METHOD FOR THE APPLICATION OF A PIGMENT DYEING COMPOSITION
BASED ON SPECIFIC ACRYLIC POLYMER AND ON SILICONE COPOLYMER,
AND APPROPRIATE DEVICE
A subject-matter of the present invention is a method for the application of a
composition for dyeing human keratinous fibres, more particularly the hair and very
especially roots, sidelocks, beard or moustache hairs, eyelashes and eyebrows. More
particularly, the method consists in employing a composition comprising an aqueous
dispersion of particles of specific acrylic polymer, a linear block silicone copolymer and
a pigment; the composition being stored in a container having a permeable end piece.
Another subject-matter of the present invention is an appropriate device for the
implementation of the method.
It is known, in the field of the dyeing of keratinous fibres, in particular human
keratinous fibres, to dye keratinous fibres by different techniques, in particular starting
from dye precursors for permanent colourings or also from direct dyes or pigments for
non-permanent colourings.
The present invention is concerned more particularly with the field of nonpermanent
colouring produced starting from pigments (in other words, starting from
colouring substances which are insoluble in the composition in which they are
present).
One of the advantages of this type of colouring, in comparison with those
deploying direct dyes or dye precursors, is that, in order to be visible, the colouring
does not require the use of a stage of prior or simultaneous bleaching of the keratinous
fibres, a bleaching stage, carried out with an oxidizing agent, such as hydrogen
peroxide or also persalts. This bleaching stage results in not insignificant damage to
the keratinous fibres, which detrimentally affects their cosmetic properties. The hair
then has a tendency to become rough, more difficult to disentangle and more brittle.
In point of fact, in the case of colouring based on a composition comprising one
or more pigments, visible colourings are obtained, also on dark hair since the surface
pigment(s) mask the colour of the fibres, whether the colour is natural or artificial.
On the other hand, the disadvantage of methods of this type lies in the temporary
nature of the colourings obtained.
The use of pigments to dye keratinous fibres is, for example, described in Patent
Application FR 2 741 530, which recommends the use, for the temporary colouring of
keratinous fibres, of a composition comprising at least a dispersion of particles of filmforming
polymer comprising at least one acid functional group and at least one
pigment dispersed in the continuous phase of the said dispersion.
The colourings obtained by this form of colouring exhibit, on the other hand, the
disadvantage of having a low resistance to shampooing operations.
Furthermore, it is known to produce coloured coatings of the hair using a
composition comprising an electrophilic monomer of cyanoacrylate type and a pigment,
in particular in the document EP 1 649 898. Such a composition makes it possible to
obtain completely coated and non-greasy hair. However, the coating obtained is not
completely satisfactory in the face of external agents, such as washing and
perspiration. Furthermore, the coating obtained is sensitive to fatty substances, such as
sebum.
It is also possible to colour the hair (coloured coating) using a pressure-sensitive
adhesive silicone copolymer, in particular a copolymer based on silicone resin and on
silicone fluid. Once deposited on the hair, these copolymers exhibit the advantage of
contributing colour in a persistent manner. On the other hand, the hair treated is rather
rough to the touch.
Other disadvantages are also met with, encountered during the use of dyeing
compositions based on pigments, such as, for example, the need to employ several
stages and associated accessories, such as a board, a brush, gloves or drying. In
addition, the time taken for the application of the composition may be regarded as too
great by the consumer or the hairdresser, in particular if the poorer performance, in
particular in terms of persistence, than that of the permanent colourings or nonpermanent
colourings deploying direct dyes is taken into consideration.
In addition to the fact that these accessories often require a degree of dexterity,
indeed even the presence of a third person, in order to use them, they may be
inappropriate in some cases, such as that of application to moustache hairs, eyelashes
or eyebrows, for example.
Another problem encountered also lies in the accuracy of the application, which
is difficult to obtain in some cases, consequently involving losses of composition, if it is
necessary to remove the poorly applied product, and also unsightly effects related to
the product overflowing onto surfaces which have to remain untreated.
Thus, the aim of the present invention is to provide a device which facilitates the
application of a dyeing composition based on pigment(s); this composition in addition
giving access to a coloured coating which is persistent towards shampooing
operations or washing operations and towards the various attacks which keratinous
fibres may be subjected to, without damage to the latter; this coating being in addition
homogenous and smooth on the keratinous fibres, leaving the latter completely
individualized.
This aim is achieved with the present invention, a subject-matter of which is thus a
method for dyeing human keratinous fibres, in particular the hair, preferably roots,
sidelocks, non-head hair, in particular beard or moustache hair, eyelashes or
eyebrows, which consists in applying a dyeing composition using a container
comprising a removable applicator end piece comprising a permeable material through
which the composition can pass, the composition being applied by bringing the
applicator into contact with the dry or wet fibres, the said composition comprising at
least one aqueous dispersion of particles of hybrid hydrophobic film-forming acrylic
polymer, at least one linear block silicone copolymer and at least one pigment.
Another subject-matter of the invention is a device appropriate for the
implementation of this method.
The term "at least one" is understood to mean "one or more".
The term "comprising a" is understood to mean "comprising at least one", unless
otherwise specified.
It is possible, by the use of such a device, to deposit in a simple and localized
way the dyeing composition included in it, without the risk of the product running,
whether in the context of a self-application or of a dyeing carried out by another person.
The application is fast and efficient, without requiring the use of additional accessories,
and the impregnation of the fibres is homogenous, whatever their length.
Furthermore, the composition applied makes it possible to obtain a coloured
coating which is visible on all types of fibres and which is persistent towards
shampooing operations or washing operations while retaining the physical qualities of
the keratinous fibre, without it being necessary to carry out a drying other than a natural
drying (in contrast to a drying carried out using a heating device). Such a coating is in
particular resistant to the external attacks which the fibres may be subjected to, such as
blow drying and perspiration. It makes it possible in particular to obtain a smooth and
homogeneous deposited layer. Furthermore, it has been found, surprisingly, that the
fibres remain completely individualized and can be styled without problems, and that
the styling properties contributed to the fibre are persistent towards shampooing
operations.
The term "individualized fibres" is understood to mean fibres which, after
application of the composition and drying, are not stuck together (or are all separated
from one another) and thus do not form clumps, the coating being formed around
virtually each fibre.
Dyeing composition
Aqueous dispersion of particles of hybrid hydrophobic film-forming acrylic polymer
The term "polymer" Is understood to mean, within the meaning of the invention, a
compound corresponding to the repetition of one or more units (these units resulting
from compounds known as monomers). This or these unit(s) is (are) repeated at least
twice and preferably at least 3 times.
The term "film-forming polymer" is understood to mean a polymer which is
capable of forming, by itself alone or in the presence of an additional film-forming
agent, a macroscopically continuous film on a support, in particular on keratinous
substances, and preferably a cohesive film.
The term "hydrophobic polymer" is understood to mean a polymer having a
solubility in water at 25°C of less than 1% by weight.
The dispersion can be a simple dispersion in the aqueous medium of the
composition.
Mention may be made, as specific case of dispersions, of latexes.
The term "hybrid acrylic polymer" is understood to mean, within the meaning of
the present invention, a polymer synthesized from at least one compound (i) chosen
from monomers having at least one (meth)acrylic acid group and/or esters of these
acid monomers and/or amides of these acid monomers and from at least one
compound (ii) other than the compounds (i), i.e. which does not comprises
(meth)acrylic acid group and/or esters of these acid monomers and/or amides of these
acid monomers..
The (meth)acrylic acid esters (also known as (meth)acrylates) are
advantageously chosen from alkyl (meth)acrylates, in particular C1-C30, preferably -
C2o and better still C1-C10 alkyl (meth)acrylates, aryl (meth)acrylates, in particular C6-
C 0 aryl (meth)acrylates, or hydroxyalkyl (meth)acrylates, in particular C2-C6
hydroxyalkyl (meth)acrylates.
Mention may be made, among alkyl (meth)acrylates, of methyl methacrylate,
ethyl methacrylate, butyl methacrylate, isobutyl methacrylate, 2-ethylhexyl
methacrylate, lauryl methacrylate or cyclohexyl methacrylate.
