Cosmetic composition based on ellagic acid or a derivative thereof and
a bacterial extract.
The present invention relates to a cosmetic composition comprising
at least a first compound chosen from ellagic acid, ethers thereof and salts of
these compounds, and at least a second particular compound, to an
antidandruff treatment process using the said composition, and to the use of
the said composition for treating dandruff conditions. In particular, the
invention also relates to the use of the combination of at least a first
compound chosen from ellagic acid, ethers thereof and salts thereof, and of
at least a second particular compound, 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 what it brings about (itching, redness, etc.), 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 genus
Malassezia (previously known as Pityrosporum) which is naturally present on
the scalp.
To treat dandruff, it is known practice to use antidandruff agents,
especially antifungal and/or antibacterial agents in a medium capable of
distributing these agents and depositing them on the teguments.
Among antidandruff agents, zinc pyrithione, piroctone ylamine and
selenium disulfide have been most particularly recommended on account of
their powerful cytostatic activity. Although they show good antidandruff
efficacy, their frequent use has the drawback of accentuating the discomfort
sensations (stinging or dryness sensations). Moreover, these antidandruff
agents are not entirely satisfactory in terms of their environmental impact.
Thus, there is a need, on the part of users of antidandruff treatments,
for compositions that show better skin tolerance, while at the same time
conserving good antidandruff efficacy and being more environmentally
friendly. In addition, antidandruff compositions that are stable and that have
good working properties, especially during the application or removal of the
compositions, are sought.
The antidandruff activity of non-fruiting non-photosynthetic bacterial
extracts is also known (FR 2 879 452).
However, although non-fruiting non-photosynthetic bacterial extracts
have good antidandruff activity, they nevertheless have the drawback of
not acting on the related nuisances such as stinging, heating sensations
and redness.
Compositions that do not have the drawbacks mentioned above and
that have reinforced antidandruff activity are sought.
The Applicant has now found, surprisingly, that the use of at least a
first compound chosen from ellagic acid, ethers thereof, and ellagic acid
salts or ethers thereof, and of at least one non-fruiting non-photosynthetic
filamentous bacterial extract makes it possible to satisfy such a need, and to
overcome the drawbacks of the prior art.
The composition according to the invention makes it possible to
efficiently eliminate and/or reduce dandruff on the hair and the scalp, while at
the same time notably reducing the scalp discomfort.
It also does not alter the cosmetic properties of the hair treated in
conjunction, especially in terms of sheen, suppleness and smoothness of the
hair.
Moreover, surprisingly, the Applicant has discovered that the
composition of the invention has a particularly pronounced anti-canities
effect, i.e. it can even more efficiently combat greying of the hair when
compared with the constituents taken individually.
One subject of the present invention is thus a cosmetic
composition comprising:
(i) from 0.01 % 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, in a content ranging
(ii) one or more extracts of one or more non-photosynthetic, non-fruiting
filamentous bacteria, and
(iii) one or more surfactants chosen from anionic and/or amphoteric or
zwitterionic surfactants.
Another subject of the invention relates to a cosmetic
antidandruff treatment process, for eliminating and/or reducing
dandruff, using the said composition.
A subject of the invention is also the use of the said composition for
eliminating and/or reducing the amount of dandruff on the hair, and for
eliminating and/or reducing the irritation and/or itching of the scalp.
Other features, aspects, objects and advantages of the present
invention will emerge even more clearly from a reading of the description and
examples which follow.
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-5,1 0-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 following chemical formula:
which comprises four fused rings.
Ellagic acid is commercially available, especially 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) 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-C20 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, the
ellagic acid ethers are chosen from 3,4-di-O-methylellagic acid, 3,3',4-tri-Omethylellagic
acid and 3,3'-di-O-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.
The composition according to the invention preferably comprises
from 0.01 % to 10% by weight, in particular 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.
The bacterial extracts that may be used according to the invention will
be chosen from non-photosynthetic, non-fruiting filamentous bacteria as
defined according to the classification in Bergey's Manual of Systemic
Bacteriology, volume 3, section 23, 9th edition 1989.
Among the bacteria that may be used, mention will be made more
particularly of bacteria belonging to the order Beggiatoales, and especially
bacteria belonging to the genus Beggiotoa, for instance various strains of
Beggiotoa alba. According to the definition, B. alba corresponds to the former
names Beggiotoa arachnoidea, B. gigantea, B. leptomiformis, B. minima and B.
mirabilis of Bergey's manual, 8th edition. Mention may moreover be made of
bacteria belonging to the genus Vitreoscilla, which is known to be close to and
often difficult to distinguish from the genus Beggiatoa. The bacteria that have
just been defined, and several of which have been described, generally have
an aquatic habitat, and may be found especially in spring water sources.
Among the bacteria that may be used, mention may be made, for
example, of Vitreoscilla beggiatoides (ATCC 431 8 1) and Beggiatoa alba
(ATCC33555).
Preferentially, according to the invention, the use of the extract of
Vitreoscilla filiformis, in particular the strain ATCC 15551 , metabolites thereof
and fractions thereof, are claimed.
