure
34
CA 02428173 2006-10-30
at ambient conditions. The term "silicone fluid" shall mean
flowable silicone materials having a viscosity of less than
1,000,000 centistokes at 25 C. The term "silicone gum" shall
mean flowable silicone materials having a viscosity of
1,000,000 centistokes at 25 C or greater. The viscosity can
be measured by a glass capillary viscometer as in Dow
Corning Corporate Test Method CTM0004, July 20, 1920, or
equivalent.
A preferred silicone material for use herein is a
polydimethyl siloxane. These silicones are available for
example from the General Electric Company in their Viscasil
and SF96 series, and from Dow Corning in their Dow Corning
200 series. -
Other suitable insoluble silicones for use herein are
disclosed in W096/32919.
When present, the cationic polymers are present at a
level of from about 0.1 to 10%, preferably from about 0.1%
to about 5%, more preferably from about i% to about 3% by
weight of composition. Suitable cationic polymers for use
herein are disclosed in W096/32919.
When present, the fatty alcohols are present at a level
of from about from about 0.1% to about 20%, preferably from
about 1% to about 15% and more preferably from about 3% to
about 10% by weight of composition. Preferred fatty alcohols
for use herein are cetyl alcohol and stearyl alcohol and
mixtures thereof.
The colouring compositions used in the methods of the
present invention can be formulated over a wide pH range,
e.g. from about 2 to about 13, but the compositions are
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formulated at high pH, preferably in a pH range of from
about 8 to about 12, more preferably from about 9 to about
11, most preferably from about 9.5 to 10.5.
The compositions may contain one or more optional
buffering agents and/or hair swelling agents (HSAs).
Several different pH modifiers can be used to adjust the pH
of the final composition or any constituent part thereof.
However, preferred compositions herein are substantially
free of additional buffering agents, buffering agents and
hair swelling agents, i.e. they comprise less than about 1%,
preferably less than about 0.5%, more preferably less than
about 0.1% by weight of such agents.
This pH adjustment can be effected by using well known
acidifying agents in the field of treating keratinous
fibres, and in particular human hair, such as inorganic and
organic acids such as hydrochloric acid, tartaric acid,
citric acid, succinic acid, phosphoric acid and carboxylic
or sulphonic acids such as ascorbic acid, acetic acid,
lactic acid, sulphuric acid, formic acid, ammonium sulphate
and sodium dihydrogenphosphate /phosphoric acid, disodium
hydrogenphosphate /phosphoric acid, potassium chloride
/hydrochloric acid, potassium dihydrogen phthalate/
hydrochloric acid, sodium citrate / hydrochloric acid,
potassium dihydrogen citrate /hydrochloric acid, potassium
dihydrogencitrate/ citric acid, sodium citrate / citric
acid, sodium tartarate/ tartaric acid, sodium lactate/
lactic acid, sodium acetate/ acetic acid, disodium
hydrogenphosphate/ citric acid and sodium chloride/ glycine
/ hydrochloric acid, succinic acid and mixtures thereof.
Examples of alkaline buffering agents are ammonium
hydroxide, ethylamine, dipropylamine, triethylamine and
alkanediamines such as 1,3-diaminopropane, anhydrous
alkaline alkanolamines such as, mono or di- ethanolamine,
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preferably those which are completely substituted on the
amine group such as dimethylaminoethanol, polyalkylene
polyamines such as diethylenetriamine or a heterocyclic
amine such as morpholine as well as the hydroxides of alkali
metals, such as sodium and potassium hydroxide, hydroxides
of alkali earth metals, such as magnesium and calcium
hydroxide, basic amino acids such as L-argenine, lysine,
alanine, leucine, iso-leucine, oxylysine and histidine and
alkanolamines such as dimethylaminoethanol and
aminoalkylp ropanediol and mixtures thereof. Also suitable
for use herein are compounds other than ammonium carbonate
or ammonium carbamate that form HC03- by dissociation in
water (hereinafter referred to as 'ion forming compounds').
Examples of suitable ion forming compounds are Na2CO3, NaHCO
3, K2CO3, NH4HCO3, CaCO3 and Ca(HCO3) and mixtures thereof.
The hair colour compositions herein, may, as will be
described later herein, comprise a final composition
containing a hair colouring agent and a conditioning agent
which have been admixed prior to application to the hair or
may comprise a single component system. As such, the
compositions herein may comprise colouring kits of a number
of separate components.
In oxidative colouring kits comprising a portion of
inorganic peroxygen oxidising agent, such as hydrogen
peroxide, which may be present in either solid or liquid
form, a buffering agent solution can be used to stabilise
hydrogen peroxide. Since hydrogen peroxide is stable in the
pH range from 2 to 4, it is preferable to use a buffering
agent having a pH within this range. Dilute acids are
suitable hydrogen peroxide buffering agents.
Catalyst
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CA 02428173 2006-10-30
The compositions herein may optionally contain a
transition metal containing catalyst for the inorganic
peroxygen oxidising agents and the, optional, preformed
peroxy acid oxidising agent(s). Suitable catalysts for use
herein are disclosed in W098/27945.
