Composition comprising ellagic acid and a particular cationic surfactant,
and cosmetic use thereof
The present invention relates to a cosmetic composition comprising ellagic acid
or a derivative thereof and at least one particular surfactant.
Ellagic acid is a compound in the form of a white powder, with a melting point
above 360°C. It is an active agent that is known in the field of cosmetics for its use as
an anti-canities active agent (EP 1 870 081 ) , antioxidant, depigmenting agent (US 5
073 545) or antipollution agent (EP 1 282 395).
Now, Inventors discovered that it may also be used as an antidandruff agent.
Dandruff problems affect up to 50% of the world's population. They affect both
men and women and are perceived as having a very negative psychosocial impact.
The appearance of dandruff is disagreeable both aesthetically and because of the
discomfort it causes, and as such many people confronted with this problem to
variable degrees wish to eliminate it efficiently and definitively.
Dandruff corresponds to excessive and visible desquamation of the scalp
resulting from excessively rapid multiplication of the epidermal cells and their
abnormal maturation. This phenomenon may be caused especially by microtrauma of
physical or chemical nature, such as excessively aggressive hair treatments, extreme
climatic conditions, nervousness, the diet, fatigue and pollution, but it has been
demonstrated that dandruff conditions usually result from a disorder of the microflora
of the scalp and are more particularly due to the excessive colonization of a fungus
belonging to the family of yeasts of the genus Malassezia (previously known as
Pityrosporum) and which is naturally present on the scalp.
There is thus great interest in upgrading this ingredient in suitable formulations.
However, since ellagic acid is very sparingly soluble in water and in the solvents and
oils commonly used in cosmetic compositions, it is thus difficult to incorporate it
uniformly into cosmetic compositions, especially into compositions that comprise an
aqueous medium, without giving rise to the formation of aggregates that might cause
instability of the composition over time and a loss of efficacy.
Now, such an unstable composition cannot be applied to the skin and/or the hair
since it cannot distribute the ellagic acid efficiently over the treated zones. The efficacy
of ellagic acid is thus compromised.
Moreover, it is known practice from patent application FR-A-2 855 051 to
disperse ellagic acid powder using a salt of a copolymer of maleic anhydride and of
diisobutylene and a copolymer of polyvinylpyrrolidone type, using a milling technique
with the aid of a ball mill, which requires long and expensive operations to make this
dispersion.
Patent application FR-A-2 893 505 describes an aqueous dispersion of ellagic
acid made with a copolymer consisting of polyethylene glycol and polypropylene glycol
blocks. However, it has been found that these aqueous dispersions do not show good
stability over time, especially after 24 hours of storage at room temperature (25°C),
since the ellagic acid particles fall to the bottom of the water and no longer remain in
suspension. The aqueous dispersion is thus no longer homogeneous after a certain
storage time, making it unsuitable for use for the manufacture of cosmetic products.
There is thus a need for aqueous compositions of ellagic acid or of a derivative
thereof that promote the dispersion of ellagic acid or of the derivative and that limit
the formation of aggregates and allow very good distribution of the active agent
during application and thus optimum efficacy, while at the same time conserving
good working properties and good cosmetic properties.
More specifically, a subject of the invention is a cosmetic composition
comprising, in a cosmetically acceptable medium:
(i) one or more compounds chosen from ellagic acid, ethers thereof and ellagic
acid salts or ethers thereof, and
(ii) one or more cationic surfactants comprising one or more permanent positive
charges as defined below.
Such a composition spreads easily on the hair and the scalp, is removed easily
with water, and gives clean, shiny, soft hair.
The composition according to the invention shows good homogeneity and good
stability on storage both at room temperature (25°C) and at higher temperatures (37
or 45°C, for example) and does not lead to the formation of aggregates.
A subject of the invention is also a non-therapeutic cosmetic treatment process
for treating keratin materials, especially the hair and the scalp, comprising the
application to the said materials of a composition as described previously. The
cosmetic treatment process is in particular a process for eliminating and/or reducing
dandruff, comprising the application of a cosmetically effective amount of the said
dispersion as an antidandruff cosmetic agent to the scalp and/or the hair.
The composition according to the invention comprises one or more compounds
(i) chosen from ellagic acid, ethers thereof and ellagic acid salts or ethers thereof.
Ellagic acid, also known as 2,3,7,8-tetrahydroxy(1 )benzopyrano(5,4,3-
cde)(1)benzopyran-5,10-dione, is a well-known molecule belonging to the polyphenol
group, and is present in the plant kingdom. Reference may be made to the Merck
Index 20th edition ( 1996), No. 3588.
Ellagic acid has the chemical formula (I) below:
which comprises four fused rings.
Ellagic acid is commercially available, for example from the company Sigma,
France.
Document FR-A-1 478 523 discloses a process for purifying ellagic acid and
also the purified ellagic acids obtained via such a process.
The ellagic acid ether(s) that may be used according to the invention are
preferably chosen from the mono-, di-, tri- or polyethers obtained by etherification of
one or more hydroxyl groups (one of the four OH groups of ellagic acid) with one or
more groups chosen from C2-C2o alkyl groups, polyoxyalkylene groups or groups
derived from one or more mono- or polysaccharides.
Such ethers are described in patent US 5 073 545. Preferably, these ellagic
acid ethers are chosen from 3,4-di-O-methylellagic acid, 3,3',4-tri-O-methylellagic
acid and 3,3'-di-0-methylellagic acid.
The ellagic acid salt(s) that may be used according to the invention are
preferably chosen from the salts of alkali metals or alkaline-earth metals, such as
sodium, potassium, calcium and magnesium, ammonium salts and amine salts such
as triethanolamine, monoethanolamine, arginine and lysine salts. Preferably, the
ellagic acid salt(s) or ethers thereof that may be used according to the invention are
chosen from the salts of alkali metals or alkaline-earth metals, especially the sodium,
potassium, calcium or magnesium salts.
Among all the compounds (i) mentioned, it is preferred to use ellagic acid and
salts thereof.
Ellagic acid and its ethers or ellagic acid salts or ether salts thereof may be
present in the cosmetic or dermatological composition according to the invention in a
content ranging from 0.1% to 10% by weight, in particular from 0.5% to 5% and
preferably from 0.2% to 2% by weight relative to the total weight of the cosmetic
composition.
The composition according to the invention comprises one or more cationic
surfactants as defined below.
In general, a cationic surfactant may bear one or more positive permanent
charges or may contain one or more cationizable functions in the composition
according to the invention. The cationic surfactants of the invention are those
bearing one or more positive permanent charges, i.e. one or more quaternized
nitrogen atoms.
As examples of cationic surfactants that may be used in the cosmetic
composition according to the invention, mention may be made of quaternary
ammonium salts that have the general formula (II) below:
8 R 10
N X -
R R
(II)
in which the radicals R8 to Rn, which may be identical or different, represent a
linear or branched aliphatic radical comprising from 1 to 30 carbon atoms or an
aromatic radical such as aryl or alkylaryl, at least one of the radicals R8 to R
comprising from 8 to 30 carbon atoms and preferably from 12 to 24 carbon atoms.
The aliphatic radicals may comprise heteroatoms especially such as oxygen,
nitrogen, sulfur and halogens.
The aliphatic radicals are chosen, for example, from C -3oalkyl, C -3oalkoxy,
polyoxyalkylene (C2-C6) , C -3o alkylamide, (Ci2-C22)alkylamido(C 2-C6)alkyl, (C12-
C22)alkylacetate, and Ci-30 hydroxyalkyl; X is an anion chosen from the group of halides,
phosphates, acetates, lactates, (CrC 4)alkyl sulfates and (Ci-C4)alkyl- or ( -
C4)alkylaryl-sulfonates.
