COSMETIC USE OF A FLOCCULANT POLYMER AS ANTIPERSPIRANT
The present invention relates to the cosmetic use of a flocculant polymer chosen
from:
(i) flocculant polymers comprising as side chain non-quaternized pyridine groups
directly linked or indirectly to the main chain, as antiperspirant active agent,
particularly in a composition not containing any antiperspirant aluminium and/or
zirconium salts;
(ii) flocculant polymers comprising as side chain non-quaternary amine groups
borne by a side substituent directly linked to the main chain; the said polymer
comprising at least one non-quaternary cationic monomer and at least one
hydrophobic nonionic monomer;
(iii) cationic polyurethane flocculant polymers;
as antiperspirant active agent, especially in a composition comprising a
cosmetically acceptable medium and more particularly not containing any
antiperspirant aluminium and/or zirconium salts.
A subject of the present invention is also a cosmetic process for treating
perspiration, which consists in applying to the surface of the skin a composition
comprising, in a cosmetically acceptable medium, at least one flocculant polymer
as defined previously, not containing any antiperspirant aluminium and/or
zirconium salts.
In the cosmetic field, it is well known to use, in topical application, antiperspirant
products containing substances that have the effect of limiting or even preventing
the flow of sweat. These products are generally available in the form of roll-ons,
sticks, aerosols or sprays.
Antiperspirant substances generally consist of aluminium salts or
aluminium/zirconium salts. Their antiperspirant efficacy is limited when they are
used alone. The use of these active agents at high concentrations in order to
obtain good efficacy leads to formulation difficulties. Furthermore, these
substances have a skin irritant potential.
There is thus a need to find novel antiperspirant active agents that can replace
aluminium salts and aluminium/zirconium salts, and that are efficient and easy to
formulate.
Patent application WO 95/241 05 proposes as antiperspirant active agents waterinsoluble
polymers that form an occlusive film on the skin. The use of standard
aluminium salts is unnecessary. The occlusive polymers proposed are of the
octylacrylamide/acrylate copolymer or vinyl acetate/butyl maleate/isobornyl
acrylate type, alone or in combination with a PVP/linear a-olefin polymer such as
PVP/eicosene.
Antiperspirant active agents also proposed in patent application WO 95/27473 are
water-insoluble film-forming polymers whose main chain is hydrocarbon-based
and which comprise pendent hydrophobic quaternary ammonium groups.
Patent application WO 01/54658 discloses anhydrous compositions containing a
cyanoacrylate monomer that reacts with sweat to form in situ by polymerization a
film on the skin that blocks the sweat ducts.
However, these occlusive film-forming polymers do not make it possible to obtain
entirely satisfactory antiperspirant efficacy, and still give rise to formulation
problems.
Moisture-absorbing polymers have been proposed as substitutes for standard
astringent salts in antiperspirant compositions in patent US 4 743 440. These
moisture-absorbing polymers may especially be water-soluble and chosen
especially from natural gums (xanthan, agar, carrageenans, guar, gelatin),
celluloses (hydroxypropylmethylcellulose, carboxymethylcellulose),
polyoxyethylenes, polyvinylpyrrolidones, carboxyvinyl polymers or vinyl
ether/maleic anhydride copolymers. In patent application WO 03/030 853, the
recommended moisture-absorbing polymers are chosen from grafted starch
homopolymers and 2-propenamide-co-propenoic acid sodium salt copolymers.
However, these moisture-absorbing polymers do not make it possible to obtain
entirely satisfactory antiperspirant efficacy, and still give rise to formulation
problems.
Water-soluble quaternary polymers have been proposed in antiperspirant
compositions in the presence of standard aluminium salts in order to improve their
efficacy. This is the case for dimethyldiallylammonium chloride in patent
application EP 222 580, which acts as an agent for retaining the antiperspirant
salt. This is the case for the water-soluble polymers comprising a Br0nsted acid in
patent application WO 02/49590, in particular those derived from maleic acid
and/or maleic anhydride, which act as co-gelling agent with the antiperspirant
salts. This is the case for polyethyleneimines (PEI) in the article Cosmetics &
Toiletries Vol. 108, August 1993, pp. 73-77, which act as agents for complexing
the aluminium salts.
Dimethyldiallylammonium chloride/acrylic acid copolymers were proposed in
patent application EP 478 327 as thickeners in aqueous liquid antiperspirant
products containing aluminium salts.
In patent US 4 690 817, film-forming polymers of vinyl alcohols containing
quaternary amine side groups were proposed in antiperspirant compositions in the
presence of standard astringent salts, as skin-conditioning agents that form a
moisturizing barrier thereon.
In patent application WO 82/01 993, polyethyleneimines were used as odour
absorbers, in particular for fatty acids, aldehydes or ketones, and more particularly
in alcohol-based deodorant products in spray or roll-on form.
The Applicant has discovered, surprisingly, that particular flocculant polymers
constitute by themselves excellent antiperspirant agents and can be readily
formulated in numerous products intended for treating perspiration and the body
odour associated with perspiration, without it being necessary to use standard
astringent salts.
The present invention relates to the cosmetic use of a flocculant polymer chosen
from:
(i) flocculant polymers comprising as side chain non-quaternized pyridine groups
directly linked or indirectly to the main chain, as antiperspirant active agent,
particularly in a composition not containing any antiperspirant aluminium and/or
zirconium salts;
(ii) flocculant polymers comprising as side chain non-quaternary amine groups
borne by a side substituent directly linked to the main chain; the said polymer
comprising at least one non-quaternary cationic monomer and at least one
hydrophobic nonionic monomer;
(iii) cationic polyurethane flocculant polymers;
as antiperspirant active agent, especially in a composition comprising a
cosmetically acceptable medium and more particularly not containing any
antiperspirant aluminium and/or zirconium salts.
A subject of the present invention is also a cosmetic process for treating
perspiration, which consists in applying to the surface of the skin a composition
comprising, in a cosmetically acceptable medium, at least one flocculant polymer
as defined previously, not containing any antiperspirant aluminium and/or
zirconium salts.
The term "antiperspirant agent" means any substance which, by itself, has the
effect of reducing or limiting the flow of sweat without it being necessary to use an
aluminium and/or zirconium antiperspirant salt.
The term "effective amount of polymer" means an amount of polymer that is
sufficient to be able to observe after application to the surface of the skin an
antiperspirant effect as defined above.
The term "cosmetically acceptable medium" means a medium that is compatible
with the skin and/or its integuments or mucous membranes, having a pleasant
colour, odour and feel and not causing any unacceptable discomfort (stinging,
tautness or redness) liable to discourage the consumer from using this
composition.
The term "flocculant polymer" means any polymer that is capable of destabilizing a
colloidal suspension indiscriminantly via a flocculation or coagulation mechanism.
The term "destabilizing colloids" means the formation of aggregates that make the
suspension unstable. As the terms "flocculation" and "coagulation" are generally
interchangeable and equivalent, we will speak in the invention of "flocculation" for
one or other of the mechanisms. The definitions of these mechanisms are given in
volume 10 of Kirk-Othmer's Encyclopaedia of Chemical Technology, 3rd edition.
The term "composition not containing any antiperspirant aluminium and/or
zirconium salts" means any composition containing not more than 1% by weight of
antiperspirant aluminium and/or zirconium salts.
A/ Flocculant polymers comprising as side chain non-quaternized pyridine
groups directly or indirectly linked to the main chain
The flocculant polymers of the invention may be in the form of homopolymer or
copolymer containing at least one monomer of non-quaternized pyridine type.
The flocculant polymers of the invention are preferably water-dispersible or watersoluble.
The term "water-dispersible polymer" means any polymer which, when introduced
into an aqueous phase (into water or into a mixture of water and linear or
branched C2-C5 monoalcohols, for instance ethanol, isopropanol or n-propanol) at
room temperature (25°C and 1 atmosphere), without pH modification, at a solids
content allows the production of a dispersion whose mean particle size is between
5 nm and 5 miti .