Mention may be made, among hydroxyalkyl (meth)acrylates, of hydroxyethyl
acrylate, 2-hydroxypropyl acrylate, hydroxyethyl methacrylate or 2-hydroxypropyl
methacrylate.
Mention may be made, among aryl (meth)acrylates, of benzyl acrylate and
phenyl acrylate.
The (meth)acrylic acid esters which are particularly preferred are the alkyl
(meth)acrylates.
According to the present invention, the alkyl group of the esters can be either
fluorinated or perfluorinated, that is to say that some or all of the hydrogen atoms of
the alkyl group are replaced with fluorine atoms.
Mention may be made, as amides of the acid monomers, for example, of
(meth)acrylamides and in particular N-alkyl(meth)acrylamides, especially N-(C 2-Ci 2
alkyl)(meth)acrylamides. Mention may be made, among N-alkyl(meth)acrylamides, of
N-ethylacrylamide, N-(t-butyl)acrylamide, N-(t-octyl)acrylamide and Nundecylacrylamide.
Mention will be made, as compounds (ii) other than the compounds (i), for
example, of the styrene monomers.
In particular, the acrylic polymer can be a styrene/acrylate copolymer and
especially a polymer chosen from the copolymers resulting from the polymerization of
at least one styrene monomer and at least one C1-C20 and preferably C1-C10 alkyl
acrylate monomer.
Mention may be made, as styrene monomer which can be used in the invention,
of styrene or omethylstyrene and preferably styrene.
The C1-C10 alkyl acrylate monomer can be chosen from methyl acrylate, ethyl
acrylate, propyl acrylate, butyl acrylate, hexyl acrylate, octyl acrylate or 2-ethylhexyl
acrylate.
Mention may be made, as acrylic polymer synthesized with styrene compound,
of the styrene/acrylate(s) copolymers sold under the name Joncryl 77 by BASF, under
the name Yodosol GH41 F by Akzo Nobel and under the name Syntran 5760 CG by
Interpolymer.
Mention may also be made, as compound (ii), of the compounds which interact
by a process other than the radical polymerization of unsaturated compounds or the
compounds resulting from such a process. Such a process can, for example, be a
polycondensation. Mention may be made, as polycondensation, of the formation of
polyurethanes, polyesters or polyamides. In addition to the acrylic monomer or
monomers, the hybrid hydrophobic film-forming polymer of the invention will then
comprise the compound resulting from the polycondensation process or the
compounds which interact in the polycondensation process.
Mention may in particular be made, as hybrid hydrophobic film-forming acrylic
copolymer of this type, of that sold under the reference Hybridur 875 Polymer
Dispersion by Air Products and Chemicals.
Use may also be made, as hybrid hydrophobic film-forming acrylic copolymer, of
the product sold under the reference Primal HG 1000 by Dow.
The hybrid hydrophobic film-forming acrylic polymer or polymers in aqueous
dispersion can be present in a content, as polymeric active materials, ranging from
0.1% to 30% by weight, more particularly from 0.5% to 20% by weight and preferably
from 1% to 15% by weight, with respect to the total weight of the composition.
Linear block silicone copolymer
The silicone copolymer used in the composition according to the invention is a
linear block copolymer, that is to say an uncrosslinked copolymer, obtained by chain
extension and not by crosslinking.
The term "block copolymer" (or "sequential copolymer") denotes a polymer
comprising at least two distinct blocks (sequences). Each block of the polymer results
from one type of monomer or from several types of different monomers. This means
that each block can be composed of a homopolymer or of a copolymer, it being
possible for this copolymer constituting the block to be in its turn a random or
alternating copolymer.
The silicone copolymer used in the composition according to the invention
preferably comprises at least two distinct silicone blocks, each block of the polymer
resulting from one type of silicone monomer or from several types of different silicone
monomers, such as mentioned below.
It should also be noted that the copolymer is "linear"; in other words, the
structure of the polymer is neither branched nor star-shaped nor grafted.
The linear block silicone copolymer is advantageously provided in the form of
particles in dispersion in an aqueous medium.
The aqueous dispersion of block copolymer particles is a silicone-in-water
(Sil/W) emulsion, the oily globules of which are composed of a silicone of high
viscosity, so that these globules appear to form "soft particles".
The size of the linear block silicone copolymer particles can vary widely.
Preferably, in the present application, the linear block silicone copolymer particles
generally exhibit a number-average size of less than or equal to 2 microns and
preferably of less than or equal to 1 micron.
The aqueous dispersions of linear block silicone copolymer particles used in the
composition according to the invention can be chosen in particular from those
described in the document EP-A-874 017, the teaching of which is incorporated here
by reference. According to this document, it is possible in particular to obtain the
silicone copolymers constituting these particles by a chain extension reaction in the
presence of a catalyst, starting from at least:
- (a) one polysiloxane (i) having at least one reactive group and preferably one or two
reactive groups per molecule; and
- (b) one organosilicone compound (ii) which reacts with the polysiloxane (i) by a chain
extension reaction.
(i) is chosen from the compounds of formula (I):
in which R and R2 represent, independently of one another, a hydrocarbon group
having from 1 to 20 carbon atoms and preferably from 1 to 10 carbon atoms, such as
methyl, ethyl, propyl or butyl, or an aryl group, such as phenyl, or a reactive group, and
n is an integer greater than 1, provided that there are on average between one and
two reactive groups per polymer.
The term "reactive group" is understood to mean any group capable of reacting
with the organosilicone compound (ii) to form a block copolymer. Mention may be
made, as reactive groups, of hydrogen; aliphatically unsaturated groups and in
particular vinyl, allyl or hexenyl groups; the hydroxyl group; alkoxy groups, such as
methoxy, ethoxy or propoxy groups; alkoxyalkoxy groups; the acetoxy group; amino
groups and their mixtures. Preferably, more than 90% and better still more than 98% of
reactive groups are at the chain end, that is to say that the R2 radicals generally
constitute more than 90% and even 98% of the reactive groups.
n can in particular be an integer ranging from 5 to 30, preferably from 10 to 30
and better still from 15 to 25.
The polysiloxanes of formula (I) are linear polymers, that is to say comprising few
branchings and generally less than 2 mol% of siloxane units. Furthermore, the R and
R2 groups can optionally be substituted by amino groups, epoxy groups or sulfurcomprising,
silicon-comprising or oxygen-comprising groups.
Preferably, at least 80% of the R groups are alkyl groups and better still methyl
groups.
Preferably, the reactive group R2 at the chain end is an aliphatically unsaturated
group and in particular a vinyl group.
Mention may in particular be made, as polysiloxanes (i), of dimethylvinylsiloxypolydimethylsiloxane,
a compound of formula (I) in which the R radicals are methyl
radicals and the R2 radicals at the chain end are vinyl radicals while the other two R2
radicals are methyl radicals.
The organosilicone compound (ii) can be chosen from polysiloxanes of formula
(I) or compounds acting as chain-extending agent. If it is a compound of formula (I),
the polysiloxane (i) will comprise a first reactive group and the organosilicone
compound (ii) will comprise a second reactive group which will react with the first. If it
is a chain-extending agent, it can be a silane, a siloxane (disiloxane or trisiloxane) or a
silazane. Preferably, the organosilicone compound (ii) is a liquid
where n is an integer greater than 1 and preferably greater than 10, for example
ranging from 2 to 100, preferably from 10 to 30 and better still from 15 to 25. According
to a specific embodiment of the invention, n is equal to 20.
The silicone block copolymers used according to the invention are
advantageously devoid of oxyalkylene group(s), in particular devoid of oxyethylene
and/or oxypropylene group(s).
The catalyst of the reaction between the polysiloxane and the organosilicone
compound can be chosen from metals and in particular from platinum, rhodium, tin,
titanium, copper and lead. It is preferably platinum or rhodium.
The dispersion of silicone copolymer particles used in the composition according
to the invention can in particular be obtained, for example, by mixing (a) water, (b) at
least one emulsifier, (c) the polysiloxane (i), (d) the organosilicone compound (ii) and
(e) a catalyst. Preferably, one of the constituents (c), (d) or (e) is added last to the
mixture, in order for the chain-extending reaction to begin only in the dispersion.
