The present invention relates to a cosmetic composition useful
for washing and/or conditioning ker atin fibres, and in particular human
keratin fibres such as the hair, which comprises one or more anionic
and one or more amphoteric or zwitter ionic surfactants, one or more
polymer(s) comprising at least one (meth) acr ylic unit , and one or more
silicones.
The invention also relates to a cosmetic process for washing
and/or conditioning keratin fibres using such a composition.
It is common practice to use detergent cosmetic compositions
such as shampoos and shower gels, based essentially on surfactants,
for washing keratin mater ials such as the hair and the skin. These
compositions are applied to the keratin mater ials, which are preferabl y
wet, and the lather generated by massaging or rubbing with the hands
or a toiletr y flannel makes it possible, after rinsing with water, to
remove the diverse t ypes o f soiling initially present on the hair or the
20 skin.
These compositions contain substantial contents of "detergent"
surfactants, which, in order to be able to formulate cosmetic
compositions with good washing power, must especially give them
good foaming p ower. The surfactants that are useful for this purpose
25 are generally of anionic, non-ionic and/or amphoteric type, and
particular ly of anionic type.
Admittedly these compositions have a good washing power, but
the intrinsic cosmetic properties associated with them nevertheless
remain fair ly poor, owing in particular to the fact that the relativel y
aggressive nature of such a cleaning tr eatment can, in the long run,
lead to more or less pronounced damage to the keratin fibres, this
damage being associated in particular with the gradual removal of the
lipids or proteins contained in or on the surface of said fibres.
3
Thus, in order to improve the cosmetic properties of the above
detergent compositions, and more particularly those which ar e to be
applied to sens itized hair ( i.e. hair which has been damaged or made
brittle, in particular under the chemical action of atmospher ic agents
and/or hair treatments such as permanent-waving, dyeing o5 r
bleaching), it is now common to introduce additional conditioning
agents such as mineral or plant oils into these compositions. These
conditioners are intended mainly to repair or limit the harmful or
undesirable effects induced by the var ious treatments or aggressions to
10 which the hair fibres ar e subjected more or less repeat edly. These
conditioners may, of course, also improve the cosmetic behaviour of
natural hair.
However, the compositions containing such conditioners are
generally presented in the form of emulsions or dispersions having
15 varying degrees of thickness and the y often have an opaque appearance
that is not ver y attr active. More and more consumers seek cosmetic
products that have an original visual appearance.
Moreover, these products may cause some drawbacks, due in
particular to the presence of oils.
20 In particular, these compositions r ich in fatt y substances ma y
be difficult to apply to the hair and may be difficult to remove, in
particular ma y require long rinsing.
Accordingly, there is a real need to make available
compositions, in particular washing compositions for human keratin
25 fibres such as hair, not presenting the drawbacks mentioned
hereinabove, i.e. that present an attractive visual appearance and that
can be applied easily to said fibres, and be rinsed quickly while
leading to enhanced cosmetic properties, notably in terms of
smoothness, softness and manageabilit y. These cosmetic properties
30 ma y also be long-lasting.
The composition should also have good detergent properties,
and notably generate good lather ing properties.
It has now been discovered that a cosmetic compositio n
comprising one or more anionic and one or more amphoteric or
4
zwitter ionic surfactants, one or more silicones, and one or more
polymer(s) comprising at least one (meth)acrylic unit , makes it
possible to achieve the objectives outlined above.
Thus, the subject of the invention is especially a cosmetic
composition comprising5 :
- one or more anionic surfactant(s) in an amount of more than or
equal to 5% by weight, relative to the total weight of the cosmetic
composition,
- one or more amphoteric or zwitterionic surfactant(s),
10 - one or more polymer(s) comprising one or more acrylic and/or
methacr ylic unit(s), and
- one or more hydroxyl-terminated silicone(s).
The composition according to the invention has ver y good
cleaning properties. It provides good creamy lather that spreads easil y
15 and uniformly on ker atin fibres and that removes all the accumulated
dirt, oils and sebum leading to better clean feel on keratinous
substrates such as the hair and the scalp. The composition has the
further advantages of being applied easily and of being r insed off
quickly.
20 Furthermore the composition according to the invention confer s
high cosmetic properties to the keratin fibres, and especially affords
them a good conditio ning. Indeed, the composition of the invent io n
provides, for instance, excellent smoothness, softness and
disentangling to the keratin fibres. The composition further provides a
25 good manageabilit y of the keratin fibres, and a good control of the
volume.
In addition, the composition according to the invention has a n
attractive and original visual appearance. It is indeed a clear and
transparent composition, which is ver y pleasant to the consumers.
30 The invention also relates to a cosmetic process for washing
and/or conditioning keratin fibres, in particular human keratin fibres
such as hair, which co nsists in applying to said keratin fibres a
composition as previously defined, and after an optional leave-o n
time, optionally removing it by r insing.
5
Other subjects, characteristics, aspects and advantages of the
invention will emerge even more clear ly on reading the descriptio n
and the example that follows.
In that which follows and unless otherwise indicated, the limit s
of a range of values are included within this range, in particular in th5 e
expressions "of between" and "ranging from ... to ...".
Moreover, the expression "at least one" used in the present
description is equivalent to the expression "o ne or more".
Anionic surfactants
10 The cosmetic composition according to the present inventio n
comprises one or more anionic surfactants in an amount of more tha n
or equal to 5% by weight, relative to the total weight of the cosmetic
composition.
The term "anionic surfactant" means a surfactant comprising,
15 as ionic or ionizable groups, only anionic groups.
In the present description, a species is termed as being
"anionic" when it bears at least one permanent negative charge or
when it can be ionized as a negatively charged species, under the
conditions of use of the composition of the invention (for example the
20 medium or the pH) and not comprising any cationic charge.
The anionic surfactants ma y be sulfate, sulfonate and/or
carboxylic (or carboxylate) surfactants. Needless to say, a mixture of
these surfactants ma y be used.
It is understood in the present descrip tion that:
25 - carboxylate anionic surfactants comprise at least one carboxylic or
carboxylate function (-COOH or -COO-) and may optionally also
comprise one or more sulfate and/or sulfonate fu nctions;
- the sulfonate anionic surfactants comprise at least one su lfonate
function (-SO3H or -SO3
– ) and may optionally also comprise one or
30 more sulfate functions, but do not comprise any carboxylate functions;
and
- the sulfate anionic surfactants comprise at least one sulfate functio n
but do not comprise any carboxylate or sulfonate functions.
6
The carboxylic anionic surfactants that may be used thus
comprise at least one carboxylic or carboxylate functio n (-COOH or -
COO-).
They ma y be chosen from the following compounds:
ac ylglycinates, ac yllact ylates, ac ylsarcosinates, acylglutamates; alkyl5 -
D-galactosideuronic acids, alkyl ether carboxylic acids, alkyl(C6 -30
aryl) ether carboxylic acids, alkylamido ether carboxylic acids; and
also the salts of these compounds.
The alkyl and/or acyl groups of these compounds comprise
10 from 6 to 30 carbon atoms, especially from 12 to 28, better still from
14 to 24 or even from 16 to 22 carbon atoms; the aryl group preferably
denoting a phenyl or benz yl group.
These compounds are possib ly polyoxyalkylenated, especiall y
polyoxyethylenated, and then preferably comprising from 1 to 50
15 ethylene oxide units and better still from 2 to 10 ethylene oxide units.
Use ma y also be made of the C6 -C2 4 alkyl monoesters of
polyglycoside-polycarboxylic acids, such as C6-C2 4 alkyl
polyglycoside-citrates, C6-C2 4 alkyl polyglycoside-tartrates and C6 -C2 4
alkyl polyglycoside-sulfosuccinates, and salts thereof.
20 Among the above carboxylic surfactants, mention ma y be made
most particular ly of polyo xyalk ylenated alkyl( amido) ether carboxylic
acids and salts thereof, in particular those comprising from 2 to 50
alkylene oxide and in particular ethylene oxide groups, such as the
compounds sold by the company Kao under the name Akypo .
25 The polyoxyalkylenated alkyl ( amido) ether carboxylic acids
that may be used are preferably chosen from those of formula (I):
R1 (OC2H4)n OCH2COOA (I)
in which:
30 - R1 represents a linear or branched C6-C2 4 alkyl or alkenyl radical, a n
alkyl(C8 -C9)phenyl radical, a radical R2CONH-CH2 -CH2 - with R2
denoting a linear or branched C9 -C21 alkyl or alkenyl radical,
preferably, R1 is a C8 -C2 0 and preferably C8 -C18 alkyl radical, and ar yl
preferably denotes phenyl,
7
- n is an integer or decimal number (aver age value) ranging from 2 to
24 and preferably from 2 to 10, and
- A denotes H, ammonium, Na, K, Li, Mg or a monoethanolamine or
triethanolamine residue.
It is also possible to use mixtures of compounds of formula (I) 5 ,
in particular mixtures of compounds containing different groups R1 .
The polyoxyalkylenated alkyl(amido) ether carboxylic acids
that are particular ly preferred are those of formula (I) in which:
- R1 denotes a C1 2 -C1 4 alkyl, cocoyl, ole yl, nonylphenyl or octylphenyl
10 radical,
- A denotes a hydro gen or sodium atom, and
- n varies from 2 to 20 and preferably from 2 to 10.
Even more preferentially, use is made of compounds of formula
(I) in which R denotes a C1 2 alkyl radical, A denotes a hydrogen or
15 sodium atom and n ranges from 2 to 10.
Preferentially, the carboxylic anio nic surfactants are chosen,
alo ne or as a mixture, from:
- acylglutamates, especially of C6 -C2 4 or even C12 -C20 , such as
stearo ylglutamates, and in particular disodium stearoylglutamate;
20 - acylsarcosinates, especially o f C6 -C2 4 or even C1 2 -C2 0 , such as
palmitoylsarcosinates, and in particular sodium palmito ylsarcosinate;
- acyllact ylates, especially of C12 -C28 or even C1 4-C2 4, such as
beheno yllact ylates, and in particular sodium behenoyllact ylate;
- C6 -C2 4, and especially C1 2 -C2 0 , ac ylglycinates;
25 - (C6 -C2 4 )alkyl ether carboxylates, and especially (C1 2 -C2 0 )alkyl ether
carboxylates;
- polyoxyalkylenated (C6 -C2 4 )alkyl(amido) ether carboxylic acids, in
particular those comprising from 2 to 50 ethylene oxide groups;
in particular in the form of alkali metal or alkaline-earth metal,
30 ammonium or amino alcohol salts.
The su lfonate anionic surfactants that may be used comprise at
least one sulfonate functio n (-SO3H or -SO3
-).
They ma y be chosen from the following compounds:
alk ylsu lfo nates, a lkyla midesulfonates, alkylar ylsu lfonates, α -
8
olefinsulfonates, paraffin sulfonates, alkylsulfosuccinates, alkyl ether
sulfosuccinates, alkylamidesulfosuccinates, alkylsulfoacetates, Nac
yltaurates, acylisethio nates; alkylsulfolaurates; and also the salts of
these compounds.
The alkyl groups of these compounds comprise from 6 to 35 0
carbon atoms, especially from 12 to 28, better still from 14 to 24 or
even from 16 to 22 carbon atoms; the aryl group preferably de noting a
phenyl or benz yl group.
These compounds are possib ly polyoxyalkylenated, especiall y
10 polyoxyethylenated, and then preferably comprising from 1 to 50
ethylene oxide units and better still from 2 to 10 ethylene oxide units.
Preferentially, the sulfonate anionic surfactants are chosen,
alo ne or as a mixture, from:
- C6 -C2 4 , and especially C1 2 -C2 0 , alkylsulfosuccinates, especiall y
15 laurylsulfosuccinates;
- C6 -C2 4, and especially C1 2 -C2 0 , alkyl ether sulfosuccinates;
- (C6 -C2 4 )acylisethionates, and preferably (C1 2 -C1 8 )acylisethionates,
in particular in the form of alkali metal or alkaline-earth metal,
ammonium or amino alcohol salts.