Moreover, it is known that culturing non-photosynthetic, non-fruiting
filamentous bacteria is relatively difficult, as is the production of pure cultures.
Use will preferentially be made of the culture described in patent application
WO 94/021 58.
The term "non-photosynthetic, non-fruiting filamentous bacteria" means
not only the culture supernatant but also the biomass obtained after culturing
the said bacteria, the envelopes or envelope fractions, or the extracts of the
biomass obtained by treating this biomass.
To prepare the extract according to the invention, the said bacteria can
be cultured and then separated from the biomass obtained, for example by
filtration, centrifugation, coagulation and/or lyophilization.
The extracts that may be used may especially be prepared according
to the process described in patent application WO-A-93/00741 . Thus, after
culturing, the bacteria are concentrated by centrifugation. The biomass
obtained is autodaved. This biomass may be lyophilized to constitute what is
known as the lyophilized extract. Any lyophilization method known to those
skilled in the art may be used to prepare this extract.
The supernatant fraction of this biomass may also be filtered in a sterile
container to remove the particles in suspension.
The terms "envelopes" and "envelope fractions" refer herein to the
bacterial wall and possibly the subjacent membranes.
The bacterial extract(s) (ii) may be used in a concentration of from
0.001 % to 10% by weight, from 0.01 % to 5% by weight, preferably from 0.05%
to 5% by weight and more particularly from 0.1 % to 3% by weight expressed as
solids relative to the total weight of the composition.
The composition according to the invention is, generally, preferably
the weight ratio of the amount of compound(s) such that the weight ratio of
the amount of compound(s) (i) to the amount of extract(s) (ii) is greater than
or equal to 0.5.
Even more preferentially, the weight ratio of the amount of
compound(s) (i) to the amount of extract(s) (ii) is greater than or equal to 0.7
and better still greater than or equal to 1.
Preferably, (i) to the amount of extract(s) (ii) is less than or equal to
50, better still less than or equal to 20, even better still less than or equal to
10 and more particularly less than 5 .
The composition according to the invention comprises one or more
surfactants chosen from anionic and/or amphoteric or zwitterionic surfactants.
The term "anionic surfactant" means a surfactant comprising as ionic
or ionizable groups only anionic groups. These anionic groups are preferably
chosen from the groups CO2H, CO2 , SO3H, SO3-, OSO3H, OSO3-,
O2 PO2 H, O2 PO2 H-, O PO 2 .
As examples of anionic surfactants (ii) that may be used in the
composition according to the invention, mention may be made of alkyl
sulfates, alkyl ether sulfates, alkylamido ether sulfates, alkylarylpolyether
sulfates, monoglyceride sulfates, alkylsulfonates, alkylamidesulfonates,
alkylarylsulfonates, alpha-olefin sulfonates, paraffin sulfonates,
alkylsulfosuccinates, alkylether sulfosuccinates, alkylamide sulfosuccinates,
alkylsulfoacetates, acylsarcosinates, acylglutamates, alkylsulfosuccinamates,
acylisethionates and N-acyltaurates, salts of alkyl monoesters of
polyglycoside-polycarboxylic acids, acyllactylates, D-galactoside-uronic acid
salts, alkyl ether carboxylic acid salts, alkyl aryl ether carboxylic acid salts,
alkylamido ether carboxylic acid salts; and the corresponding non-salified
form is of all these compounds; the alkyl and acyl groups of all these
compounds comprising from 6 to 24 carbon atoms and the aryl group
denoting a phenyl group.
These compounds may be oxyethylenated and then preferably
comprise from 1 to 50 and more particularly from 1 to 10 ethylene oxide units.
The salts of C6-24 alkyl monoesters of polyglycoside-polycarboxylic
acids may be chosen from C6-24 alkyl polyglycoside citrates, C6-24 alkyl
polyglycosides tartrates and C6-24 alkyl polyglycoside sulfosuccinates.
When the anionic surfactant(s) (ii) are in salt form, they may be
chosen from alkali metal salts such as the sodium or potassium salt and
preferably the sodium salt, the ammonium salts, the amine salts and in
particular amino alcohol salts or the alkaline-earth metal salts such as the
magnesium salt.
Examples of amino alcohol salts that may especially be mentioned
include the salts of mono-, di- and triethanolamine, the salts of mono-, di- or
triisopropanolamine, and the salts of 2-amino-2-methyl-1-propanol, of 2-
amino-2-methyl-1 ,3-propanediol and of tris(hydroxymethyl)aminomethane.
The alkali metal or alkaline-earth metal salts and in particular the
sodium or magnesium salts are preferably used.
Among all the anionic surfactants (ii) mentioned, use is preferably
made of alkyl(C6-24) sulfates, alkyl(C6-24) ether sulfates comprising from 1
to 50 ethylene oxide units, especially in the form of alkali metal, ammonium,
and alkaline-earth metal salts, o r a mixture of these compounds.
In particular, use is preferably made of alkyl(C1 2-20) sulfates,
alkyl(C1 2-20) ether sulfates comprising from 2 to 10 ethylene oxide units,
especially in the form of alkali metal, ammonium, amino alcohol and alkalineearth
metal salts, o r a mixture of these compounds. Better still, use is made
of sodium lauryl ether sulfate containing 2.2 mol of ethylene oxide.