Mention may be made, as emulsifiers capable of being used in the preparation
process described above in order to obtain the aqueous dispersion of particles, of nonionic
or ionic (anionic, cationic or amphoteric) emulsifiers. They are preferably nonionic
emulsifiers which can be chosen from polyalkylene glycol ethers of fatty alcohols
comprising from 8 to 30 carbon atoms and preferably from 10 to 22 carbon atoms;
polyoxyalkylenated and in particular polyoxyethylenated sorbitan alkyl esters, where
the alkyl radical comprises from 8 to 30 carbon atoms and preferably from 10 to 22
carbon atoms; polyoxyalkylenated and in particular polyoxyethylenated alkyl esters,
where the alkyl radical comprises from 8 to 30 carbon atoms and preferably from 10 to
22 carbon atoms; polyethylene glycols; polypropylene glycols; diethylene glycols; and
their mixtures. The amount of emulsifier(s) is generally from 1% to 30% by weight, with
respect to the total weight of the reaction mixture.
The emulsifier used to obtain the aqueous dispersion of particles is preferably
chosen from polyethylene glycol ethers of fatty alcohols and their mixtures and in
particular polyethylene glycol ethers of alcohols comprising 12 or 13 carbon atoms and
from 2 to 100 oxyethylene units and preferably from 3 to 50 oxyethylene units, and
their mixtures. Mention may be made, for example, of C12- C13 Pareth-3, C12- C13
Pareth-23 and their mixtures.
According to a specific embodiment of the invention, the dispersion of silicone
copolymer particles is obtained from dimethylvinylsiloxy-polydimethylsiloxane (ou
divinyldimethicone), as compound (i), and from the compound of formula (II) with
preferably n=20, as compound (ii), preferably in the presence of a catalyst of platinum
type, and the dispersion of particles is preferably obtained in the presence of C12- C13
Pareth-3 and C12- C13 Pareth-23, as emulsifiers.
Use may in particular be made, as dispersion of silicone copolymer particles, of
the product sold under the name HMW 2220 by Dow Corning (CTFA name:
divinyldimethicone/dimethicone copolymer/Ci2-Ci 3 Pareth-3/Ci 2-Ci 3 Pareth-23), which
is a 60% aqueous dispersion of divinyldimethicone/dimethicone copolymer comprising
C 2-Ci 3 Pareth-3 and C 2-Ci 3 Pareth-23, the said dispersion comprising approximately
60% by weight of copolymer, 2.8% by weight of C 2-Ci 3 Pareth-23, 2% by weight of
C 2-Ci 3 Pareth-3 and 0.31% by weight of preservatives, the remainder to 100% being
water.
The linear block silicone copolymer or copolymers can be present, for example,
in an amount, as polymeric active materials, ranging from 0.1% to 30% by weight,
better still from 0.5% to 20% by weight and even better still from 1% to 15% by weight,
with respect to the total weight of the composition.
According to one embodiment, the hybrid hydrophobic film-forming acrylic
polymer or polymers and the linear block silicone copolymer or copolymers are present
in a hybrid hydrophobic film-forming acrylic polymer(s) to linear block silicone
copolymer(s) ratio by weight (as polymeric active materials) ranging from 0.2 to 10,
better still from 0.5 to 5 and even better still from 1 to 3.
When the hybrid hydrophobic film-forming acrylic polymer has a glass transition
temperature which is too high for the desired use, a plasticizer can be combined
therewith so as to lower this temperature of the mixture used. The plasticizer can be
chosen from the plasticizers normally used in the field of application and in particular
from compounds which can be solvents for the polymer.
Preferably, the plasticizer has a molecular weight of less than or equal to 5000
g/mol, preferably of less than or equal to 2000 g/mol, preferably of less than or equal to
1000 g/mol and more preferably of less than or equal to 900 g/mol. The plasticizer
advantageously has a molecular weight of greater than or equal to 100 g/mol.
Thus, the composition can additionally comprise at least one plasticizing agent. In
particular, mention may be made, alone or as a mixture, of the usual plasticizers, such
as:
- glycols and their derivatives, such as diethylene glycol ethyl ether, diethylene
glycol methyl ether, diethylene glycol butyl ether, diethylene glycol hexyl ether, ethylene
glycol ethyl ether, ethylene glycol butyl ether or ethylene glycol hexyl ether;
- polyethylene glycols, polypropylene glycols, polyethylene glycol/polypropylene
glycol copolymers and their mixtures, in particular polypropylene glycols of high
molecular weight, for example having a molecular weight ranging from 500 to 15 000,
such as, for example:
- glycol esters;
- propylene glycol derivatives and in particular propylene glycol phenyl ether,
propylene glycol diacetate, dipropylene glycol ethyl ether, tripropylene glycol methyl
ether, diethylene glycol methyl ether or dipropylene glycol butyl ether. Such compounds
are sold by Dow Chemical under the names Dowanol PPH and Dowanol DPnB;
- acid esters, in particular carboxylic acid esters, such as citrates, phthalates,
adipates, carbonates, tartrates, phosphates or sebacates;
- esters resulting from the reaction of a monocarboxylic acid of formula RuCOOH
with a diol of formula HOR12OH with R and R12 , which are identical or different,
representing a saturated or unsaturated and linear, branched or cyclic hydrocarbon
chain preferably comprising from 3 to 15 carbon atoms and optionally comprising one
or more heteroatoms, such as N, O or S, in particular the monoester resulting from the
reaction of isobutyric acid and octanediol, such as 2,2,4-trimethyl-1 ,3-pentanediol, such
as that sold under the reference Texanol Ester Alcohol by Eastman Chemical;
- oxyethylenated derivatives, such as oxyethylenated oils, in particular vegetable
oils, such as castor oil; and
- their mixtures.
More particularly, the plasticizser can be chosen from esters of at least one
carboxylic acid comprising from 1 to 7 carbon atoms and of a polyol comprising at least
4 hydroxyl groups.
The polyol can be a cyclized or non-cyclized monosaccharide -
polyhydroxyaldehyde (aldose) or polyhydroxyketone (ketose). The polyol is preferably a
cyclized monosaccharide in the hemiacetal form.
The polyol can be a mono- or polysaccharide comprising from 1 to 10
monosaccharide units, preferably from 1 to 4 monosaccharide units and more
preferably one or two monosaccharide units. The polyol can be chosen from erythritol,
xylitol, sorbitol, glucose, sucrose, lactose or maltose.
The polyol is preferably a disaccharide. Mention may be made, among
disaccharides, of sucrose (also known as a-D-glucopyranosyl-(1-2 )- -Dfructofuranose),
lactose (also known as -D-galactopyranosyl-(1-4 )- -Dglucopyranose)
and maltose (also known as a-D-glucopyranosyl-(1-4 )- -Dglucopyranose),
and preferably of sucrose.
The ester can be composed of a polyol esterified by at least two different
monocarboxylic acids or by at least three different monocarboxylic acids.
The ester can be a copolymer of two esters, in particular a copolymer i) of a
sucrose substituted by benzoyl groups and ii) of a sucrose substituted by acetyl and/or
isobutyryl groups.
The carboxylic acid is preferably a monocarboxylic acid comprising from 1 to 7
carbon atoms and preferably from 1 to 5 carbon atoms, for example chosen from acetic
acid, n-propanoic acid, isopropanoic acid, n-butanoic acid, isobutanoic acid, tertbutanoic
acid, n-pentanoic acid and benzoic acid.
The ester can be obtained from at least two different monocarboxylic acids.
According to one embodiment, the acid is a linear or branched acid which is
unsubstituted.
The acid is preferably chosen from acetic acid, isobutyric acid, benzoic acid and
their mixtures.
According to a preferred embodiment, the ester is sucrose diacetate hexa(2-
methylpropanoate), such as that sold under the name Sustane SAIB Food Grade
Kosher by Eastman Chemical.
According to another embodiment, the plasticizer can be chosen from esters of an
aliphatic or aromatic polycarboxylic acid and of an aliphatic or aromatic alcohol
comprising from 1 to 10 carbon atoms.