20 The sulfate anionic surfactants that may be used comprise at
least one sulfate function (-OSO3H or -OSO3
-).
They may be chosen from the following compounds: alkyl
sulfates, alkyl ether sulfates, alkylamido ether sulfates, alkylar yl
polyether sulfates, monoglycer ide sulfates; and also the salts of these
25 compounds.
The alkyl groups of these compounds comprise from 6 to 30
carbon atoms, especially from 12 to 28, better still from 14 to 24 or
even from 16 to 22 carbon atoms; the aryl group preferably denoting a
phenyl or benz yl group.
30 These compounds are possib ly polyoxyalkylenated, especiall y
polyoxyethylenated, and then preferably comprising from 1 to 50
ethylene oxide units and better still from 2 to 10 ethylene oxide units.
9
Preferentially, the sulfate anionic surfactants are chosen, alone
or as a mixture, from:
- alkyl sulfates, especially of C6-C2 4 or even C1 2 -C2 0 ,
- alkyl ether sulfates, especially of C6 -C2 4 or even C1 2 -C2 0 , preferabl y
comprising from 2 to 20 ethylene oxide units5 ;
in particular in the form of alkali metal or alkaline-earth metal,
ammonium or amino alcohol salts.
When the anionic surfactant is in salt form, the said salt ma y
be chosen from alkali metal salts, such as the sodium or potassium
10 salt, ammonium salts, amine salts and in particular amino alcohol
salts, and alkaline-earth metal salts, such as the magnesium salt.
Examples of amino alcohol salts that ma y be mentio ned include
monoethano lamine, diethanolamine and triethanolamine salts,
monoisopropanolamine, diisopropanolamine or triisopropanolamine
15 salts, 2-amino-2-methyl-1-propanol salts, 2-amino-2-methyl-1,3-
propanediol salts and tris(hydroxymethyl)aminomethane salts.
Alkali metal or alkaline-earth metal salts and in particular the
sodium or magnesium salts are preferab ly used.
Preferentially, the anio nic surfactants are chosen, alone or as a
20 mixture, from:
- C6 -C2 4 , and especially C1 2 -C2 0 , alkyl sulfates;
- C6 -C2 4 , and especially C1 2 -C2 0 , alkyl ether sulfates; preferabl y
comprising from 2 to 20 ethylene oxide units;
- C6 -C2 4 , and especially C1 2 -C2 0 , alkylsulfosuccinates, especiall y
25 laurylsulfosuccinates;
- C6 -C2 4 , and especially C1 2 -C2 0 , alkyl ether sulfosuccinates;
- (C6 -C2 4 )acylisethionates and preferably (C1 2-C1 8)acylisethionates;
- C6 -C2 4 , and especially C1 2-C2 0, acylsarcosinates; especiall y
palmitoylsarcosinates;
30 - (C6 -C2 4 )alkyl ether carboxylates, preferably (C1 2 -C2 0 )alkyl ether
carboxylates;
- polyoxyalkylenated (C6-C2 4)alkyl(amido) ether carboxylic acids and
salts thereof, in particular those comprising from 2 to 50 alkylene
oxide and in particular ethylene oxide groups;
10
- C6 -C2 4 , and especially C1 2 -C2 0 , acylglutamates;
- C6 -C2 4 , and especially C1 2 -C2 0 , acylglycinates;
in particular in the form of alkali metal or alkaline-earth metal,
ammonium or amino alcohol salts.
The anio nic surfactants suitable in the composition of th5 e
present invention can be oxyethylenated and then preferably comprise
from 1 to 50 ethylene oxide units.
The anionic surfactants used in the composition of the present
invention are preferably chosen from sulphate and sulfonate anionic
10 surfactants.
The anionic surfactants are most preferab ly chosen from
sulfosuccinates such as in particular C12 -C20 alkylsulfosuccinates and
C1 2-C2 0 alkyl ether sulfosuccinates, and alkyl ether sulphates having a
C1 2-C2 0 alkyl group and comprising from 1 to 20 ethylene oxide units,
15 preferably from 2 to 5 ethylene oxide units (OE), and mixtures thereof.
Such compounds are preferably used under the form of salts , and
preferably sodium salts.
More preferably, the surfactants are chosen from alkyl ether
sulphates having a C12 -C20 alkyl group and comprising from 1 to 20
20 ethylene oxide units, and preferably from 2 to 5 ethylene oxide units.
The amount of anionic surfactants present in the cosmetic
composition of the present invention advantageously r anges from 5 to
30% by weight, more preferentially from 8 to 25% by weight, and eve n
more preferably from 10 to 20% by weight, relative to the total weight
25 of the cosmetic composition.
Amphoteric or zwitterionic surfactants
The cosmetic composition according to the present inventio n
further comprises one or more amphoteric or zwitterio nic surfactants.
The amphoteric or zwitter ionic surfactant(s) that may be used
30 in the present invention ma y especially be secondary or tertiar y
aliphatic amine derivatives, optionally quaternized, in which the
aliphatic group is a linear or branched chain containing from 8 to 22
carbon atoms, the said amine derivatives containing at least one
anionic group, for instance a carboxylate, sulfonate, sulphate,
11
phosphate or phosphonate group. Mention may be made in particular of
(C8-C2 0)alkylbetaines, sulfobetaines, (C8 -C20 )alkylamido(C3 -
C8 )alkylbetaines or (C8-C2 0)alkylamido(C6-C8 )alkylsulfobetaines.
Among the secondary or tertiar y aliphatic amine derivatives,
optionally quaternized, that may be used, as defined abo ve, mentio 5 n
ma y also be made of the compounds of respective structures (II) and
(III) below:
Ra -C(O)-N(Z)CH2 (CH2 )mN+(Rb)(Rc )-CH2C(O)O- , M+, X- (II)
10
wherein,
- Ra represents a C6 -C30 alkyl or alkenyl group derived from an acid
RaCOOH preferably present in hydrolys ed coconut oil, or a heptyl,
nonyl or undecyl group;
15 - Rb represents a beta-hydroxyethyl group;
- Rc represents a carboxymethyl group;
- M+ represents a cationic counter ion derived from an alkali metal or
alkaline-earth metal, such as sodium, an ammonium ion or an io n
derived from an organic amine; and
20 - X- represents an organic or mineral anionic counter ion, preferab ly
chosen from halides, acetates, phosphates, nitrates, (C1 -C4)alkyl
sulphates, (C1 -C4 )alkyl or (C1 -C4)alkylaryl sulfonates, in particular
methyl sulphate and ethyl sulphate;
- m is equal to 0, 1 or 2; and
25 - Z represents a hydrogen atom or a hydroxyethyl or carboxymethyl
group.
Or alternatively M+ and X- are absent;
Ra’ -C(O)-N(Z)-CH2 -(CH2)m’ -N(B)(B') (III)
30
wherein
- B represents the group -CH2 -CH2 -O-X';
- B' represents the group -(CH2 )zY', with z = 1 or 2;
12
- X' represents the group -CH2 -C(O)OH, -CH2 -C(O)OZ’, -CH2-CH2 -
C(O)OH, -CH2 -CH2 -C(O)OZ’, or a hydrogen atom;
- Y' represents the group –C(O)OH, -C(O)OZ’, -CH2-CH(OH)-SO3H
or the group -CH2 -CH(OH)-SO3 -Z’;
- Z' represents a cationic counterion derived from an alkali metal o5 r
alkaline-earth metal, such as sodium, an ammonium ion or an io n
derived from an organic amine;
- Ra ’ represents a C6 -C30 alkyl or C6 -C3 0 alkenyl group of an acid
Ra ’ -COOH, which is preferably present in coconut oil or in hydrolysed
10 linseed oil, or an alkyl group, especially a C1 7 alkyl group and its iso
form, or an unsaturated C1 7 group;
- m' is equal to 0, 1 or 2; and
- Z represents a hydrogen atom or a hydroxyethyl or carboxymethyl
group.
15 The compounds of this type are classified in the CTFA
dictionar y, 5th edition, 1993, under the names disodium
cocoamphodiacetate, disodium lauroamphodiacetate, disodium
caprylamphodiacetate, disodium capryloamphodiacetate, disodium
cocoamphodipropionate, disodium lauroamphodipropionate, disodium
20 caprylamphodipropionate, disodium capryloamphodipropionate,
lauroamphodipropionic acid, cocoamphodipropionic acid and
hydroxyethylcarboxymethylcocamidopropylamine.
Examples that may be mentioned include the
cocoamphodiacetate sold by the company Rhodia under the trade name
25 Miranol® C2M Concentrate or under the trade name Miranol Ultra C
32 and the product sold by the company Chimex under the trade name
Chimexane HA.
Use ma y also be made of compounds of formula (III’ ) :
30 Ra ’ ’ -NH-CH(Y’’)-(CH2 )n-C(O)NH(CH2)n’ -N(Rd)(Re ) (III’)
wherein,
- Y’’ represents the group –C(O)OH, -C(O)OZ'', -CH2-CH(OH)-
SO3H or the group CH2-CH(OH)-SO3-Z'';
13
- Rd and Re , independently of each other, represent a C1-C4 alkyl or
hydroxyalkyl radical;
- Z" represents a cationic counterion derived from an alkali metal or
alkaline-earth metal, such as sodium, an ammonium ion or an io n
derived from an organic amine5 ;
- Ra " represents a C6 -C30 alkyl or alkenyl group of an acid Ra ' '-
C(O)OH which is preferably present in coconut oil or in hydrolysed
linseed oil; and
- n and n' denote, independently of each other, an integer ranging
10 from 1 to 3.
Among the compounds of formula (III’), mention ma y be made
of the compound classified in the CTFA dictionar y under the name
sodium diethylaminopropyl cocoaspartamide and sold by the compan y
Chimex under the name Chimexane HB.
15 Among the abovementioned amphoteric or zwitter ionic
surfactants, it is preferred to use (C8 -C2 0 )alkylbetaines such as
cocoylbetaine, (C8 -C2 0 )alkylamido(C2 -C8 )alkyl)betaines such as
cocoylamidopropylbetaine, and mixtures thereof.
More preferentially, the amphoteric or zwitterionic
20 surfactant(s) are chosen from (C8 -C2 0 )alkylbetaines, and even more
preferably cocoylbetaine.
The amount of the amphoteric or zwitter ionic surfactant( s)
present in the cosmetic composition of the present inventio n
advantageously ranges from 0.1 to 15% by weight, more preferentiall y
25 from 0.5 to 10% by weight, and even more preferably from 1 to 5% b y
weight, relative to the total weight of the cosmetic composition.
Acrylic or methacylic polymers
The cosmetic composition according to the present inventio n
further comprises one or more polymer(s) comprising one or more
30 acrylic and/or methacr ylic units. These polymers are non-silicone, i.e.
they do not contain any silicon (Si) atom.
By “acr ylic or methacr ylic units”, it is understood units
corresponding to acr ylic or methacr ylic acid monomer s and/or their
salts, and/or their derivatives such as esters (for examp le
14
(meth)acr ylates) or amides (for example (meth)acrylamide), optionall y
substituted.