The term "water-soluble polymer" means any polymer which, when introduced into
water or into a mixture of water and linear or branched C2-C5 monoalcohols, for
instance ethanol, isopropanol or n-propanol, without pH modification at 25°C, to a
mass concentration equal to 1%, allows the production of a macroscopically
homogeneous and transparent solution, i.e. a solution with a minimum light
transmission value, at a wavelength equal to 500 nm, through a sample 1 cm
thick, of at least 80% and preferably at least 90%.
The molar masses of these polymers generally range from 1000 to 20 000 000
g/mol and preferably between 5000 and 1 000 000 g/mol.
The polymers may be crosslinked or non-crossl inked.
Among the flocculant polymers comprising non-quaternized pyridine groups that
are pendent relative to the main chain, which may be used in the compositions of
the invention, mention may be made of homopolymers or copolymers comprising
at least one monomer (A) to (F) defined below:
B ) (C) (D) (E) (F)
where:
X =O, or NH
R 1 represents a hydrogen atom or an alkyl group containing from 1 to 3 carbon
atoms, preferably methyl;
A is a linear or branched C1-C6 and preferably C2-C3 alkyl group; a Ci-C4
hydroxyalkyl group, preferably monohydroxyalkyl;
The monomers corresponding to the preferred units among (A)-(F) are:
2-vinylpyridine; 4-vinylpyridine; N-(4-pyridyl)propylmethacrylamide, N-
4(pyridyl)ethyl methacrylate.
According to one particular form of the invention, the flocculant polymer also
comprises units consisting of at least one cationic monomer other than a pyridine
unit, which may be chosen from quaternary ammonium monomers and
(meth)acrylamide monomers, or mixtures thereof.
Among these additional cationic monomers, mention may be made of those
having the following formulae:
(G)
(H) (I) (J) (K) (L)
in which:
R 9 and R10 independently represent a linear or branched Ci-Cs alkyl group, a
benzyl group, a C1-C5 hydroxyalkyl group or a linear or branched amido(Ci-
C4)alkyl group;
R3 and R4 independently represent a hydrogen atom or a linear or branched alkyl
group having from 1 to 6 carbon atoms, and preferably methyl or ethyl;
R3 and R4 may form with the nitrogen atom a 5- to 8-membered non-aromatic
nitrogenous heterocycle, for instance pyrrolidine, piperazine or piperidine;
R5 represents a hydrogen atom or an alkyl group containing from 1 to 3 carbon
atoms, preferably methyl;
A is a linear or branched C1-C6 and preferably C2-C3 alkyl group; a Ci-C4
hydroxyalkyl group, preferably monohydroxyalkyl;
R6, R 7 and Rs, which may be identical or different, represent a hydrogen atom or a
linear or branched C1-C6 alkyl group or a benzyl radical;
X denotes a mineral anion such as a halide (chloride, bromide or iodide) or an
organic anion such as a (Ci-C4) alkyl sulfate (methyl sulfate or ethyl sulfate).
The preferred units of formula (G) are diallyldimethylammonium chloride
(DADMAC) and diallyldiethylammonium chloride (DADEAC).
The preferred units of formula (H) are methacrylamide or acrylamide and more
particularly acrylamide.
The units (I), (J), (K) or (L) may be chosen from methylaminoethyl methacrylate
benzyl dimethylaminoethylacrylate chloride (DMAEA-BCQ)
acryloyloxyethyltrimethylammonium chloride (AETAC)
methacryloyloxyethyltrimethylammonium chloride (METAC)
methylacrylamidopropyltrimethylammonium chloride (MAPTAC)
acrylamidopropyltrimethylammonium chloride (APTAC)
acryloyloxyethyltrimethylammonium methosulfate (AETAMS)
methacryloyloxyethyltrimethylammonium methosulfate (METAMS)
acryloyloxyethyldiethylmethylammonium chloride
methacryloyloxyethyldiethylmethylammonium chloride or the equivalents thereof
neutralized with a methyl sulfate, vinylimidazole, piperidine ethylmethacrylate or
piperazine ethylmethacrylate.
The most preferential are benzyl dimethylaminoethylacrylate chloride (DMAEABCQ),
acryloyloxyethyltrimethylammonium chloride (AETAC),
methacryloyloxyethyltrimethylammonium methosulfate (METAMS) and
methylaminoethyl methacrylate.
According to one particular form of the invention, the flocculant polymer also
comprises units consisting of at least one anionic monomer preferably chosen
from those having the following formula:
H2C=C
V)— (¾")—
with
Y is a group chosen from -COOH, -SO3H, -OSO3H, -PO3H2 and -OPO3H2. It is
understood that, according to the prior art, the groups SO4H and PO4H2 are
linked to R'2 via the oxygen atom, whereas the groups SO3H and PO3H are linked
to R'2, respectively, via the atoms S and P.
- R is as defined previously,
- Z is a divalent group chosen from -COO-, -CONH-, -CONCH3- , -OCO- or -O-, -
SO2- -CO-O-CO- or -CO-CH2-CO-, preferably Z is chosen from COO and CONH,
- x' = 0 or 1, preferably 1,
- R'2 is a saturated or unsaturated, optionally aromatic, linear, branched or cyclic
carbon-based divalent radical of 1 to 30 carbon atoms, which may comprise 1 to
18 heteroatoms chosen from O, N, S, F, Si and P; the heteroatom(s) may be
intercalated in the chain of the said radical R'2 or alternatively the said radical R'2
may be substituted with one or more groups comprising them such as hydroxyl or
amino.
Among the preferred anionic monomers M when they are present, mention may be
made of maleic anhydride, acrylic acid, methacrylic acid, crotonic acid, itaconic
acid, fumaric acid, maleic acid, 2-carboxyethyl acrylate (CH2=CH-C(O)-O-(CH 2)2-
COOH); styrenesulfonic acid, 2-acrylamido-2-nnethylpropanesulfonic acid,
vinylbenzoic acid, vinylphosphoric acid and sulfopropyl (meth)acrylate, and salts
thereof.
According to one particular form of the invention, the flocculant polymer also
comprises units consisting of at least one nonionic monomer.
The additional nonionic monomers may be chosen especially from those having
the following formula, alone or as a mixture:
in which:
- R'i is hydrogen or -CH3;
- Z is a divalent group chosen from -COO-, -CONH-, -CONCH3-, -OCO-,
-SO2, -CO-O-CO-, -CO-CH2-CO- and -O-; preferably COO or CONH;
- x is 0 or 1;
- R" is a saturated or unsaturated, optionally aromatic, linear, branched or cyclic
carbon-based radical of 1 to 30 carbon atoms, which may comprise 1 to 18
heteroatoms chosen from O, N, S, F, Si and P; the heteroatom(s) may be
intercalated in the chain of the said radical or alternatively the said radical R" may
be substituted with one or more groups comprising them such as hydroxyl, ester,
amide, urethane or urea.
In particular, R" may be a methyl, ethyl, propyl, isopropyl, n-butyl, isobutyl, tertbutyl,
phenyl or benzyl radical or a radical of formula -CH2-CH2-CH2OH, -CH2-CH2-
OH, -CH2-CH2-CH2OH o furfuryl.
The additional nonionic monomers may be chosen especially from the monomers
below: methyl methacrylate, methyl acrylate, ethyl methacrylate, ethyl acrylate,
propyl acrylate, isopropyl acrylate, tetrahydrofurfuryl methacrylates, butyl
methacrylate, 2-ethylhexyl acrylate, stearyl methacrylate, acrolein,
tetrahydrofurfuryl acrylate, 2-hydroxyethyl methacrylate, 2-hydroxyethyl acrylate,
ethoxyethyl methacrylate, ethoxyethyl acrylate, N-isopropylacrylamide, Nisopropylmethacrylamide,
N,N-dimethylacrylamide, N,N-dimethylmethacrylamide,
vinyl acetate, methyl vinyl ether, ethyl vinyl ether, vinylpyrrolidone,
vinylcaprolactam, N-vinylacetamide, hydroxypropyl acrylate, N-vinyllactam,
acrylamide, N-methylacrylamide, N,N-dimethylacrylamide, N-methyl-Nvinylacetamide,
N-vinylformamide, N-methyl-N-vinylformamide, vinyl alcohol
(copolymerized in the form of vinyl acetate and then hydrolysed).