When they are present, the amount of anionic surfactant(s) preferably
ranges from 0.1 % to 50% by weight and better still from 4% to 30% by weight
relative to the total weight of the composition.
The amphoteric o r zwitterionic surfactant(s) that may be used in the
present invention may especially be derived from secondary or tertiary
aliphatic amines, optionally quaternized, in which the aliphatic group is a
linear o r branched chain comprising from 8 to 22 carbon atoms, th the said
amine derivatives containing at least one anionic group, for instance a
carboxylate, sulfonate, sulfate, phosphate o r phosphonate group. Mention
may be made in particular of alkyl(C8-2o)betaines, sulfobetaines, (Cs-2o
alkyl)amido(C2-8 alkyl)betaines and (Cs-2o alkyl)amido(C2-8 alkyl)sulfobetaines.
Among the secondary o r tertiary aliphatic amine derivatives,
optionally quaternized, which may be used, as defined above, mention may
also be made of the compounds having the respective structures (A1 ) and
(A2)
Ra-CON HCH2CH2 -_Nr(Rb)(Rc)(CH2COO ) (A1 )
in which:
Ra represents a C 10-C30 alkyl o r alkenyl group derived from an acid
Ra-COOH preferably present in hydrolysed coconut oil, o r a heptyl, nonyl o r
undecyl group,
Rb represents a beta-hydroxyethyl group, and
Rc represents a carboxymethyl group;
and
Ra'-CONHCH2CH2-N(B)(B') (A2)
in which:
B represents -CH2CH2OX
B' represents -(CH2) -Y', with z = 1 or 2,
X' represents the group -CH2-COOH, CH2-COOZ', -CH2CH2-COOH,
-CH2CH2-COOZ', or a hydrogen atom,
Y' represents -COOH, -COOZ', the group -CH2-CHOH-SO3H or
-CH2-CHOH-SO3Z',
Z' represents an ion derived from an alkali metal or alkaline-earth
metal, such as sodium, an ammonium ion (NH4+) or an ion derived from an
organic amine, in particular from amino alcohols.
Examples of amino alcohols that may especially be mentioned
include mono-, di- and triethanolamine, mono-, di- and triisopropanolamine,
2-amino-2-methyl-1 -propanol, 2-amino-2-methyl-1 ,3-propanediol and
tris(hydroxymethyl)aminomethane.
Ra' represents a C 10-C30 alkyl or alkenyl group of an acid Ra'-COOH
preferably present in coconut oil or in hydrolysed linseed oil, an alkyl group,
especially of C i 7 and its iso form, or an unsaturated C i group.
These compounds are classified in the CTFA dictionary, 5th edition,
1993, under the names disodium cocoamphodiacetate, disodium
lauroamphodiacetate, disodium caprylamphodiacetate, disodium
capryloamphodiacetate, disodium cocoamphodipropionate, disodium
lauroamphodipropionate, disodium caprylamphodipropionate, disodium
capryloamphodipropionate, lauroamphodipropionic acid and
cocoamphodipropionic acid.
By way of example, mention may be made of the
cocoamphodiacetate sold by the company Rhodia under the trade name
Miranol® C2M Concentrate.
Among the amphoteric or zwitterionic surfactants mentioned above
that are preferably used are (Cs-2o alkyl)betaines and (Cs-2o alkyl )amido(C2 -8
alkyl)betaines such as cocamidopropylbetaine, and mixtures thereof. More
preferentially, the amphoteric or zwitterionic surfactants(s) are chosen from
cocamidopropylbetaine and cocoylbetaine.
When they are present, the amount of the amphoteric or zwitterionic
surfactants(s) is preferably within the range from 0.01 % to 20% by weight and
better still from 0.5% to 10% 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 aqueous-alcoholic 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~1 . This viscosity may be measured
using a cone/plate viscometer (Haake R600 rheometer or the like).
The thickener(s) may be chosen from sodium chloride, fatty acid
amides obtained from C 10-C30 carboxylic acids (coconut acid
monoisopropanol-, diethanol- or monoethanol-amide, oxyethylenated
carboxylic acid monoethanolamide alkyl ether), cellulose-based thickeners
(hydroxyethycellulose, hydroxypropylcellulose, carboxymethylcellulose), guar
gum and 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: AeryIates/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 T21 0 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 C 10-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 surfactants chosen from nonionic surfactants.
Examples of nonionic surfactants that may be used in the cosmetic
composition according to the invention are described, for example, in the
"Handbook of Surfactants" by M.R. PORTER, published by Blackie & Son
(Glasgow and London), 1991 , pp. 116-1 78. They are especially chosen from
polyethoxylated, or polyglycerolated alcohols, alpha-diols, (Ci_2o)alkylphenols
and fatty acids, containing a fatty chain comprising, for example, from 8 to 18
carbon atoms, ethylene oxide or propylene oxide groups possibly ranging
especially from 2 to 50, and the number of glycerol groups possibly ranging
especially from 2 to 30.