The aliphatic or aromatic alcohol comprises from 1 to 10 carbon atoms, preferably
from 1 to 8 carbon atoms, for example from 1 to 6 carbon atoms. It can be chosen from
R10H alcohols, such that R 1 represents methyl, ethyl, propyl, isopropyl, butyl, hexyl,
ethylhexyl, decyl, isodecyl, benzyl or benzyl substituted by an alkyl comprising from 1
to 3 carbon atoms, and their mixtures.
The aliphatic or aromatic polycarboxylic acid preferably comprises from 3 to 12
carbon atoms, preferably from 3 to 10 carbon atoms, preferably from 3 to 8 carbon
atoms, for example 6 or 8 carbon atoms.
The aliphatic or aromatic polycarboxylic acid is advantageously chosen from
dicarboxylic acids and tricarboxylic acids.
Mention may be made, among aliphatic dicarboxylic acids, of those of formula
HOOC-(CH2)n-COOH, in which n is an integer ranging from 1 to 10, preferably ranging
from 2 to 8, for example equal to 2, 4, 6 or 8.
Preference is given to dicarboxylic acids chosen from succinic acid, adipic acid
and sebacic acid.
Mention may be made, among aromatic dicarboxylic acids, of phthalic acid.
Mention may be made, among tricarboxylic acids, of triacids which correspond to
the formula:
in which R represents an -H, -OH or -OCOR' group in which R' represents an
alkyl group having from 1 to 6 carbon atoms. Preferably, R represents an -OCOCH3
group.
The tricarboxylic acid is chosen in particular from acetylcitric acid, butyroylcitric
acid or citric acid.
Use may be made, among tricarboxylic acid esters, of esters derived from citric
acid (or citrates), such as tributyl acetylcitrate, triethyl acetylcitrate, triethylhexyl
acetylcitrate, trihexyl acetylcitrate, trihexyl butyroylcitrate, triisodecyl citrate, triisopropyl
citrate, tributyl citrate and tri (2-ethyIhexyI) citrate. Mention may be made, as
commercial references for plasticizers mentioned above, of the Citroflex range sold by
Vertellus, with in particular Citroflex A4 and Citroflex C2.
Mention may be made, among adipic acid esters, of dibutyl adipate and di(2-
ethylhexyl) adipate.
Mention may be made, among sebacic acid esters, of dibutyl sebacate, di(2-
ethylhexyl) sebacate, diethyl sebacate and diisopropyl sebacate.
Mention may be made, among succinic acid esters, of di(2-ethylhexyl) succinate
and diethyl succinate.
Mention may be made, among phthalic acid esters, of benzyl butyl phthalate,
dibutyl phthalate, diethylhexyl phthalate, diethyl phthalate and dimethyl phthalate.
Advantageously, the plasticizer or plasticizers can be present in the composition
in a content such that the ratio by weight of the hybrid hydrophobic film-forming acrylic
polymer or polymers to the plasticizer or plasticizers varies from 0.5 to 100, preferably
from 1 to 50 and preferably from 1 to 10.
Pigments
The composition comprises pigments.
Such a composition makes it possible to obtain coloured and persistant coatings,
without damaging the keratinous fibres.
The term "pigment" is understood to mean white or coloured particles of any
shape which are insoluble in the composition in which they are present.
The pigments which can be used are chosen in particular from organic and/or
inorganic pigments known in the art, in particular those which are described in Kirk-
Othmer's Encyclopedia of Chemical Technology and in Ullmann's Encyclopedia of
Industrial Chemistry.
They can be natural, of natural origin, or not.
These pigments can be provided in the pigment powder or paste form. They can
be coated or uncoated.
The pigments can be chosen, for example, from inorganic pigments, organic
pigments, lakes, special effect pigments, such as pearlescent agents or glitter, and
their mixtures.
The pigment can be an inorganic pigment. The term "inorganic pigment" is
understood to mean any pigment which corresponds to the definition of Ullmann's
Encyclopedia in the "Inorganic Pigment" chapter. Mention may be made, among
inorganic pigments of use in the present invention, of ochres, such as red ochre (clay
(in particular kaolinite) and iron hydroxide (for example haematite)), brown ochre (clay
(in particular kaolinite) and limonite) or yellow ochre (clay (in particular kaolinite) and
goethite); titanium dioxide, optionally surface-treated; zirconium or cerium oxides; zinc,
(black, yellow or red) iron or chromium oxides; manganese violet, ultramarine blue,
chromium hydrate and ferric blue; or metal powders, such as aluminium powder or
copper powder.
Mention may also be made of alkaline earth metal carbonates (such as calcium
carbonate or magnesium carbonate), silicon dioxide, quartz and any other compound
used as inert filler in cosmetic compositions, provided that these compounds contribute
colour or whiteness to the composition under the conditions under which they are
employed.
The pigment can be an organic pigment. The term "organic pigment" is
understood to mean any pigment which corresponds to the definition of Ullmann's
Encyclopedia in the "Organic Pigment" chapter.
The organic pigment can in particular be chosen from nitroso, nitro, azo,
xanthene, pyrene, quinoline, anthraquinone, fluoran or phthalocyanine compounds,
compounds of metal complex type, or isoindolinone, isoindoline, quinacridone,
perinone, perylene, diketopyrrolopyrrole, indigo, thioindigo, dioxazine,
triphenylmethane or quinophthalone compounds.
Use may also be made of any inorganic or organic compound which is insoluble
in the composition and which is conventional in the cosmetics field, provided that these
compounds contribute colour or whiteness to the composition under the conditions
under which they are employed, for example guanine, which, according to the
refractive index of the composition, is a pigment.
In particular, the white or coloured organic pigments can be chosen from
carmine, carbon black, aniline black, azo yellow, quinacridone, phthalocyanine blue,
the blue pigments codified in the Color Index under the references CI 42090, 69800,
69825, 73000, 74100 and 74160, the yellow pigments codified in the Color Index
under the references CI 11680, 11710, 15985, 19140, 20040, 2 1100, 2 1108, 47000
and 47005, the green pigments codified in the Color Index under the references CI
61565, 61570 and 74260, the orange pigments codified in the Color Index under the
references CI 11725, 15510, 45370 and 7 1 105, the red pigments codified in the Color
Index under the references CI 12085, 12120, 12370, 12420, 12490, 14700, 15525,
15580, 15620, 15630, 15800, 15850, 15865, 15880, 17200, 26100, 45380, 45410,
58000, 73360, 73915 and 75470, or the pigments obtained by oxidative polymerization
of indole or phenol derivatives, as are described in Patent FR 2 679 771 .
Mention may also be made, as example, of pigment pastes formed of organic
pigment, such as the products sold by Hoechst under the names:
- Cosmenyl Yellow 10G: Pigment Yellow 3 (CI 11710);
- Cosmenyl Yellow G: Pigment Yellow 1 (CI 11680);
- Cosmenyl Orange GR: Pigment Orange 43 (CI 7 1105);
- Cosmenyl Red R: Pigment Red 4 (CI 12085);
- Cosmenyl Carmine FB: Pigment Red 5 (CI 12490);
- Cosmenyl Violet RL: Pigment Violet 23 (CI 51319);
- Cosmenyl Blue A2R: Pigment Blue 15.1 (CI 74160);
- Cosmenyl Green GG: Pigment Green 7 (CI 74260);
- Cosmenyl Black R: Pigment Black 7 (CI 77266).
The pigments in accordance with the invention can also be in the form of
composite pigments, as are described in Patent EP 1 184 426. These composite
pigments can be composed in particular of particles comprising an inorganic core, at
least one binder, which provides for the attachment of the organic pigments to the
core, and at least one organic pigment which at least partially covers the core.
The organic pigment can also be a lake. The term "lake" is understood to mean
dyes adsorbed onto insoluble particles, the combination thus obtained remaining
insoluble during use.
The inorganic substrates onto which the dyes are adsorbed are, for example,
alumina, silica, calcium sodium borosilicate, calcium aluminium borosilicate and
aluminium.