Heavy metal ion secruestrant
The compositions herein may contain as an optional
component a heavy metal ion sequestrant. By heavy metal ion
sequestrant it is meant herein components which act to
sequester (chelate or scavenge) heavy metal ions. These
components may also have calcium and magnesium chelation
capacity, but preferentially they show selectivity to
binding heavy metal ions such as iron, manganese and copper.
Such sequestering agents are valuable in hair colouring
compositions as herein described for the delivery of
controlled oxidising action as well as for the provision of
good storage stability of the hair colouring products.
Heavy metal ion sequestrants are generally present at a
level of from about 0.005%. to about 20%, preferably from
about 0. 01 % to about 10%, more preferably from about 0.05%
to about 2% by weight of the compositions.
Suitable sequestering agents are disclosed in W098/27945.
Thickeners -
The compositions of the present invention may
additionally include a thickener at a level of from about
0.05% to about 20%, preferably from about 0.1o to about 10%,
more preferably from about 0.5% to about 5% by weight.
Thickening agents suitable for use in the compositions
herein are selected from oleic acid, cetyl alcohol, oleyl
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alcohol, sodium chloride, cetearyl alcohol, stearyl alcohol,
synthetic thickeners such as Carbopol, Aculyn and Acrosyl
and mixtures thereof. Preferred thickeners for use herein
are Aculyn 22 (RTM), steareth-20 methacrylate copolymer;
Aculyn 44 (RTM) polyurethane resin and Acusol 830 (RTM),
acrylates copolymer which are available from Rohm and Haas,
Philadelphia, PA, USA. Additional thickening agents
suitable for use herein include sodium alginate or gum
arabic, or cellulose derivatives, such as methyl cellulose
or the sodium salt of carboxymethylcellulose or acrylic
polymers.
Diluent
Water is the preferred diluent for the compositions
according to the present invention. However, the
compositions according to the present invention may include
one or more solvents as additional diluent materials.
Generally, solvents suitable for use in the colouring
compositions of the present invention are selected to be
miscible with water and innocuous to the skin. Solvents
suitable for use as additional diluents herein include C1-C
20 mono- or polyhydric alcohols and their ethers, glycerine,
with monohydric and dihydric alcohols and their ethers
preferred. In these compounds, alcoholic residues containing
2 to 10 carbon atoms are preferred. Thus, a preferred group
includes ethanol, isopropanol, n-propanol, butanol,
propylene glycol, ethylene glycol monoethyl ether, and
mixtures thereof. Water is the preferred principal diluent
in the compositions according to the present invention.
Principal diluent, as defined herein, means, that the level
of water present is higher than the total level of any other
diluents.
39
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The diluent is present at a level preferably of from
about 5% to about 99.98%, preferably from about 15o to about
99.5%, more preferably at least from about 30% to about 99%,
and especially from about 50% to about 98% by weight of the
compositions herein.
Enzyme
A further additional material useful in the hair
colouring compositions herein is one or more enzymes.
Suitable enzymatic materials include the commercially
available lipases, cutinases, amylases, neutral and alkaline
proteases, esterases, cellulases, pectinases, lactases and
peroxidases conventionally incorporated . into detergent
compositions. Suitable enzymes are discussed in US Patents
3,519,570 and 3,533,139 and in W098/27945.
Surfactant Materials
The compositions herein can additionally contain a
surfactant system. Suitable surfactants for inclusion in the
compositions for use in the invention generally have a
lipophilic chain length of from about 8 to about 22 carbon
atoms and can be selected from anionic, cationic, nonionic,
amphoteric, zwitterionic surfactants and mixtures thereof.
Particularly preferred are cationic, nonionic and mixtures
thereof. Suitable surfactants for use herein are disclosed
in W098/27945.
Particularly preferred surfactants are
surfactants of the general formula
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(R1)n(E1)m
I
N-.,`~/T
(R3)n(E3) m ~E2)m(R2)n
Wherein Rl, R2, and R3 represent either hydrogen or
organic radicals with n equal to 0 or an integer. The
radicals may be saturated, unsaturated or aromatic in nature
with carbon chain lengths of 1 to 24. RI, R2 and R3 may
contain heteroatoms such as, but not limited to, oxygen,
nitrogen and sulphur. El, E2 and E3 represent
polyethyleneoxide moieties with ethyleneoxide sub-units such
that m can be zero or an integer. The degree of ethoxylation
of E1, E2 and E3 can be the same or different. T represents a
hydrogen that, depending on the pH and solvents used in the
system, may or may not be attached to the nitrogen.
For preferred methods herein, it is preferable that the
hair conditioning and colour composition comprises less than
about 20% surfactant, preferably less than about 10%
surfactant. It is also preferable that the hair colour
altering compositions comprise less than about 5% anionic
surfactant .