The polymers containing a non-quaternized pyridine unit may advantageously be
totally or partially neutralized relative to the pyridine unit with an organic acid or an
inorganic acid:
Neutralization of the amine units, belonging to the functionalized pyridine polymer,
may be performed with a mineral acid, such as sulfuric acid, hydrochloric acid,
hydrobromic acid, hydriodic acid, phosphoric acid or boric acid; or alternatively
with an organic acid, which may comprise one or more carboxylic, sulfonic or
phosphonic acid groups. They may be linear, branched or cyclic aliphatic acids, or
alternatively unsaturated or aromatic acids. These acids may also include one or
more heteroatoms chosen from O, N, Si, F and P, for example in the form of
hydroxyl groups. The neutralizers of organic acid type may be chosen from linear,
branched or cyclic aliphatic acids and/or unsaturated or aromatic acids, and may
especially comprise 1 to 1000 carbon atoms and especially 2 to 500 carbon
atoms. They contain at least one Br0nsted acid function, and especially one or
more carboxylic, sulfonic and/or phosphonic acid groups. They may also include
one or more heteroatoms chosen from O, N, Si, F and P, for example in the form
of hydroxyl groups.
Linear, branched or cyclic, saturated or unsaturated, optionally aromatic fatty acids
containing 6 to 32 carbon atoms, especially 8 to 28, and comprising at least one
COOH or sulfonic acid (-SO3H) function, may be used in particular as neutralizer.
Linear, branched or cyclic, saturated or unsaturated, optionally aromatic hydroxy
acids and especially a-hydroxy acids containing 2 to 32 and especially 6 to 28
carbon atoms, and comprising at least one COOH or sulfonic acid (-SO3H)
function, may also be used.
Alkylbenzenesulfonic acids in which the alkyl group may comprise from 4 to 30
and especially 6 to 24 carbon atoms may also be used.
Amphoteric neutralizers may also be used, especially of the alkylbetaine or
alkylamidopropylbetaine type, in which the alkyl group may comprise 1 to 30,
especially 4 to 24 or even 6 to 22 carbon atoms; mention may be made in
particular of cocamidopropylbetaine.
Mention may be made especially of a-hydroxyethanoic (or glycolic) acid, -
hydroxyoctanoic acid, a-hydroxycaprylic acid, ascorbic acid, acetic acid, benzoic
acid, behenic acid, capric acid, citric acid, caproic acid, caprylic acid,
dodecylbenzenesulfonic acid, 2-ethylcaproic acid, folic acid, fumaric acid,
galactaric acid, gluconic acid, 2-hexadecyleicosanoic acid, hydroxycaproic acid,
12-hydroxystearic acid, isolauric (or 2-butyloctanoic) acid, isomyristic (or 2-
hexyloctanoic) acid, isoarachidic (or 2-octyldodecanoic) acid, isolignoceric (or 2-
decyltetradecanoic) acid, lactic acid, lauric acid, malic acid, myristic acid, oleic
acid, palmitic acid, propionic acid, sebacic acid, stearic acid, tartaric acid,
terephthalic acid, trimesic acid, undecylenic acid, propylbetaine,
cocamidopropylbetaine and betaine hydrochloride of formula
[(CH3)3N+CH2CO2H.Cr], and also mixtures thereof.
Preferably, caproic acid, 2-ethylcaproic acid, oleic acid, behenic acid, stearic acid,
acetic acid, citric acid, tartaric acid, betaine hydrochloride and/or gluconic acid,
and preferentially betaine hydrochloride and/or behenic acid, may be used as
neutralizer.
Among the polymers of the invention that are particularly preferred, mention may
be made of:
- poly(4-vinylpyridine) homopolymers, such as the products sold under the trade
names Reilline 4 10; Reilline 420; Reilline 4200 sold by Reilly Industries, Inc. or PM
60 K and 160 K sold by Aldrich;
- poly(2-vinylpyridine) homopolymers, such as the products sold under the trade
names Raluplate LEV 170; Reilline 2200 by Reilly Industries, Inc.; and Poly(2-
vinylpyridine-co-styrene) 130 K (Aldrich);
- poly(4- or 2-vinylpyridine)-co-styrene copolymers such as those sold by Aldrich;
- poly(4- or 2-vinylpyridine)-co-butyl methacrylate copolymers such as those sold
by Aldrich;
- poly(4- or 2-vinylpyridine) crosslinked with divinylbenzene, for instance Poly(4-
vinylpyridine), 2% crosslinked with divinylbenzene, sold by Aldrich, and Poly(4-
vinylpyridine) ReillexTM 402 crosslinked with divinylbenzene, sold by Reilly
Industries, Inc.;
- block copolymers comprising at least one block comprising a pyridine monomer,
for instance diblock polymers comprising a polyethylene glycol (PEG) or
polyisobutylene block and a poly(4- or 2-vinylpyridine) block;
- neutralized polymers, such as Poly(4-vinylpyridinium p-toluenesulfonate) and
Poly(4-vinylpyridine hydrochloride) 2% crosslinked with divinylbenzene, sold by
Aldrich.
The polymers according to the invention may preferably be conveyed in aqueous
medium, i.e. they are preferably water-soluble or water-dispersible. The dissolution
or dispersion in water may be performed by direct dissolution of the polymer if it is
soluble, or by neutralization of the amine units so as to make the polymer soluble
or dispersible in water. The aqueous dissolution or dispersion may also be
performed via an intermediate dissolution step in an organic solvent followed by
addition of water before evaporation of the organic solvent.
B/ Water-dispersible flocculant polymers comprising as side chain nonquaternary
amine groups borne by a side substituent directly linked to the
main chain; the said polymer comprising at least one non-quaternary
cationic monomer and at least one hydrophobic nonionic monomer;
The term "hydrophobic nonionic monomer" means any monomer not comprising
any ionic groups (anionic, cationic or amphoteric) and not being soluble in water or
in a mixture of water and of linear or branched C2-C5 monoalcohols, such as
ethanol, isopropanol or n-propanol, without pH modification, at a solids content of
1% by weight, at room temperature (25°C, 1 atm.).
These flocculant polymers of the invention may be in the form of homopolymer or
copolymer containing at least one monomer of tertiary, secondary or primary
amine type. They may be linear, branched or hyperbranched polymers. These
polymers may be in random, block or alternating form. It may be a case of a
polymer blend composition.
The molar masses of these polymers generally range from 1000 to 20 000 000
g/mol and preferably between 5000 and 1 000 000 g/mol.
The polymer necessarily comprises at least one non-quaternary cationic monomer
and at least one hydrophobic nonionic monomer. It may optionally comprise an
anionic monomer. It may also optionally comprise a small amount of difunctional
monomer thus allowing the production of crosslinked polymers.