Mention may be made, among the dyes, of carminic acid. Mention may also be
made of the dyes known under the following names: D&C Red 2 1 (CI 45 380), D&C
Orange 5 (CI 45 370), D&C Red 27 (CI 45 410), D&C Orange 10 (CI 45 425), D&C
Red 3 (CI 45 430), D&C Red 4 (CI 15 510), D&C Red 33 (CI 17 200), D&C Yellow 5
(CI 19 140), D&C Yellow 6 (CI 15 985), D&C Green (CI 6 1 570), D&C Yellow 10 (CI
47 005), D&C Green 3 (CI 42 053) or D&C Blue 1 (CI 42 090).
Mention may be made, as examples of lakes, of the product known under the
following name: D&C Red 7 (CI 15 850:1 ) .
The pigment can also be a special effect pigment. The term "special effect
pigments" is understood to mean pigments which generally create a coloured
appearance (characterized by a certain shade, a certain vividness and a certain
brightness) which is not uniform and which changes as a function of the conditions of
observation (light, temperature, angles of observation, etc.). They thereby contrast with
coloured pigments, which provide a conventional opaque, semi-transparent or
transparent uniform colour.
There exist several types of special effect pigments: those with a low refractive
index, such as fluorescent, photochromic or thermochromic pigments, and those with a
higher refractive index, such as pearlescent agents, interferential pigments or glitter.
Mention may be made, as examples of special effect pigments, of pearlescent
pigments, such as mica covered with titanium or with bismuth oxychloride, coloured
pearlescent pigments, such as mica covered with titanium and with iron oxides, mica
covered with iron oxide, mica covered with titanium and in particular with ferric blue or
chromium oxide or mica covered with titanium and with an organic pigment as defined
above, and pearlescent pigments based on bismuth oxychloride. Mention may be
made, as pearlescent pigments, of the following pearlescent agents: Cellini sold by
Engelhard (mica-Ti0 2-lake), Prestige sold by Eckart (mica-Ti0 2) , Prestige Bronze sold
by Eckart (mica-Fe 20 3) or Colorona sold by Merck (mica-Ti02-Fe 20 3) .
Mention may be also be made of pearlescent agents of gold colour sold in
particular by Engelhard under the names of Brilliant Gold 212G (Timica), Gold 222C
(Cloisonne), Sparkle Gold (Timica), Gold 4504 (Chromalite) and Monarch Gold 233X
(Cloisonne); bronze pearlescent agents sold in particular by Merck under the names
Bronze Fine (17384) (Colorona) and Bronze (17353) (Colorona) and by Engelhard
under the name Super Bronze (Cloisonne); orange pearlescent agents sold in
particular by Engelhard under the names Orange 363C (Cloisonne) and Orange MCR
101 (Cosmica) and by Merck under the names Passion Orange (Colorona) and Matte
Orange (17449) (Microna); brown-coloured pearlescent agents sold in particular by
Engelhard under the names Nu-Antique Copper 340XB (Cloisonne) and Brown
CL4509 (Chromalite); pearlescent agents with a copper glint sold in particular by
Engelhard under the name Copper 340A (Timica); pearlescent agents with a red glint
sold in particular by Merck under the name Sienna Fine (17386) (Colorona);
pearlescent agents with a yellow glint sold in particular by Engelhard under the name
Yellow (4502) (Chromalite); red-coloured pearlescent agents with a gold glint sold in
particular by Engelhard under the name Sunstone G012 (Gemtone); pink pearlescent
agents sold in particular by Engelhard under the name Tan Opale G005 (Gemtone);
black pearlescent agents with a gold glint sold in particular by Engelhard under the
name Nu-Antique Bronze 240 AB (Timica); blue pearlescent agents sold in particular
by Merck under the name Matte Blue (17433) (Microna); white pearlescent agents with
a silvery glint sold in particular by Merck under the name Xirona Silver; golden green
pinkish orangey pearlescent agents sold in particular by Merck under the name Indian
Summer (Xirona); and their mixtures.
Mention may also be made, still as examples of pearlescent agents, of particles
comprising a borosilicate substrate coated with titanium oxide.
Particles comprising a glass substrate coated with titanium oxide are sold in
particular under the name Metashine MC1080RY by Toyal.
Finally, mention may also be made, as examples of pearlescent agents, of
polyethylene terephthalate glitter, in particular that sold by Meadowbrook Inventions
under the name Silver 1P 0.004X0.004 (silvery glitter).
It is also possible to envisage multilayer pigments based on synthetic substrates,
such as alumina, silica, calcium sodium borosilicate, calcium aluminium borosilicate
and aluminium.
The special effect pigments can also be chosen from reflective particles, that is
to say in particular particles having a size, a structure, in particular a thickness of the
layer or layers of which it is composed and their physical and chemical nature, and a
surface condition which allow them to reflect incident light. This reflection may, if
appropriate, have an intensity sufficient to create, at the surface of the composition or
mixture, when the latter is applied to the substrate to be made up, highlight points
visible to the naked eye, that is to say more luminous points which contrast with their
surroundings by appearing to sparkle.
The reflective particles can be selected so as not to detrimentally affect, to a
significant extent, the colouring effect generated by the colouring agents which are
combined with them and more particularly so as to optimize this effect in terms of
colour rendition. They can more particularly have a yellow, pink, red, bronze, orangey,
brown, gold and/or coppery colour or glint.
These particles can exhibit varied forms and can in particular be in the platelet or
globular form, especially the spherical form.
The reflective particles, whatever their form, may or may not exhibit a multilayer
structure and, in the case of a multilayer structure, may exhibit, for example, at least
one layer of uniform thickness, in particular of a reflective material.
When the reflective particles do not exhibit a multilayer structure, they can be
composed, for example, of metal oxides, in particular of titanium or iron oxides
obtained synthetically.
When the reflective particles exhibit a multilayer structure, they can, for example,
comprise a natural or synthetic substrate, in particular a synthetic substrate, at least
partially coated with at least one layer of a reflective material, in particular of at least
one metal or metal material. The substrate can be made of one or more organic and/or
inorganic materials.
More particularly, it can be chosen from glasses, ceramics, graphite, metal
oxides, aluminas, silicas, silicates, in particular aluminosilicates and borosilicates,
synthetic mica and their mixtures, this list not being limiting.
The reflective material can comprise a layer of metal or of a metal material.
Reflective particles are described in particular in the documents
JP-A-091 88830, JP-A-1 0 158450, JP-A-1 0 158541 , JP-A-07258460 and JP-A-
05017710.
Mention may also be made, still by way of example of reflective particles
comprising an inorganic substrate coated with a layer of metal, of the particles
comprising a borosilicate substrate coated with silver.
Particles comprising a glass substrate coated with silver, in the form of platelets,
are sold under the name Microglass Metashine REFSX 2025 PS by Toyal. Particles
comprising a glass substrate coated with nickel/chromium/molybdenum alloy are sold
under the names Crystal Star GF 550 and GF 2525 by this same company.
Use may also be made of particles comprising a metal substrate, such as silver,
aluminium, iron, chromium, nickel, molybdenum, gold, copper, zinc, tin, magnesium,
steel, bronze or titanium, the said substrate being coated with at least one layer of at
least one metal oxide, such as titanium oxide, aluminium oxide, iron oxide, cerium
oxide, chromium oxide, silicon oxides and their mixtures.
Mention may be made, as examples, of aluminium powder, bronze powder or
copper powder coated with Si0 2 sold under the name Visionaire by Eckart.
Mention may also be made of pigments with an interference effect which are not
attached to a substrate, such as liquid crystals (Helicones HC from Wacker) or
interference holographic glitter (Geometric Pigments or Spectra f/x from Spectratek).
Special effect pigments also comprise fluorescent pigments, whether these are
substances which are fluorescent in daylight or which produce ultraviolet fluorescence,
phosphorescent pigments, photochromic pigments, thermochromic pigments and
quantum dots, for example sold by Quantum Dots Corporation.