Optional Materials
A number of additional optional materials can be added
to the compositions herein described each at a level of from
about 0.001o to about 50, preferably from about 0.01% to
about 3%, more preferably from about 0.05% to about 2% by
weight of composition. Such materials include proteins and
polypeptides and derivatives thereof; water-soluble or
solubilizable preservatives such as DMDM Hydantoin, Germall
115, methyl, ethyl, propyl and butyl esters of
hydroxybenzoic acid, EDTA, Euxyl (RTM) K400, natural
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preservatives such as benzyl alcohol, potassium sorbate and
bisabalol, benzoic acid, sodium benzoate and 2-
phenoxyethanol; ~ antioxidants such as sodium sulphite,
hydroquinone, sodium bisulphite, sodium metabisulphite and
thyoglycolic acid, sodium dithionite, erythrobic acid and
other mercaptans; dye removers such as oxalic acid,
sulphated castor oil, salicylic acid and sodium
thiosulphate; H202 stabilisers such as tin compounds such as
sodium stannate, stannic hydroxide and stannous octoate,
acetanilide, phenacetin colloidal silica such as magnesium
silicate, oxyquinoline sulphate, sodium phosphate, and
tetrasodium pyrophosphate; and p-hydroxybenzoates;
moisturising agents such as hyaluronic acid, chitin, and
starch-grafted sodium polyacrylates such as Sanwet (RTM) IM-
1000, IM-1500 and IM-2500 available from Celanese
Superabsorbent Materials, Portsmith, VA, USA and described
in US-A-4,076,663 as well as methyl cellulose, starch,
higher fatty alcohols, paraffin oils, fatty acids and the
like; solvents; anti-bacterial agents such as Oxeco (phenoxy
isopropanol); low temperature phase modifiers such as
ammonium ion sources (e.g. NH4 Cl); viscosity control agents
such as magi~esium sulfate and other,electrolytes; quaternary
amine compounds such as distearyl-, dilauryl-, di-
hydrogenated beef tallow-, dimethyl ammonium chloride,
dicetyldiethyl ammoniumethylsulphate, ditallowdimethyl
ammonium methylsulphate, disoya dimethyl ammonium chloride
and dicoco dimethyl ammonium chloride; enzyme stabilisers
such as water soluble sources of calcium or borate species;
Ti02 and Ti02-coated mica; perfumes and perfume
solubilizers; and zeolites such as Valfour BV400 and
derivatives thereof and Ca2+/Mg2+ sequestrants such as
polycarboxylates, amino polycarboxylates, polyphosphonates,
amino polyphosphonates etc. and water softening agents such
as sodium citrate.
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Method of use
It is important that hair conditioning and colouring
compositions be in a form which is easy and convenient to
prepare and use by the consumer, since the oxidising agent
must remain in contact with the hair for a certain period of
time and not run or drip off of the hair, possibly causing
eye or skin irritation. In order to provide a composition
which is easy for the consumer to apply to the hair without
dripping the viscosity of the composition should be
controlled.
The conditioning and colouring composition may be
provided as a single composition containing all the
necessary conditioning and colouring ingredients. When the
colouring composition comprises oxidative colouring agents
and oxidising agents, it is preferably provided in the form
of two components, one of which contains the oxidative
colouring agent and the second of which contains the
oxidising agent. The conditioning agent may be present in
either of these components or as a separate third component.
When the composition is provided in the form of two
components these may be made up into the composition before
application to the hair or applied separately to form a
single composition on the hair. Percentages and amounts when
discussed in this specification refer to percentages and
amounts in the final composition on the hair.
Consequently the colouring and conditioning composition
can be provided as a single pack or in kit form as
separately packaged components to maintain stability, and,
if so desired, mixed by the user immediately prior to
application to the hair.
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Preferably the colouring and conditioning composition
is provided in the form of at least two components, a first
component comprising an oxidising agent and a second
component comprising a hair colouring agent. The
aminofunctional polysiloxane conditioning agent may be
comprised within the first or second component or may be
comprised within a third component. The first and second
components can either be mixed by the user immediately prior
to application to the hair or can be applied separately. In
one embodiment of the present invention the oxidising
component comprises a stabilised cream comprising an
inorganic peroxygen oxidising agent, most generally hydrogen
peroxide in an amount such that the final concentration of
the colouring composition as used on the hair is from about
0.05% to about 6% by weight. It may also contain additional
agents as herein before described.
The first and second components and the third component
if present, are separately packaged and the separate
packages may be connected (e.g. as two or three chambers in
a single aerosol dispenser) or may be entirely separate
(e.g. two or three non-connected sachets). Preferably, they
are in the form of separately packaged but associated (e.g.
in attached packages) components.
When the components are packaged separately in
associated packages these may be in the form of a single
package having several chambers, one chamber for each
separate component. A preferred pack herein is a pack having
two chambers, one chamber comprising a first component
comprising a hair colouring agent and a second chamber
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comprising a second component comprising an oxidising agent.
Either or both of the first and second components may
contain an aminofunctional polysiloxane, or alternatively
the aminfunctional polysiloxane may be present in a third
chamber. The two components can be mixed either outside the
pack, for example, by hand, or within the pack, for example
by a mechanical means of mixing. It is preferable that the
two components are mixed sufficiently in order to provide a
homogeneous hair colouring composition for application to
the hair. Such a pack provides a product which is easy and
convenient to use. The colouring compositions can also be
packaged within blister packs and sachets. For instance, a
single sachet may contain sufficient for a single
application when two different sachets are mixed together. A
blister pack may contain a predetermined number of the two
different component compositions, each blister containing
sufficient composition for one application when the two are
mixed.