The cationic monomer, or a salt thereof, is preferably chosen from monomers of
formula (I):
in which:
Rii is a hydrogen atom or a linear or branched hydrocarbon-based radical, of the
type CpH2p+ i , with p being an integer between 1 and 12 inclusive (in particular, R
may represent a methyl, ethyl, propyl or butyl radical (preferably, Rn represents
hydrogen or a methyl radical));
- Z is a divalent group chosen from -COO-, -CONH-, -CONCH3-, -OCO- or -O-
, -SO2- -CO-O-CO- or -CO-CH2-CO-, (preferably Z is chosen from COO and
CONH);
- x = 0 or 1, preferably 1;
R12 is a saturated or unsaturated, optionally aromatic, linear, branched or cyclic
carbon-based divalent radical of 1 to 30 carbon atoms, which may comprise 1 to
18 heteroatoms chosen from O, N, S, F, Si and P; the heteroatom(s) may be
intercalated in the chain of the said radical R2.
the said radical R12 may be substituted with one or more groups comprising them
such as hydroxyl or a group NH2, NHR' or NR'R" with R' and R", which may be
identical or different, representing a linear or branched C1-C22 alkyl, especially
methyl or ethyl;
R12 may also be an alkylene radical such as methylene, ethylene, propylene, nbutylene,
isobutylene, tert-butylene, n-hexylene, n-octylene, n-dodecylene, noctadecylene,
n-tetradecylene or n-docosanylene); a phenylene radical -CeH -
(ortho, meta or para), optionally substituted with a C1-C12 alkyl radical optionally
comprising 1 to 25 heteroatoms chosen from N, O, S, F, Si and/or P; or
alternatively a benzylene radical -C6H -CH2- , optionally substituted with a C1-C12
alkyl radical optionally comprising 1 to 25 heteroatoms chosen from O, N, S, F, Si
and P;
R12 may also be a radical of formula -CH2-O-CO-O-, CH2-CH2-O-CO-O-, -CH2-COO-,
-CH2-CH2-CO-O-, -[(CH2)5-CO-O]n- , -CH2-CH(CH3)-O-, -(CH2)2-O-, -CH2-OCO-
NH-, -CH2-CH2-O-CO-NH-; -CH2-NH-CO-NH- or -CH2-CH2-NH-CO-NH-, -CH2-
CHOH-, -CH2-CH2-CHOH-, -CH2-CH2-CH(NH2)-, -CH2-CH(NH2)-, -CH2-CH2-
CH(NHR')-, -CH2-CH(NHR'")-, -CH2-CH2-CH(NR'"R"")-, -CH2-CH(NR'"R"")-, -CH2-
CH2-CH2-NR'"-, -CH2-CH2-CH2-O-; -CH2-CH2-CHR'-O- with R'" and R""
representing a linear or branched C1-C22 alkyl optionally comprising 1 to 12
heteroatoms chosen from O, N, S, F, Si and P;
R12 may be a mixture of these radicals;
m is 0 or 1;
X is
a) either a guanidino or amidino group having the following formulae
Guanidino Amidino
b) or a group of formula -N(Ri 3)(Ri 4) or
-P(Ri 3)(Ri ) with Ri3 and Ri4 representing, independently of each other:
(i) a hydrogen atom;
(ii) a linear, branched or cyclic, saturated or unsaturated, optionally
aromatic alkyl group, comprising from 1 to 18 carbon atoms, which may
comprise 1 to 10 heteroatoms chosen from O, N, S, F, Si and P;
(iii) Ri3 and Ri4 may form, with the nitrogen or phosphorus atom, a first
saturated or unsaturated, optionally aromatic ring comprising in total 5,
6, 7 or 8 atoms, and especially 4, 5 or 6 carbon atoms and/or 2 to 4
heteroatoms chosen from O, S and N; the said first ring possibly being
fused with one or more other saturated or unsaturated, optionally
aromatic rings, each comprising 5, 6 or 7 atoms, and especially 4, 5, 6
or 7 carbon atoms and/or 2 to 4 heteroatoms chosen from O, S and N;
For example, R13 and Ri4 may be chosen from hydrogen or a methyl, ethyl, propyl,
isopropyl, n-butyl, t-butyl, isobutyl, octyl, lauryl or stearyl group. Preferably, R 6 and
R7 are chosen, independently of each other, from H, CH3 and C2H5.
c) a group R'3-N-R'4 in which R'3 and R4 form, with the nitrogen atom, a saturated
ring comprising in total 5, 6, 7 or 8 atoms, and especially 4, 5 or 6 carbon atoms
and/or 2 to 4 heteroatoms chosen from O, S and N; the said ring possibly being
fused with one or more other saturated rings, each comprising 5, 6 or 7 atoms,
and especially 4, 5, 6, 7 or 8 carbon atoms and/or 2 to 4 heteroatoms chosen from
O, S and N.
The cationic units (amines) of the monomer of formula (I) may optionally be
neutralized at this stage, in the manner described later.
Among the non-quaternary amine cationic monomers of formula (I) that are
preferred, mention may be made of:

Among the monomers of formula (I) that are particularly preferred, mention may be
made of dimethylaminopropyl(meth)acrylamide,
dimethylaminoethyl(meth)acrylamide, diethylaminoethyl (meth)acrylate,
dimethylaminoethyl (meth)acrylate, vinylimidazole and morpholinoethyl
(meth)acrylate, and mixtures thereof.
The copolymer may, of course, comprise a mixture of different cationic monomers
of formula (I).
The cationic monomers of formula (I) are preferably present in a proportion of from
5% to 80% by weight relative to the weight of the final polymer, especially from 7%
to 30% by weight and preferably from 10% to 20% by weight.
The flocculant polymer of the invention also comprises units consisting of at
least one hydrophobic nonionic monomer preferably chosen from those of
formula ( Ila) or (Mb) below:
,HC:
(lib)
Ό
X'
R
in which:
X' represents an oxygen atom or a group NH, and
R1 represents a linear, branched, cycloaliphatic or aromatic C2-C60 hydrocarbonbased
group, which may contain one or more atoms chosen from O, S and P; the
said group may further contain at least a polyoxyalkylenated chain (a
polyoxyethylanated and/or polyoxypropylated chain) ;
R2 represents a hydrogen atom or a methyl group.
Among these nonionic comonomers, the ones that are preferred in particular are
ethyl, isobornyl, n-butyl, n-hexyl, 2-ethylhexyl, n-nonyl, lauryl, n-octadecyl, isooctyl,
isodecyl, hydroxyethyl or hydroxypropyl acrylate, methyl, butyl, n-hexyl, 2-
ethylhexyl, ethoxyethyl, isodecyl, methoxyethyl methacrylate, C 1-30-PEG alkoxy
methacrylate (with 5 to 30 ethylene oxide units), vinyl propionate, and vinyl
neoalkanoates such as vinyl neononanoate and vinyl neododecanoate, or
mixtures thereof.
Particularly preferred comonomers of this group are n-butyl acrylate and 2-
ethylhexyl acrylate.
The flocculant polymers of the present invention may also contain a highly
hydrophobic nonionic monomer chosen from vinyl monomers bearing a silicone
side chain, chlorotrifluoroethylene, tetrafluoroethylene, and vinyl, allylic or
(meth)acrylic monomers bearing a perhalogenated, in particular perfluoro,
hydrocarbon-based side chain, such as perfluorohexyl (meth)acrylate or
perfluorooctyl (meth)acrylate. These monomers will preferably be present in small
amounts relative to the weight of the final polymer.
The nonionic monomers of formula ( Ila) or (Mb) are preferably present in a
proportion of from 10% to 95% by weight relative to the weight of the final polymer,
especially from 20% to 90% by weight and preferably from 30% to 85% by weight.
The flocculant polymer of the invention may also comprise units consisting of at
least one additional ionic monomer, chosen from the anionic monomers of formula
in which:
- Rii, Zi, x, Ri2 and m have the same meanings as those given above for formula
(i);
- Y is a group chosen from -COOH, -SO3H, -OSO3H, -PO3H2 and -OPO3H2; it is
understood that, according to the prior art, the groups SO4H2 and PO4H2 are linked
to Ri2 via the oxygen atom, whereas the groups SO3H and PO3H are linked to Ri2,
respectively, via the S and P atoms.