Quantum dots are luminescent semiconductor nanoparticles capable of emitting,
under light excitation, radiation exhibiting a wavelength of between 400 nm and 700
nm. These nanoparticles are known from the literature. In particular, they can be
synthesized according to the processes described, for example, in US 6 225 198 or
US 5 990 479, in the publications which are cited therein and in the following
publications: Dabboussi B.O. et al., "(CdSe)ZnS core-shell quantum dots: synthesis
and characterisation of a size series of highly luminescent nanocristallites", Journal of
Physical Chemistry B, vol. 101 , 1997, pp 9463-9475, and Peng, Xiaogang et al.,
"Epitaxial growth of highly luminescent CdSe/CdS core/shell nanocrystals with
photostability and electronic accessibility", Journal of the American Chemical Society,
vol. 119, No. 30, pp 7019-7029.
The variety of the pigments which can be used in the present invention makes it
possible to obtain a rich palette of colours and also specific optical effects, such as
metallic effects or interference effects.
The size of the pigment used in the cosmetic composition according to the
present invention is generally between 10 nm and 200 , preferably between 20 nm
and 80 and more preferably between 30 nm and 50 .
The pigments can be dispersed in the product by virtue of a dispersing agent.
The dispersing agent serves to protect the dispersed particles from the
agglomeration or flocculation thereof. This dispersing agent can be a surfactant, an
oligomer, a polymer or a mixture of several of them carrying one or more functionalities
having a strong affinity for the surface of the particles to be dispersed. In particular,
they can become attached physically or chemically to the surface of the pigments.
These dispersants additionally exhibit at least one functional group compatible with or
soluble in the continuous medium. Use is made in particular of esters of 12-
hydroxystearic acid, in particular, and of C8 to C20 fatty acid and of polyol, for instance
glycerol or diglycerol, such as poly(12-hydroxystearic acid) stearate with a molecular
weight of approximately 750 g/mol, such as that sold under the name of Solsperse
2 1 000 by Avecia, polyglyceryl-2 dipolyhydroxystearate (CTFA name), sold under the
reference Dehymyls PGPH by Henkel, or polyhydroxystearic acid, such as that sold
under the reference Arlacel P100 by Uniqema, and their mixtures.
Mention may be made, as other dispersant which can be used in the
compositions of the invention, of the quaternary ammonium derivatives of
polycondensed fatty acids, such as Solsperse 17 000, sold by Avecia, or
polydimethylsiloxane/oxypropylene mixtures, such as those sold by Dow Corning
under the references DC2-5185 and DC2-5225 C.
The pigments used in the cosmetic composition according to the invention can
be surface-treated with an organic agent.
Thus, the pigments surface-treated beforehand of use in the context of the
invention are pigments which have been completely or partially subjected to a surface
treatment of chemical, electronic, electrochemical, mechanochemical or mechanical
nature with an organic agent, such as those which are described in particular in
Cosmetics and Toiletries, February 1990, Vol. 105, pp 53-64, before being dispersed
in the composition in accordance with the invention. These organic agents can, for
example, be chosen from waxes, for example carnauba wax and beeswax; fatty acids,
fatty alcohols and their derivatives, such as stearic acid, hydroxystearic acid, stearyl
alcohol, hydroxystearyl alcohol, lauric acid and their derivatives; anionic surfactants;
lecithins; sodium, potassium, magnesium, iron, titanium, zinc or aluminium salts of
fatty acids, for example aluminium stearate or laurate; metal alkoxides; polyethylene;
(meth)acrylic polymers, for example polymethyl methacrylates; polymers and
copolymers comprising acrylate units; alkanolamines; silicone compounds, for
example silicones or polydimethylsiloxanes; fluorinated organic compounds, for
example perfluoroalkyl ethers; or fluorosilicone compounds.
The surface-treated pigments of use in the cosmetic composition according to
the invention may also have been treated with a mixture of these compounds and/or
have undergone several surface treatments.
The surface-treated pigments of use in the context of the present invention can
be prepared according to surface treatment techniques well known to a person skilled
in the art or found as such commercially.
Preferably, the surface-treated pigments are covered with an organic layer.
The organic agent with which the pigments are treated can be deposited on the
pigments by solvent evaporation, chemical reaction between the molecules of the
surface agent or creation of a covalent bond between the surface agent and the
pigments.
The surface treatment can thus be carried out, for example, by chemical reaction
of a surface agent with the surface of the pigments and creation of a covalent bond
between the surface agent and the pigments or fillers. This method is described in
particular in Patent US 4 578 266.
Preferably, use will be made of an organic agent covalently bonded to the
pigments.
The agent for the surface treatment can represent from 0.1% to 50% by weight,
preferably from 0.5% to 30% by weight and more preferentially still from 1% to 10% by
weight of the total weight of the surface-treated pigments.
Preferably, the surface treatments of the pigments are chosen from the following
treatments:
- a PEG-silicone treatment, such as the AQ surface treatment sold by LCW;
- a methicone treatment, such as the SI surface treatment sold by LCW;
- a dimethicone treatment, such as the Covasil 3.05 surface treatment sold by
LCW;
- a dimethicone/trimethylsiloxysilicate treatment, such as the Covasil 4.05 surface
treatment sold by LCW;
- a magnesium myristate treatment, such as the MM surface treatment sold by
LCW;
- an aluminium dimyristate treatment, such as the Ml surface treatment sold by
Miyoshi;
- a perfluoropolymethylisopropyl ether treatment, such as the FHC surface
treatment sold by LCW;
- an isostearyl sebacate treatment, such as the HS surface treatment sold by
Miyoshi;
- a perfluoroalkyl phosphate treatment, such as the PF surface treatment sold by
Daito;
- an acrylate/dimethicone copolymer and perfluoroalkyl phosphate treatment,
such as the FSA surface treatment sold by Daito;
- a polymethylhydrosiloxane/perfluoroalkyl phosphate treatment, such as the
FS01 surface treatment sold by Daito;
- an acrylate/dimethicone copolymer treatment, such as the ASC surface
treatment sold by Daito;
- an isopropyl titanium triisostearate treatment, such as the ITT surface treatment
sold by Daito;
- an acrylate copolymer treatment, such as the APD surface treatment sold by
Daito;
- a perfluoroalkyl phosphate/isopropyl titanium triisostearate treatment, such as
the PF + ITT surface treatment sold by Daito.
Preferably, the pigment is chosen from inorganic pigments or inorganic/organic
mixed pigments.
The amount of pigment(s) can vary from 0.0 1% to 30% by weight, more
particularly from 0.05% to 20% by weight and preferably from 0.1% to 15% by weight,
with respect to the total weight of the composition.
The composition of the invention can comprise other coloured or colouring
entities, such as direct dyes or dye precursors.
Thickening agent
According to a preferred embodiment, the composition according to the invention
comprises at least one thickening agent chosen from polymeric or non-polymeric and
inorganic or organic thickening agents, and their mixtures.
The term "thickener" is understood to mean a compound which modifies the
rheology of the medium in which it is incorporated.
According to a specific embodiment of the invention, the composition comprises
at least one inorganic thickener.
Preferably, the thickener or thickeners is/are chosen from fumed silica, clays or
their mixtures.
The fumed silicas can be obtained by high-temperature pyrolysis of a volatile
silicon compound in an oxhydric flame, producing a finely divided silica. This process
makes it possible in particular to obtain hydrophilic silicas which exhibit a large number
of silanol groups at their surface. Such hydrophilic silicas are sold, for example, under
the names Aerosil 130®, Aerosil 200®, Aerosil 255®, Aerosil 300® and Aerosil 380®
by Degussa and Cab-O-Sil HS-5®, Cab-O-Sil EH-5®, Cab-O-Sil LM-130®, Cab-O-Sil
MS-55® and Cab-O-Sil M-5® by Cabot.
It is possible to chemically modify the surface of the said silica via a chemical
reaction which brings about a reduction in the number of silanol groups. It is possible
in particular to replace silanol groups with hydrophobic groups: a hydrophobic silica is
then obtained.
The hydrophobic groups can be:
- trimethylsiloxyl groups, which are obtained in particular by treating fumed silica
in the presence of hexamethyldisilazane. Silicas thus treated are known as "Silica
silylate" according to the CTFA (6th edition, 1995). They are sold, for example, under
the references Aerosil R812® by Degussa and Cab-O-Sil TS-530® by Cabot.