The polymer(s) comprising one or more acrylic and/or
methacr ylic units may be chosen from homopolymer s or copolymer s
derived from acrylic and/or methacr ylic monomers, and preferably fro5 m
homo- or copolymer s resulting from the (co)polymerization of one or
more monomers including one or more monomers of structure (IV) :
H2C
R1
COR2
C
(IV)
10 in which,
- R1 denotes a hydrogen atom or a linear or branched C1 -C4 alkyl
radical,
- R2 denotes a hydroxyl r adical, a NR3R4 radical or a linear or
branched C1 -C12 alkoxy radical, said alkoxy r adical being optionall y
15 substituted b y one or more hydroxyl radicals, b y a quaternar y
ammonium radical (N+R5R6R7 ;Y- ) or by a NR8R9 radical,
- R3 and R4 , which may be identical or different, denote a hydroge n
atom or a linear or branched C1 -C1 2 alkyl radical, optionall y
substituted by one or more hydroxyl radicals, b y a quaternar y
20 ammonium radical (N+R5R6R7 ;Y-), by a NR8R9 radical or by a sulfonic
group (-SO3H), and
- R5 , R6 and R7, which may be identical or different, denote a linear or
branched C1 -C18 alkyl rad ical or a benzyl radical, preferably a linear
or branched C1 -C6 alkyl radical;
25 - R8 and R9 , which may be identical or different, denote a hydroge n
atom or a linear or branched C1 -C6 alkyl radical; and
- Y- denotes an anion derived from a mineral or organic acid or a
halide, preferably bromide, chloride, acetate, borate, citrate, tartrate,
bisulfate, bisulfite, methosulfate, sulfate or phosphate anion.
30 Preferably, R1 denotes a hydrogen atom or a methyl radical.
The polymer( s) comprising one or more acrylic and/or
methacr ylic units suitable for the present invention are preferab ly
15
chosen from cationic polymer s, amphoteric polymers and mixtures
thereof. Most preferably, they are chosen from cationic polymers.
The cationic charge densit y of the polymers comprising one or
more acrylic and/or methacr ylic units may preferably be lower than or
equal to 5 meq/g, more preferentially lower than or equal to 4 meq/5 g,
and better still lower than or equal to 3 meq/g. This cationic charge
densit y advantageously ranges from 0.5 to 5 meq/g, better still from 1 to
4 meq/g, and even more preferably from 1.5 to 3 meq/g.
The term "cationic polymer" means any polymer comprising
10 cationic groups and/or groups that can b e ionized to cationic groups,
and not comprising anionic groups and/or groups that can be ionized to
anionic groups. Preferably, the cationic polymer is hydrophilic or
amphiphilic. The preferred cationic polymers are chosen from those
that contain units comprising primar y, secondary, tertiary and/or
15 quaternary amine groups that ma y either form part of the main polymer
chain or may be borne by a side substituent directly connected thereto.
The polymer s comprising one or more acrylic and/or
methacr ylic units that can be used in the present invention ar e
preferably chosen from homopolymers or copolymers derived from
20 acrylic or methacrylic ester s or amides and comprising at least one of
the units of the following formulae:
R1
CH2
O
NH
R
N+ R7 R5
R6
Y-
(V)
R1
CH2
O
NH
R
N
R8 R9 (VI)
16
R1
CH2
O
O
R
NR5 + R7
R6
Y-
(VII)
R1
CH2
O
O
R
N
R8 R9 (VIII)
in which:
- R1 , which ma y be identical or different, denote a hydrogen atom or a
5 CH3 radical;
- R, which may be identical or different, denote a linear or branched
C1 -C1 2 alkyl radical, preferably a linear C1 -C6 alkyl radical, optionall y
substituted by one or more hydroxyl radicals;
- R5 , R6 and R7, which may be identical or different, denote a linear or
10 branched C1 -C18 alkyl rad ical or a benzyl radical, preferably a linear
or branched C1 -C6 alkyl radical;
- R8 and R9 , which may be identical or differe nt, denote a hydroge n
atom or a linear or branched C1-C6 alkyl radical, preferably methyl or
ethyl; and
15 - Y- denotes an anion derived from a mineral or organic acid or a
halide, preferably bromide, chloride, acetate, borate, citrate, tartrate,
bisulfate, bisulfite, methosulfate, sulfate or phosphate anion.
Preferably, the polymer s comprising acrylic and/or methacrylic
units are chosen from homopolymer s or copolymers der ived from
20 acrylic or methacr ylic amides, and more preferentially from
homopolymers or copolymers comprising at least one unit of formula
(V) or (VI).
More particularly the polymers comprising acr ylic and/or
methacr ylic units are chosen from copolymers compris ing at least one
25 unit of formula (V) as defined previously, and more preferabl y
comprising at least one unit of formula (V) in which R1 denotes a
17
hydrogen atom, R represents a linear alkyl group having 3 carbo n
atoms and R5 , R6 and R7 represent a methyl.
The polymer s comprising one or more acrylic and/or
methacr ylic unit( s) may also contain o ne or more units derived from
comonomers that may be selected from the families of acr ylamides5 ,
methacr ylamides, diacetone acr ylamides, acr ylamides and
methacr ylamides substituted on the nitrogen with lower (C1 -C4 ) alkyls ,
acrylic or methacrylic acids or esters thereof, vinyllactams such as
vinylp yrrolidone or vinylcaprolactam, and vinyl esters, preferably
10 selected from the families of acr ylamide and methacr ylamides, and
more preferentially from the family of acrylamides.
Among these copolymer s, mention may be made of:
- copolymers of acrylamidopropyltrimonium chloride and acrylamide,
such as the product sold under the name Salcare® SC 60 by the
15 company BASF,
- copolymers of acrylamide and of dimethylaminoethyl methacr ylate
quaternized with dimethyl sulfate or with a dimethyl halide, such as
the product sold under the name HERCOFLOC b y the company
Hercules,
20 - copolymers of acr ylamide and of methacr ylo yloxyethyltrimethyl
ammonium chloride, such as those sold under the name BINA QUAT
P 100 by the company Ciba Geigy,
- copolymers of acr ylamide and of methacr ylo yloxyethyltrimethyl
ammonium methosulfate, such as the product sold under the name
25 RETEN by the company Her cules,
- quaternized or non-quaternized vinylp yr rolidone/dialkylaminoalkyl
acrylate or methacrylate copolymer s, such as the products sold under
the names GAFQUAT by the company ISP, for instance
GAFQUAT 734 or GAFQUAT 755, or alternatively the products known
30 as COPOLYMER 845, 958 and 937. These polymers are described in
detail in FR 2 077 143 and FR 2 393 573,
- dimethylaminoethyl methacr ylate/vinylcaprolactam/vinylp yrrolidone
terpolymers, such as the product sold under the name GAFFIX VC 713
by the company ISP,
18
- vinylp yrrolidone/methacr ylamidoprop yldimethylamine copolymers,
such as those sold under the name STYLEZE CC 10 by ISP,
- quaternized vinylp yrrolidone/dimethylaminopropylmethacrylamide
copolymer s such as the product sold under the name GAFQUAT
HS 100 b y the company ISP5 ,
- preferably crosslinked polymers of methacr ylo yloxy(C1 -
C4 )alkyltr i(C1 -C4 )alkylammonium salts, such as the polymers obtained
by homopolymer ization of dimethylaminoethyl methacr ylate
quaternized with methyl chloride, or by copolymerization of
10 acrylamide with dimethylaminoethyl methacrylate quaternized wit h
methyl chloride, the homopolymer ization or copolymerization being
optionally followed by crosslinking with an olefinically unsaturated
compound, more particular ly methylenebisacr ylamide. A crosslinked
or non-crosslinked acrylamide/methacr ylo ylo x y
15 ethyltrimethylammonium chloride copolymer (20/80 b y weight) in the
form of a dispersion containing 50% by weight of the said copolymer
in mineral oil may be used more particularly. Such a dispersion is sold
under the name SALCARE® SC 92 by the company BASF. A
crosslinked or non-crosslinked methacr ylo yloxye thyltr imethyl
20 ammonium chloride homopolymer containing about 50% by weight of
the homopolymer in mineral oil or in a liquid ester can also be used.
Such dispersions are sold under the names SALCARE® SC 95 and
SALCARE® SC 96 by the company BASF.
The polymer s comprising one or more acrylic and/or
25 methacr ylic units that can be used in the present invention can also be
chosen from amphoteric polymer s.
The term "amphoteric polymer " means any polymer comprising
cationic groups and/or groups that can be ionized to cationic groups,
and comprising anio nic groups and/or groups that can be ionized to
30 anionic groups
Amphoteric polymers can be chosen more particularly from
amphoteric polymers comprising a repetition of:
(i) one or more units derived from a monomer of (meth)acrylamide
type,
19
(ii) one or more units derived from a monomer of
(meth)acr ylamidoalkyltrialkylammonium type, and
(iii) one or more units derived from an acidic monomer of
(meth)acr ylic acid type.
Preferably, the units derived from a monomer o5 f
(meth)acr ylamide type (i) are units of structure (IX) below:
CH2
O R2
R1
(IX)
in which:
10 - R1 denotes a hydrogen atom or CH3 radical; and
- R2 denotes a NR3R4 radical, wherein R3 and R4, which may be
identical or different, denote a hydrogen atom or a linear or branched
C1 -C1 2 alkyl radical, optionally substituted b y one or more hydroxyl
radicals, preferably R2 denotes an amino, a dimethylamino, a tert15
butylamino, a dodecylamino or a -NH-CH2OH radical.
Preferably, the said amphoteric polymer comprises a repetitio n
of only one unit of formula (IX).
The unit derived from a monomer of (meth)acr ylamide type of
formula (IX) in which R1 denotes a hydrogen atom and R2 is an amino
20 radical (NH2 ) is particular ly preferred. It corresponds to the
acrylamide monomer per se.
Preferably, the units derived from a monomer of
(meth)acr ylamidoalkyltrialkylammonium type (ii) are units of
structure (X) below:
25
20
CH2
R1
O NH
CH2
N+
R7
R5
R6
n
Y-
(X)
in which:
- R3 denotes a hydrogen atom or CH3 radical;
- R5 , R6 and R7 , which ma y be identical or different, denote a linear
or branched C1 -C6 alkyl radical, preferably a linear or branched C1 -5 C4
alkyl radical;
- n denotes an integer ranging from 1 to 6, preferably from 1 to 4; and
- Y- denotes an anion derived from a mineral or organic acid or a
halide, preferably bromide, chloride, acetate, borate, citrate, tartrate,
10 bisulfate, bisulfite, methosulfate, sulfate or phosphate anion.
Preferably, the said amphoteric polymer comprises a repetitio n
of only one unit of formula (X).
Among these units der ived from a monomer of
(meth)acr ylamidoalkyltrialkylammonium type of formula (X), the ones
15 that are preferred are those derived from the
methacr ylamidopropyltrimethylammonium chloride monomer, for
which R1 denotes a methyl radical, n is equal to 3, R5 , R6 and R7
denote a methyl r adical, and Y- denotes a chloride anion.
Preferably, the u nits derived from a monomer of (meth)acrylic
20 acid type ( iii) are units of formula (XI) :
CH2
R1
O R2
(XI)
21
in which:
- R1 denotes hydrogen atom or CH3 radical; and
- R2 denotes a hydroxyl radical or a NR3R4 radical, wherein R3 and
R4 , which may be identical or different, denote a hydrogen atom or a
linear or branched C1 -C1 2 alkyl radical optionally substituted by 5 a
sulfonic group (-SO3H), preferably R2 denotes a –NH-C(CH3 )2-CH2 -
SO3H radical.
The preferred units of formula (XI) correspond to the acrylic
acid, methacrylic acid and 2-acrylamino-2-methylpropanesulfonic acid
10 monomers.
Preferably, the unit derived from a monomer of (meth)acrylic
acid type of formula (XI) is that derived from acr ylic acid, for whic h
R1 denotes a hydrogen atom and R2 denotes a hydroxyl radical.
The acidic monomer(s) of (meth)acrylic acid type may be non15
neutralized or partially or totally neutralized with an organic or
mineral base.
Preferably, the said amphoteric polymer comprises a repetitio n
of only one unit of formula (XI).