According to the present invention it is particularly
preferred that the composition contains an oxidative
colouring agent and thus according to a another aspect of
the invention there is provided a method for colouring and
conditioning hair comprising the steps of applying to the
hair a hair colouring composition which preferably contains
at least one oxidative colouring agent and at least one
oxidising agent and a hair conditioning composition
comprising a aminofunctional polysiloxane and subsequently
rinsing the composition from the hair. The aminofunctional
polysiloxane conditioner may be applied to the hair prior to
the application of the hair colouring composition, at the
same time as the hair colouring composition is applied or
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after the hair colouring composition has been applied.
Another aspect of the invention provides a kit for use
in colouring and conditioning hair. This kit comprises (a) a
hair colouring composition which contains at least one
colouring agent and (b) a hair conditioning composition
which comprises an aminofunctional polysiloxane and (c)
instructions to apply the colour composition to the hair and
to leave the colouring composition on the hair and then
rinse the colouring composition from the hair and to apply
the hair conditioning composition to the hair in a separate
step.
According to another aspect of the invention a kit is
provided for use in colouring and conditioning hair
comprising (a) a hair colouring composition which contains
at least one colouring agent and at least one oxidising
agent and (b) a separately packaged hair conditioning
composition which contains an aminofunctional polysiloxane
conditioner. The compositions and the instructions may have
any of the preferred features discussed above in the context
of the method of the invention where appropriate.
The kit of the invention may comprise a series of
separately packaged doses of each composition, each dose
being appropriate for a single application, and the kit as a
whole being sufficient to allow the consumer to carry out
the method for a period.
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Test Methods and Example compositions
Particle size determination:
The particle size is determined according to the
standard microscopy analysis method for particle size. The
particle size is determined in neat (no dilution) dye
product (the final dye containing product, prior to any
mixing with peroxide). Within the context of this
application the amino functionalised particle is clearly
discernible and although there are many other features
associated with other components in the dye formulation that
are clearly evident in the micrograph (i.e. lamella
structures associated with fatty alcohol), the amino
functionalised silicones form distinct droplets that are
typically clear. It is recommended, as was the case herein,
that a product without the amino functionalised silicone be
prepared as a placebo reference.
Sample Preparation:
A small drop of the sample product is placed on a
standard microscope slide, either side of the droplet is
placed two standard cover slips upon which a third cover
slip is placed directly above the droplet and hence bridging
the other two cover slips. Said third cover slip is then
pressed down until it contacts the other two cover slips -
thereby trapping product. The sample thickness is therefore
guaranteed to always be the same (namely the thickness of
the standard cover slip) and given this is larger than the
diameter, of particles reduces the chances of sample
preparation affecting (deforming) the particles. The
preferred sample amount is thus that defined by the volume
of the void under said third cover slip (too little and the
sample will not contact the underside of said third cover
slip, too much and the sample will ooze from the side on
compression of said third cover slip).
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Particle Size Measurement:
The particle size method is typical of those known in
the art, and utilizes a standard Nikon optical microscope,
with standard transmitted light using xl0 objective. To aid
accuracy, a Lucia G software (by Nikon) is used with the
following procedure. The first step of analysis requires the
user to scan and select a field that is representative of
the bulk - this typically requires multiple preparations for
accuracy. The observed image is transmitted via JVC video
camera to a standard monitor and each particle is measured
by using the standard Measure macro; namely, clicking on
each side of the particle. - hence measuring a diameter. To
account for none spherical particles, the `diameter' is
always assessed horizontally across the monitor. By
measuring in one plane, the technique automatically
compensates for non spherical geometry and due to the large
number of particles measured results in an equivalent
average diameter. Although equivalent diameters may be
determined by measuring the major and minor axes and
calculating equivalent diameter via aspect ratio equations,
the above technique provides equally accurate results.
Since it is typical human nature to count the largest
particles first and thus to ensure that all particles are
counted and measured, a small (typically using an erasable
pen) dot should be placed on the monitor over each counted
particle. The count procedure is continued until every
single visible particle is counted within the field. In,the
case of a very small particle size distribution, this may
result in over 400 counts. In the case of larger particle
sizes, one might expect approximately 100 counts per field,
however in such cases additional fields would be selected to
ensure at least 200 separate particles are counted. Net, in
all cases at least 200 separate particles should be measured
and in all cases all particles (in practice the upper limit
being 400-500) in one field are counted. On average, across
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all the examples sighted herein, about 300 particles would
be measured per sample. Analysis can be as below (standard
volume average calculated by hand to demonstrate the
technique) or, more typically, using the macro. that
automatically sorts the data reporting a volume average
(assuming a spherical geometry based on the diameter
measured above).