Among the preferred anionic monomers, mention may be made of maleic
anhydride, acrylic acid, methacrylic acid, crotonic acid, itaconic acid, fumaric acid,
maleic acid, 2-carboxyethyl acrylate (CH2=CH-C(O)-O-(CH 2)2-COOH);
styrenesulfonic acid, 2-acrylamido-2-methylpropanesulfonic acid, vinylbenzoic
acid, vinylphosphoric acid and sulfopropyl (meth)acrylate, and salts thereof.
The introduction of these anionic comonomers makes it possible to adjust the
equilibrium of the charges, to modify the hydrophilic nature and thus the solubility
of the polymers obtained, or alternatively to modify the compatibility of the
polymers with certain other ingredients of the formulation.
It is generally desirable for the overall charge of the polymers of the invention to be
positive, i.e. for the total number of positive charges borne by the polymers to be
greater than the number of negative charges.
The anionic monomers of formula (III) are preferably present in a proportion of
from 10% to 40% by weight relative to the weight of the final polymer, especially
from 15% to 30% by weight and preferably from 20% to 25% by weight.
Among the cationic or amphoteric radical copolymers described above, the
Applicant has obtained particularly advantageous results with the following
polymers:
• copolymers of butyl acrylate and of dimethylaminoethyl methacrylate,
• copolymers of butyl acrylate and of dimethylaminopropylmethacrylamide, and
• copolymers of 2-ethylhexyl acrylate and of dimethylaminopropylmethacrylamide.
The cationic flocculant polymers of the present invention may be prepared by
statistical radical solution, bulk, dispersion or emulsion polymerization, which are
familiar to those skilled in the art, in the presence of a radical initiator. Preferably,
the polymers are obtained by solution polymerization.
The positive charges of the polymers may be introduced by copolymerization of
monomers bearing a protonated tertiary amine function, but the protonation of the
amine function may also take place after polymerization. Preferably, the
protonation of the amine functions takes place after polymerization.
Although, the molecular mass of the cationic polymers of the present invention is
not a determining factor for the present invention, polymers with a numberaverage
molar mass of between 1000 and 20 000 000, better still between 5000
and 5 000 000 and preferably between 5000 and 1 000 000 g/mol are preferably
used.
The cationic flocculant polymers of the present invention that are dispersible in
water are in latex form, i.e. in the form of dispersions of fine particles, with a mean
size of between 5 nm and 5 miti , preferably between 5 nm and 600 nm and better
still between 5 nm and 400 nm, in an aqueous phase. This water-dispersed form
of the polymers of the present invention offers the advantage of having low
viscosities and are easier to manipulate and to incorporate into cosmetic
compositions than solutions.
The protonating agents for the amine functions of the polymers of the present
invention are chosen from cosmetically acceptable organic or mineral acids.
Among the cosmetically acceptable mineral acids, an example that may be
mentioned is hydrochloric acid.
The organic acids used as protonating agents may comprise one or more
carboxylic, sulfonic or phosphonic acid groups. They may be linear, branched or
cyclic aliphatic acids, or alternatively unsaturated or aromatic acids. These acids
may also include one or more heteroatoms chosen from O, N, Si, F and P, for
example in the form of hydroxyl groups. The neutralizers of organic acid type
may be chosen from linear, branched or cyclic aliphatic acids and/or unsaturated
or aromatic acids, and may especially comprise 1 to 1000 carbon atoms and
especially 2 to 500 carbon atoms. They contain at least one Br0nsted acid
function, and especially one or more carboxylic, sulfonic and/or phosphonic acid
groups. They may also include one or more heteroatoms chosen from O, N, Si,
F and P, for example in the form of hydroxyl groups.
Linear, branched or cyclic, saturated or unsaturated, optionally aromatic fatty acids
containing 6 to 32 carbon atoms, especially 8 to 28, and comprising at least one
COOH or sulfonic acid (-SO3H) function, may be used in particular as neutralizer.
Linear, branched or cyclic, saturated or unsaturated, optionally aromatic hydroxy
acids and especially a-hydroxy acids containing 2 to 32 and especially 6 to 28
carbon atoms, and comprising at least one COOH or sulfonic acid (-SO3H)
function, may also be used.
Alkylbenzenesulfonic acids in which the alkyl group may comprise from 4 to 30
and especially 6 to 24 carbon atoms may also be used.
Amphoteric neutralizers may also be used, especially of the alkylbetaine or
alkylamidopropylbetaine type, in which the alkyl group may comprise 1 to 30,
especially 4 to 24 or even 6 to 22 carbon atoms; mention may be made in
particular of cocamidopropylbetaine.
Among the cosmetically acceptable organic acids that may especially be
mentioned are a-hydroxyethanoic (or glycolic) acid, a-hydroxyoctanoic acid, -
hydroxycaprylic acid, ascorbic acid, acetic acid, benzoic acid, behenic acid, capric
acid, citric acid, caproic acid, caprylic acid, dodecylbenzenesulfonic acid, 2-
ethylcaproic acid, folic acid, fumaric acid, galactaric acid, gluconic acid, 2-
hexadecyleicosanoic acid, hydroxycaproic acid, 12-hydroxystearic acid, isolauric
(or 2-butyloctanoic) acid, isomyristic (or 2-hexyloctanoic) acid, isoarachidic (or 2-
octyldodecanoic) acid, isolignoceric (or 2-decyltetradecanoic) acid, lactic acid,
lauric acid, malic acid, myristic acid, oleic acid, palmitic acid, propionic acid,
sebacic acid, stearic acid, tartaric acid, terephthalic acid, trimesic acid,
undecylenic acid, propylbetaine, cocamidopropylbetaine and betaine hydrochloride
of formula [(CH 3)3N +CH2CO2H-Cr], and also mixtures thereof.
Preferably, caproic acid, 2-ethylcaproic acid, oleic acid, behenic acid, stearic acid,
acetic acid, citric acid, tartaric acid, betaine hydrochloride and/or gluconic acid,
and preferentially betaine hydrochloride and/or behenic acid, may be used as
neutralizer.
CI Flocculant cationic polyurethane polymers
The flocculant cationic polyurethane polymers of the invention are preferably
water-dispersible or water-soluble.
The molar masses of these polymers generally range from 1000 to 20 000 000
g/mol, preferably between 2000 and 1 000 000 g/mol and even more preferentially
between 3000 and 50 000 g/mol.
The polymers may be crosslinked or non-crossl inked.
Among the flocculant cationic polyurethane polymers comprising one or more
quaternary cationic or tertiary amine functions that are pendent relative to the main
chain or as an end function, which may be used in the compositions of the
invention, mention may be made of the polymers of types (I) and (II) defined
below:
Two types of polyurethane in accordance with the invention may be distinguished:
- polyurethanes of type ( 1 ) comprising a tertiary or quaternary amine function as
pendent functions on the main chain, and
- polyurethanes of type (2) necessarily comprising a tertiary or quaternary amine
function at the end of the main chain and optionally tertiary or quaternary amine
functions as pendent functions on the main chain.
The cationic polyurethanes of type ( 1 ) according to the invention comprise at least:
(a1 ) cationic units derived from at least one tertiary or quaternary amine bearing at
least two reactive functions containing labile hydrogen, and
(a2) nonionic units derived from oligomers or from nonionic polymers bearing at
their ends reactive functions containing labile hydrogen, and
(a3) nonionic units derived from nonionic monomer compounds containing at least
two functions containing labile hydrogen, and
(b) units derived from at least one diisocyanate.
The cationic polyurethanes of type (2) according to the invention comprise at least:
(a2) nonionic units derived from oligomers or from nonionic polymers bearing at
their ends reactive functions containing labile hydrogen, and
(a3) nonionic units derived from nonionic monomer compounds containing at least
two functions containing labile hydrogen, and
(a4) units consisting of at least one tertiary amine and containing only one function
containing labile hydrogen, the tertiary amine function possibly being quaternized,
and
(b) units derived from at least one diisocyanate, and
(a1 ) optionally cationic units derived from at least one tertiary or quaternary amine
bearing at least two reactive functions containing labile hydrogen.