According to a preferred embodiment of the invention, the
20 amphoteric polymer(s) of this type comprise at least 30 mol% of units
derived from a monomer of (meth)acrylamide type (i). Preferably, the y
comprise from 30 mol% to 70 mol% and more preferably from 40
mol% to 60 mol% of units derived from a monomer of
(meth)acr ylamide type.
25 The content of units derived from a monomer of
(meth)acr ylamidoalkyltrialkylammonium type (ii) may advantageousl y
be from 10 mol% to 60 mol% and preferentially from 20 mol% to 55
mol%.
The content of units derived from an acidic monomer of
30 (meth)acr ylic acid type ( iii) may advantageously be from 1 mol% to 20
mol% and preferentially from 5 mol% to 15 mol%.
According to a particularly preferred embodiment of the
invention, the amphoteric polymer of this type comprises:
22
- from 30 mol% to 70 mol% and more preferably from 40 mol% to 60
mol% of units derived from a monomer of (meth)acrylamide t ype ( i),
- from 10 mol% to 60 mol% and preferentially from 20 mol% to 55
mol% of units derived from a monomer of
(meth)acr ylamidoalkyltrialkylammonium type (ii), an5 d
- from 1 mol% to 20 mol% and preferentially from 5 mol% to 15 mol%
of units derived from a monomer of (meth)acrylic acid type (iii).
Amphoteric polymers of this type may also comprise additional
units, other than the units der ived from a monomer of
10 (meth)acr ylamide t ype, of (meth)acr ylamidoalkyltr ialkylammonium
type and of (meth)acr ylic acid type as described above.
However, according to a preferred embodiment of the
invention, the said amphoteric polymers consist solely of units derived
from monomers (i) of (meth)acrylamide t ype, (ii) of
15 (meth)acr ylamidoalkyltrialkylammonium type and (iii) of
(meth)acr ylic acid type.
As examples of amphoteric polymers that are particular l y
preferred, mention may be made of acrylamide/
methacr ylamidopropyltrimethylammonium chloride/ acr ylic acid
20 terpolymers. Such polymer s are listed in the CTFA Dictionar y
(International Cosmetic Ingredient Dictionar y) under the name
Polyquaternium 53. Corresponding products are especially sold under
the names Merquat 2003 and Merquat 2003 PR by the company Nalco.
Another preferred type of amphoteric polymer s is the polymer
25 comprising a repetition of:
(i) One or more non ionic units derived from a monomer of
(meth)acr ylate t ype,
(ii) One or more units derived from a monomer of
(meth)acr ylamidoalkyltrialkylammonium type, and
30 (iii) One or more units derived from an acidic monomer of
(meth)acr ylic acid type.
The monomer of (meth)acr ylamidoalkyltrialkylammo nium type
and the acidic monomer of (meth)acr ylic acid type (monomers ( ii) and
(iii) respectively) are as described above.
23
The non ionic monomers (i) of (meth)acr ylate type are
preferably chosen from C1 -C4 alky acrylates and methacr ylates. A
preferred monomer is methyl acr ylate.
As particularly preferred examples of such amphoter ic
polymers, mention may be made of acrylic acid5 /
methylacr ylamidoprop yltriméthylammonium chloride/ methyl acrylates
terpolymers. Such polymers are listed in the CTFA International
Cosmetic Ingr edient Dictionar y under the name polyquaternium 47.
Corresponding products are especially sold under the names Merquat
10 2001 and Merquat 2001N by the company Nalco.
As another type of amphoter ic polymer that ma y be used,
mention may also be made of copolymers based on (meth)acr ylic acid
and on a dialkyldiallylammonium salt, such as copolymers of
(meth)acr ylic acid and of dimethyldiallylammonium chloride.
15 Such polymers are listed in the CTFA International Cosmetic
Ingred ient Dictionary under the name polyquaternium 22. An example
of corresponding product is sold under the name Merquat 280 by the
company Nalco.
The polymer( s) comprising one or more acrylic and/or
20 methacr ylic units are preferably chosen from
acrylamidopropyltrimonium chlor ide/ acrylamide copolymers,
acrylamide/ methacr ylamidopropyltrimethylammonium chloride/
acrylic acid terpolymers, acrylic acid/
methylacr ylamidoprop yltrimethylammonium chloride/ methyl acrylates
25 terpolymers, (meth)acr ylic acid/ dimethyldiallylammonium chloride
copolymer s and mixtures thereof.
The amount of polymer(s) comprising one or more acrylic
and/or methacr ylic units present in the cosmetic composition of the
present invention advantageously ranges from 0.01 to 5% by weight,
30 preferably from 0.015 to 5% by weight, more preferentially from 0.02
to 3% by weight, better still from 0.04 to 2% by weight, and even more
preferentially from 0.05 to 1% by weight, relative to the total weight
of the cosmetic composition.
24
Hydroxyl-terminated silicone
The cosmetic composition according to the present inventio n
further comprises one or more hydroxyl-terminated silico nes. Such
silicones can be chosen in particular from non-amino hydroxylterminated
silico nes5 .
In the present invention, the term “silicone” is intended to
denote, in accordance with what is generally ac cepted, any
organosilicon polymer or oligomer of linear or cyclic, branched or
crosslinked structure, of var iable molecular weight, obtained b y
10 polymerization and/or polycondensation of suitably functionalized
silanes, and consisting essentially of a repetition of main units in
which the silicon atoms are linked together via oxygen atoms ( siloxane
bond -Si-O-Si-), optionally substituted hydrocarbon-based radicals
being directly linked via a carbon atom to the said silicon atoms. The
15 hydrocarbon-based radicals that are the most common are alkyl
radicals, especially C1 -C10 alkyl r adicals, and in particular methyl,
fluoroalkyl radicals, the alkyl part of which is C1 -C10 , and aryl
radicals and in particu lar phenyl.
According to the present invention, the term “non-amino
20 hydroxyl-terminated silicone” denotes any hydroxyl-terminated
silicone not containing at least one primary, secondary or tertiar y
amine, or a quaternary ammonium group.
Organopolysiloxanes, and notably hydroxyl-terminated
organopolysiloxanes, are defined in greater detail in Walter Noll’s
25 Chemistry and Technology of Silicones (1968), Academic Press.
Preferably, the hydroxyl-terminated silicones are chosen from
hydroxyl-terminated polyalkylsiloxanes, and more preferentially from
α,ω-dihydroxy polydialkylsiloxanes that are polyd ialkylsiloxanes
containing silanol end groups (also known as α,ω-silanol groups).
30 Preferably, the hydroxyl-terminated silicones are chosen from
hydroxyl-terminated polydimethylsiloxanes, more preferentiall y
polydimethylsilo xanes containing silanol end groups (or α,ω-silanol
groups), and better still from polydimethylsiloxanes containing
25
dimethylsilano l end groups (Dimethiconol according to the CTFA
name) such as the oils of the 48 series from the company Rhodia.
Products that may be used more particularly are the mixtures
formed from a polydimethylsiloxane hydroxylated at the end of the
chain (known as dimethiconol according to the nomenclature of th5 e
CTFA dictionar y) and from a cyclic polydimethylsiloxane (known as
cyclomethicone according to the nomenclature of the CTFA
dictionar y), such as the product Q2 1401 sold by the company Dow
Corning.
10 Among the hydroxyl-terminated silicones suitable for the
present invention, examples that may be mentioned include the
products sold under the following names:
- Xiameter PMX-1501 fluid from the company Dow Corning, whic h
corresponds to a mixture of α,ω-dihydroxy polydimethylsiloxane and
15 of cyclopenta dimethylsiloxane,
- Xiameter PMX-1503 fluid from the company Dow Corning, whic h
corresponds to a mixture of α,ω-dihydroxy polydimethylsiloxane and
of polydimethylsiloxane 5 cSt,
- Belsil GB 1020 from the company Wacker, which corresponds to a
20 mixture of dimethico ne and of dimethiconol, and
- Xiameter MEM-1785 emulsion from the company Dow Corning) ,
which corresponds to an emulsion of dimethiconol and teadodecylbenzenesulfonate.
Mention could be made of dimethiconol emulsions, for example
25 with anionic surfactants, preferably having a low particle size such as
less than 500 nm, more preferentially less than 200 nm, and better still
less than 100 nm.
More preferentially, the hydro xyl-terminated silicones are
chosen from polydimethylsiloxanes containing dimethylsilanol end
30 groups (also known as dimethiconol), preferably in emulsion form, and
more preferentially in microemulsion form having particle size
preferably lower than or equal to 100 nm.
26
The hydroxyl-terminated silicones, which can be used in t he
present invention prefer ably have a viscosit y lower or equal to 60 000
cst at 25°C and shear rate 1s-1 .
The viscosit y may be measured at 25°C with viscosimeters or
rheometer s preferably with cone-plan geometry5 .
According to a preferred embodiment, the hydroxyl-terminated
silicone is a dimethiconol microemulsion of internal phase viscosit y
ranging from 25 000 to 50 000 cSt, having particle size preferabl y
lower than or equal to 100 nm.
10 The amount of hydroxyl-terminated silicone(s) present in t he
cosmetic composition of the present inventio n advantageously ranges
from 0.1 to 15% by weight, more preferentially from 0.5 to 10% b y
weight, and better still from 1 to 5% by weight, relative to the total
weight of the cosmetic composition.
15 The weight ratio between the amount of hydroxyl-terminated
silicone(s) and the amount of polymer( s) comprising one or more
acrylic and/or methacr ylic units, present in the cosmetic compositio n
according to the invention, is preferably greater than or equal to 1,
more preferentially greater than or equal to 2, and better still greater
20 than or equal to 4. This weight ratio is advantageously ranging from 1
to 40, preferably from 2 to 35, more preferably from 4 to 30.
Additional silicones
The cosmetic composition according to the present inventio n
ma y further comprise one or more additional silicones different from
25 the hydroxyl terminated silicone(s) descr ibed above.
The additional silicones may be volatile or non-volatile.
When they are volatile, the additio nal silicones are more
particular ly chosen from those with a boiling point of between 60°C
and 260°C, and even more particular ly from:
30 (i) cyclic silicones comprising from 3 to 7 and preferably 4 to
5 silicon atoms.
These are, for example, octamethylcyclotetrasiloxane sold
especially under the name Volatile Silicone 7207 b y the company
Union Carbide or Silbione 70045 V 2 by the company Rho dia,
27
decamethylcyclopentasiloxane sold under the name Volatile Silicone
7158 by the company Union Carbide, and Silbione 70045 V 5 by the
company Rhodia, and mixtures thereof.
Mention may also be made of cyclocopolymers of the
dimethylsiloxane/methylalkylsiloxane type, such as Volatile Silicon5 e
FZ 3109 sold by the company Union Carbide, of chemical structure:
10 Mention may also be made of mixtures of cyclic silicones wit h
organosilicon compounds, such as the mixture of
octamethylc
yclotetra siloxane a nd tetrakis(tr imethylsilyl)-
pentaerythr itol (50/50) and the mixture of octamethylcyclo -
tetrasiloxane and oxy-1,1’-bis(2,2,2’,2’,3,3’-hexatr imethyl15
silyloxy)neopentane;
(ii) linear vo latile silicones containing 2 to 9 silicon atoms and
having a viscosity of les s than or equal to 5×10 -6 m2 /s at 25°C. An
example is decamethyltetr asilo xane sold in particular under the name
SH 200 by the company Toray Silicone. Silicones belonging to this
20 category are also described in the article published in Cosmetics and
Toiletr ies, Vol. 91, Jan. 76, pp. 27-32, Todd & Byers Volatile Silicone
Fluids for Cosmetics.
When the additional silicones are non-volatile, use is
preferably made of polyalkylsiloxanes, polyar ylsiloxanes,
25 polyalkylarylsiloxanes, silicone gums and resins, and
polyorganosiloxanes modified with organofunctional groups, and
mixtures thereof.