Among the quaternary ammonium salts of formula (II), the ones preferably
used are, on the one hand, tetraalkylammonium chlorides, for instance
dialkyldimethylammonium chlorides or alkyltrimethylammonium chlorides, in which
the alkyl radical comprises from about 12 to 22 carbon atoms, in particular
behenyltrimethylammonium chloride, distearyldimethylammonium chloride,
cetyltrimethylammonium chloride, or benzyldimethylstearylammonium chloride, or,
on the other hand, distearoylethylhydroxyethylmethylammonium methosulfate,
dipalmitoylethylhydroxyethylammonium methosulfate or
distearoylethylhydroxyethylammonium methosulfate, or else, finally,
palmitylamidopropyltrimethylammonium chloride or
stearamidopropyldimethyl(myristyl acetate)ammonium chloride sold under the name
Ceraphyl® 70 by the company Van Dyk.
quaternary di- or triammonium salts in particular of formula (IV):
++
2X-
(IV)
in which R16 denotes an alkyl radical comprising approximately 16 to 30
carbon atoms, optionally hydroxylated and/or interrupted with one or more oxygen
atoms, R17 is chosen from hydrogen, an alkyl radical comprising from 1 to 4 carbon
atoms and a group [(R16a)(R17a)(R18a)N + -(CH2)3-,Y-], R16a, R17a, R18a, R18,
R19, R20 and R21 , which may be identical or different, are chosen from hydrogen
and an alkyl radical comprising from 1 to 4 carbon atoms, and X and Y-, which may
be identical or different, are halides, acetates, phosphates, nitrates, (Ci-C4)alkyl
sulfates, (CrC 4)alkyl-sulfonate or (Ci-C4)alkylaryl-sulfonates, in particular methyl
sulfate or ethyl sulfate. Such compounds are, for example, Finquat CT-P sold by the
company Finetex (Quaternium-89) and Finquat CT sold by the company Finetex
(Quaternium-75),
- quaternary ammonium salts containing at least one ester function, especially
such as those of formula (V) below:
in which:
R22 is chosen from CrC 6 alkyl and CrC 6 hydroxyalkyl or dihydroxyalkyl
radicals;
- R23 is chosen from:
- the radical
- radicals R27, which are linear or branched, saturated or unsaturated C1-C22
hydrocarbon-based radicals,
- a hydrogen atom,
- R25 is chosen from:
O
II
R2 —C—
- the radical
- radicals R29, which are linear or branched, saturated or unsaturated Ci-C 6
hydrocarbon-based radicals,
- a hydrogen atom,
R24, R26 and R28, which may be identical or different, are chosen from linear or
branched, saturated or unsaturated C7-C21 hydrocarbon-based radicals;
r, s and t , which may be identical or different, are integers ranging from 2 to 6;
y is an integer ranging from 1 to 10;
x and z , which may be identical or different, are integers ranging from 0 to 10;
X is a simple or complex, organic or mineral anion;
with the proviso that the sum x + y + z is from 1 to 15, that when x is 0, then
R23 denotes R27 and that when z is 0, then R25 denotes R2g.
The alkyl radicals R22 may be linear or branched, but more particularly linear.
R22 preferably denotes a methyl, ethyl, hydroxyethyl or dihydroxypropyl radical,
and more particularly a methyl or ethyl radical.
Advantageously, the sum x + y + z is from 1 to 10.
When R23 is a hydrocarbon-based radical R27, it may be long and may contain
from 12 to 22 carbon atoms, or may be short and may contain from 1 to 3 carbon
atoms.
When R25 is a hydrocarbon-based radical R2g, it preferably contains 1 to 3
carbon atoms.
Advantageously, R24 , 26 and R28, which may be identical or different, are
chosen from linear or branched, saturated or unsaturated Cn-C 2 i hydrocarbonbased
radicals, and more particularly from linear or branched, saturated or
unsaturated Cn-C 2 i alkyl and alkenyl radicals.
Preferably, x and z , which may be identical or different, are equal to 0 or 1.
Advantageously, y is equal to 1.
Preferably, r, s and t , which may be identical or different, are equal to 2 or 3,
and even more particularly are equal to 2 .
The anion X is preferably a halide (chloride, bromide or iodide), a (C
C4)alkyl sulfate or a (CrC 4)alkyl- or (Ci-C 4)alkylaryl-sulfonate. However, methanesulfonate,
phosphate, nitrate, tosylate, an anion derived from an organic acid, such as
acetate or lactate, or any other anion that is compatible with the ammonium contain
ing an ester function, may be used.
The anion X is even more particularly chloride, methyl sulfate and or ethyl
sulfate.
Use is made more particularly in the composition according to the invention of
the ammonium salts of formula (V) in which:
- R22 denotes a methyl or ethyl radical,
- x and y are equal to 1;
- z is equal to 0 or 1;
- r, s and t are equal to 2 ;
- R23 is chosen from:
- the radical
- methyl, ethyl or C14-C22 hydrocarbon-based radicals,
- a hydrogen atom;
- R25 is chosen from:
O
II
-2 C —
- the radical
- a hydrogen atom;
- R24 , R26 and R28, which may be identical or different, are chosen from linear or
branched, saturated or unsaturated C13-C17 hydrocarbon-based radicals and
preferably from linear or branched, saturated or unsaturated C13-C17 alkyl and alkenyl
radicals.
The hydrocarbon-based radicals are advantageously linear.
Examples that may be mentioned include the compounds of formula (V) such
as the diacyloxyethyldimethylammonium,
diacyloxyethylhydroxyethylmethylammonium,
monoacyloxyethyldihydroxyethylmethylammonium, triacyloxyethylmethylammonium
and monoacyloxyethylhydroxyethyldimethylammonium salts (chloride or methyl
sulfate in particular), and mixtures thereof. The acyl radicals preferably contain 14 to
18 carbon atoms and are obtained more particularly from a plant oil such as palm oil
or sunflower oil. When the compound contains several acyl radicals, these radicals
may be identical or different.
These products are obtained, for example, by direct esterification of
triethanolamine, triisopropanolamine, an alkyldiethanolamine or an
alkyldiisopropanolamine, which are optionally oxyalkylenated, with fatty acids or with
fatty acid mixtures of plant or animal origin, or by transesterification of the methyl
esters thereof. This esterification is followed by a quaternization using an alkylating
agent such as an alkyl halide (preferably a methyl or ethyl halide), a dialkyi sulfate
(preferably dimethyl or diethyl sulfate), methyl methanesulfonate, methyl paratoluenesulfonate,
glycol chlorohydrin or glycerol chlorohydrin.
Such compounds are sold, for example, under the names Dehyquart® by the
company Henkel, Stepanquat® by the company Stepan, Noxamium® by the
company CECA or Rewoquat® WE 18 by the company Rewo-Witco.
The composition according to the invention preferably contains a mixture of
quaternary ammonium salts of mono-, di- and triesters with a weight majority of
diester salts.
Examples of mixtures of ammonium salts that may be used include the mixture
containing 15% to 30% by weight of acyloxyethyldihydroxyethylmethylammonium
methyl sulfate, 45% to 60% of diacyloxyethylhydroxyethylmethylammonium methyl
sulfate and 15% to 30% of triacyloxyethylmethylammonium methyl sulfate, the acyl
radicals containing from 14 to 18 carbon atoms and being derived from palm oil that
is optionally partially hydrogenated.
It is also possible to use the ammonium salts containing at least one ester
function that are described in patents US-A-4 874 554 and US-A-4 137 180.
Among the quaternary ammonium salts of formula (II), the ones preferably
used are, on the one hand, tetraalkylammonium chlorides, for instance
dialkyldimethylammonium chlorides or alkyltrimethylammonium chlorides, in which
the alkyl radical comprises from about 12 to 22 carbon atoms, in particular
behenyltrimethylammonium chloride, distearyldimethylammonium chloride,
cetyltrimethylammonium chloride, or benzyldimethylstearylammonium chloride, or,
on the other hand, distearoylethylhydroxyethylmethylammonium methosulfate,
dipalmitoylethylhydroxyethylammonium methosulfate or
distearoylethylhydroxyethylammonium methosulfate, or else, finally,
palmitylamidopropyltrimethylammonium chloride or
stearamidopropyldimethyl(myristyl acetate)ammonium chloride sold under the name
Ceraphyl® 70 by the company Van Dyk.