The term "reactive functions containing labile hydrogen" means functions that are
capable, after loss of a hydrogen atom, of forming covalent bonds with the
isocyanate functions of the compounds forming the units (b). Examples of such
functions that may be mentioned include hydroxyl, primary amine (-NH2) or
secondary amine (-NHR) groups, or alternatively thiol groups (-SH). The
polycondensation of compounds bearing these reactive functions containing labile
hydrogen with diisocyanates makes it possible, depending on the nature of the
reactive functions bearing the labile hydrogen (-OH, -NH2, -NHR or -SH), to
obtain, respectively, polyurethanes, polyureas or polythio-urethanes. For the sake
of simplicity, all these polymers are grouped in the present patent application
under the term "polyurethanes".
When the tertiary or quaternary amines forming the units (a1 ) bear more than two
functions containing labile hydrogen, the polyurethanes obtained have a branched
structure.
In one preferred embodiment of the polyurethanes of the present invention, the
tertiary or quaternary amines forming the cationic units (a1 ) bear only two reactive
functions containing labile hydrogen and the polyurethanes obtained by
polycondensation consequently have an essentially linear structure. It is also
obviously possible to use a mixture of difunctional amines containing a small
proportion of amines bearing more than two reactive functions containing labile
hydrogen.
The tertiary or quaternary amines forming the cationic units (a1 ) are preferably
chosen from compounds corresponding to one of the following formulae:
in which each Ra independently represents a linear or branched C 1-C6 alkylene,
C3-C6 cycloalkylene or arylene group (preferably phenylene or benzylene), all
possibly being substituted with one or more halogen atoms and comprising one or
more heteroatoms chosen from O, N, P and S, each Rb independently represents
a C 1-C6 alkyl, C3-C6 cycloalkyl or aryl group (preferably phenyl or benzyl), all
possibly being substituted with one or more halogen atoms and comprising one or
more heteroatoms chosen from O, N, P and S, each X independently represents
an oxygen or sulfur atom or a group NH or NRc, in which Rc represents a C 1-C6
alkyl group, and A represents a physiologically acceptable counterion.
As tertiary amines that are particularly preferred for obtaining the cationic
polyurethanes of elastic nature of the present invention, mention may be made of
N-methyldiethanolamine and N-tert-butyldiethanolamine.
The tertiary and quaternary amines forming the cationic units (a1 ) of the
polyurethanes of the present invention may also be polymers containing tertiary
and/or quaternary amine functions, bearing at their ends reactive functions
containing labile hydrogen. The weight-average molar mass of these polymers
bearing tertiary and/or quaternary amine functions is preferably between 400 and
10 000.
Examples of such suitable polymers bearing amine functions that may be
mentioned include polyesters derived from the polycondensation of Nmethyldiethanolamine
and of adipic acid. When the amines forming the cationic
units (a1 ) are compounds bearing tertiary amine function(s), some or all of these
amine functions must be neutralized with a suitable neutralizer chosen from
physiologically acceptable organic or mineral acids. Examples of preferred acids
that may be mentioned include hydrochloric acid and acetic acid.
The term "unit (a2)" means a water-soluble or water-insoluble oligomeric or
polymeric group terminated at each of its ends with a group containing labile
hydrogens. Examples of hydrophilic polymers that may be mentioned include
polyethers, sulfonated polyesters and sulfonated polyamides, or a mixture of these
polymers. The hydrophilic compound is preferably a polyether and especially a
poly(ethylene oxide) or poly(propylene oxide). Examples of hydrophobic polymers
that may be mentioned include polyethylenes and polyisobutylenes, and
copolymers thereof.
The term "unit (a3)" included in the preparation of the polyurethanes of formulae (I)
and (II) means a compound of formula: HX-R2-XH in which each X independently
represents an oxygen or sulfur atom or a group NH or NRc, in which Rc
represents a C1-C6 alkyl group and more particularly each X is an oxygen atom; R2
represents a linear or branched alkylene radical containing from 1 to 20 carbon
atoms, optionally comprising a saturated or unsaturated ring, an arylene radical,
one or more of the carbon atoms possibly being replaced with a heteroatom
chosen from N, S, O and P. When they are not polymers, examples that may be
mentioned include ethylene glycol, diethylene glycol and propylene glycol.
Monomers (a4) that may be mentioned include compounds comprising on the
same molecule a tertiary amine unit and a primary or secondary amine unit.
Examples that may be mentioned include the following diamines: N,N-dimethyl-
1,4-butanediamine, N,N-dimethyl-1 ,3-propanediamine, N,N-diethyl-1 ,3-
propanediamine, N,N-dibutyl-1 ,3-propanediamine, N,N-dimethyl-1 ,2-
propanediamine, N,N-dimethyl-1 ,2-ethanediamine, N,N-diethyl-1 ,2-ethanediamine.
Compound (b) included in the preparation of the polyurethanes of types ( 1 ) and (2)
is a diisocyanate corresponding to the formula: O=C=N-Ri-N=C=O in which R
represents a linear or branched alkylene radical containing from 1 to 20 carbon
atoms, optionally comprising a saturated or unsaturated ring, an arylene radical,
one or more of the carbon atoms possibly being replaced with a heteroatom
chosen from N, S, O and P. Examples that may be mentioned include
methylenediphenyl diisocyanate, methylenecyclohexane diisocyanate, isophorone
diisocyanate, toluene diisocyanate, naphthalene diisocyanate, butane diisocyanate
and hexane diisocyanate.
The synthesis of the polyurethanes of type I is described in patent FR 0 116 598.
The polyurethanes of the invention containing tertiary amine cationic units may
advantageously be totally or partially neutralized relative to the tertiary amine units
with an organic acid or an inorganic acid.
Neutralization of the amine units, belonging to the polyurethane polymer, may thus
be performed with a mineral acid, such as sulfuric acid, hydrochloric acid,
hydrobromic acid, hydriodic acid, phosphoric acid or boric acid; or alternatively
with an organic acid, which may comprise one or more carboxylic, sulfonic or
phosphonic acid groups. They may be linear, branched or cyclic aliphatic acids, or
alternatively unsaturated or aromatic acids. These acids may also include one or
more heteroatoms chosen from O, N, Si, F and P, for example in the form of
hydroxyl groups. The neutralizers of organic acid type may be chosen from linear,
branched or cyclic aliphatic acids and/or unsaturated or aromatic acids, and may
especially comprise 1 to 1000 carbon atoms and especially 2 to 500 carbon
atoms. They contain at least one Br0nsted acid function, and especially one or
more carboxylic, sulfonic and/or phosphonic acid groups. They may also include
one or more heteroatoms chosen from O, N, Si, F and P, for example in the form
of hydroxyl groups.
Linear, branched or cyclic, saturated or unsaturated, optionally aromatic fatty acids
containing 6 to 32 carbon atoms, especially 8 to 28, and comprising at least one
COOH or sulfonic acid (-SO3H) function, may be used in particular as neutralizer.
Linear, branched or cyclic, saturated or unsaturated, optionally aromatic hydroxy
acids and especially a-hydroxy acids containing 2 to 32 and especially 6 to 28
carbon atoms, and comprising at least one COOH or sulfonic acid (-SO3H)
function, may also be used.
Alkylbenzenesulfonic acids in which the alkyl group may comprise from 4 to 30
and especially 6 to 24 carbon atoms may also be used.
Amphoteric neutralizers may also be used, especially of the alkylbetaine or
alkylamidopropylbetaine type, in which the alkyl group may comprise 1 to 30,
especially 4 to 24 or even 6 to 22 carbon atoms; mention may be made in
particular of cocamidopropylbetaine.