These additional silicones ar e more particular ly chosen from
polyalkylsiloxanes, among which mention may be made mainly of
28
polydimethylsilo xanes containing trimethylsilyl end gro ups
(Dimethicone according to the CTFA name) having a viscosit y of from
5×10-6 to 2.5 m2 /s at 25°C and preferably 1×10- 5 to 1 m2 /s. The
viscosit y of the silicones is measured, for example, at 25°C according
to standard ASTM 445 Appendix C5 .
Among these polyalkylsilo xanes, mention may be made, in a
non- limiting manner, of the following commercial products:
- the Silbione oils of the 47 and 70 047 series or the Mirasil oils sold
by the company Rhodia, for instance the oil 70 047 V 500 000,
10 - the oils of the Mir as il series sold by the company Rhodia,
- the oils of the 200 series from the company Dow Corning, such as,
more particular ly, DC200 with a viscosit y of 60 000 cSt,
- the Viscasil oils from the company General Electr ic and certain oils
of the SF series (SF 96, SF 18) from the company General Electric.
15 In this category of polyalkylsiloxanes, mention may also be
made of the products sold under the names Abil Wax 9800 and 9801 b y
the company Goldschmidt, which are poly(C1 -C2 0 )alkylsiloxanes.
The polyalkylarylsiloxanes are particular ly chosen from linear
and/or branched polydimethylmethylphenylsiloxanes and
20 polydimethyldiphenylsiloxanes with a viscosity of from 1×10 -5 to
5×10-2m²/s at 25°C.
Among these polyalkylar ylsiloxanes, examples that may be
mentioned include the products sold under the following names:
- Silbione oils of the 70 641 series from the company Rhodia,
25 - the oils of the Rhodorsil 70 633 and 763 series from the company
Rhodia,
- the oil Dow Corning 556 Cosmetic Grade Fluid from the compan y
Dow Corning,
- silicones of the PK ser ies from the company Ba yer, such as the
30 product PK20,
- the silicones of the PN and PH series from the company Bayer, such
as the products PN1000 and PH1000,
- certain oils of the SF series from the company General Electr ic,
such as SF 1023, SF 1154, SF 1250 and SF 1265.
29
The additional silicones that ma y be present in the compositio n
according to the invention are especially polydiorganosilo xanes having
high number-average molecular masses of between 200 000 and
1 000 000, used alone or as a mixture in a solvent. This solvent can be
chosen from volatile silicones, polydimethylsiloxane (PDMS) oils5 ,
polyphenylmethylsiloxane (PPMS) oils, isoparaffins, polyisobutylenes,
methylene chloride, pentane, dodecane and tridecane, or mixtures
thereof.
Mention may be made more particular ly of the following
10 products:
- polydimethylsiloxane gums,
- polydimethylsiloxane/methylvinylsilo xane gums,
- polydimethylsiloxane/diphenylsiloxane gums,
- polydimethylsiloxane/phenylmethylsiloxane gums,
15 - polydimethylsiloxane/diphenylsiloxane/methylvinylsiloxane gums.
Products that may be used more particularly are the following
mixtures:
- mixtures formed from a polyd imethylsiloxane gum with a
cyclic silicone, such as the product SF 1214 Silicone Fluid from the
20 company Gener al Electr ic, this product being an SF 30 gum
corresponding to a dimethicone, having a number -aver age molecular
weight of 500 000, dissolved in the oil SF 1202 Silicone Fluid
corresponding to decamethylc yclopentasiloxane,
- mixtures of two PDMSs with different visco sities, and more
25 particular ly of a PDMS gum and a PDMS oil, such as the product SF
1236 from the company Gener al Electric. The product SF 1236 is a
mixture of a gum SE 30 defined above, with a viscosit y of 20 m²/s and
of an oil SF 96 with a viscosit y of 5×10-6 m²/s. This product preferabl y
comprises 15% of gum SE 30 and 85% of an oil SF 96.
30 The organopolysiloxane resins that may be present in the
composition according to the invention are crosslinked siloxane
systems co ntaining the following units: R2SiO2 /2 , R3SiO1 /2 , RSiO3 / 2
and SiO4 /2 in which R represents a hydrocarbon group containing 1 to
16 carbon atoms or a phenyl group. Among these products, the ones
30
that are particular ly preferred are those in which R denotes a C1 -C4
alkyl group, more particularly methyl, or a phenyl group.
Among these r esins, mentio n may be made of the product sold
under the name Dow Corning 593 or those sold under the names
Silicone Fluid SS 4230 and SS 4267 by the company General Electr ic5 ,
which are silicones of dimethyl/tr imethyls iloxane structure.
Mention may also be made of the trimethyl siloxysilicate t ype
resins sold in particular under the names X22-4914, X21-5034 and
X21-5037 by the company Shin-Etsu.
10 The organomodified silicones that may be present in the
composition accord ing to the invention are silicones as defined above
and comprising in their structure one or more organofunctional groups
attached via a hydrocarbon-based group.
Among the organomodified silicones, mention may be made of
15 polyorganosiloxanes comprising:
- polyethyleneoxy and/or polypropyleneoxy groups optionall y
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 711 by the
20 company Union Carbide, and the (C1 2)alkylmethicone copolyol sold b y
the company Dow Corning under the name Q2 5200, or in particular
the silicone of INCI name PEG-12 dimethicone such as the product
XIAMETER OFX-0193 FLUID sold b y Dow Corning.
- thiol groups, such as the products sold under the names
25 GP 72 A and GP 71 from the company Genesee,
- alkoxylated groups, such as the product sold under the name
Silicone Copolymer F-755 by SWS Silicones and Abil Wax 2428, 2434
and 2440 by the company Goldschmidt,
- hydroxylated groups, such as the polyorganosiloxanes
30 containing a hydroxyalkyl function, descr ibed in French patent
application FR 2 589 476,
- acyloxyalkyl groups, for instance the polyorganosiloxanes
described in patent US-A-4 957 732,
31
- anionic groups of the carboxylic acid type, for instance in the
products descr ibed in patent EP 186 507 from the company Chisso
Corporation, or of the alkylcarboxylic type, such as those present in
the product X-22-3701E from the company Shin-Etsu; 2-hydroxyalkyl
sulfonate; 2-hydroxyalkyl thiosulp hate such as the products sold b 5 y
the company Goldschmidt under the names Abil S201 and Abil S255.
According to the invention, silicones comprising a polysilo xane
portion and a non-silicone organic chain portion, one of the two
portions constituting the main chain of the polymer and the other
10 being gr afted onto the said main chain, can also be used. These
polymers are descr ibed, for example, in patent applications EP-A-
412,704, ep-a-412,707, ep-a-640,105 and WO95/00578, ep-a-582,152
and WO93/23009 and U.S. Pat. Nos. 4,693,935, 4,728,571 and
4,972,037. These polymers are prefer ably anionic or non- ionic.
15 The additional silicones used in the composition of the
invention may also be chosen from amino silicones.
For the purposes of the present invention, the term “amino
silicone” means any silicone comprising at least one primar y,
seco ndary or tertiar y amine function or a quaternar y ammonium group.
20 The amino silicones that may be used in the cosmetic
composition according to the present inve ntion are chosen from:
(a) the compounds corresponding to formula (XII) below:
(R1 )a (T)3 - aSi[OSi(T)2]n[OSi(T) b(R1 )2 -b ]mOSi(T)3 - a (R1 )a (XII)
25
wherein,
- T is a hydrogen atom or a phenyl, hydroxyl (-OH) or C1-C8 alkyl
group, and preferably methyl, or a C1 -C8 alkoxy, preferably methoxy,
- a denotes the number 0 or an integer from 1 to 3, and preferably 0,
30 - b denotes 0 or 1, and in particular 1,
- m and n are numbers such that the sum (n + m) can range especiall y
from 1 to 2000 and in particular from 50 to 150, it being possible for n
to denote a number from 0 to 1999 and in particu lar from 49 to 149,
32
and for m to denote a number from 1 to 2000 and in particular from 1
to 10, and
- R1 is a monovalent group of formula -CqH2 qL in which q is a number
from 2 to 8 and L is an optionally quaternized amino group chose n
from the following groups5 :
-N(R2 )-CH2 -CH2-N(R2 )2 ;
-N(R2 )2,
-N+(R2 )3 Q- ,
-N+(R2 ) (H)2 Q- ,
10 -N+(R2 )2HQ- ,
-N(R2 )-CH2 -CH2-N+(R2 )(H)2 Q- ,
wherein, R2 may denote a hydrogen atom, a phenyl, a benz yl or
a saturated monovalent hydrocarbon-based group, for example a C1 -C2 0
alkyl group, and Q- represents a halide ion, for instance fluoride,
15 chloride, bromide or iodide.
In particular, the amino silicones corresponding to the
definition of formula (XII) are chosen from the compounds
corresponding to formula (XIII) below:
O Si O Si
CH3
CH3 R'
Si
CH3
CH3
R O Si
CH3
CH3
R"
(CH2)2
NH2
A
n
m
NH
I
20 (XIII)
wherein, R, R’ and R”, which may be identical or different, denote a
C1 -C4 alkyl group, preferably CH3 ; a C1 -C4 alkoxy group, preferabl y
methoxy; or OH; A represents a linear or branched, C3 -C8 and
33
preferably C3 -C6 alkylene group; m and n are integers dependent on
the molecular weight and whose sum is between 1 and 2000.
According to a first possibility, R, R’ and R”, which may be
identical or differ ent, represent a C1-C4 alkyl or hydrox yl group, A
represents a C3 alkylene group and m and n are such that the weight 5 -
average molecular mass of the compound is between 5000 and 500 000
approximately. Compounds of this t ype are referred to in the CTFA
dictionar y as “amodimethicones”.
According to a second possibilit y, R, R’ and R”, which may be
10 identical or different, each represent a C1-C4 alkoxy or hydroxyl
group, at least one of the groups R or R” is an alkoxy group and A
represents a C3 alkylene group. The hydroxy/alko xy mole ratio is
preferably between 0.2/1 and 0.4/1 and advantageously equal to 0.3/1.
Moreover, m and n are such that the weight-average molecular mass of
15 the compound is between 2000 and 10 6. More particularly, n is
between 0 and 999 and m is between 1 and 1000, the sum of n and m
being between 1 and 1000.
In this category of compounds, mention may be made, inter
alia, of the product Belsil® ADM 652 sold by the company Wacker.
20 According to a third possibilit y, R and R”, which are different,
each represent a C1 -C4 alkoxy or hydroxyl group, at least one of the
groups R or R” being an alkoxy group, R’ representing a methyl group
and A representing a C3 alkylene group. The hydroxy/alkoxy mole
ratio is preferably between 1/0.8 and 1/1.1 and advantageously equal
25 to 1/0.95. Moreover, m and n are such that the weight- average
molecular mass of the compound is between 2000 and 200 000. More
particular ly, n is between 0 and 999 and m is between 1 and 1000, the
sum of n and m being between 1 and 1000.
More particularly, mention may be made of the product Fluid
30 WR® 1300 sold by the company Wacker.
Note that the molecular mass of these silicones is determined
by gel permeation chromatography (ambient temperature, polyst yr ene
standard; μ styr agem columns; elu ent THF; flow rate 1 mm/minute;
34
200 μl of a solu tion containing 0.5% b y weight of silicone in T HF are
injected, and detection is performed by refractometr y and UV-metry).
A product corresponding to the definition of formula (XIII) is
in particular the polymer known in the CTFA dictionar y as
Trimethylsilyl Amodimethicone, corresponding to formula (XIV5 )
below:
SiO
CH3
CH3
n
m
Si(CH3)3
NH2
SiO
CH2
CH3
CHCH3
CH2
NH
(CH3)3 SiO
(CH2)2
(XIV)
10 wherein, n and m have the meanings given above in accordance wit h
formula (XII).