As with all microscope methods, this method is
susceptible to error and does rely upon manual preparation
of the sample between a plate and cover slip. However,
multiple samples and high measurement counts, as used
herein, minimize this error. Whilst other methods such as
Horiba scattering techniques or Lasentec (Lasentec M100F),
could be considered it has been determined that colloid and
particle structures not associated with the active were a
source of interference. The microscope method is limited in
that particles of less than 1 micron are not discernible,
however in the context of this application such particles
are not preferred and further would not greatly impact
volume average particle size.
Analysis examples (number of observations with an
approximate size of)
The following example bases 1 to 4 exemplify identical dye
emulsion base formulations for blond shades (See dye base
emulsion formula A) which have been manufactured to produce
various particle sizes according to the present invention:
Base 1:- One pot process
Base 2:- Oil in water process
Base 3:- One pot process
Base 4:- Phase inversion process.
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Particle size (g.m) BASE 1 BASE 2 BASE 3 BASE 4
1 31 124 6 0
2 57 122 2 6
3 30 90 62 20
29 55 80 100
7 13 16 44 63
38 20 53 79
31 4 18 22
12 0 11 22
4 0 5 1
5 1 12 4
1 0 7 0
0 0 0 0
0 0 0 0
0 0 3 0
0 0 0 0
100 0 0 1 0
Total number of 251 432 304 317
particles counted
Volume average 12.48 5.61 19.65 11.54
particle size
assuming sphere.
The term average particle size as used herein refers to
discrete amino functionalised silicones and also to discrete
particles that consist of a mixture of the amino
functionalised silicone and a polycation or cationic
polymers - while not bound by theory such particles have
been referred to as coascervates and form discrete particles
consisting localised concentrations of the amino
functionalised silicone that are associated with the
hydrophobic environment of the polycation .or cationic
polymers. Examples of suitable cationic polymers include
cationic cellulose (polyquaternium 10) and hydrophobically
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modified cationic cellulose (i.e. Amerchol's quatrisoft
LM200), cationic guar (guar hydroxypropyltrimonium
chloride), merquat 100 (polyquaternium 6), Merquat 550
(polyquaternium 7), Luviquat (polyquaternium-16) and Gafquat
755N (polyquaternium 11).
Treatment of switches with hair care compositions
Hair Switches
The hair switches utilised in the following test are:-
Virgin light brown hair 2 g x 8" Hair, (3 switches are
required per test).
Water Settings
The water settings utilised for the following tests are:-
Tap water, hardness 15 - 16 gpg.
Water flow rate 6+ 0.5 L/min.
Water Temperature 37 + 2 C.
Sample preparation
In order to assess the performance of the present
inverition on hair which is regularly coloured, the hair
swtich samples utilised in the test are firstly treated with
a market product hair colourant (namely L'Oreal, Excellence
No. 6) according to the manufacturers' instructions.
Following this treatment the samples are then washed as
described below 4 times.
1. Wet switch for 10seconds.
2. Apply 0.4 ml of Prell shampoo on the hair switch, using
a syringe.
3. Lather for 30 seconds using milking action,
distributing shampoo on both sides of hair switch.
4. Rinse for 30 seconds.
5. Repeat steps 2,3 and 4 once.
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6. Hot air dry, brushing with a vent brush, whilst blow
drying on a high heat/high speed for a total of 3
minutes (1 minute on each side and 1 minute with
brushing).
Initial treatment of sample
The switch is hung above a sink and wetted for 30
seconds with water. Excess water is squeezed out of the
switch. 3.Ograms of the conditioning composition or 9.Ograms
of the colouring composition to be tested is applied on the
top end of the switch and spread evenly down to the bottom
end, then milked into the switch. The colouring composition
is then left on the switch for 30 minutes or a conditioning
composition is left on the switch for 5 minutes. The switch
is then rinsed with water. Excess water is squeezed out of
the switch. The initial average combing index value and the
initial average sensory index value are calculated by
carrying out the combing test and the sensory test described
herein on the wet switches
Final treatment of sample
The switches are then washed as described 18 times.
1. Wet switch for lOseconds.
2. Apply 0.4 ml of Prell shampoo on the hair switch, using
a syringe.
3. Lather for 30 seconds using milking action,
distributing shampoo on both sides of hair switch.
4. Rinse for 30 seconds.
5. Repeat steps 2,3 and 4 once.
6. Hot air dry, brushing with a vent brush, whilst blow
drying on a high heat/high speed for a total of 3
minutes (1 minute on each side and 1 minute with
brushing).
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7. The final average combing index value and the final
average sensory index values are calculated by carrying
out the combing tests as described herein from the sample
wetted again for 10 seconds.
Sensory evaluation and descriptive analysis panels
Sensory evaluation is designed to measure, analyze &
interpret reactions to prodvct characteristics as perceived
by the senses of sight, smell, taste, touch and hearing. A
commonly used sensory evaluation technique is descriptive
analysis. Descriptive analysis is a complete, detailed and
objective characterization of the sensory properties of a
product using screened and qualified panelists that are
specifically trained for this purpose. Descriptive analysis
provides information about the perceived sensory properties
(or attributes) and the strength of each sensory attribute
in quantitative terms. Panelists are trained to rate the
intensity of a large number of sensory properties, while
ignoring personal preferences. Each sensory attribute is
meticulously defined, and panelists are presented with
reference materials that represent high, medium and low
intensities of each sensory attribute. Panelists work in
isolation in a sensory booth, and assess all sensory
characteristics of one sample before moving to the next
sample. Care is taken to blind and randomize the samples,
and to control the environment (lighting, temperature,
humidity).