Mention may also be made of copolymers of ethylene oxide and
propylene oxide, oxyethylenated fatty acid esters of sorbitan, fatty acid
esters of sucrose, optionally oxyalkylenated alkylpolyglycosides,
alkylglucoside esters, N-alkyl glucamine and N-acylmethylglucamine
derivatives, aldobionamides and amine oxides.
When they are present, the amount of the nonionic surfactant(s)
preferably ranges from 0.01 % to 20% by weight and better still from 0.2% to
10% by weight relative to the total weight of the composition.
The composition according to the invention is generally used in
topical application.
In particular, the composition according to the invention may be in
any galenical form normally used for topical application.
The cosmetic composition used according to the invention may be a
rinse-out or leave-in composition. In particular, it may be a shampoo, a
cream, a mousse (aerosol or non-aerosol), a paste, a gel, an emulsion or a
lotion. Preferably, the cosmetic composition is a shampoo or a gel.
In a first preferred embodiment, the composition according to the
invention is in the form of a gel. In this case, it comprises at least one
thickener that is preferably present in an amount sufficient to obtain a gel.
The term "gel" or "gelled composition" means a composition with a
viscosity ranging from 100 cps to 500 000 cps and better still from 200 cps to
100 000 cps at room temperature (25°C) and at atmospheric pressure ( 1 bar)
and at a shear rate of 1 s~1 . This viscosity may be measured using a
cone/plate viscometer (Haake R600 rheometer or the like).
This particular form allows the composition to remain localized at the
point of application. Thus, the composition does not run, which reduces the
risks of contact of the composition with the eyes.
The thickener(s) may be chosen from those mentioned hereinabove.
In a second preferred embodiment, the composition according to the
invention is in the form of a shampoo. In this case, the composition comprises
one or more surfactants that are preferably present in an amount sufficient to
wash the hair.
The surfactants(s) may be chosen from those defined previously.
Preferably, the total amount of anionic, nonionic, amphoteric and
zwitterionic surfactants is then at least 3% by weight relative to the total
weight of the composition. Even more preferentially, the composition
according to the invention has a total content of anionic, nonionic, amphoteric
and zwitterionic surfactants ranging from 4% to 50% by weight and better still
from 5% to 20% by weight relative to the total weight of the composition.
The composition according to the invention generally comprises a
cosmetically acceptable medium. The medium is formed from water and/or
optionally one or more cosmetically acceptable organic solvents. Preferably,
the medium is formed from water and optionally one or more cosmetically
acceptable organic solvents.
The organic solvent(s) may be chosen from Ci-C4 lower alcohols,
such as ethanol, isopropanol, tert-butanol or n-butanol; polyols such as
glycerol, propylene glycol and polyethylene glycols; polyol ethers, for
instance dipropylene glycol monomethyl ether; and mixtures thereof.
Preferably, the cosmetic composition used according to the invention
contains an amount of organic solvents ranging from 0.05% to 60%,
preferably from 0.5% to 50% and better still from 1% to 40% by weight
relative to the total weight of the composition.
The composition according to the invention may also comprise
one or more conditioning agents.
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
comprising cationic polymers, cationic surfactants, silicones, in
particular organosiloxanes, linear or branched C8-C30 hydrocarbons,
linear or branched C8-C30 fatty alcohols, esters of a C8-C30 fatty acid
and of a CrC 30 fatty alcohol, including esters of a C8-C30 fatty acid and
of a C8-C3o fatty alcohol, esters of a C -C7 acid or diacid 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 000 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:
( )
X
(IV)
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, represents 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 polymers 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
methacryloyloxy-ethyltrimethylammonium 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
methacryloyloxy-ethyltrimethylammonium methosulfate sold under the name
Reten by the company Hercules,
quaternized or non-quaternized
vinyl-pyrrolidone/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/-vinyl-pyrrolidone 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/dimethylaminopropyl-methacrylamide 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
bis-azetidinium, 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 bis-haloacyldiamine, a bisalkyl
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 6 15 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 10 1 by the company Hercules in the case of the adipic
acid/epoxypropyl/diethylenetriamine copolymer.
(6) Cyclopolymers of alkyldiallylamine or of
dialkyldiallyl-ammonium, such as the homopolymers or copolymers containing,
as main constituent of the chain, units corresponding to formula (V) or (VI):
-(CH2) - 12)-CH 2-
in which k and t are equal to 0 or 1, the sum k + t being equal to 1; R 12
denotes a hydrogen atom or a methyl group; R 10 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 has preferably 1 to 5 carbon atoms,
a lower (C1 -C4) amidoalkyl group, or R 10 and R 11 may denote, jointly 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 90 406.
R 10 and R 11, independently of each other, preferably denote an alkyl
group having from 1 to 4 carbon atoms and more particularly 1 carbon atom.