- dimethylsilyloxyl or polydimethylsiloxane groups, which are obtained in
particular by treating fumed silica in the presence of polydimethylsiloxane or
dimethyldichlorosilane. Silicas thus treated are known as "Silica dimethyl silylate"
according to the CTFA (6th edition, 1995). They are sold, for example, under the
references Aerosil R972® and Aerosil R974® by Degussa and Cab-O-Sil TS-610®
and Cab-O-Sil TS-720® by Cabot.
The fumed silica preferably exhibits a particle size which can be nanometric to
micrometric, for example ranging from approximately 5 to 200 nm.
Clays are well known products which are described, for example, in the
publication "Mineralogie des argiles" [Mineralogy of Clays], S. Caillere, S. Henin and
M. Rautureau, 2nd Edition, 1982, Masson.
Clays are silicates including a cation which can be chosen from calcium,
magnesium, aluminium, sodium, potassium or lithium cations, and their mixtures.
Mention may be made, as examples of such products, of clays of the family of
the smectites, such as montmorillonites, hectorites, bentonites, beidellites or
saponites, and also of the family of the vermiculites, stevensite or chlorites.
These clays can be of natural or synthetic origin. Use is preferably made of clays
which are cosmetically compatible with and acceptable to keratinous substances.
Mention may be made, as clay which can be used according to the invention, of
synthetic hectorites (also known as laponites), such as the products sold by Laporte
under the name Laponite XLG, Laponite RD and Laponite RDS (these products are
sodium magnesium silicates and in particular lithium magnesium sodium silicates);
bentonites, such as the product sold under the name Bentone HC by Rheox;
magnesium aluminium silicates, in particular hydrated, such as the product sold by
R.T. Vanderbilt Company under the name Veegum Ultra, or calcium silicates and in
particular that in synthetic form sold by the company CELITE ET WALSH ASS under the
name Micro-Cel C.
The organophilic clay can be chosen from montmorillonite, bentonite, hectorite,
attapulgite or sepiolite, and their mixtures. The clay is preferably a bentonite or a
hectorite.
These clays can be modified with a chemical compound chosen from quaternary
ammoniums, tertiary amines, amine acetates, imidazolines, amine soaps, fatty
sulfates, alkylarylsulfonates, amine oxides and their mixtures.
Mention may be made, as organophilic clays, of quaternium-18 bentonites, such
as those sold under the names Bentone 3, Bentone 38 and Bentone 38V by Rheox,
Tixogel VP by United Catalyst and Claytone 34, Claytone 40 and Claytone XL by
Southern Clay; stearalkonium bentonites, such as those sold under the names
Bentone 27 by Rheox, Tixogel LG by United Catalyst and Claytone AF and Claytone
APA by Southern Clay; and quaternium-18/benzalkonium bentonites, such as those
sold under the names Claytone HT and Claytone PS by Southern Clay.
The thickener can also be chosen from organic compounds.
Mention may be made, for example, of the following polymeric or non-polymeric
products:
- C10-C30 fatty amides, such as lauric acid diethanolamide,
- the polyglyceryl (meth)acrylate polymers sold under the Hispagel or Lubragel
names by Hispano Quimica or Guardian,
- polyvinylpyrrolidone,
- polyvinyl alcohol,
- crosslinked acrylamide polymers and copolymers, such as those sold under the
names PAS 5161 or Bozepol C by Hoechst or Sepigel 305 by SEPPIC, or alternatively
the crosslinked methacryloyloxyethyltrimethylammonium chloride
homopolymers sold under the name Salcare SC95 by Allied Colloid,
- associative polymers and in particular associative polyurethanes.
Such thickeners are described in particular in Application EP-A-1 400 234.
Preferably, the composition comprises at least one inorganic thickening agent
which is preferably chosen from clays and more advantageously still from smectites.
The thickening agent is present in the composition in a total content ranging from
0.1% to 10% by weight, with respect to the weight of the composition.
The composition according to the invention comprises water, which can
preferably be present in a content ranging from 20% to 98% by weight, with respect to
the weight of the composition.
The compositions can also comprise at least one agent commonly used in
cosmetics, for example chosen from reducing agents, fatty substances, organic
solvents or oils, softening agents, anti-foaming agents, moisturizing agents, UV
screening agents, peptizing agents, solubilizing agents, fragrances, anionic, cationic,
non-ionic or amphoteric surfactants, proteins, vitamins, propellants, oxyethylenated or
non-oxyethylenated waxes, paraffins or C 0-C3o fatty acids, such as stearic acid or
lauric acid.
The above additives are generally present in an amount for each of them of
between 0.01% and 20% by weight, with respect to the weight of the composition.
Of course, a person skilled in the art will take care to choose this or these
optional additive(s) so that the advantageous properties intrinsically attached to the
formation of the coating in accordance with the invention are not, or not substantially,
detrimentally affected.
The composition according to the invention can be provided in particular in the
form of a suspension, a dispersion, a gel, an emulsion, in particular an oil-in-water
(O/W), water-in-oil (W/O) or multiple (W/O/W or polyol/O/W or 0/W/O) emulsion, a
cream, a foam, a stick, a dispersion of vesicles, in particular of ionic or non-ionic lipids,
a two-phase or multiphase lotion, a spray or a paste. The composition can also be
provided in the form of a lacquer.
A person skilled in the art can choose the appropriate formulation form, and also
its method of preparation, on the basis of his general knowledge, taking into account
first the nature of the constituents used, in particular their solubility in the support, and
secondly the application envisaged for the composition.
Device
As indicated above, the composition is present in a container comprising a
removable applicator end piece comprising a permeable material through which the
said composition can pass.
Advantageously, the container further comprises a removable stopper fitted to the
said applicator on the container.
Reference may be made to figure 1, which , however, is presented only by way of
indication and without any implied limitation of the device.
Figure 1 shows an exploded perspective view of a container 3 comprising a removable
applicator end piece 2 comprising a permeable material through which the said
composition can pass and a removable stopper 1 that fits to the said applicator on the
container.
Such a device employed in the process according to the invention is described in
particular in Patent US 5 961 665 (Fishmann).
Advantageously, the container comprising the composition can comprise an
annular narrowing to help it to be grasped in the hand.
The container can, for example, be in the form of a small flexible or rigid bottle.
Alternatively, a bottle made of thermoplastic material, for example of PET, can be
used . The bottle has, for example, a capacity of 6 ml. The bottle comprises a side wall
in the form of a cylinder of revolution , one end of which is closed by a base. The
second end is formed by a portion having a narrowed diameter, which ends in a free
edge defining an opening.
An applicator end piece is provided to be fitted onto the bottle and to be snapfastened
or screwed onto the abovementioned opening of the bottle.
The end piece is provided in the form of a substantially cylindrical shell having a
uniform circular diameter over a large part of its length. It could have any other form,
for example a frustoconical form, becoming progressively smaller until it defines a
circular portion.
The end piece has, for example, a diameter of approximately 15 mm. Axial ribs
can be provided on the internal wall of the shell. They can comprise a radial
indentation which , in the fitted position of the shell, will become housed in the opening
of the bottle, thereby allowing the shell to be snap-fastened onto the bottle.
Alternatively, it is possible to provide for the internal wall of the shell to be supplied
with a thread intended to interact with a thread provided on the neck of the bottle.
The applicator end piece can comprise a cylindrical skirt, which provides sealing
between the opening of the bottle and the outlet orifice.
The applicator end piece is advantageously obtained by moulding a single piece
of a preferably thermoplastic material, in particular of a polyethylene, of a
polypropylene, of a polyethylene terephthalate, of a polyvinyl chloride or of a
polyamide.
The applicator, in particular in the form of a pad, makes it possible to regulate the
flow of composition which it allows to pass, and to prevent it from running.
Advantageously, the applicator, in particular pad, comprises a valve stem and an
integral spring which makes possible the dispensing of an appropriate amount of
composition.
The permeable material through which the dyeing composition can pass can be a
felt, a flock coating, a foam or an end piece of roll-on type (the roll-on can be a sphere
or a cylinder or else can have an ovoid shape of the rugby ball type) and preferably a
foam, preferably a polymeric foam, for example made of polyurethane.