Such compounds are described, for example, in patent EP
95238. A compound of formula (XIV) is sold, for example, under the
name Q2-8220 by the company OSI.
15 (b) the compounds corresponding to formula (XV) below:
+ -
r s
CHOH CH2 N (R )3 Q
R
R
R3
3
3
Si R
R
Si O Si O Si O
R
R CH2
R
R
R3
3
3
3 3
3
4 3
(XV)
wherein,
35
- R3 represents a C1-C1 8 monovalent hydrocarbon-based group, and in
particular a C1 -C1 8 alkyl or C2 -C18 alkenyl group, for example methyl,
- R4 represents a divalent hydrocarbon-based group, especially a C1 -
C1 8 alkylene group or a divalent C1 -C1 8 , and for example C1 -C8 ,
alkyleno xy group5 ,
- Q- is a halide ion, in particular chloride;
- r represents a mean statistical value from 2 to 20 and in particular
from 2 to 8, and
- s represents a mean statistical value from 20 to 200 and in particular
10 from 20 to 50.
Such compounds are described more particular ly in patent US-4
185 087.
A compound falling within this class is the product sold by the
company Union Carbide under the name Ucar Silicone ALE 56.
15 (c) quaternar y ammonium silicones especially of formula
(XVI):
O Si
R7
CH2 CHOH CH2 N+
R7
R7
R7 R7
R8
R7
R6 R8 N+
R7
R7
CH2CH CH2
OH
R6 Si
r (XII)
2X20
wherein,
- R7 , which may be identical or different, represent a monovalent
hydrocarbon-based group containing from 1 to 18 carbon atoms, and in
particular a C1 -C18 alkyl group, a C2 -C1 8 alkenyl group or a ring
comprising 5 or 6 carbon atoms, for example methyl,
25 - R6 represents a divalent hydrocarbon-based group, especially a C1 -
C1 8 alkylene group or a divalent C1 -C1 8 , and for example C1 -C8 ,
alkyleno xy group linked to the Si via an SiC bond,
- R8 , which ma y be identical or different, represent a hydrogen atom, a
monovalent hydrocarbon-based group containing from 1 to 18 carbon
(XVI)
36
atoms, and in particular a C1 -C18 alkyl group, a C2-C1 8 alkenyl group
or a group -R6-NHCOR7 ;
- X- is an anio n such as a halide ion, especially chlor ide, or an organic
acid salt (acetate, etc.); and
- r represents a mean statistical value from 2 to 200 and in particula5 r
from 5 to 100.
These silicones are described, for example, in patent
application EP-A-0 530 974.
d) the amino silicones of formula (XVII) below:
10
O
(CnH2n)
NH
(CmH2m)
NH2
Si Si O Si
R3
R5
R4
R1
R2
x 3
(XVII)
wherein,
- R1 , R2, R3 and R4 , which may be identical or different, denote a C1 -
15 C4 alkyl group or a phenyl group,
- R5 denotes a C1-C4 alkyl group or a hydroxyl group,
- n is an integer ranging from 1 to 5,
- m is an integer ranging from 1 to 5, and
- x is chosen such that the amine number is between 0.01 and 1 meq/g.
20 When these compounds are used, one particular ly advantageous
embodiment involves their combined use with cationic and/or nonionic
surfactants.
By way of example, use may be made of the product sold under
the name Cationic Emulsion DC939 b y the company Dow Corning, a
25 cationic surfactant, namely tr imethylcetylammonium chloride and a
nonionic surfactant of formula C1 3H2 7 -(OC2H4 )12 -OH, known under the
CTFA name Trideceth-12.
37
Another commercial product that ma y be used according to the
invention is the product sold under the name Dow Corning Q2 7224 b y
the company Dow Corning, comprising, in combination, trimethylsil yl
amodimethicone of formula (XIV) descr ibed above, a nonionic
surfactant of formula C8H1 7 -C6H4 -(OCH2CH2 )40 -OH, known under th5 e
CTFA name Octo xyno l-40, a second nonionic surfactant of formula
C1 2H2 5-(OCH2 -CH2)6 -OH, known under the CTFA name Isolaureth-6,
and propylene glycol.
The silicones of the invention ma y also be silicones grafted
10 with anionic groups, such as the compounds VS 80 or VS 70 sold b y
the company 3M.
Preferentially, the amino silicones used in the prese nt
invention ar e the products sold under the names DC 8194, DC 8299,
DC 1689, DC 5-7113, DC 8500, DC 8566, DC8170 and DC 8401 by the
15 company Dow Corning.
According to the invention, the additional silicones can be used
in the form of emulsions, and more preferably in the form of
microemulsions t ypically having particle size lower than or equal to
100 nm.
20 Additional cationic polymers
The cosmetic composition according to the present inventio n
ma y further comprise one or more additional cationic polymers
different from the polymers comprising one or more acrylic and/or
methacr ylic units described above. These optional additional cationic
25 polymers do not contain any acr ylic and/or methacr ylic unit and are
non silicone polymers.
The additional cationic polymer s that ma y be used preferabl y
have a weight-average molar mass (Mw) of between 500 and 5×10 6
approximately and preferably between 103 and 3×106 approximately.
30 Among the additional cationic polymers, mention ma y be made
more particular ly of:
(1) Cationic polysacchar ides, especially cationic celluloses and
galactomannan gums. Among the cationic polysaccharides, mentio n
ma y be made more particularly of cellulose ether derivatives
38
comprising quaternary ammonium groups, cationic cellulose
copolymer s or cellulose d erivatives grafted with a water-soluble
quaternary ammonium monomer and catio nic galactomannan gums.
The cellulose ether derivatives comprising quaternar y
ammonium groups are especially descr ibed in French patent 1 492 5975 ,
and mention may be made of the polymer s sold under the name
UCARE POLYMER “JR” (JR 400 LT, JR 125 and JR 30M) or “LR”
(LR 400 or LR 30M) by the company Amerchol. These polymers are
also defined in the CTFA dictionar y as quaternary ammoniums of
10 hydroxyethylcellulose that have reacted wit h an epoxide substituted
with a trimethylammonium group.
Cationic cellulose copolymers or cellulose derivatives grafted
with a water-soluble quaternary ammonium monomer are described
especially in US patent 4 131 576, and mention ma y be made of
15 hydroxyalkylcelluloses, for instance hydroxymethyl-, hydroxyethyl- or
hydroxyprop ylcelluloses grafted, in particular, with a
methacr ylo ylethyltrimethylammonium,
methacr ylamidopropyltrimethylammonium or
dimethyld iallylammonium salt. The commercial products
20 corresponding to this definition are more particular ly the products sold
under the names CELQUAT L 200 and CELQUAT H 100 by the
company National Starch.
The cationic galactomannan gums are described more
particular ly in US patents 3 589 578 and 4 031 307, and mention ma y
25 be made of guar gums comprising cationic tr ialkylammonium groups.
Use is made, for example, of guar gums modified with a 2,3 -
epoxypropyltrimethylammonium salt ( for example, chloride). Such
products are especially sold under the names JAGUAR C13 S,
JAGUAR C 15, JAGUAR C 17 or JAGUAR C162 by the compan y
30 Rhodia.
(2) Polymers formed from piperazinyl units and divale nt
alkylene or hydroxyalkylene r adicals containing straight or branched
chains, optionally interrupted with oxygen, sulfur or nitrogen atoms o r
39
with aromatic or heterocyclic r ings, and also the oxidation and/or
quaternization products of these polymers.
(3) Water-soluble polyamino amides prepared in particular b y
polycondensation of an acidic compound with a polyamine; these
polyamino amides can be crosslinked with an epihalohydr in, 5 a
diepoxide, a dianhydr ide, an unsaturated dianhydr ide, a bisunsaturated
derivative, a bis-halohydr in, a bis-azetidinium, a bishaloac
yldiamine, a bis-alkyl halide or alternatively with an oligomer
resulting from the reaction of a difunctio nal compound which is
10 reactive with a bis-halohydr in, a bis-azetidinium, a bishaloac
yldiamine, 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 the y
15 comprise one or more tertiar y amine functions, the y can be
quaternized.
(4) Polyamino amide derivatives resulting from the
condensation of polyalkylene polyamines with polycarboxylic acids
followed by alkylation with b ifunctional agents. Mention may be
20 made, for example, of adipic
acid/dialkylaminohydroxyalkyldialkylenetriamine polymers in whic h
the alkyl radical comprises from 1 to 4 carbon atoms and preferabl y
denotes methyl, ethyl or propyl. Among these derivatives, mentio n
ma y be made more particular ly of the adipic
25 acid/dimethylaminohydroxypropyl/diethylenetr iamine polymers sold
under the name CARTARETINE F, F4 or F8 by the company Sandoz.
(5) Polymers obtained by reacting a polyalkylene polyamine
comprising two primar y amine groups and at least one secondar y
amine group with a dicarboxylic acid chosen from diglycolic acid and
30 saturated aliphatic dicarboxylic acids containing from 3 to 8 carbo n
atoms; the mole ratio between the polyalkylene polyamine and the
dicarboxylic acid preferably being between 0.8:1 and 1.4:1; the
resulting polyamino amide being reacted with ep ichlorohydr in in a
mole ratio of epichlorohydrin relative to the secondar y amine group of
40
the polyamino amide preferably of between 0.5:1 and 1.8:1. Polymer s
of this t ype are sold in particu lar under the name HERCOSETT 57 b y
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/diethylenetr iamine copolymer5 .
(6) Cyclopolymers of alkyldiallylamine or of
dialkyldiallylammonium, such as the homopolymer s or copolymers
containing, as main constituent of the chain, units corresponding to
formula (XVIII) or (XIX):
10
CR12
H C 2
N+
CH2
C(R12)-CH2-
(CH2)k
-(CH2)t-
R10 R11
(I) Y-
(XVIII)
CR12
H C 2
N
CH2
C(R12)-CH2-
(CH2)k
-(CH2)t-
R10
(II)
(XIX)
in which:
15 - k and t are equal to 0 or 1, the sum k + t being equal to 1;
- R1 2 denotes a hydrogen atom or a methyl radical;
- R1 0 and R11 , independently of each other , denote a C1-C6 alkyl group,
a hydroxyl(C1 -C5 )alkyl group, a C1 -C4 amidoalkyl group; or
alternatively R1 0 and R1 1 may denote, together with the nitrogen atom
20 to which they are attached, an heterocyclic group such as piperidinyl
or morpholinyl; R1 0 and R11 , independently of each other, preferabl y
denote a C1-C4 alkyl group; and
41
- Y- is an anion such as bromide, chloride, acetate, borate, citrate,
tartrate, bisulfate, bisulfite, su lfate or phosphate.
Mention ma y be made more particularly of the
dimethyld iallylammonium salt (for example chloride) homopolymer
sold for example under the name MERQUAT 100 by the compan 5 y
Nalco.