Among the polymers defined above, mention may be made more
particularly of the dimethyldiallylammonium chloride homopolymer sold under
the name Merquat l OO 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:
R
13 R15
in which formula (VII):
R 13, R14, R15 and R 16, 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 R 13, R14, R 15
and R 16, 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 R 13, R14, R 15 and R 16 represent a linear or
branched C 1-C6 alkyl group which is substituted by a nitrile, ester, acyl, amide
or -CO-O-R1 7-D or -CO-NH-R1 7-D group in which R 17 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, R 13 and R 15 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)p-,
n and p are integers ranging from 2 to 20 approximately
in which D denotes:
a) a glycol residue of formula: -O-Z-O-, where Z denotes a linear or
branched hydrocarbon-based radical or a group corresponding to one of the
following formulae:
-(CH2-CH2-O)x -CH2-CH2-
-[CH2-CH(CH3)-O]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 4 13 907 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:
in which R 18, R 19, 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 (VIII) is that for which
R 18, R 19, 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 (IX):
R22 R24
— N+ - (CH2) - NH - CO - (CH2)u -CO - NH (CH2)v - N+ - A—
R23 (IX) R25 Xin
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-
O-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 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 13 1 576, such as hydroxyalkylcelluloses, for instance
hydroxymethyl-, hydroxyethyl- or hydroxypropylcelluloses grafted, in particular,
with a methacryloylethyl-trimethylammonium,
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:
Preferably, these polypeptides are of plant origin.
The following may especially be mentioned:
- wheat, soybean or rice protein hydrolysates modified with
cocodimonium hydroxypropyl groups,
- wheat, soybean, jojoba, oat or rice protein hydrolysates modified
with hydroxypropyl trimonium groups,
- wheat, soybean or jojoba protein hydrolysates modified with
lauridimonium hydroxypropyl groups,
- jojoba, soybean or rice protein hydrolysates modified with
steardimonium hydroxypropyl groups.
Among these products, an example that may be mentioned is the
product sold by the company Cognis under the name Gluadin WQ or by the
company Croda under the name Hydrotriticum WQ PE or Croquat Soya.
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.
The conditioning agent(s) that may be used according to the
invention may be chosen from cationic surfactants.
The term "cationic surfactant" means a surfactant that is positively
charged when it is contained in the composition according to the invention.
This 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 surfactant(s) that may be used as conditioning
agents according to the present invention are preferably chosen from
primary, secondary or tertiary fatty amines, optionally
polyoxyalkylenated, or salts thereof, and quaternary ammonium salts,
and mixtures thereof.
The fatty amines generally comprise at least one C8-C30
hydrocarbon-based chain. Among the fatty amines that may be used
according to the invention, examples that may be mentioned include
stearylamidopropyldimethylamine and distearylamine.
Examples of quaternary ammonium salts that may especially be
mentioned include:
those corresponding to the general formula (XII) below:
(XII)
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 2 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 -30 alkyl, C -30 alkoxy, polyoxyalkylene (C2-C6) , C -30
alkylamide, (C 2-C22 )alkylamido(C2-C 6)alkyl, (C 2-C22)alkylacetate, and
C-i-30 hydroxyalkyl; X is an anion chosen from the group of halides,
phosphates, acetates, lactates, (C C4)alkyl sulfates and (C C4)alkylor
(C C4)alkylaryl-sulfonates.
Among the quaternary ammonium salts of formula (XII),
preference is given, on the one hand, to tetraalkylammonium chlorides,
for instance or alkyltrimethylammonium chlorides in which the alkyl
radical contains approximately 12 to 22 carbon atoms, in particular
behenyltrimethylammonium chloride, distearyldimethylammonium
chloride, cetyltrimethylammonium chloride and
benzyldimethylstearylammonium chloride, or else, on the other hand,
to palmitylamidopropyltrimethylammonium chloride or the
stearamidopropyldimethyl(myristyl acetate)ammonium chloride sold
under the name Ceraphyl® 70 by the company Van Dyk.
- quaternary ammonium salts of imidazoline, for instance those
of formula (XIII) below:
in which R 2 represents an alkyl or alkenyl radical comprising
from 8 to 30 carbon atoms, for example fatty acid derivatives of tallow,
Ri3 represents a hydrogen atom, a C C4 alkyl radical or an alkyl or
alkenyl radical comprising from 8 to 30 carbon atoms, R represents a
C C4 alkyl radical, R 5 represents a hydrogen atom or a C C4 alkyl
radical, X is an anion chosen from the group of halides, phosphates,
acetates, lactates, (C C4)alkyl sulfates and (C C4)alkyl- or (C
C4)alkylaryl-sulfonates. Preferably, R 2 and R 3 denote a mixture of
alkenyl or alkyl radicals comprising from 12 to 2 1 carbon atoms, for
example fatty acid derivatives of tallow, R 4 denotes a methyl radical
and R 5 denotes a hydrogen atom. Such a product is sold, for example,
under the name Rewoquat® W 75 by the company Rewo;
- quaternary di- or triammonium salts in particular of formula
(XIV):
++
Rl7 Rl
R1 -N-(CH2)3-N-R 2 1
2XR
R20
(XIV)
in which R 16 denotes an alkyl radical comprising approximately
16 to 30 carbon atoms, optionally hydroxylated and/or interrupted with
one or more oxygen atoms, R 17 is chosen from hydrogen, an alkyl
radical comprising from 1 to 4 carbon atoms and a group
[(R1 6a)(R1 7a)(R1 8a)N+-(CH2)3-,Y], R 16a, R 17a, R 18a, R 18 , R 19 ,
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, (C C4)alkyl sulfates, (C C4)alkylsulfonate
or (CrC 4)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, such as those of formula (XV) below:
o -
2 - C- (OC 2 )Y N (C H2 O)X- R2 3 X-
(XV)
in which:
R22 is chosen from C C6 alkyl and C C6 hydroxyalkyl or
dihydroxyalkyl radicals;
- R2 3 is chosen from:
O
- the radical 6 C
- radicals R2 7, which are linear or branched, saturated or
unsaturated C C22 hydrocarbon-based radicals,
- a hydrogen atom,
- R2 5 is chosen from:
O
- the radical C
- radicals R29, which are linear or branched, saturated or
unsaturated C C6 hydrocarbon-based radicals,
- a hydrogen atom,
R24 , 26 and R28, which may be identical or different, are chosen
from linear or branched, saturated or unsaturated C -C2i hydrocarbonbased
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 R29.