Among all the cationic surfactants that may be present in the composition
according to the invention, the ones preferably chosen are cetyltrimethylammonium
salts, behenyltrimethylammonium salts,
dipalmitoylethylhydroxyethylmethylammonium salts,
distearoylethylhydroxyethylmethylammonium salts and methyl(C9-Ci 9)alkyl (Cio-
C2o)alkylamidoethylimidazolium salts, and mixtures thereof.
The cationic surfactant(s) may be present in a content ranging from 0.01% to
15% by weight relative to the total weight of the cosmetic or dermatological
composition, preferably ranging from 0.1% to 10% by weight and more preferentially
from 0.2% to 5% by weight.
Preferably, the cationic surfactant(s) (ii)/compound(s) (i) weight ratio ranges from
0.1 to 50, even more preferentially from 0.5 to 25, better still from 1 to 10 and even
better still from 1 to 5.
The cosmetically acceptable medium is formed from water or from a mixture of
water and of at least one cosmetically acceptable solvent preferably chosen from -
C4 lower alcohols, such as ethanol, isopropanol, tert-butanol or n-butanol; polyols
such as glycerol, propylene glycol and polyethylene glycols; and mixtures thereof.
In the composition according to the invention, the water may be present in a
content ranging from 10% to 95% by weight and preferably ranging from 20% to 95%
by weight relative to the total weight of the composition.
The composition according to the invention may also comprise one or more
thickeners.
For the purposes of the present invention, the term "thickener" means an agent
which, when introduced at 1% by weight in an aqueous solution or an aqueousalcoholic
solution containing 30% ethanol, and at pH 7, makes it possible to achieve
a viscosity of at least 100 cps and preferably of at least 500 cps, at 25°C and at a
shear rate of 1 s This viscosity may be measured using a cone/plate viscometer
(Haake R600 rheometer or the like).
The thickener(s) may be chosen from fatty acid amides obtained from C10-C30
carboxylic acids (coconut acid monoisopropanol-, diethanol- or monoethanolamide,
oxyethylenated carboxylic acid monoethanolamide alkyl ether), nonionic cellulosebased
thickeners (hydroxyethylcellulose, hydroxypropylcellulose,
carboxymethylcellulose), guar gum and nonionic derivatives thereof (hydroxypropyl
guar), gums of microbial origin (xanthan gum, scleroglucan gum), crosslinked
homopolymers and copolymers based on acrylic acid or methacrylic acid or
acrylamidopropanesulfonic acid and the associative polymers as described below.
The associative polymer(s) that may be used according to the invention are
water-soluble polymers that are capable, in aqueous medium, of reversibly
combining with each other or with other molecules.
Their chemical structure comprises hydrophilic zones and hydrophobic zones
characterized by at least one fatty chain preferably comprising from 10 to 30 carbon
atoms.
The associative polymer(s) that may be used according to the invention may
be of anionic, cationic, amphoteric or nonionic type, such as the polymers sold under
the names Pemulen TR1 or TR2 by the company Goodrich ( INCI: Acrylates/C 10-30
Alkyl Acrylate Crosspolymer), Salcare SC90 by the company Ciba, Aculyn 22, 28,
33, 44 or 46 by the company Rohm & Haas and Elfacos T210 and T212 by the
company Akzo.
Among all the thickeners mentioned, use is preferably made of homopolymers
and copolymers based on acrylic acid or methacrylic acid, which are preferably
crosslinked (add the preference in B094751 FR) the fatty acid amides obtained from
a C10-C30 carboxylic acid.
Preferably, the cosmetic composition comprises from 0.1% to 20% by weight
and better still from 0.2% to 10% by weight of thickener(s) relative to the total weight
of the composition.
The composition according to the invention may also comprise one or more
conditioning agents other than the cationic surfactants (ii).
According to the present invention, the term "conditioning agent" denotes any
compound that can improve the cosmetic properties of the hair, in particular the
softness, disentangling, feel and static electricity.
Preferably, the conditioning agent is chosen from the group of cationic
polymers, organosiloxanes, linear or branched C8-C30 hydrocarbons, linear or
branched C8-C30 fatty alcohols, esters of a C8-C30 fatty acid and of a C1-C30
alcohol, esters of a C1-C7 acid or diacid and of a C8-C30 fatty alcohol, esters of a
C8-C30 fatty acid and of a C8-C30 fatty alcohol, ceramides or ceramide analogues,
and mixtures of these compounds.
The term "cationic polymer" means a polymer that is positively charged when it
is contained in the composition according to the invention. This polymer may bear
one or more positive permanent charges or may contain one or more cationizable
functions in the composition according to the invention.
The cationic polymer(s) that may be used as conditioning agents according to
the present invention are preferably chosen from polymers comprising primary,
secondary, tertiary and/or quaternary amine groups forming part of the polymer chain
or directly attached thereto, and having a molecular weight of between 500 and
about 5 000 000 and preferably between 1000 and 3 000 000.
When the conditioning agent is a cationic polymer, it is preferably chosen from
those that contain units comprising primary, secondary, tertiary and/or quaternary
amine groups that may either form part of the main polymer chain, or may be borne
by a side substituent directly attached thereto.
Among the cationic polymers that may be mentioned more particularly are
polymers of the polyamine, polyamino amide and polyquaternary ammonium type.
These are known products. They are described, for example, in French patents 2
505 348 and 2 542 997.
Among these polymers, mention may be made of:
( 1 ) homopolymers or copolymers which are derived from acrylic or methacrylic
esters or amides and comprise at least one of the units of the following formulae:
CH2 - C — - CH.-CO
O
O O
I I XA
A
N R N+ - R8
R R4 R
(VI), 7 (VII)
in which:
R3 and R4, which may be identical or different, represent hydrogen or an alkyl
group containing from 1 to 6 carbon atoms and preferably methyl or ethyl;
R5, which may be identical or different, denote a hydrogen atom or a CH3
radical;
A, which may be identical or different, represent a linear or branched alkyl group
of 1 to 6 carbon atoms, preferably 2 or 3 carbon atoms, or a hydroxyalkyl group of 1 to
4 carbon atoms;
R6, R7 and R8, which may be identical or different, represent an alkyl group
containing from 1 to 18 carbon atoms or a benzyl radical and preferably an alkyl group
containing from 1 to 6 carbon atoms;
X denotes an anion derived from a mineral or organic acid, such as a
methosulfate anion or a halide such as chloride or bromide.
The copolymers of family (1) can also contain one or more units derived from
comonomers which may be chosen from the family of acrylamides, methacrylamides,
diacetone acrylamides, acrylamides and methacrylamides substituted on the nitrogen
with lower (C1-C4) alkyls, acrylic or methacrylic acids or esters thereof, vinyllactams
such as vinylpyrrolidone or vinylcaprolactam, and vinyl esters.
Thus, among these copolymers of the family ( 1 ) , mention may be made of:
- copolymers of acrylamide and of dimethylaminoethyl methacrylate quaternized
with dimethyl sulfate or with a dimethyl halide, such as the product sold under the
name Hercofloc by the company Hercules,
- the copolymers of acrylamide and of methacryloyloxyethyltrimethylammonium
chloride described, for example, in patent application EP-A-080 976 and sold under the
name Bina Quat P 100 by the company Ciba Geigy,
- the copolymer of acrylamide and of methacryloyloxyethyltrimethylammonium
methosulfate sold under the name Reten by the company Hercules,
quaternized or non-quaternized vinylpyrrolidone/dialkylaminoalkyl acrylate or
methacrylate copolymers, such as the products sold under the name Gafquat by the
company ISP, such as, for example, Gafquat 734 or Gafquat 755, or alternatively the
products known as Copolymer 845, 958 and 937. These polymers are described in
detail in French patents 2 077 143 and 2 393 573,
dimethylaminoethyl methacrylate/vinylcaprolactam/vinylpyrrolidone terpolymers,
such as the product sold under the name Gaffix VC 713 by the company ISP,
vinylpyrrolidone/methacrylamidopropyldimethylamine copolymers sold in
particular under the name Styleze CC 10 by ISP,
- quaternized vinylpyrrolidone/dimethylaminopropylmethacrylamide copolymers
such as the product sold under the name Gafquat HS 100 by the company ISP, and
- crosslinked polymers of methacryloyloxyalkyl(C1-C4)trialkyl(C1-C4)ammonium
salts, such as the polymers obtained by homopolymerization of dimethylaminoethyl
methacrylate quaternized with methyl chloride, or by copolymerization of acrylamide
with dimethylaminoethyl methacrylate quaternized with methyl chloride, the
homopolymerization or copolymerization being followed by crosslinking with an
olefinically unsaturated compound, more particularly methylenebisacrylamide. A
crosslinked acrylamide/methacryloyloxyethyltrimethylammonium chloride copolymer
(20/80 by weight) in the form of a dispersion containing 50% by weight of the said
copolymer in mineral oil can be used more particularly. This dispersion is sold under
the name Salcare® SC 92 by the company Ciba. A crosslinked
methacryloyloxyethyltrimethylammonium chloride homopolymer, for example as a
dispersion in mineral oil or in a liquid ester, can also be used. These dispersions are
sold under the names Salcare® SC 95 and Salcare® SC 96 by the company Ciba.