Mention may be made especially of a-hydroxyethanoic (or glycolic) acid, -
hydroxyoctanoic acid, a-hydroxycaprylic acid, ascorbic acid, acetic acid, benzoic
acid, behenic acid, capric acid, citric acid, caproic acid, caprylic acid,
dodecylbenzenesulfonic acid, 2-ethylcaproic acid, folic acid, fumaric acid,
galactaric acid, gluconic acid, glycolic acid, 2-hexadecyleicosanoic acid,
hydroxycaproic acid, 12-hydroxystearic acid, isolauric (or 2-butyloctanoic) acid,
isomyristic (or 2-hexyloctanoic) acid, isoarachidic (or 2-octyldodecanoic) acid,
isolignoceric (or 2-decyltetradecanoic) acid, lactic acid, lauric acid, malic acid,
myristic acid, oleic acid, palmitic acid, propionic acid, sebacic acid, stearic acid,
tartaric acid, terephthalic acid, trimesic acid, undecylenic acid, propylbetaine,
cocamidopropylbetaine and betaine hydrochloride of formula
[(CH3)3N+CH2CO2H Cr], and also mixtures thereof.
Preferably, caproic acid, 2-ethylcaproic acid, oleic acid, behenic acid, stearic acid,
acetic acid, citric acid, tartaric acid, betaine hydrochloride and/or gluconic acid,
and preferentially betaine hydrochloride and/or behenic acid, may be used as
neutralizer.
The polyurethanes of the invention containing tertiary amine cationic units may
advantageously be quaternized. Preferably, the quaternizing agent, when it exists,
is a hydrophobic group. Thus, the hydrophobic group is introduced via the
quaternizing agent. This quaternizing agent is a compound of the type RQ or R'Q,
in which R and R' are such that:
Q denotes a leaving group such as a halide, a sulfate, etc.
R and R' both independently represent a hydrophobic group.
The term "hydrophobic group" means a radical or polymer containing a saturated
or unsaturated, linear or branched hydrocarbon-based chain, which may contain
one or more heteroatoms such as P, O, N or S, or a radical containing a perfluoro
or silicone chain. When the hydrophobic group denotes a hydrocarbon-based
radical, it comprises at least 1 carbon atom, preferably from 4 to 25 carbon atoms
and in particular from 6 to 2 1 carbon atoms. Preferentially, the hydrocarbon-based
group is derived from a monofunctional compound.
The second types of units forming the polyurethanes of the present invention are
macromolecular units, known as units (a2), derived from nonionic polymers
bearing at their ends reactive functions containing labile hydrogen and preferably
having a glass transition temperature (Tg), measured by differential enthalpy
analysis, of less than 10°C. These polymers preferably have a weight-average
molar mass of between 400 and 30 000 and more particularly between 1000 and
10 000 g/mol. The nonionic polymers capable of forming the nonionic units (a2)
are chosen, for example, from polyethers, polyesters, polysiloxanes, copolymers
of ethylene and of butylene, polycarbonates and fluoro polymers. Polyethers are
most particularly preferred, and, among these, poly(tetramethylene oxide) and
hydrogenated or non-hydrogenated polymers of ethylene and butylene.
The diisocyanates forming the units (b) are preferably chosen from aliphatic,
alicyclic and aromatic diisocyanates. Diisocyanates that are more preferred are
chosen from methylenediphenyl diisocyanates, methylenecyclohexane
diisocyanate, isophorone diisocyanate, toluene diisocyanate, naphthalene 10-
diisocyanate, butane diisocyanate and hexyl diisocyanate. Needless to say, these
diisocyanates may be used alone or in the form of a mixture of two or more
diisocyanates.
As indicated above, the cationic polyurethanes of the present invention may
contain, in addition to the units (a1 ) , (a2) and (b), preferably present in the
polyurethanes of the present invention, a certain fraction of units (a3) derived from
nonionic monomer compounds containing at least two functions containing labile
hydrogen. These units (a3) are derived, for example, from neopentyl glycol,
hexaethylene glycol or aminoethanol.
The units (a1 ) must be present in a sufficient amount to give the polymers their
positive charge responsible for their flocculation property.
In general, the units (a1 ) represent from 1% to 90% and preferably from 5% to
60% by weight, the units (a2) from 10% to 80% and preferably from 40% to 70%
by weight, the units (a3) from 0 to 50% by weight and preferably from 0 to 30% by
weight, and the units (a4) from 0 to 10% and preferably from 0 to 5% by weight of
the total polymer.
The units (b) are present in an essentially stoichiometric amount relative to the
sum of the units (a1 ) , (a2), (a3) and optionally (a4). Specifically, the production of
polyurethanes with high molar masses assumes a number of isocyanate functions
that is virtually identical to the number of functions containing a labile hydrogen. A
person skilled in the art will select an optional molar excess of one or other type of
function to adjust the molar mass to the desired value.
The polyurethanes in accordance with the invention may be prepared according to
the standard polyaddition techniques used for the manufacture of polyurethanes.
The polymers according to the invention are preferably conveyed in aqueous
medium, i.e. they are water-soluble or water-dispersible. Preferably, the polymers
are water-dispersible. The dissolution or dispersion in water may be performed by
direct dissolution of the polymer if it is soluble, or by neutralization of the amine
units so as to make the polymer soluble or dispersible in water. The aqueous
dissolution or dispersion may also be performed via an intermediate dissolution
step in an organic solvent followed by addition of water before evaporation of the
organic solvent.
The flocculant polymers used as antiperspirant active agents are preferably
present in the compositions according to the invention in amounts ranging from
0.1 % to 50% by weight and more preferentially from 1% to 20% by weight relative
to the total weight of the composition.
GALENICAL FORMS
The composition according to the invention may be in any galenical form
conventionally used for topical application and especially in the form of aqueous
gels, or aqueous or aqueous-alcoholic solutions. By adding a fatty or oily phase, it
may also be in the form of dispersions of lotion type, emulsions of liquid or semiliquid
consistency of milk type, obtained by dispersing a fatty phase in an aqueous
phase (O/W) or conversely (W/O), or suspensions or emulsions of soft, semi-solid
or solid consistency of the cream or gel type, or alternatively multiple emulsions
(W/O/W or O/W/O), microemulsions, vesicular dispersions of ionic and/or nonionic
type, or wax/aqueous phase dispersions. These compositions are prepared
according to the usual methods.
The compositions may especially be conditioned in pressurized form in an aerosol
device or in a pump-action bottle; conditioned in a device equipped with a
perforated wall, especially a grille; conditioned in a device equipped with a ball
applicator ("roll-on"); conditioned in the form of wands (sticks) or in the form of
loose or compacted powder. In this regard, they contain the ingredients generally
used in products of this type, which are well known to those skilled in the art.
According to one particular form of the invention, the compositions according to
the invention may be anhydrous.
The term "anhydrous composition" means a composition containing less than 2%
by weight of water, or even less than 0.5% water, and especially free of water, the
water not being added during the preparation of the composition but
corresponding to the residual water provided by the mixed ingredients.
According to another particular form of the invention, the compositions according
to the invention may be solid, in particular in wand or stick form.
The term "solid composition" means that the maximum force measured by
texturometry during the penetration of a probe into the sample of formula must be
at least equal to 0.25 newtons, in particular at least equal to 0.30 newtons and
especially at least equal to 0.35 newtons, assessed under precise measuring
conditions as follows.
The formulae are poured hot into jars 4 cm in diameter and 3 cm deep. Cooling is
performed at room temperature. The hardness of the formulae is measured after
an interval of 24 hours. The jars containing the samples are characterized in
texturometry using a texturometer such as the machine sold by the company Rheo
TA-XT2, according to the following protocol: a stainless-steel ball probe 5 mm in
diameter is brought into contact with the sample at a speed of 1 mm/s. The
measuring system detects the interface with the sample, with a detection threshold
equal to 0.005 newtons. The probe penetrates 0.3 mm into the sample, at a speed
of 0.1 mm/s. The measuring machine records the change in force measured in
compression over time, during the penetration phase. The hardness of the sample
corresponds to the average of the maximum force values detected during
penetration, over at least three measurements.