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 R2 , 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 R29, it preferably
contains 1 to 3 carbon atoms.
Advantageously, R24 , R26 and R28, which may be identical or
different, are chosen from linear or branched, saturated or unsaturated
-C2 hydrocarbon-based radicals, and more particularly from linear
or branched, saturated or unsaturated Cn-C2 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 (C C4)alkyl- or (C C4)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 containing an ester
function, may be used.
The anion X is even more particularly chloride, methyl sulfate
or ethyl sulfate.
Use is made more particularly in the composition according to
the invention of the ammonium salts of formula (XV) in which:
- R22 denotes a methyl or ethyl radical,
- x and y are equal to ;
- z is equal to 0 or 1;
- r , s and t are equal to 2 ;
- R2 3 is chosen from:
O
- the radical R 6 C
- methyl, ethyl or C 4-C22 hydrocarbon-based radicals,
- a hydrogen atom;
- R2 5 is chosen from:
O
- the radical R C
- a hydrogen atom;
- R24, R26 and R2s, which may be identical or different, are
chosen from linear or branched, saturated or unsaturated C 13-C1
hydrocarbon-based radicals and preferably from linear or branched,
saturated or unsaturated C 3-C1 alkyl and alkenyl radicals.
The hydrocarbon-based radicals are advantageously linear.
Examples that may be mentioned include the compounds of
formula (XV) 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 C 10-C30 fatty acids or with mixtures of
C 10-C30 fatty acids 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 dialkyl 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 may contain, for
example, a mixture of quaternary ammonium salts of mono-, di- and
triesters with a weight majority of diester salts.
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.
The cationic surfactant(s) that may particularly preferably be
used according to the invention are the compounds of formula (XII) or
of formula (XV).
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, methyl(CcrCi9)alkyl(CioC
2o)alkylamidoethylimidazolium salts, the stearamidopropyldimethylamine
salt and the stearamidopropyl dimethylammoniunn salt, and mixtures thereof.
Among the silicones 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
7 58® 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 3 109® 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 nf s at 25°C.
Such a silicone is, for example, hexamethyldisiloxane sold
under the name Silbione 70041 V0.65® by 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 to 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 0 6
nf s, and preferably less than 2.6 nf s, i.e.:
- containing trimethylsilyl end groups, for instance, in a nonlimiting
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, Abil Wax
9800® and Abil Wax 9801®, which are poly(C -20)alkylsiloxanes.
Among the 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 PN 1000® and PH 1000®;
- 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:
) mixtures formed from a polydimethylsiloxane hydroxylated at
the end of the chain (Dimethiconol according to the CTFA
nomenclature) and of a 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*1 06 m2/s ( 15% SE 30® gum
and 85% SF 96® oil).
The product CF 1241® is a mixture of an SE 30® gum (33%)
and of a PDMS (67%), 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: R2S1O2/2, RSi0 3/2 and Si0 4/2 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-
22-8 9®, 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 Q2-841 3®;
c) thiol groups, as in the silicones X 2-8360® from the company
Dow Corning or GP 72A® and GP 7 1® from Genesee;
d) non-quaternized amine groups, such as GP 4 Silicone Fluid®
from Genesee, GP 7 100® 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, such as the polyorganosiloxanes
containing a C2-C1 8 hydroxyalkyl function, described, for example, in
patent application FR 85/1 6334.