(2) polymers formed from piperazinyl units and divalent alkylene or
hydroxyalkylene radicals containing straight or branched chains, optionally interrupted
with oxygen, sulfur or nitrogen atoms or with aromatic or heterocyclic rings, and also
the oxidation and/or quaternization products of these polymers. Such polymers are
especially described in French patents 2 162 025 and 2 280 361 .
(3) water-soluble polyamino amides prepared in particular by polycondensation of
an acidic compound with a polyamine; these polyamino amides can be crosslinked with
an epihalohydrin, a diepoxide, a dianhydride, an unsaturated dianhydride, a
bisunsaturated derivative, a bis-halohydrin, a bisazetidinium, a bis-haloacyldiamine, a
bis-alkyl halide or alternatively with an oligomer resulting from the reaction of a
difunctional compound which is reactive with a bis-halohydrin, a bis-azetidinium, a bishaloacyldiamine,
a bis-alkyl halide, an epihalohydrin, a diepoxide or a bis-unsaturated
derivative; the crosslinking agent being used in proportions ranging from 0.025 to
0.35 mol per amine group of the polyamino amide; these polyamino amides can be
alkylated or, if they contain one or more tertiary amine functions, they can be
quaternized. Such polymers are especially described in French patents 2 252 840 and
2 368 508.
(4) polyamino amide derivatives resulting from the condensation of polyalkylene
polyamines with polycarboxylic acids followed by alkylation with difunctional agents.
Mention may be made, for example, of adipic
acid/dialkylaminohydroxyalkyl-dialkylene-triamine polymers in which the alkyl radical
contains from 1 to 4 carbon atoms and preferably denotes methyl, ethyl or propyl. Such
polymers are especially described in French patent 1 583 363.
Among these derivatives, mention may be made more particularly of the adipic
acid/dimethylaminohydroxypropyl/diethylenetriamine polymers sold under the name
Cartaretine F, F4 or F8 by the company Sandoz.
(5) The polymers obtained by reaction of a polyalkylene polyamine containing two
primary amine groups and at least one secondary amine group with a dicarboxylic acid
chosen from diglycolic acid and saturated aliphatic dicarboxylic acids having from 3 to
8 carbon atoms. The mole ratio between the polyalkylene polyamine and the
dicarboxylic acid is between 0.8: 1 and 1.4: 1; the polyamino amide resulting therefrom
is reacted with epichlorohydrin in a mole ratio of epichlorohydrin relative to the
secondary amine group of the polyamino amide of between 0.5: 1 and 1.8: 1. Such
polymers are described in particular in US patents 3 227 615 and 2 961 347.
Polymers of this type are sold in particular under the name Hercosett 57 by
the company Hercules Inc. or alternatively under the name PD 170 or Delsette 101 by
the company Hercules in the case of the adipic acid/epoxypropyl/diethylenetriamine
copolymer.
(6) cyclopolymers of alkyldiallylamine or of dialkyldiallylammonium, such as the
homopolymers or copolymers containing, as main constituent of the chain, units
corresponding to formula (X) or (XI):
in which formulae k and t are equal to 0 or 1, the sum k + t being equal to 1; R12
denotes a hydrogen atom or a methyl radical; R10 and R 11, independently of one
another, denote an alkyl group having from 1 to 6 carbon atoms, a hydroxyalkyl group
in which the alkyl group preferably has 1 to 5 carbon atoms, a lower (C1-C4)
amidoalkyl group, or R10 and R 11 may denote, together with the nitrogen atom to
which they are attached, heterocyclic groups, such as piperidinyl or morpholinyl; Y is
an anion such as bromide, chloride, acetate, borate, citrate, tartrate, bisulfate, bisulfite,
sulfate or phosphate. These polymers are especially described in French patent
2 080 759 and in its Certificate of Addition 2 190 406.
R10 and R 11, independently of one another, preferably denote an alkyl group
having from 1 to 4 carbon atoms.
Among the polymers defined above, mention may be made more particularly of
the dimethyldiallylammonium chloride homopolymer sold under the name Merquat 100
by the company Nalco (and its homologues of low weight-average molecular mass)
and the copolymers of diallyldimethylammonium chloride and of acrylamide, sold under
the name Merquat 550.
(7) the quaternary diammonium polymer containing repeating units corresponding
to the formula:
3 R 5
1 (XII)
in which formula (XII):
R13, R14, R15 and R16, which may be identical or different, represent
aliphatic, alicyclic or arylaliphatic groups containing from 1 to 20 carbon atoms, or lower
hydroxyalkylaliphatic groups, or else R13, R14, R15 and R16, together or separately,
constitute, with the nitrogen atoms to which they are attached, heterocycles optionally
containing a second heteroatom other than the nitrogen, or else R13, R14, R15 and
R16 represent a linear or branched C1-C6 alkyl group which is substituted with a nitrile,
ester, acyl, amide or CO-0-R17-D or -CO-NH-R17-D group in which R17 is an alkylene
group and D is a quaternary ammonium group;
A 1 and B 1 represent polymethylene groups containing from 2 to 20 carbon
atoms, which may be linear or branched, saturated or unsaturated, and which may
contain, linked to or intercalated in the main chain, one or more aromatic rings or one
or more oxygen or sulfur atoms or sulfoxide, sulfone, disulfide, amino, alkylamino,
hydroxyl, quaternary ammonium, ureido, amide or ester groups, and
X denotes an anion derived from a mineral or organic acid;
A 1, R13 and R15 may form, with the two nitrogen atoms to which they are
attached, a piperazine ring; moreover, if A 1 denotes a saturated or unsaturated, linear
or branched alkylene or hydroxyalkylene group, B 1 may also denote a group (CH2)n-
CO-D-OC-(CH2)pn
and p are integers ranging from 2 to 20 approximately
in which D denotes:
a) a glycol residue of formula: -0-Z-0-, where Z denotes a linear or branched
hydrocarbon-based radical or a group corresponding to one of the following formulae:
-(CH2-CH2-0)x -CH2-CH2-
-[CH2-CH(CH3)-0]y-CH2-CH(CH3)-
where x and y denote an integer from 1 to 4, representing a defined and
unique degree of polymerization or any number from 1 to 4 representing an average
degree of polymerization;
b) a bis-secondary diamine residue such as a piperazine derivative;
c) a bis-primary diamine residue of formula: -NH-Y-NH-, where Y denotes a
linear or branched hydrocarbon-based radical, or alternatively the divalent radical
-CH2-CH2-S-S-CH2-CH2-;
d) a ureylene group of formula: -NH-CO-NH-;
Preferably, X is an anion such as chloride or bromide.
These polymers generally have a number-average molecular mass of
between 1000 and 100 000.
Polymers of this type are described in particular in French patents 2 320 330,
2 270 846, 2 3 16 271 , 2 336 434 and 2 413 907 and US patents 2 273 780, 2 375 853,
2 388 614, 2 454 547, 3 206 462, 2 261 002, 2 271 378, 3 874 870, 4 001 432,
3 929 990, 3 966 904, 4 005 193, 4 025 617, 4 025 627, 4 025 653, 4 026 945 and
4 027 020.