A descriptive analysis panel requires 10 panelists, because
the high level of training ensures a low level of
variability in the data (small standard deviations).
Panelists only qualify when their ratings are consistent
from test-to-test, when their ratings are consistent with
that of the panel, and when they are sensitive enough to
discriminate small differences. Performance of descriptive
analysis panels and individual panelists is monitored
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closely. Typically, each product is evaluated by all
panelists once or twice, and the mean attribute ratings
across the panelists or panelist means is calculated.
Because the intensity scores are recorded in relation to a
universal scale, the relative intensities among attributes
and among products can be compared. Descriptive analysis
ratings are used for quality control & shelf life studies,
for product development, and for claim substantiation. The
ASTM Guideline E 1958 - 98 `Standard Guide for Sensory Claim
Substantiation" states that descriptive analysis data are
suitable for claim substantiation if the panel shows good
consistency and robustness, and when the relationship
between descriptive sensory attributes and consumer
responses is established.
Descriptive Analysis Panel
External Descriptive Analysis Panel at Product Perceptions
A panel consisting of 10 trained females, was used to
conduct the tests.
Ease of detangling:
Technigue:With the wide end of the comb, comb 3 times to
remove tangles. Assess the difficulty of removing tangles
from the sample hair. If longer is needed to remove all the
tangles, continue to comb with wide end until all tangles
are removed.
Definition: Hard to detangle = The time and force required
remove all tangles from the sample hair with the wide end of
a comb, from very ea'sy (one stroke) to very difficult (many
strokes/lot of force required).
The following sensory anchors are used to define the end
points of the scale:
Low Anchor = Pantene Dry/Permed/Damaged Conditioner (as
available in Europe)
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High Anchor = Bleached Hair as prepared using hair treated
with a marketed hair bleaching product (Clairol Born Blonde)
according to the manufacturer's instructions.
Ease of combing
Technique:Once the tangles are removed, use the narrow end
of the comb, and gently slide down the hair sample 3 times.
Assess the amount of resistance encountered at the 3rd
combing (because some small tangles may still be removed at
the first combing stroke).
Definition: Combing resistance = The force required to slide
the narrow end of the comb down the length of the hair
sample after removing tangles, from no resistance (no force)
to very resistarice ( a lot of force required).
The following sensory anchors are used to define the end
points of the scale:
Low Anchor = Pantene Dry/Permed/Damaged Conditioner (as
available in Europe)
High Anchor = Standard conventional Styling Pomade/Styling
Wax
No Coating (dry)
Technique: After the switch is combed through, assess the
visual amount of coating on the dry hair sample. Assess the
amount of coating you can see on the hair (regardless of the
type of coating).
Definition: Not Coated = The lack of product coating or
residue seen on the hair sample (regardless of the type of
coating) , from very coated (low anchor) to not coated (high
anchor
The following sensory anchors are used to define the end
points of the scale:
Low Anchor = Vaseline
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High Anchor = Prell Shampoo (as available in the US)
No Residue
Technique: After the switch is combed, assess the amount of
coating on the dry hair sample using a`milking' motion with
thumb and index/middle finger. Assess the amount of coating
you can feel on the hair when milking.
Definition: No Residue = The lack of product coating or
residue felt on the hair sample(regardless of the type of
coating), from coated (low anchor) to very coated (high
anchor).
The following sensory anchors are used to define the end
points of the scale:
Low Anchor = Vaseline
High Anchor = Prell Shampoo (as available in the US)
Not Greasy
Technique: After the switch has been combed and assessed as
outlined above for dry residue, assess the greasy feel of
any residual coating on the hair using a`milking' motion
with the thumb and index/middle finger. Assess the amount of
greasiness you can feel on the hair when milking.
Definition: Greasiness = The degree to which the residue on
hair seems greasy in nature (as opposed to waxy, oily, stiff
etc.). This attribute is specific in quantifying the amount
of a specific type of coating. The scale is from very greasy
(low anchor) to not greasy (high anchor).
The following sensory anchors are used to define the end
points of the scale:
Low Anchor = Vaseline
High Anchor = Prell Shampoo (as available in the US)
Combing Index values and Sensory Index Values
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The combing and sensory index values are calculated
according to the following formulae:
Combing Index value =
[{Ease of De-Tangling}Sample}/[{Ease of De-Tangling} Virgin]
+[{Ease of Combing] Test }/ [Ease of Combing] Virgin} / 2
Sensory Index value =
{[No Residue] Test / [No Residue] Virgin + [Not Greasy]
Test / [Not Greasy] Virgin + [Not Coated] Test /[Not
Coated] Virgin} / 3
Example compositions
The colouring composition was made up before each
application by mixing the peroxide cream with the dye cream.
The dye cream and the peroxide cream compositions are
prepared as described herein after.