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) (C8-C22)acyloxy(C2-C1 8)alkyl groups, for instance the
polyorganopolysiloxanes described in patent application FR 88/ 7433;
i) quaternary ammonium groups, as in the products X2 8 1 08®
and X2 8 1 09® 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 (C1 2)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-41 2
704, EP-A-41 2 707, 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:
O CH3 CH CH
II I
H2C = C - C - 0 — (CH2)3— Si— O Si - O - Si— (CH„), - CH,
I I
CH3 CH3 CH, CH,
(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 (PDMS) onto which are grafted, via a connecting
unit of thiopropylene type, mixed polymer units of the poly(meth)acrylic
acid type and of the polyalkyl (meth)acrylate type and
polydimethylsiloxanes (PDMS) 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 containing trimethylsilyl end groups, such as oils
with a viscosity of between 0.2 and 2.5 nf 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, and more
particularly the oil 70 047 V 500 000 sold by the company Rhodia
Chimie, 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-C30o
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 npentadecane,
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 CrC 30 alcohol including esters of a
C8-C30 fatty acid and of C8-C30 fatty alcohols, or an ester of a C C
acid or diacid 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,
dioctyl, myristyl myristate, stearyl myristate, cetyl palmitate, myristyl
stearate, stearyl stearate and cetyl stearate, 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:
R3CHOH— CH— CH2OR2
NH
C=0
(XIX)
in which:
- R denotes a linear or branched, saturated or unsaturated alkyl
radical, derived from C 4-C30 fatty acids, this radical possibly being
substituted with a hydroxyl group in the alpha position or a hydroxyl
group in the omega position esterified with a saturated or unsaturated
C 6-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 C 5-C26 hydrocarbonbased
radical in the alpha position, this radical possibly being
substituted with one or more C C 4 alkyl radicals;
it being understood that, in the case of these natural ceramides
or glycoceramides, R3 may also denote a C 5-C26 alpha-hydroxyalkyl
radical, the hydroxyl group being optionally esterified with a C 6-C30
alpha-hydroxyacid.
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 denotes a saturated or
unsaturated alkyl derived from C 6-C2 2 fatty acids; R2 denotes a
hydrogen atom; and R3 denotes a saturated linear C 5 radical.
Such compounds are, for example:
- N-linoleoyldihydrosphingosine,
- N-oleoyldihydrosphingosine,
- N-palmitoyldihydrosphingosine,
- N-stearoyldihydrosphingosine,
- N-behenoyldihydrosphingosine,
or mixtures of these compounds.
Even more preferentially, use is made of ceramides for which
R 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)i2-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, used is preferably made of one
or more conditioning agents chosen from silicones and cationic polymers.
The cosmetic composition according to the invention preferably
comprises at least 0.01 % by weight and more preferentially from 0.05% to
10% by weight of conditioning agent(s), relative to the total weight of the
composition.
The cosmetic composition according to the invention may have a pH
of between 3 and 10 and preferentially between 5 and 7 . This pH may be
adjusted by means of acidifying and basifying agents conventionally
used in cosmetics.
The cosmetic composition used according to the invention may also
contain one or more adjuvants that are common in cosmetics, such as hairloss
counteractants, oxidizing agents, vitamins and provitamins including
panthenol, plant, animal, mineral or synthetic oils, waxes, sunscreens,
mineral or organic, coloured or uncoloured pigments, dyes, nacreous
agents and opacifiers, sequestrants, plasticizers, solubilizers,
antioxidants, hydroxy acids, fragrances, antidandruff agents other than
the compounds (i) and (ii) as defined previously, and preserving
agents. The adjuvants(s) that may be used in the cosmetic composition
of the invention are different from the compounds defined previously.
The amounts of these various adjuvants are those conventionally
used in the fields under consideration.
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.
Another subject of the invention consists of a cosmetic antidandruff
treatment process, for improving and/or reducing dandruff, and especially that
caused by yeasts of the genus Malassezia, characterized in that it comprises
the application of a cosmetically effective amount of a composition according
to the invention to the hair and the scalp. The composition may then be
optionally rinsed out with water.
A subject of the invention is also the use of the combination of at
least one compound (i) as defined above and of at least one compound (ii) as
defined previously, preferably in a weight ratio of the amount of compound(s)
(i) to the amount of compound(s) (ii) of greater than or equal to 0.5, preferably
greater than or equal to 0.7 and better still greater than or equal to 1, as an
antidandruff agent. The use of the said combination makes it possible to
eliminate and/or reduce dandruff on the hair and the scalp while limiting the
irritation and itching of the scalp.
Finally, a subject of the invention is the use of the combination of at
least one compound (i) as defined above and of at least one compound (ii) as
defined previously, preferably in a weight ratio of the amount of compound(s)
(i) to the amount of compound(s) (ii) of greater than or equal to 0.5, preferably
greater than or equal to 0.7 and better still greater than or equal to 1, as an
anti-canities agent.
The examples that follow are intended to illustrate the invention,
without, however, having any limiting nature.
Example of preparation of the bacterial extract:
The process for preparing a biomass containing the bacterial strain
Vitreoscilla filiformis comprises the culturing of the bacteria in an oxygenated
sterile medium, in the presence of mineral salts and sugars; the harvesting; and
then centrifugation, of the culture medium comprising the bacteria, to obtain a
biomass, which is placed in bottles and then sterilized. Rupture of the cells
resulting from the sterilization causes decantation of the biomass as a sludge
essentially containing cell membranes and coagulated proteins. A
homogeneous biomass is reconstituted by agitation before use.
The following compositions were prepared according to the following
tables. The amounts are indicated as weight percentages of active material
(AM) relative to the total weight of each composition.