Use may be made more particularly of polymers which are composed of
repeating units conforming to the formula:
18 ^20
- N+(CH 2)r - (CH2)s — (XIII)
R1 R2 1 Xin
which R18, R19, R20 and R21 , which may be identical or different, denote an
alkyl or hydroxyalkyi group having from about 1 to 4 carbon atoms, r and s are integers
varying from 2 to 20 approximately, and X is an anion derived from a mineral or
organic acid.
One particularly preferred compound of formula (XIII) is that for which R18, R19,
R20 and R21 represent a methyl radical and r = 3, s = 6 and X = CI, which is called
Hexadimethrine chloride according to the INCI (CTFA) nomenclature.
(8) polyquaternary ammonium polymers composed of units of formula (XIV):
2 R24
— N+ - (CH 2) - NH - CO - (CH 2)u -CO - NH (CH 2)v - N+ - A —
R 23 (XIV) x _ 25
in which formula:
R22, R23, R24 and R25, which may be identical or different, represent a
hydrogen atom or a methyl, ethyl, propyl, b-hydroxyethyl, b-hydroxypropyl or
-CH2CH2(OCH2CH2)pOH radical,
in which p is equal to 0 or to an integer between 1 and 6, with the proviso that
R22, R23, R24 and R25 do not simultaneously represent a hydrogen atom,
t and u, which may be identical or different, are integers between 1 and 6,
v is equal to 0 or to an integer between 1 and 34,
X denotes an anion such as a halide,
A denotes a radical of a dihalide or represents preferably -CH2-CH2-0-CH2-
CH2-.
Such compounds are especially described in patent application EP-A-122 324.
Among these products, examples that may be mentioned include Mirapol® A 15,
Mirapol® AD1 , Mirapol® AZ1 and Mirapol ®175 sold by the company Miranol.
(9) quaternary polymers of vinylpyrrolidone and of vinylimidazole, for instance the
products sold under the names Luviquat® FC 905, FC 550 and FC 370 by the
company BASF.
(10) cationic polysaccharides, especially cationic celluloses and galactomannan
gums.
Among the cationic polysaccharides, mention may be made more particularly of
cellulose ether derivatives comprising quaternary ammonium groups, cationic cellulose
copolymers or cellulose derivatives grafted with a water-soluble quaternary ammonium
monomer and cationic galactomannan gums.
The cellulose ether derivatives comprising quaternary ammonium groups
described in French patent 1 492 597. These polymers are also defined in the CTFA
dictionary as quaternary ammoniums of hydroxyethylcellulose that have reacted with
an epoxide substituted with a trimethylammonium group.
Cationic cellulose copolymers or cellulose derivatives grafted with a water-soluble
monomer of quaternary ammonium, and described especially in US patent 4 131 576,
such as hydroxyalkylcelluloses, for instance hydroxymethyl-, hydroxyethyl- or
hydroxypropyl- celluloses grafted, in particular, with a
methacryloylethyltrimethylammonium, methacrylamidopropyltrimethylammonium or
dimethyldiallylammonium salt.
The cationic galactomannan gums are described more particularly in US patents
3 589 578 and 4 031 307, in particular guar gums containing cationic trialkylammonium
groups. Guar gums modified with a salt (e.g. chloride) of 2,3-
epoxypropyltrimethylammonium are used, for example.
Other cationic polymers that may be used in the context of the invention are
cationic proteins or cationic protein hydrolysates, polyalkyleneimines, in particular
polyethyleneimines, polymers containing vinylpyridine or vinylpyridinium units,
condensates of polyamines and of epichlorohydrin, quaternary polyureylenes and chitin
derivatives.
The cationic proteins or protein hydrolysates are, in particular, chemically
modified polypeptides bearing quaternary ammonium groups at the end of the chain, or
grafted thereon. Their molecular mass may vary, for example, from 1500 to 10 000 and
in particular from 2000 to 5000 approximately. Among these compounds, mention may
be made especially of:
- collagen hydrolysates bearing triethylammonium groups, such as the products
sold under the name Quat-Pro E by the company Maybrook and referred to in the
CTFA dictionary as Triethonium Hydrolyzed Collagen Ethosulfate;
- collagen hydrolysates bearing trimethylammonium and
trimethylstearylammonium chloride groups, sold under the name Quat-Pro S by the
company Maybrook and referred to in the CTFA dictionary as Steartrimonium
Hydrolyzed Collagen;
- animal protein hydrolysates bearing trimethylbenzylammonium groups, such
as the products sold under the name Crotein BTA by the company Croda and referred
to in the CTFA dictionary as Benzyltrimonium hydrolyzed animal protein;
- protein hydrolysates bearing on the polypeptide chain quaternary ammonium
groups comprising at least one alkyl radical containing from 1 to 18 carbon atoms.
Among these protein hydrolysates, mention may be made, inter alia, of:
- Croquat L in which the quaternary ammonium groups comprise a C12 alkyl
group;
- Croquat M in which the quaternary ammonium groups comprise C10-C18 alkyl
groups;
- Croquat S in which the quaternary ammonium groups comprise a C18 alkyl
group;
- Crotein Q in which the quaternary ammonium groups comprise at least one
alkyl group containing from 1 to 18 carbon atoms.
These various products are sold by the company Croda.
Other quaternized proteins or hydrolysates are, for example, those corresponding
to formula (XV):
in which X is an anion of an organic or mineral acid, A denotes a protein residue
derived from collagen protein hydrolysates, R29 denotes a lipophilic group comprising
up to 30 carbon atoms, and R30 represents an alkylene group containing from 1 to 6
carbon atoms. Mention may be made, for example, of the product sold by the company
Inolex under the name Lexein QX 3000, referred to in the CTFA dictionary as
Cocotrimonium Collagen Hydrolysate.
Mention may also be made of quaternized plant proteins such as wheat, corn or
soybean protein: as quaternized wheat protein, mention may be made of the products
sold by the company Croda under the names Hydrotriticum WQ or QM, referred to in
the CTFA dictionary as Cocodimonium hydrolysed wheat protein, Hydrotriticum QL
referred to in the CTFA dictionary as Laurdimonium hydrolysed wheat protein, or
Hydrotriticum QS, referred to in the CTFA dictionary as Steardimonium hydrolysed
wheat protein.
Among all the cationic polymers that may be used in the context of the present
invention, it is preferred to use cationic cyclopolymers, in particular
dimethyldiallylammonium chloride homopolymers or copolymers, sold under the
names Merquat 100, Merquat 550 and Merquat S by the company Nalco, quaternary
polymers of vinylpyrrolidone and of vinylimidazole, and cationic polysaccharides, and
mixtures thereof.
Among the organosiloxanes that may be used as conditioning agents in
accordance with the present invention, mention may be made, in a non-limiting
manner, of:
I. Volatile silicones:
These silicones have a boiling point of between 60°C and 260°C. Among the
silicones of this type that are mentioned are:
(i) cyclic silicones comprising from 3 to 7 and preferably 4 to 5 silicon atoms.
These are, for example, octamethylcyclotetrasiloxane sold under the name
Volatile Silicone 7207® by the company Union Carbide or Silbione 70045 V2® by the
company Rhone-Poulenc, decamethylcyclopentasiloxane sold under the name Volatile
Silicone 7158® by the company Union Carbide, and Silbione 70045 V5® by the
company Rhone-Poulenc, and mixtures thereof. Mention is also made of cyclopolymers
of the dimethylsiloxane/methylalkylsiloxane type, such as Volatile Silicone FZ 3109®
sold by the company Union Carbide, which is a dimethylsiloxane/methyloctylsiloxane
cyclopolymer;
(ii) linear volatile silicones containing 2 to 9 silicon atoms and having a viscosity
of less than or equal to 5 10 6 m2/s at 25°C.
Such a silicone is, for example, hexamethyldisiloxane sold under the name
Silbione 70041 V0,65® by the company Rhone-Poulenc. This type of product is
described in the article by Todd & Byers "Volatile silicone fluids for cosmetics",
Cosmetics and Toiletries, Vol. 9 1, Jan 76, pages 27 32.