For use, the stopper is removed in order to allow the product to be applied by the
applicator.
The user takes hold of the bottle, inverts it or tips it and applies the end piece to
the fibres to be coloured. It then suffices for the user to apply pressure, one or more
times, to the applicator end piece (padding).
Application Method
The composition described above, included in a container also as described
above, can be employed on dry or wet keratinous fibres and also on any type of fibre,
light or dark, natural or dyed, or permanent-waved, bleached or straightened.
According to a specific embodiment of the method of the invention, the fibres are
washed before application of the composition described above.
The application to the fibres can be carried out by any conventional means, in
particular using a comb, a brush, including a fine brush, or the fingers.
After the application of the composition, the fibres can be left to dry or dried, for
example at a temperature of greater than or equal to 30°C. According to a specific
embodiment, this temperature is greater than 40°C. According to a specific
embodiment, this temperature is greater than 45°C and less than 220°C.
The drying, if it is employed, can be carried out immediately after the application
or after a leave-in time which can range from 1 minute to 30 minutes.
Preferably, if the fibres are dried, they are dried, in addition to a contribution of
heat, with a flow of air. This flow of air during the drying makes it possible to improve
the individualization of the coating.
During the drying, a mechanical action can be exerted on the locks, such as
combing, brushing or running the fingers through the hair. This operation can likewise
be carried out once the fibres have dried, naturally or otherwise.
The drying stage of the method of the invention can be carried out with a hood
dryer, a hair dryer, a straightening iron, a Climazone, etc.
When the drying stage is carried out with a hood dryer or a hair dryer, the drying
temperature is between 40°C and 110°C and preferably between 50°C and 90°C.
When the drying stage is carried out with a smoothing iron, the drying
temperature is between 110°C and 220°C and preferably between 140°C and 200°C.
Once the drying is complete, a final rinsing or shampooing operation can
optionally be carried out.
The invention will be illustrated more fully with the aid of the non-limiting examples that
follow. Unless otherwise mentioned, the amounts indicated are expressed in grams.
EXAMPLES
Composition examples:
0.6 g of composition A is applied, with the applicator according to the invention,
to a moustache.
After a few seconds, the fibres are dry and coloured and the black colour is
homogenous and persistent towards several shampooing operations.
A dyed moustache is obtained, the hairs of which are individualized and the
colour of which is persistent towards washing.
Composition B
Styrene/acrylates copolymer in aqueous dispersion, sold 20 g, i.e. 9.43% as AM
by BASF under the name Joncryl 77.
Divinyldimethicone/dimethicone copolymer in aqueous 7.9 g, i.e. 4.76% as AM
emulsion, sold by Dow Corning under the reference
HMW 2220 Non-Ionic Emulsion
Clay (Magnesium Aluminium Silicate), sold by Vanderbilt 1.8 g
under the name Veegum granules
Black 2 in aqueous dispersion, from Daito Kasei Kogyo 9 g, i.e. 2.25% as AM
under the name WD-CB2
Water q.s. 100 g
0.6 g of composition A is applied, with the applicator according to the invention, to a
moustache.
After a few seconds, the fibres are dry and coloured and the black colour is
homogenous and persistent towards several shampooing operations.
A dyed moustache is obtained, the hairs of which are individualized and the
colour of which is persistent towards washing.
CLAIMS
1. Method for dyeing human keratinous fibres, in particular the hair, preferably
roots, sidelocks, non-head hair, in particular beard or moustache hair, eyelashes or
eyebrows, which consists in applying a dyeing composition using a container
comprising a removable applicator comprising a permeable material through which the
composition can pass, the composition being applied by bringing the applicator into
contact with the dry or wet fibres, the said composition comprising at least one
aqueous dispersion of particles of hybrid hydrophobic film-forming acrylic polymer, at
least one linear block silicone copolymer and at least one pigment.
2. Method according to the preceding claim, characterized in that the dyeing
composition comprises at least one linear block silicone copolymer provided in the
form of particles in dispersion in an aqueous medium.
3. Method according to either one of the preceding claims, in which the dyeing
composition comprises at least one linear block silicone copolymer obtained by a chain
extension reaction in the presence of a catalyst, starting from at least:
(a) one polysiloxane (i) having at least one reactive group and preferably one or
two reactive groups per molecule; and
(b) one organosilicone compound (ii) which reacts with the polysiloxane (i) by a
chain extension reaction.
4. Method according to the preceding claim, characterized in that the
organopolys mpounds of formula (I):
R2_
in which R and R2 represent, independently of one another, a hydrocarbon
group having from 1 to 20 carbon atoms or an aryl group or a reactive group, and
n is an integer greater than 1, provided that there are on average between one
and two reactive groups per polymer.
5. Method according to the preceding claim, characterized in that the reactive
group is chosen from hydrogen; aliphatically unsaturated groups; the hydroxyl group;
alkoxy groups; alkoxyalkoxy groups; the acetoxy group; amino groups; and their
mixtures.
6. Method according to either one of Claims 4 and 5, characterized in that R
represents a methyl group and R2 at the chain end represents a vinyl group.
7. Method according to any one of Claims 3 to 6, characterized in that the
organosilicone compound (ii) is chosen from polysiloxanes of formula (I) or compounds
acting as chain-extending agent such as a silane, a siloxane or a silazane.
8. Method according to any one of Claims 3 to 7, characterized in that the
of formula (II):
where n is an integer greater than 1 and preferably greater than 10, preferably
equal to 20.
9. Method according to any one of Claims 2 to 8, characterized in that the
dispersion is an aqueous dispersion of divinyldimethicone/dimethicone copolymer.
10. Method according to one of the preceding claims, in which the dyeing
composition exhibits a content of linear block silicone copolymer(s), expressed as
polymeric active materials, ranging from 0.1 % to 30% by weight, more particularly from
0.5% to 20% by weight and preferably from 1% a 15% by weight, with respect to the
total weight of the composition.
11. Method according to any one of the preceding claims, in which the dyeing
composition comprises at least one hybrid film-forming acrylic polymer synthesized
from at least one monomer having at least one (meth)acrylic acid group and/or esters
of these acid monomers and/or amides of these acid monomers and from a least one
styrene compound.
12. Method according to any one of the preceding claims, in which the dyeing
composition comprises at least one hybrid film-forming acrylic polymer chosen from
styrene/acrylate copolymers, in particular a copolymer resulting from the
polymerization of at least one styrene monomer and of at least one C-I-C-IO alkyl
acrylate monomer, preferably chosen from methyl acrylate, ethyl acrylate, propyl
acrylate, butyl acrylate, hexyl acrylate, octyl acrylate or 2-ethylhexyl acrylate.
13. Method according to any one of the preceding claims, in which the hybrid
hydrophobic film-forming acrylic polymer or polymers in aqueous dispersion is or are
present in a content, as active materials, ranging from 0.1% to 30% by weight, more
particularly from 0.5% to 20% by weight and preferably from 1% to 15% by weight,
relative to the total weight of the composition.
14. Method according to any one of the preceding claims, in which the hybrid
hydrophobic film-forming acrylic polymer or polymers in aqueous dispersion and the
linear block silicone copolymer or copolymers are present in a hybrid hydrophobic filmforming
acrylic polymer(s) to linear block silicone copolymer(s) ratio by weight (as
active materials) ranging from 0.2 to 10, advantageously from 0.5 to 5 and preferably
from 1 to 3.
15. Method according to any one of the preceding claims, in which the amount
of pigment(s) ranges from 0.01% to 30% by weight, more particularly from 0.05% to
20% by weight and preferably from 0.1% to 15% by weight, with respect to the total
weight of the composition.
16. Method according to any one of the preceding claims, in which the
composition additionally comprises at least one inorganic thickening agent preferably
chosen from clays, preferably a smectite.
17. Method according to any one of the preceding claims, in which the
application of the composition is optionally followed by a drying of the fibres.
18. Device including a composition defined according to any one of Claims 1 to
16, comprising a container comprising a removable applicator comprising a permeable
material through which the said composition can pass; a removable stopper fitted to
the said removable applicator on the container.