Example 1: Leave-on aqueous-alcoholic gel
The gel obtained is stable over time and has satisfactory rheology.
When applied to the scalp and the hair, this gel shows good cosmetic
performance qualities, in particular a good feel and a good antidandruff effect.
Example 2 : Antidandruff shampoo
Composition 2 weight% of AM
Cocamidopropylbetaine as an aqueous solution
containing 38% by weight of active material 2.4
(Tegobetaine F50 from Evonik Goldschmidt)
Sodium benzoate 0.5
Sodium lauryl ether sulfate containing 2.2 mol of
ethylene oxide, at 26% by weight in aqueous
15.54
solution (Texapon AOS 225 UP sold by the
company Cognis)
Extract of Vitreoscilla filiformis as an aqueous
dispersion containing 5% active material, prepared 0.5
according to the method indicated above ( 1 )
Ellagic acid 1
1-(Hexadecyloxy)-2-octadecanol/cetyl alcohol
2.5
mixture (47/53 by weight)
Salicylic acid 0.2
Coconut monoisopropanolamide (Comperlan 100
0.25
sold by the company Cognis)
Polydimethylsiloxane (Mirasil DM 500 000 sold by
2
the company Rhodia)
Propylene glycol 0.1
Salicylic acid 0.2
Glycerol 2
Fragrance 0.5
Carboxyvinyl polymer (Carbopol 980 Polymer sold
0.3
by the company Lubrizol)
Sodium chloride 1.1
pH agent qs pH 5.3
Water qs 100
The shampoo obtained is stable over time and has satisfactory
rheology.
When applied to the hair and the scalp and rinsed out, this shampoo
has good working qualities (ease of application, soft, pleasant lather, ease of
removal), good cosmetic performance qualities (softness, smoothness) and
a satisfactory antidandruff effect, in particular on repeated application.
CLAIMS
1. Cosmetic composition comprising:
(i) from 0.01 % 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, in a content ranging
(ii) one or more extracts of one or more non-photosynthetic, non-fruiting
filamentous bacteria, and
(iii) one or more surfactants chosen from anionic and/or amphoteric or
zwitterionic surfactants.
2 . Composition according to Claim 1, characterized in that the salt(s)
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-C20 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 any one of the preceding claims,
characterized in that it comprises 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 the preceding claims,
characterized in that the said non-photosynthetic non-fruiting filamentous
bacterial extract is an extract of Vitreoscilla filiformis.
7 . Composition according to any one of the preceding claims,
characterized in that the said non-photosynthetic non-fruiting filamentous
bacteria extract is present in a proportion of from 0.001 % to 10% by weight
and preferably from 0.01 % to 5% by weight expressed as solids relative to the
total weight of the composition.
8 . Composition according to one of the preceding claims,
characterized in that the compound(s) (i) and the extract(s) (ii) are present
in a weight ratio of the amount of compound(s) (i) to the amount of
compound(s) (ii) of greater than or equal to 0.5.
9 . Composition according to any one of the preceding claims,
characterized in that the weight ratio of the amount of compound(s) (i) to the
amount of extract(s) (ii) is greater than or equal to 0.7 and better still greater
than or equal to 1.
10 . Composition according to any one of the preceding claims,
characterized in that it comprises one or more thickeners.
11. Composition according to any one of the preceding claims,
characterized in that it comprises one or more conditioning agents preferably
chosen from silicones and cationic polymers.
12 . Composition according to any one of the preceding claims,
characterized in that it comprises one or more additives chosen from hairloss
counteractants, oxidizing agents, vitamins and provitamins including
panthenol, plant, animal, mineral or synthetic oils, waxes, sunscreens,
mineral or organic, coloured or uncoloured pigments, dyes, nacreous
agents and opacifiers, sequestrants, plasticizers, solubilizers, acidifying
agents, basifying agents, antioxidants, hydroxy acids, fragrances,
antidandruff agents other than the compounds (i) and extracts (ii) as
defined in Claims 1 to 1 , and preserving agents.
13 . Cosmetic treatment process for eliminating and/or reducing the
amount of dandruff on the hair and the scalp, characterized in that it
comprises the application of a cosmetically effective amount of a cosmetic
composition as defined in any one of Claims 1 to 12 to the hair and the scalp.
14. Use of a cosmetic composition as defined in any one of Claims 1
to 12, for eliminating and/or reducing the amount of dandruff on the hair and
the scalp.
15 . Use of a combination of: (i) one or more compounds chosen from
ellagic acid, ethers thereof and ellagic acid salts or ethers thereof, and
(ii) one or more extracts of one or more non-photosynthetic, non-fruiting
filamentous bacteria, and
as an antidandruff agent in a cosmetic composition as defined in one of
Claims 1 to 12 .
16 . Use of a combination of: (i) one or more compounds chosen from
ellagic acid, ethers thereof and ellagic acid salts or ethers thereof, and
(ii) one or more extracts of one or more non-photosynthetic, non-fruiting
filamentous bacteria,
as an anti-canities agent in a cosmetic composition as defined in one of
Claims 1 to 12 .