II. Non-volatile silicones
These silicones are mainly constituted by polyalkylsiloxanes, polyarylsiloxanes,
polyalkylarylsiloxanes and organomodified polysiloxanes, and mixtures thereof. They
may be in the form of oils, gums and resins.
Among the polyalkylsiloxanes, mention may be made mainly of linear
polydimethylsiloxanes with a viscosity of greater than 5 <10 6 m2/s, and preferably less
than 2.6 m2/s, i.e.:
- containing trimethylsilyl end groups, for instance, in a non-limiting manner,
the Silbione® oils of the 70047 series sold by the company Rhone-Poulenc, the oil
Wacker Belsil DM 60000 from Wacker or certain Viscasil® products from the company
General Electric,
- containing trihydroxysilyl end groups of the 48 V® series from the company
Rhone-Poulenc.
In this class of polyalkylsiloxanes, mention may also be made of the
polyalkylsiloxanes sold by the company Goldschmidt under the names Abil Wax 9800®
and Abil Wax 9801®, which are poly(C1-20)alkylsiloxanes.
Among these polyalkylarylsiloxanes, mention may be made of linear and/or
branched polydimethylphenylsiloxanes and polydimethyldiphenylsiloxanes, with a
viscosity from 10 5 to 5 10 2 m2/s, for instance:
- the oil Rhodorsil® 763 from Rhone-Poulenc,
- the Silbione® oils of the 70641 series from Rhone-Poulenc, such as the oils
Silbione 70641 V30® and Silbione 70641 V200®,
- the product DC 556® Cosmetic Grade Fluid from Dow Corning,
- the silicones of the PK series from Bayer, such as PK20®,
- the silicones of the PN and PH series from Bayer, such as the products
PN1000® and PH1000®;
- certain oils of the SF series from General Electric, such as SF 1250®, SF
1265®, SF 1154® and SF 1023®.
The silicone gums in accordance with the present invention are
polydiorganosiloxanes with a high number-average molecular mass of between 200
000 and 1 000 000, used alone or as a mixture in a solvent chosen from volatile
silicones, polydimethylsiloxane (PDMS) oils, polyphenylmethylsiloxane (PPMS) oils,
isoparaffins, methylene chloride, pentane, dodecane, tridecane and tetradecane, or
mixtures thereof.
Mention is made, for example, of compounds having the following structures:
- poly[(dimethylsiloxane)/(methylvinylsiloxane)] gums,
- poly[(dimethylsiloxane)/(diphenylsiloxane)] gums,
- poly[(dihydrogenodimethylsiloxane)/(divinylsiloxane)] gums,
- poly[(dimethylsiloxane)/(phenylmethylsiloxane)] gums,
- poly[(dimethylsiloxane)/(diphenylsiloxane)/(methylvinylsiloxane)] gums.
Mention may be made of the gum Mirasil DM 300 000 from the company Rhodia.
Examples that may also be mentioned, in a non-limiting manner, include the following
mixtures:
1) mixtures formed from a polydimethylsiloxane hydroxylated at the end of the
chain (dimethiconol according to the CTFA nomenclature), and of a cyclic
polydimethylsiloxane (cyclomethicone according to the CTFA nomenclature), such as
the products Q2 1401® or Dow Corning 1501 Fluid sold by the company Dow Corning;
2) mixtures formed from a polydimethylsiloxane gum with a cyclic silicone, such
as the product SF 1214 Silicone Fluid® from General Electric, which is a gum SE 30®
of MW 500 000 (-Mn) dissolved in SF 1202 Silicone Fluid®
(decamethylcyclopentasiloxane);
3) mixtures of two PDMSs of different viscosities, especially of a PDMS gum and
a PDMS oil, such as the products SF 1236® and CF 1241® from the company General
Electric. The product SF 1236® is a mixture of an SE 30® gum defined above, with a
viscosity of 20 m2/s, and of an SF 96® oil with a viscosity of 5 106 m2/s (15% by weight
of SE 30® gum and 85% by weight of SF 96® oil, relative to the total weight of the
mixture).
The product CF 1241® is a mixture of an SE 30® gum (33% by weight) and of a
PDMS (67% by weight), with a viscosity of 10 3 m2/s.
The organopolysiloxane resins that may be used in accordance with the invention
are crosslinked siloxane systems containing the following units: R2Si02/2, RSi03/2
and Si04/2 in which R represents a hydrocarbon group containing 1 to 6 carbon atoms
or a phenyl group. Among these products, those particularly preferred are the ones in
which R denotes a lower alkyl radical or a phenyl radical.
Among these resins, mention may be made of the product sold under the name
Dow Corning 593® or those sold under the names Silicone Fluid SS 4230 and Silicone
Fluid SS 4267 by the company General Electric, which are
dimethyl/trimethylpolysiloxanes.
The organomodified silicones in accordance with the present invention are
silicones as defined above, comprising in their general structure one or more
organofunctional groups directly attached to the siloxane chain or attached via a
hydrocarbon-based radical.
Mention is made, for example, of silicones comprising:
a) perfluoro groups such as trifluoroalkyls, for instance those sold by the
company General Electric under the names FF.150 Fluorosilicone Fluid® or by the
company Shin-Etsu under the names X-22-819®, X-22-82®, X-22-821® and X-22-
822®;
b) hydroxyacylamino groups, for instance those described in patent application
EP 0 342 834 and in particular the silicone sold by the company Dow Corning under
the name Q2-8413®;
c) thiol groups, as in the silicones X 2-8360® from the company Dow Corning or
GP 72A® and GP 71® from Genesee;
d) non-quaternized amine groups, such as GP 4 Silicone Fluid® from Genesee,
GP 7100® from Genesee, Q2 8220® from Dow Corning, AFL 40® from Union Carbide
or the silicone known as Amodimethicone in the CTFA dictionary;
e) carboxylate groups, for instance the products described in patent EP 186 507
from Chisso Corporation;
f) hydroxylated groups, for instance polyorganosiloxanes containing a
hydroxyalkyl function, for example those described in patent application FR 85/16334,
corresponding to formula (XVI) below:
, -Si- -0- 0—- Si(R ,)2
- Si R 3
OH
(XVI)
in which:
- the radicals R 1, which may be identical or different, are chosen from methyl and
phenyl radicals, at least 60 mol% of the radicals R 1 being methyl radicals;
- the radical R'1 is a C2-C18 hydrocarbon-based divalent alkylene chain unit;
- p is between 1 and 30 inclusive;
- q is between 1 and 150 inclusive.
Mention may be made most particularly of the product sold by Dow Corning
under the name DC 190;
g) alkoxylated groups, for instance in the silicone copolymer F 755® from SWS
Silicones and the products Abil Wax 2428®, Abil Wax 2434® and Abil Wax 2440® from
the company Goldschmidt;
h) acyloxyalkyl groups, for instance the polyorganopolysiloxanes described in
patent application FR 88/17433, corresponding to formula (XVII) below:
( ) - i — Si— - - Si- -0 -Si (R ) ;
I
R R R'
OCOR" OH
(XVII)
in which:
- R2 denotes methyl, phenyl, OCOR" or hydroxyl, only one of the radicals R2
per silicon atom may be OH;
- R'2 denotes methyl or phenyl, at least 60 mol% of all the radicals R2 and R'2
are methyl;
- R" denotes C8-C20 alkyl or alkenyl;
- R denotes a linear or branched C2-C1 8 divalent hydrocarbon-based alkylene;
- r is between 1 and 120 inclusive;
- p is between 1 and 30 inclusive;
- q is 0 or is less than 0.5 p, p + q being between 1 and 30 inclusive:
the polyorganosiloxanes of formula (XVII) may contain groups:
in proportions not exceeding 15% of the sum p + q + r ;
i) quaternary ammonium groups, as in the products X2 8108® and X2 8109® and
the product Abil K 3270® from the company Goldschmidt;
j ) amphoteric or betaine groups, as in the product sold by the company
Goldschmidt under the name Abil B 9950®;
k) bisulfite groups, as in the products sold by the company Goldschmidt under the
names Abil S 201® and Abil S 255®.