Examples of final dYe cream formulations
The following dye cream formulations are to be mixed 1:1
with the peroxide cream.
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Dye Cream Formula for Dark Shades o in use
Water QS to 50
Emulsion Base 22.5000
Dye premix 14.0000
Decyl glucoside 0.5000
( opt ional )
30% Aqueous Ammonium hydroxide 4.1300
Dye Cream Formula for Reds and Browns % in use
Water QS to 50
Emulsion Base 22.5000
Dye premix 14.0000
Decyl glucoside 0.5000
(optional)
30o Aqueous Ammonium hydroxide 5.1000
Dye Cream Formula for Blondes % in use
Water QS to 50
Emulsion Base 22.5000
Dye premix 14.0000
Decyl glucoside 0.5000
(optional)
30% Aqueous Ammonium hydroxide 6.0000
Examples of Dye emulsion base formulations
The following are examples of the emulsion base premix
formulation
Dye Emulsion Base Formula A % w/w in Use
Water As Required
Ceteareth 25 0.5400
Cetyl Alcohol 0.8100
Stearyl Alcohol 1.6300
Sodium Benzoate 0.0557
Phenoxyethanol 0.0668
Benzyl Alcohol 0.0668
Steareth 2 0.2700
Tetrasodium EDTA 0.0223
Di-PEG-2 Soyamine IPDI 0.2115
Lowenol S216 from Lowenstein 2.1150
DC Q2-8220 from Dow Corning 1.5000
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Dye Emulsion Base Formula B % w/w in Use
Water As Required
Ceteareth 25 1.5000
Cetyl Alcohol 2:2500
Stearyl Alcohol 2.2500
Sodium Benzoate 0.0557
Phenoxyethanol 0.0668
Benzyl Alcohol 0.0668
Tetrasodium EDTA 0.0223
DC Q2-8220 from Dow Corning 2.0000
Dye Emulsion Base Formula C % w/w in Use
Water As Required
Ceteareth 25 1.5000
Cetyl Alcohol 2.2500
Stearyl Alcohol 2.2500
Sodium Benzoate 0.0557
Phenoxyethanol 0.0668
Benzyl Alcohol 0.0668
Tetrasodium EDTA 0.0223
SF1923 Fluid from General 2.0000
Electric
Dye Cream Emulsion Making Methods
The Dye Base Emulsions described and exemplified hereinabove
can be manufactured utilising any one of the standard
approaches, these include:
= Oil in water process
= Phase Inversion process
= One-pot process
The amount of shear should be controlled to allow the
desired particle size to be achieved which can be determined
utilising the test method described herein.
An example Dye Base Emulsion making method is given below.
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One-Pot Process for Making Dye Cream Emulsion
1. Add water to vessel. Heat to above the melt temperature
of the fatty alcohols with agitation.
2. Add Fatty Alcohols and any Ethoxylated Fatty Alcohols,
e.g. Ceteareth-25, Cetyl, Stearyl and Steareth-2, and
allow to melt. Increase agitation.
3. If used add other surfactants such as Dihydroxyethyl
Soyamine Dioleate (Lowenol S216) and/or Peg-3 Cocamine
(Lowenol C243 from Lowenstein) and/or PEG-5 Cocamine
(Ethomeen C/15 from Akzo Nobel).
4. Continue mixing with shear.
5. Begin cooling with shear adding preservatives at
appropriate temperature.
6. During cooling add silicone containing conditioning
agent with mixing. Mix until homogeneous and desired
particle size achieved.
7. Cool to room temperature.
Final Dye Cream Making Method
Below is an example of how the final dye cream can be
manufactured:
To the dye cream emulsion add the following:
= Decyl glucoside (if used) then mix to give a homogenous
product
= Dye premix containing: water, anti-oxidants, solvents,
precursors and couplers, then mix to give a homogenous
product
= Ammonium hydroxide, then mix to give a homogenous final
product
Dye premix formulations:
The following is a list of typical couplers and
precursors used to formulate various shade ranges.
p-Phenylenediamine
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p-Aminophenol
N4,N4-bis Hydroxyethyl-p-PD sulphate
o-Aminophenol
p-Methylaminophenol
2,5,Diamonotoluene Sulphate
m-Aminophenol
4-amino-2-hydroxytoluene
Resorcinol
2-methyl resorcinol
2-Amino-3-Hydroxypyridine
2-Amino-4-Hydroxyethylaminoanisole sulphate
2-methyl-5-hydroxyethylaminophenol
m-Phenylenediamine.sulphate
1-phenyle-3-methyl-5-pyrazolone
Naphthol
Additionally the dye premix formulations may comprise the
following additional materials:-
Water
Reducing Agents such as Sodium Sulphite
Anti-oxidants such as D and L-Ascorbic Acid
Metal Chelants such as EDTA
Solvents such as glycols and alchols
Examples of Total Dye Levels used in Various Shades
Shade % w/w in use
Blondes 0.0001 to 4.0000
Reds 0.0010 to 4.0000
Browns 0.0100 to 4.0000
Blacks 0.1000 to 4.0000
Dye premix making method
The dye premix may be manufactured using any one of the
standard approaches such as
= oil in water process
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= phase inversion process
= one pot process
An example of a dye premix manufacturing method is as
follows:
1. With mixing add water to the following:
solvents, anti-oxidants, precursors and couplers
2. If required warm to solubilize
3. Cool to room temperature
Hydrogen Peroxide Cream Making Method
Example of an Hydrogen Peroxide Emulsion Base
Hydrogen Peroxide Emulsion Base % w/w in Formula
Formula
Purified Water QS to 100
Ceteareth-25 4.17
Cetyl Alcohol 6.25
Stearyl Alcohol 6.25
Hydrogen peroxide emulsion base method
The Hydrogen Peroxide Emulsion Base described herein can be
made by any of the standard approaches, these include:
= Oil in water process
= Phase Inversion process
= One-pot process
An example of a Hydrogen Peroxide Emulsion Base making
method is given below.