(7) Quaternar y diammonium polymers comprising repeating
units of formula:
N+
R13
R14
A1 N+
R15
R16
B1
X- X-
(XX)
10 in which:
- R1 3 , R1 4, R15 and R1 6, which may be identical or different,
represent aliphat ic, alicyclic or ar ylaliphatic radicals comprising from
1 to 20 carbon atoms, or C1-C1 2 hydroxyalkylaliphatic radicals,
or else R1 3 , R1 4 , R1 5 and R1 6 , together or separately, constitute,
15 with the nitrogen atoms to which they are attached, heterocycles
optionally comprising a second non-nitrogen heteroatom,
or else R1 3 , R1 4 , R1 5 and R1 6 represent a linear or branched C1 -
C6 alkyl radical substituted with a nitr ile, ester, acyl, amide or -CO-OR1
7-D or -CO-NH-R17 -D group in which R17 is an alkylene and D is a
20 quaternary ammonium group;
- A1 and B1 represent divalent polymethylene groups
comprising from 2 to 20 carbon atoms, linear or branched, saturated or
unsaturated, and which may contain, linked to or intercalated in the
main chain, one or more aromatic r ings or one or more oxygen or
25 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;
it being understood that A1, R1 3 and R1 5 can form, with the two
nitrogen atoms to which the y are attached, a piperazine ring;
30 in addition, if A1 denotes a linear or branched, saturated or
unsaturated alkylene or hydroxyalkylene r adical, B1 ma y also denote a
42
group (CH2)n-CO-D-OC-(CH2 ) p- wherein n and p, which may be
identical or different, denote an integer from 2 to 20, and wher ein D
denotes:
a) a glycol residue of formula -O-Z-O-, in which Z denotes a
linear or branched hydrocarbon-based radical, or a grou5 p
corresponding to one of the following formulae: -(CH2 -CH2 -O) x-CH2 -
CH2 - and -[CH2-CH(CH3 )-O]y-CH2 -CH(CH3 )-, where x and y denote a n
integer from 1 to 4, representing a defined and unique degree of
polymerization or any number from 1 to 4 representing an average
10 degree of polymer ization;
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
15 else 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 have a number-aver age molar mass (Mn) generally of
20 between 1000 and 100 000.
Mention ma y be made more particularly of polymers that are
composed of repeating units corresponding to the formula:
N+
R2
R1
(CH2)n N+
R4
R3
(CH2)p
X- X-
(XXI)
25 in which R1 , R2 , R3 and R4, which ma y be identical or different, denote
an alkyl or hydroxyalkyl radical containing from 1 to 4 carbon atoms,
n and p are integers ranging from 2 to 20, and X- is an anio n derived
from an organic or mineral acid.
A particularly preferred compound of formula (XXI) is that for
30 which R1, R2, R3 and R4 represent a methyl rad ical and n = 3, p = 6
43
and X = Cl, known as Hexadimethr ine chloride according to the INCI
(CTFA) nomenclature.
(8) Polyquaternar y ammonium polymer s comprising units of
formula (XXII) :
5
N+
R19
R18
(CH2)r NH CO (CH2)q CO NH (CH2)s
R21
R20
N+ A
XX-
(V)
(XXII)
in which:
- R1 8 , R1 9 , R2 0 and R2 1 , which may be identical or different, represent
a hydrogen atom or a methyl, ethyl, prop yl,  -hydroxyethyl,  -
10 hydroxyprop yl or
-CH2CH2 (OCH2CH2) pOH group, in which p is equal to 0 or to an
integer between 1 and 6, with the proviso that R18, R19, R20 and R21
do not simultaneously represent a hydrogen atom,
- r and s, which ma y be identical or different, are integers between 1
15 and 6,
- q is equal to 0 or to an integer between 1 and 34,
- X- denotes an anion such as a halide,
- A denotes a dihalide radical or preferably represents -CH2 -CH2 -OCH2
-CH2 -.
20 Examples that ma y be mentioned include the products Mirapol ®
A15, Mirapol® AD1, Mirapol® AZ1 and Mirapol® 175 sold by the
company Miranol.
(9) Quaternar y polymers of vinylpyrrolidone and of
vinylimidazole, for instance the products sold under the names
25 Luviquat® FC 905, FC 550 and FC 370 by the company BASF.
(10) Polyamines such as Polyquart® H sold by Cognis, referred
to under the name Polyethylene glycol (15) tallow polyamine in the
CTFA dictionary.
(11) Polymers comprising in their structure:
30 (a) one or more units corresponding to formula (A) below:
44
CH2 CH
NH2
(A)
(b) optionally, one or more units corresponding to formula (B) below:
CH2 CH
NH C
O
H
(B)
In other words, these polymers may be chosen especially fro5 m
homopolymers or copolymers comprising one or more units derived
from vinylamine and optionally one or more units derived from
vinylformamide.
Preferably, these cationic polymers are chosen from polymers
10 comprising, in their structure, from 5 mol% to 100 mol% of unit s
corresponding to formula (A) and from 0 to 95 mol% of units
corresponding to formula (B), preferentially from 10 mol% to 100
mol% of units corresponding to formula (A) and from 0 to 90 mol% of
units corresponding to formula (B).
15 These polymer s may be obtained, for example, by partial
hydrolysis of polyvinylformamide. This hydrolysis may be performed
in an acidic or basic medium.
The weight-average molecu lar mass of the said polymer,
measured b y light scattering, ma y range from 1000 to 3 000 000 g/mol,
20 preferably from 10 000 to 1 000 000 g/mol and more particularly from
100 000 to 500 000 g/mol.
The polymers comprising units of formula (A) and optional l y
units of formula (B) are sold especially under the name Lupamin b y
the company BASF, for instance, and in a non- limiting manner, the
25 products sold under the names Lupamin 9095, Lupamin 5095, Lupamin
1095, Lupamin 9030 (or Luviquat 9030) and Lupamin 9010.
Other additional cationic polymers that may be used in the
context of the invention are cationic proteins or catio nic protein
hydrolysates, polyalkyleneimines, in particular polyethyleneimines,
30 polymers comprising vinylp yr idine or vinylp yr idinium units,
45
condensates of polyamines and of epichlorohydrin, quaternar y
polyureylenes and chitin derivatives.
The additional cationic polymers, different from the polymer s
comprising one or more acrylic and/or methacr ylic units described
above, are preferably chosen from the cationic polysacchar ide5 s
corresponding to the general family (1) .
More preferentially the additional cationic polymer s are chose n
from cationic guar gums comprising trialkylammonium groups
(preferably C1 -C6 alkyl groups, and more preferentially methyl
10 groups), better still from hydroxyl(C1 -C4 )alkyl guar gums comprising
trialkylammonium groups, and even more preferably the additional
cationic polymers are chosen from guar hydroxyprop yltrimonium
chlorides.
According to a preferred embodiment of the present invention,
15 the composition can comprise:
- one or more polymer(s) comprising o ne or more acrylic and/or
methacr ylic units, preferably chosen from acrylamidoprop yltrimonium
chloride/ acrylamide copolymers, acrylamide/
methacr ylamidopropyltrimethylammonium chloride/ acr ylic acid
20 terpolymers, acr ylic acid/ methylacr ylamidoprop yltriméthylammonium
chloride/ methyl acr ylates terpolymers, (meth)acr ylic acid/
dimethyld iallylammonium chloride copolymer s and mixtures thereof,
and
- one or more additional cationic polymers, different from the
25 polymers comprising one or more acrylic and/or methacrylic unit s
described above, preferably chosen from the catio nic polysacchar ides
corresponding to the general family (1); more preferentially chose n
from cationic guar gums comprising tr ialkylammonium groups; better
still from hydroxyalkyl guar gums comprising tr ialkylammonium
30 groups; and even more preferably the additional polymers ar e chose n
from guar hydroxypropyltrimonium chlorides.
Mention can be made of a mixture of guar
hydroxyprop yltr imonium chloride and acrylamidoprop yltrimonium
chloride/acr ylamide copolymer, such as the product N-Hance 4572
46
sold by Ashland. The amount of additional cationic polymer(s),
different from the cationic polymer s comprising one or more acrylic
and/or methacr ylic units, present in the cosmetic composition of the
present invention, preferably ranges from 0.01 to 5% by weight, more
preferentially from 0.05 to 2% b y weight, and better still from 0.1 t5 o
1% b y weight, relative to the total weight of the cosmetic composition.
Additives
The cosmetic composition according to the present inventio n
ma y further comprise one or more additive( s) other than the
10 compounds of the inventio n.
As additives that ma y be used in accordance with the invention,
mention ma y be made of fatt y substances, anionic or non- ionic
polymers, additional amphoteric polymer s different from the
amphoteric polymers comprising one or more acrylic and/or
15 methacr ylic units previously descr ibed, cationic or non- ionic
surfactants, antidandruff agents, anti-seborrhoea agents, agents for
preventing hair loss and/or for promoting hair regrowth, fatt y
substances, vitamins and provitamins including panthenol, sunscreens,
mineral or organic pigments, sequestrants, plasticizers, solubilizers,
20 acidifying agents, mineral or organic thickeners, especially polymer ic
thickeners, opacifiers or nacreous agents, antioxidants, hydroxy acids,
fragrances and preserving agents.
Needless to sa y, a person skilled in the art will take car e to
select this or thes e optional additional compound(s) such that the
25 advantageous properties intrinsically associated with the cosmetic
composition according to the invention are not, or are not
substantially, adver sely affected by the envisaged addition(s).
The above additive s may generally be present in an amount, for
each of them, of between 0.001% and 20% by weight, relative to the
30 total weight of the cosmetic composition.
The cosmetic composition of the present invention is
advantageously transparent. The transparenc y of the cosmetic
composition may be character ized by measuring its transmittance.
47
The transmittance measurements are carried out at 25°C and at
atmospheric pressure, with a UV-Visible spectrophotometer,
SHIMADZU UV-1800.
The transmittance of the composition according to the present
invention, measured at ambient temperature (25°C) and atmospher 5 ic
pressure, is prefer ably greater than or equal to 80%, more preferabl y
greater than or equal to 85%, and better still greater than or equal to
90%. Advantageously the transmittance r anges from 80 to 100%, and
preferably from 90 to 100% (measurement at 600 nm).
10 The present invention also relates to a cosmetic process for
washing and/or conditioning keratin fibres, which consists in applying
to the said kerat in fibres a composition as described above, and after
an optional leave-on time, removing it by rinsing.
The leave-on time of the composition on the ker atin fibres ma y
15 range from 2 seconds to 15 minutes, better still from 5 seconds to 10
minutes and even better still from 10 seconds to 5 minutes.
The composition may be applied to wet or dry keratin fibres.
In the present invention, the term “keratin fibres” denotes
human keratin fibres, and in particular human hair.
20 The examples that follow serve to illustrate the inventio n
without, however, being limiting in nature.
EXAMPLES
25 In the examples that follow and unless otherwise indicated, the
amounts are given as mass percentages of active matter (am) relative
to the total weight of the composition.
Example 1
30
a. Compositions
The following compositions A1 and A2 (invention) and B1 and
B2 (comparative) were prepared from the ingr edients indicated in the
table below (% of active matter).
48
A1
invention
A2
invention
B1
comparative
B2
comparative
Ac ylamidopropyl
trimonium chloride/
acrylamide copolymer
0.075 0.25 - -
Guar hydroxypropyl
trimonium chloride
0.175 - - 0.25
Polyquaternium-10 - - 0.25 -
Dimethiconol 2 2 2 2
Sodium laureth su lfate 13.86 13.86 13.86 13.86
Coco betaine 1.8 1.8 1.8 1.8
Ceteareth-20 0.064 0.064 0.064 0.064
PEG-55 propylene glycol
oleate
0.16 0.16 0.16 0.16
PEG-5 ceteth-20 0.1 0.1 0.1 0.1
TEA-dodecylbenzenesulfonate
1.28 1.28 1.28 1.28
Propylene glycol 0.16 0.16 0.16 0.16
Sodium chloride 1.9 1.9 1.9 1.9
preservatives qs qs qs qs
water Qs 100 Qs 100 Qs 100 Qs 100
Weight ratio
dimethiconol/acrylic
polymer
26.7 8 - -
b. Protocol
Locks of hair have been shampooed 5 times with each of the
above compositions.
The silicon (Si) deposition has been measured by a WDXRF Optim’ 5 x
Thermofischer (Wavelength Dispersion) XRF system on samples of
250 mg of hair. This measurement has been repeated three times for
each sample corresponding to compositions A1, A2, B1 and B2.