I) polyethyleneoxy and/or polypropyleneoxy groups optionally comprising C6-C24
alkyl groups, such as the products known as dimethicone copolyol sold by the
company Dow Corning under the name DC 1248 or the oils Silwet L 722, L 7500, L 77
and L 7 11 by the company Union Carbide, and the (C12)alkylmethicone copolyol sold
by the company Dow Corning under the name Q2 5200;
According to the invention, silicones comprising a polysiloxane portion and a
portion formed from a non-silicone organic chain, one of the two portions forming the
main chain of the polymer and the other being grafted onto the said main chain, may
also be used. These polymers are described, for example, in patent applications
EP-A-412 704, EP-A-412 707, EP-A-640 105 and WO 95/00578, EP-A-582 152 and
WO 93/23009 and patents US 4 693 935, US 4 728 571 and US 4 972 037. These
polymers are preferably anionic or nonionic.
Such polymers are, for example, copolymers that may be obtained by radical
polymerization from the monomer mixture formed from:
a) 50 to 90% by weight of tert-butyl acrylate;
b) 0 to 40% by weight of acrylic acid;
c) 5 to 40% by weight of a silicone macromer of formula:
H C = C - (CH 2)3 - CH3
(XVIII)
with v being a number ranging from 5 to 700; the weight percentages being
calculated relative to the total weight of the monomers.
Other examples of grafted silicone polymers are especially polydimethylsiloxanes
(PDMSs) onto which are grafted, via a connecting unit of thiopropylene type, mixed
polymer units of the poly(meth)acrylic acid type and of the polyalkyi (meth)acrylate type
and polydimethylsiloxanes (PDMSs) onto which are grafted, via a connecting unit of
thiopropylene type, polymer units of the polyisobutyl (meth)acrylate type.
According to the invention, all the silicones may also be used in the form of
emulsions, nanoemulsions or microemulsions.
The polyorganosiloxanes that are particularly preferred in accordance with
the invention are:
- non-volatile silicones chosen from the family of polydialkylsiloxanes con
taining trimethylsilyl end groups, such as oils with a viscosity of between 0.2 and 2.5
m2/s at 25°C, such as the oils of the series DC200 from Dow Corning, in particular
the product with a viscosity of 60 000 cSt, of the series Silbione 70047 sold by the
company Rhodia Chimie, silicone gums and polydialkylsiloxanes containing dimethylsilanol
end groups such as dimethiconols, or polyalkylarylsiloxanes such as
the oil Silbione 70641 V 200 sold by the company Rhodia Chimie;
- polysiloxanes containing amine groups such as amodimethicones or
trimethylsilyl amodimethicones;
The viscosities of the silicones may especially be determined by the standard
ASTM D445-97 (viscometry).
When the conditioning agent of the composition according to the invention is a
hydrocarbon, it is a linear or branched C8-C300 hydrocarbon.
Among the hydrocarbons that are liquid at room temperature corresponding to
this definition mention may be made especially of isododecane, isohexadecane and
isomers thereof (such as 2,2,4,4,6,6-heptamethylnonane), isoeicosane, isotetracosane,
isomers of the said compounds, n-nonadecane, n-dodecane, n-undecane, n-tridecane
and n-pentadecane, and mixtures of these hydrocarbons. Use is preferably made
according to the invention of isododecane or an isomer thereof.
When the conditioning agent is a fatty alcohol, it is of the linear or branched,
saturated or unsaturated C8-C30 type. Among the latter agents, examples that may be
mentioned include 2-butyloctanol, lauryl alcohol, oleyl alcohol, 2-octyldodecanol,
isocetyl alcohol, isostearyl alcohol and behenyl alcohol, and mixtures thereof.
When the conditioning agent is a fatty ester, it may be either an ester of a C8-
C30 fatty acid and of a C1-C30 alcohol, or an ester of a C1-C7 acid or diacid and of a
C8-C30 fatty alcohol, or an ester of a C8-C30 fatty acid and of a C8-C30 fatty alcohol.
Among these esters, examples that may be mentioned include ethyl, isopropyl, 2-
ethylhexyl and 2-octyldecyl palmitate, isopropyl, butyl, cetyl and 2-octyldecyl myristate,
butyl and hexyl stearate, hexyl and 2-hexyldecyl laurate, isononyl isononanoate, dioctyl
malate, myristyl myristate and cetyl palmitate, and mixtures thereof.
The ceramides or ceramide analogues, such as glycoceramides, which may be
used as conditioning agents in the compositions according to the invention are known
per se and are natural or synthetic molecules that may correspond to the general
formula (XIX) below:
FLCHOH— CH—C OF
C=0
in which:
- R 1 denotes a linear or branched, saturated or unsaturated alkyl radical, derived
from C14-C30 fatty acids, this radical possibly being substituted with a hydroxyl group
or a hydroxyl group in the omega position esterified with a saturated or unsaturated
C16-C30 fatty acid;
- R2 denotes a hydrogen atom or a radical (glycosyl)n, (galactosyl)m or
sulfogalactosyl, in which n is an integer ranging from 1 to 4 and m is an integer ranging
from 1 to 8;
- R3 denotes a saturated or unsaturated C15-C26 hydrocarbon-based radical in
the alpha position, this radical possibly being substituted with one or more C1-C14 alkyl
radicals;
it being understood that, in the case of these natural ceramides or
glycoceramides, R3 may also denote a C15-C26 alpha-hydroxyalkyl radical, the
hydroxyl group being optionally esterified with a C16-C30 alpha-hydroxy acid.
The ceramides that are preferred in the context of the present invention are those
described by Downing in Arch. Dermatol, Vol. 123, 1381-1384, 1987, or those
described in French patent FR 2 673 179.
The ceramide(s) that are more particularly preferred according to the invention
are the compounds for which R 1 denotes a saturated or unsaturated alkyl derived from
C16-C22 fatty acids; R2 denotes a hydrogen atom and R3 denotes a saturated linear
C15 radical.
Such compounds are, for example:
- N-linoleoyldihydrosphingosine,
- N-oleoyldihydrosphingosine,
- N-palmitoyldihydrosphingosine,
- N-stearoyldihydrosphingosine,
- N-behenoyldihydrosphingosine,
or mixtures of these compounds.
Even more preferentially, used is made of ceramides for which R 1 denotes a
saturated or unsaturated alkyl radical derived from fatty acids; R2 denotes a galactosyl
or sulfogalactosyl radical; and R3 denotes a group -CH=CH-(CH2)12-CH3.
By way of example, mention may be made of the product formed from a mixture
of these compounds, sold under the trade name Glycocer by the company Waitaki
International Biosciences.
Among all these conditioning agents, use is preferably made of one or more
conditioning agents chosen from organosiloxanes and cationic polymers.
The cosmetic composition according to the invention preferably contains from
0.01% to 20% by weight and more preferentially from 0.05% to 10% by weight of
conditioning agent(s), other than the cationic surfactants (ii), relative to the total weight
of the composition.
The composition according to the invention may also comprise one or more
standard additives that are well known in the art, other than the compounds defined
previously. As examples of additives that may be used according to the invention,
mention may be made of silanes, anionic surfactants, amphoteric or zwitterionic
surfactants, nonionic surfactants, proteins, protein hydrolysates, vitamins, reducing
agents, plasticizers, softeners, antifoams, moisturizers, pigments, clays, mineral
fillers, UV-screening agents, mineral colloids, peptizers, solubilizers, fragrances,
preserving agents, nacreous agents, propellants and mineral or organic thickeners;
these additives being different from the compounds defined hereinabove.
A person skilled in the art will take care to select the optional additive(s) and
the amount thereof such that they do not harm the properties of the compositions of
the present invention.
The additive(s) are generally present in the composition according to the
invention in an amount ranging from 0 to 20% by weight relative to the total weight of
the composition.
The compositions according to the invention may be in any galenical form
conventionally used for topical application and especially in the form of aqueous or
aqueous-alcoholic solutions, oil-in-water (O/W) or water-in-oil (W/O) or multiple
emulsions (triple: W/O/W or 0/W/O), aqueous gels, or dispersions of a fatty phase in
an aqueous phase by means of spherules, these spherules possibly being polymer
nanoparticles such as nanospheres and nanocapsules or lipid vesicles of ionic and/or
nonionic type (liposomes, niosomes or oleosomes). These compositions are prepared
according to the usual methods.