One-Pot Process for Making Hydrogen Peroxide Emulsion Base
1.Add water to vessel. With agitation heat to above the
melt temperature of the fatty alcohols
2.Add Fatty Alcohols and any Ethoxylated Fatty Alcohols and
allow to melt. Increase agitation.
3.Continue mixing with shear until emulsion has formed
4.Begin cooling stopping shear at appropriate temperature.
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5.Cool to room temperature
Chelator Premix to Stabilise Peroxide
%,w/w in Formula
Purified Water QS to 15.0000
Metal Chelators 0.0010 to 1.0000%
Phosphoric Acid and/or Sodium Adjust to pH 1 - 5
Hydroxide
Example Making Method for Chelant Premix
1.Dissolve the chelants in the water phase
2.Adjust pH with phosphoric acid and/or sodium hydroxide as
required
6% Hydrogen Peroxide Cream
% w/w Addition
Hydrogen Peroxide Emulsion Base 36.00
Chelator Premix 15.00
Water QS to 100
35% Hydrogen Peroxide 17.71
pH Adjustment Gap To pH 1- 5
Example Making Method for 6% Hydrogen Peroxide Cream
To the Hydrogen Peroxide Emulsion Base add the following
with agitation: Water, Chelant Premix and 35% Hydrogen
Peroxide Solution, mix until homogeneous . Adjust pH to
between one and five with appropriate amounts of phosphoric
acid and / or sodium hydroxide
9% Hydrogen Peroxide Cream
% w/w Addition
Hydrogen Peroxide Emulsion Base 36.00
Chelator Premix 15.00
Water QS to 100
35% Hydrogen Peroxide 26.57
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pH Adjustment Gap To pH 1
Example Making Method for 9% Hydrogen Peroxide Cream
To the Hydrogen Peroxide Emulsion Base add the following
with agitation: Water, Chelant Premix and 35% Hydrogen
Peroxide Solution, mix until homogeneous . Adjust pH to
between one and five with appropriate amounts of phosphoric
acid and / or sodium hydroxide
Results:
The following table show the results for the tests carried
out in order to determine the average Combing Index Value
and the average Sensory Index Value for a number of
compositions according to the present invention and samples
of products on the market, namely L'Oreal Excellence No6 and
Revlon Colorstay utilised according to the manufactures
instructions. The reference sample utilised is virgin hair.
Example 1: Hair dye composition according of the present
invention.
The switch samples for example 1 were treated with the dye
cream for blondes containing dye emulsion base B and 9%
hydrogen peroxide cream as described herein above.
Example 2: Hair conditioning composition of the present
invention.
The switch samples for example 2 treated with the dye cream
for blondes containing dye emulsion base B but excluding the
dye premix, and excluding 9% hydrogen peroxide cream.
The switches were then treated with the dye cream for
blondes containing the dry emulsion B, (but excluding the
aminofunctional silicones) and the 9a hydrogen peroxide
cream.
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Revlon Reference example
The switch samples were treated with L'Oreal Excellence No6
but excluding the use of the L'Oreal in box conditioner and,
then treated with the Revlon colorstay in-box conditioner.
L'Oreal Reference example
The switch samples were treated with L'Oreal Excellence No6
according to the manufacture's instructions including the
application of the L'Oreal in-box conditioner.
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initial (1) (2) Virgin Revlon L'Oreal
Dry app. Coat. 90 93 94 70.33 91
Dry residue 93 93 89 83.78 91
Dry residue greasy 98 98 98 89 94
Sensory index 1.00 1.01 1.00 0.87 0.98
Final
Dry app. coat 93 91 96 82.67 91
Dry residue 94 93 91 82.11 91
Dry residue greasy 98 98 98 92.89 98
Sensory index 1.00 0.99 1.00 0.90 0.98
Initial
Detangling 92 93 84 92.78 85
Combing 94 95 89 92.56 87
Combing index 1.08 1.09 1.00 1.07 0.99
Final
Detangling 91 92 87 90.45 69
Combing 93 94 93 93.78 57
Combing index 1.02 1.03 1.00 1.02 0.70
From the table it can be clearly seen that the Example 1 and
2 formulations of the present invention provide both initial
and long term sensory and combing benfits.
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