10
49
c. Results
The results thus obtained are given in the table below (average
for three measurements).
A1
invention
A2
invention
B1
comparative
B2
comparative
Average Silicon
deposition (ppm)
1560 ± 71
6459
±178
108 ± 7 699 ± 22
5
The results thus obtained show that compositions A1 and A2
according to the present invention lead to significantly higher silico n
deposition compared to compositions B1 and B2.
10 Example 2
The following compositions A3, A4 and A5 (invention) and B3
(comparative) were prepared from the ingr edients indicated in the
table below (% in active matter).
15
A3
invention
A4
invention
A5
invention
B3
comparative
Polyquaternium-47
1
(0.2% am)
- - -
Polyquaternium-22 -
0.5
(0.2% am)
- -
Ac ylamidopropyl
trimonium chloride/
acrylamide
copolymer
- - 0.15% am -
Guar hydroxypropyl
trimonium chloride
- - - 0.2% am
Dimethiconol 1 2 2 2
Sodium laureth
sulfate
11,5 11,5 11,5 11,5
50
Coco betaine 2,4 2,4 2,4 2,4
PEG-7 glyceryl
cocoate
1.2 - - -
PEG-5 ceteth-20 0.1 0.1 0.1 0.1
preservatives qs qs qs qs
Sodium chloride 2 2 1.5 1.5
water Qs 100 Qs 100 Qs 100 Qs 100
Weight ratio
dimethiconol/acrylic
polymer

CLAIMS
1. Cosmetic composition comprising :
- one or more anionic surfactant(s) in an amount of more than or
equal to 5% by weight, relative to the total weight of the cosmetic
composition5 ,
- one or more amphoteric or zwitterionic surfactant(s),
- one or more polymer(s) comprising one or more acrylic and/or
methacr ylic unit(s), and
- one or more hydroxyl-terminated silicone(s).
2. Composition according to claim 1, wherein the anionic
surfactants are chosen, alone or as a mixture, from:
- C6 -C2 4 , and especially C1 2 -C2 0 , alkyl sulfates;
- C6 -C2 4 , and especially C1 2 -C2 0 , alkyl ether sulfates; preferabl y
comprising from 2 to 20 ethylene oxide units;
- C6 -C2 4 , and especially C1 2 -C2 0 , alkylsulfosuccinates, especiall y
laurylsulfosuccinates;
- C6 -C2 4 , and especially C1 2 -C2 0 , alkyl ether sulfosuccinates;
- (C6 -C2 4 )acylisethionates, and preferably (C1 2-C1 8)acylisethionates;
- C6 -C2 4 , and especially C1 2-C2 0, acylsarcosinates; especiall y
palmitoylsarcosinates;
- (C6 -C2 4 )alkyl ether carboxylates, preferably (C1 2 -C2 0 )alkyl ether
carboxylates;
- polyoxyalkylenated (C6-C2 4)alkyl(amido) ether carboxylic acids and
salts thereof, in particular those comprising from 2 to 50 alkylene
oxide and in particular ethylene oxide groups;
- C6 -C2 4 , and especially C1 2 -C2 0 , acylglutamates;
- C6 -C2 4 , and especially C1 2 -C2 0 , acylglycinates;
in particular in the form of alkali metal or alkaline -earth metal,
ammonium or amino alcohol salts.
3. Composition according to any one of the preceding claims,
wherein the amount of anionic surfactants ranges from 5 to 30% b y
weight, preferably from 8 to 25% b y weight, and more preferentiall y
from 10 to 20% by weight, relative to the total weight of the cosmetic
composition.
4. Composition according to any one of the preceding claims5 ,
wherein the amphoteric or zwitter ionic surfactants are chosen from
seco ndary or tertiary aliphatic amine derivatives, optionall y
quaternized, in which the aliphatic group is a linear or branched chain
comprising from 8 to 22 carbon atoms, said amine derivatives
containing at least one anionic group, for instance a carboxylate,
sulfonate, sulfate, phosphate or phosphonate group, and preferably the
amphoteric or zwitter ionic surfactants are chosen from (C8 -
C2 0)alkylbetaines such as cocoylbetaine, (C8 -C20 )alkylamido(C2 -
C8 )alkylbetaines such as cocoylamidopropylbetaine, and mixtures
thereof.
5. Composition according to any one of the preceding claims,
wherein the amount of amphoteric or zwitterionic surfactants ranges
from 0.1 to 15% by weight, preferably from 0.5 to 10% by weight, and
more preferentially from 1 to 5% by weight, relative to the total
weight of the cosmetic composition
6. Composition according to any one of the preceding claims,
wherein the polymer( s) comprising one or more acrylic and/or
methacr ylic unit(s) are chosen from homopolymer s or copolymers
derived from acrylic and/or methacr ylic monomers, and preferabl y
from homopolymer s or copolymer s resulting from the polymer izatio n
of one or more monomers including one or more monomers of
structure (IV) :
H2C
R1
COR2
C
(IV)
in which,
- R1 denotes a hydrogen atom or a linear or branched C1 -C4 alkyl
radical,
- R2 denotes a hydroxyl r adical, a NR3R4 radical or a linear or
branched C1 -C12 alkoxy radical, said alkoxy r adical being optionall y
substituted b y one or more hydroxyl radicals, b y a quaternar 5 y
ammonium radical (N+R5R6R7 ;Y- ) or by a NR8R9 radical,
- R3 and R4 , which may be identical or different, denote a hydroge n
atom or a linear or branched C1 -C1 2 alkyl radical, optionall y
substituted by one or more hydroxyl radicals, b y a quaternar y
ammonium radical (N+R5R6R7 ;Y-), by a NR8R9 radical or by a sulfonic
group (-SO3H), and
- R5 , R6 and R7, which may be identical or different, denote a linear or
branched C1 -C18 alkyl rad ical or a benzyl radical, preferably a linear
or branched C1 -C6 alkyl radical;
- R8 and R9 , which may be identical or different, denote a hydroge n
atom or a linear or branched C1 -C6 alkyl radical; and
- Y- denotes an anion derived from a mineral or organic acid or a
halide, preferably bromide, chloride, acetate, borate, citrate, tartrate,
bisulfate, bisulfite, methosulfate, sulfate or phosphate anion.
7. Composition according to any one of the preceding claims,
wherein the cationic charge densit y of the polymers comprising one or
more acrylic and/or methacr ylic units is lower than or equal to 5
meq/g, preferably lower than or equal to 4 meq/g, more preferentiall y
lower than or equal to 3 meq/g, better still this cationic charge densit y
ranges from 0.5 to 5 meq/g, even more preferably from 1 to 4 meq/g,
and still from 1.5 to 3 meq/g.
8. Composition according to any one of the preceding claims,
wherein the polymers comprising one or more acrylic and/or
methacr ylic units are chosen from homopolymer s or copolymers
derived from acrylic or methacr ylic esters or amides and comprising at
least one of the units of the following formulae:
R1
CH2
O
NH
R
N+ R7 R5
R6
Y-
(V)
R1
CH2
O
NH
R
N
R8 R9 (VI)
R1
CH2
O
O
R
NR5 + R7
R6
Y-
(VII)
R1
CH2
O
O
R
N
R8 R9 (VIII)
in which:
- R1 , which ma y be identical or different, denote a hydrogen atom or a
CH3 radical;
- R, which may be identical or different, denote a linear or branched
C1 -C1 2 alkyl radical, preferably a linear C1 -C6 alkyl radical, optionall y
substituted by one or more hydroxyl radicals;
- R5 , R6 and R7, which may be identical or different, denote a linear or
branched C1 -C18 alkyl rad ical or a benzyl radical, preferably a linear
or branched C1 -C6 alkyl radical;
- R8 and R9 , which may be identical or different, denote a hydroge n
atom or a linear or branched C1-C6 alkyl radical, preferably methyl or
ethyl; and
- Y- denotes an anion derived from a mineral or organic acid or a
halide, preferably bromide, chloride, acetate, borate, citrate, tartrate,
bisulfate, bisulfite, methosulfate, sulfate or phosphate anion.
9. Composition according to the preceding claim, wherein t he
polymers comprising one or more acrylic and/or methacrylic unit s
further contain one or more units derived from comonomers that ar e
selected from the families of acr ylamides, methacr ylamides, diaceton5 e
acrylamides, acr ylamides and methacr ylamides substituted on the
nitrogen with lower (C1 -C4 ) alkyls, acrylic or methacrylic acids or
ester s thereof, vinyllactams such as vinylp yrrolidone or
vinylcaprolactam, and vinyl esters, preferably selected from the
families of acr ylamide and methacr ylamides, and more preferentiall y
from the family of acr ylamides.
10. Composition according to any one of claims 1 to 7, wherein
the polymer s comprising one or more acrylic and/or methacr ylic units
are chosen from amphoteric polymers, and preferably from amphoteric
polymers comprising a repetition of:
(i) one or more units derived from a monomer of (meth)acrylamide
type,
(ii) one or more units derived from a monomer of
(meth)acr ylamidoalkyltrialkylammonium type, and
(iii) one or more units derived from an acidic monomer of
(meth)acr ylic acid type.
11. Composition according to any one of the preceding claims,
wherein the polymer( s) comprising one or more acrylic and/or
methacr ylic units are chosen from acrylamidoprop yltrimonium
chloride/ acrylamide copolymers, acrylamide/
methacr ylamidopropyltrimethylammonium chloride/ acr ylic acid
terpolymers, acr ylic acid/ methylacr ylamidoprop yltrimethylammonium
30 chloride/ methyl acr ylates terpolymers, (meth)acr ylic acid/
dimethyld iallylammonium chloride copolymers and mixtures ther eof.
12. Composition according to any one of the preceding claims,
wherein the amount of polymer(s) comprising one or more acrylic
and/or methacr ylic unit( s) ranges from 0.01 to 5% by weight,
preferably from 0.015 to 5% by weight, more preferentially from 0.02
to 3% by weight, better still from 0.04 to 2% by weight, and even more
preferably from 0.05 to 1% by weight, relative to the total weight of
the cosmetic composition5 .
13. Composition according to any one of the preceding claims,
wherein the hydroxyl-terminated silicones are chosen from hydroxylterminated
polyalkylsiloxanes, preferably from polyd ialkylsiloxanes
containing silanol end groups, and more preferentially from
polydimethylsilo xanes containing silanol end groups.
14. Composition according to any one of the preceding claims,
wherein the hydroxyl-terminated silicones are chosen from one or
more polydimethylsiloxanes containing dimethylsilanol end groups,
preferably in emulsion form, and more preferentially in microemulsio n
form having particle size preferably lower than or equal to 100 nm.
15. Composition according to any one of the preceding claims,
wherein the amount of hydroxyl-terminated silicone(s) ranges from 0.1
to 15% by weight, preferably from 0.5 to 10% by weight, and more
preferentially from 1 to 5% by weight, r elative to the total weight of
the cosmetic composition.
16. Composition according to any one of the preceding claims,
wherein the weight ratio between the amount of hydroxyl-terminated
silicone(s) and the amount of polymer( s) comprising one or more
acrylic and/or methacrylic units is greater than or equal to 1,
preferably greater than or eq ual to 2, more preferentially greater tha n
or equal to 4, better still this weight ratio ranges from 1 to 40, eve n
more preferably from 2 to 35, and still from 4 to 30.
17. Composition according to any one of the preceding claims,
35 wherein it further comprises one or more additional cationic
polymer(s) different from the polymer( s) comprising one or more
acrylic and/or methacrylic unit(s).
18. Cosmetic process for washing and/or conditioning keratin
fibres, in particular human keratin fibres such as hair, which consist5 s
in applying to said keratin fibres a composition as defined in anyone
of the preceding claims, and after an optional leave -on time,
optionally removing it by r insing.