In addition, the compositions used according to the invention may be more or
less fluid and may have the appearance of a white or coloured cream, a pomade, a
milk, a lotion, a serum, a paste or a mousse. They may be optionally applied to the
keratin materials in aerosol form. They may also be in solid form, for example in the
form of a stick.
Needless to say, a person skilled in the art will take care to select the optional
compound(s) to be added to the composition according to the invention, such that the
advantageous properties intrinsically associated with the composition in accordance
with the invention are not, or are not substantially, adversely affected by the
envisaged addition(s).
Another subject of the invention consists of a cosmetic process for treating the
scalp and keratin fibres, in particular human keratin fibres such as the hair,
comprising the application of a composition according to the invention to the scalp
and the said keratin fibres. After an optional leave-in time preferably ranging from 1
to 15 minutes, the composition is then preferably rinsed out with water. Preferably,
the said process is intended for conditioning the said keratin fibres and/or for an
antidandruff treatment for eliminating and/or reducing dandruff, and especially that
caused by yeasts of the genus Malassezia.
A subject of the invention is also the use of a composition according to the
invention for caring for keratin fibres, in particular human keratin fibres such as the
hair.
A subject thereof is also the use of a composition according to the invention for
antidandruff treatment for eliminating and/or reducing dandruff, especially that
caused by yeasts of the genus Malassezia.
The examples that follow are intended to illustrate the invention, without,
however, having any limiting nature.
Example 1:
Two antidandruff haircare products having the following composition were
prepared:
Ellagic acid 1 0.7
Dipalmitoylethylhydroxyethylmethylammonium
methosulfate at 30% by weight in cetylstearyl
0.3 g AM 1.8 g AM
alcohol
(Dehyquart F30 - Cognis)
Behenyltrimethylammonium chloride at 80% by
weight of active material (Genamin KDMP -
Clariant) 0.48 g AM
Cetyltrimethylammonium chloride at 25% by weight 0.625 g AM
of active material (Dehyquart A OR from Cognis)
Polydimethylsiloxane containing aminoethyl
iminopropyl groups, as a cationic emulsion at 60%
by weight in water (Dow Corning 2-8299 Cationic
Emulsion from Dow Corning) 1.54 g AM
Liquid jojoba wax 0.1 g
Cetyl alcohol 3.7 g 4.5 g
Myristyl alcohol, sold under the trade name Nacol 0.4 g
The compositions are prepared according to the following procedure:
Water, citric acid, ellagic acid, preserving agents, hydroxyethylcellulose and
behenyltrimethylammonium chloride, if it is present, are placed in a container. The
mixture is heated to 50°C. The cetyltrimethylammonium chloride, if it is present, is
added. The mixture is heated to 60°C. The cetyl alcohol, the myristyl alcohol, if it is
present, the mixture of esters, the liquid jojoba wax, if it is present, and the
dipalmitoylethylhydroxyethylmethylammonium methosulfate are added. The mixture is
heated to 70°C and maintained at this temperature until the solid fatty substances have
melted. It is cooled to 30°C.
A fine, homogeneous dispersion of ellagic acid in the composition is obtained.
The composition is stable over time (no macroscopic change after two months of
storage at room temperature (25°C) or at 45°C).
When applied to the hair and the scalp, this care product promotes the spreading
of the ellagic acid onto the scalp, which promotes the antidandruff efficacy. The hair
shows during and after the treatment good cosmetic properties especially in terms of
softness, smoothness and disentangling.
Example 2:
An antidandruff haircare product having the following composition was prepared:
Ellagic acid 1 g
Behenyltrimethylammonium chloride at 80% by
weight of active material (Genamin KDMP -
Clariant) 1.6 g AM
Methylalkylalkylamidoethylimidazolium methosulfate
as a 75% solution in propylene glycol (Varisoft W 2.5 g AM
575 PG - Evonik Goldschmidt)
Candelilla wax 0.3 g
Stearyl alcohol 2 g
Isopropyl myristate 0.8 g
C12/C15 alkyl benzoate (Tegosoft TN - Evonik
Goldschmidt) 5 g
Sorbitan monolaurate oxyethylenated with 20 mol
of ethylene oxide (Tween 20 LQ - Croda) 0.3
Potato starch modified with 2-
chloroethylaminodipropionic acid at 86% in water
and neutralized with sodium hydroxide (Structure
Solanace - Akzo Nobel) 2.6 g AM
Fragrance, preserving agents qs
Deionized water qs qs 100 g
A fine, homogeneous dispersion of ellagic acid in the composition is obtained.
The composition is stable over time (no macroscopic change after two months of
storage at room temperature (25°C) or at 45°C).
When applied to the hair and the scalp, this care product promotes the spreading
of the ellagic acid onto the scalp, which promotes the antidandruff efficacy. The hair
shows during and after the treatment good cosmetic properties especially in terms of
softness, smoothness and disentangling.
11/107432 PCT/EP2011/052933
CLAIMS
1. Cosmetic composition comprising, in a cosmetically acceptable medium:
(i) from 0.1% to 10% by weight, relative to the total weight of the composition,
of one or more compounds chosen from ellagic acid, ethers thereof, and ellagic acid
salts or ethers thereof,
(ii) one or more cationic surfactants comprising one or more permanent positive
charges chosen from
- the quaternary ammonium salts corresponding to the general formula (II)
below:
8 R 10
N X -
R R
(II)
in which the radicals R8 to Rn, which may be identical or different, represent a
linear or branched aliphatic radical, comprising from 1 to 30 carbon atoms and
possibly comprising heteroatoms, or alternatively an aromatic radical, at least one of
the radicals R8 to R comprising from 8 to 30 carbon atoms;
- quaternary ammonium salts containing at least one ester function.
2. Composition according to Claim 1, characterized in that the ellagic acid salt(s)
and ether salts thereof are chosen from alkali metal or alkaline-earth metal salts,
especially the sodium, potassium, calcium or magnesium salts.
3. Composition according to Claim 1 or 2, characterized in that the ether(s) are
chosen from mono-, di-, tri- or polyethers obtained by etherification of one or more
hydroxyl groups of ellagic acid with one or more groups chosen from C2-C2o alkyl
groups, polyoxyalkylene groups and groups derived from one or more mono- or
polysaccharides.
4. Composition according to any one of the preceding claims, characterized in
that compound (i) is ellagic acid or a salt thereof.
5. Composition according to one of Claims 1 to 4, characterized in that the ellagic
acid, ethers thereof or the ellagic acid salts or ether salts thereof are present in a
011/107432 PCT/EP2011/052933
content ranging from 0.1% to 5% by weight and better still from 0.2% to 2% by weight
of compound(s) (i) relative to the total weight of the composition.
6. Composition according to any one of Claims 1 to 5, characterized in that the
cationic surfactant(s) are chosen from cetyltrimethylammonium salts,
behenyltrimethylammonium salts, dipalmitoylethylhydroxyethylmethylammonium salts,
distearoylethylhydroxyethylmethylammonium salts and methyl(C9-Ci 9)alkyl (Cio-
C2o)alkylamidoethylimidazolium salts, and mixtures thereof.
7. Composition according to any one of the preceding claims, characterized in
that the cationic surfactant(s) are present in a content ranging from 0.01% to 15% by
weight relative to the total weight of the cosmetic or dermatological composition,
preferably ranging from 0.1% to 10% by weight and more preferentially from 0.2% to
5% by weight.
8. Composition according to any one of the preceding claims, characterized in
that the cationic surfactant(s) (ii)/compound(s) (i) weight ratio ranges from 0.1 to 50,
even more preferentially from 0.5 to 25 and better still from 1 to 10.
9. Non-therapeutic cosmetic treatment process for treating keratin materials,
comprising the application to the said materials of a composition as described in one of
Claims 1 to 8.
10. Cosmetic treatment process for eliminating and/or reducing dandruff,
comprising the application of a cosmetically effective amount of the composition
according to one of Claims 1 to 8.