AQUEOUS PHASE
The compositions according to the invention intended for cosmetic use may
comprise at least one aqueous phase. They are especially formulated as aqueous
lotions or as water-in-oil or oil-in-water emulsions or as multiple emulsions (oil-inwater-
in-oil or water-in-oil-in-water triple emulsion (such emulsions are known and
described, for example, by C. Fox in "Cosmetics and Toiletries" - November 1986 -
Vol. 10 1 - pages 101 - 1 12)).
The aqueous phase of the said compositions contains water and generally other
water-soluble or water-miscible solvents. The water-soluble or water-miscible
solvents comprise monoalcohols with a short chain, for example of Ci-C4, such as
ethanol or isopropanol; diols or polyols, for instance ethylene glycol, 1,2-propylene
glycol, 1,3-butylene glycol, hexylene glycol, diethylene glycol, dipropylene glycol,
2-ethoxyethanol, diethylene glycol monomethyl ether, triethylene glycol
monomethyl ether and sorbitol. Propylene glycol and glycerol, propane-1 ,3-diol,
will be used more particularly.
EMULSIFIERS
a) Oil-in-water emulsifiers
As emulsifiers that may be used in the oil-in-water emulsions or oil-in-water-in-oil
triple emulsions, examples that may be mentioned include nonionic emulsifiers
such as oxyalkylenated (more particularly polyoxyethylenated) fatty acid esters of
glycerol; oxyalkylenated fatty acid esters of sorbitan; oxyalkylenated
(oxyethylenated and/or oxypropylenated) fatty acid esters; oxyalkylenated
(oxyethylenated and/or oxypropylenated) fatty alcohol ethers; sugar esters such as
sucrose stearate; and mixtures thereof, such as the mixture of glyceryl stearate
and PEG-40 stearate.
Mention may also be made of fatty alcohol/alkylpolyglycoside emulsifying mixtures
as described in patent applications WO 92/06778, WO 95/1 3863 and WO
98/47610, for instance the commercial products sold by the company SEPPIC
under the name Montanov®.
b) Water-in-oil emulsifiers
Among the emulsifiers that may be used in the water-in-oil emulsions or water-inoil-
in-water-in-oil triple emulsions, examples that may be mentioned include alkyl
dimethicone copolyols corresponding to formula (I) below
H3 CH
I
CH
CH3 - S i -Si 0 | Si - C+ Si CH, (I)
CH,
R
in which:
R i denotes a linear or branched C12-C20 and preferably C12-C18 alkyl group;
R 2 denotes the group: ~CnH2n~(-OC2H 4-)x~(-OC 3 H6-)y ~O— R 3 ,
R 3 denotes a hydrogen atom or a linear or branched alkyl radical comprising from
1 to 12 carbon atoms;
a is an integer ranging from 1 to 500;
b is an integer ranging from 1 to 500;
n is an integer ranging from 2 to 12 and preferably from 2 to 5;
x is an integer ranging from 1 to about 50 and preferably from 1 to 30;
y is an integer ranging from 0 to about 49 and preferably from 0 to 29, with the
proviso that when y is other than zero, the ratio x/y is greater than 1 and preferably
ranges from 2 to 11.
Among the alkyl dimethicone copolyol emulsifiers of formula (I) that are preferred,
mention will be made more particularly of Cetyl PEG/PPG-1 0/1 Dimethicone and
more particularly the mixture Cetyl PEG/PPG-1 0/1 Dimethicone and Dimethicone
(INCI name), for instance the product sold under the trade name Abil EM90 by the
company Goldschmidt, or alternatively the mixture (Polyglyceryl-4 Stearate and
Cetyl PEG/PPG-1 0 (and) Dimethicone (and) Hexyl Laurate), for instance the
product sold under the trade name Abil WE09 by the same company.
Among the water-in-oil emulsifiers, mention may also be made of the dimethicone
copolyols corresponding to formula (II) below
H3 - ( )
in which:
R4 denotes the group: ~CmH2m~(-OC2H4-)s~(-OC 3 H6-)t ~O— R5,
R5 denotes a hydrogen atom or a linear or branched alkyl radical comprising from
1 to 12 carbon atoms,
c is an integer ranging from 1 to about 500;
d is an integer ranging from 1 to about 500;
m is an integer ranging from 2 to 12 and preferably from 2 to 5;
s is an integer ranging from 1 to about 50 and preferably from 1 to 30;
t is an integer ranging from 0 to about 50 and preferably from 0 to 30; with the
proviso that the sum s+t is greater than or equal to 1.
Among these preferential dimethicone copolyol emulsifiers of formula (II), use will
particularly be made of PEG-1 8/PPG-1 8 Dimethicone and more particularly the
mixture Cyclopentasiloxane (and) PEG-18/PPG-1 8 Dimethicone (INCI name),
such as the product sold by the company Dow Corning under the trade name
Silicone DC5225 C or KF-6040 from the company Shin-Etsu.
According to one particularly preferred form, use will be made of a mixture of at
least one emulsifier of formula (I) and of at least one emulsifier of formula (II).
Use will be made more particularly of a mixture of PEG-1 8/PPG-1 8 Dimethicone
and Cetyl PEG/PPG-1 0/1 Dimethicone and even more particularly a mixture of
(Cyclopentasiloxane (and) PEG-1 8/PPG-1 8 Dimethicone) and of Cetyl PEG/PPG-
10/1 Dimethicone and Dimethicone or of (Polyglyceryl-4-stearate and Cetyl
PEG/PPG-1 0 (and) Dimethicone (and) Hexyl Laurate).
Among the water-in-oil emulsifiers, mention may also be made of nonionic
emulsifiers derived from fatty acids and polyol, alkylpolyglycosides (APG) and
sugar esters, and mixtures thereof.
As nonionic emulsifiers derived from fatty acids and polyol, use may be made
especially of fatty acid esters of polyol, the fatty acid especially containing a C8-
C24 alkyl chain, and the polyols being, for example, glycerol and sorbitan.
Fatty acid esters of polyol that may especially be mentioned include isostearic acid
esters of polyols, stearic acid esters of polyols, and mixtures thereof, in particular
isostearic acid esters of glycerol and/or sorbitan.
Stearic acid esters of polyols that may especially be mentioned include the
polyethylene glycol esters, for instance PEG-30 Dipolyhydroxystearate, such as
the product sold under the name Arlacel P 135 by the company ICI.
Glycerol and/or sorbitan esters that may be mentioned, for example, include
polyglyceryl isostearate, such as the product sold under the name Isolan Gl 34 by
the company Goldschmidt; sorbitan isostearate, such as the product sold under
the name Arlacel 987 by the company ICI; sorbitan glyceryl isostearate, such as
the product sold under the name Arlacel 986 by the company ICI, the mixture of
sorbitan isostearate and polyglyceryl isostearate (3 mmol) sold under the name
Arlacel 1690 by the company Uniqema, and mixtures thereof.
The emulsifier may also be chosen from alkylpolyglycosides with an HLB of less
than 7, for example those represented by the general formula ( 1 ) below:
R-O-(G)x ( 1 )
in which R represents a branched and/or unsaturated alkyl radical comprising from
14 to 24 carbon atoms, G represents a reduced sugar comprising 5 or 6 carbon
atoms, and x is a value ranging from 1 to 10 and preferably from 1 to 4, and G
especially denotes glucose, fructose or galactose.
The unsaturated alkyl radical may comprise one or more ethylenic unsaturations,
and in particular one or two ethylenic unsaturations.
As alkylpolyglycosides of this type, mention may be made of alkylpolyglucosides
(G = glucose in formula (I)), and especially the compounds of formula (I) in which
R more particularly represents an oleyl radical (unsaturated Cis radical) or
isostearyl (saturated Cis radical), G denotes glucose, x is a value ranging from 1 to
2, especially isostearyl glucoside or oleyl glucoside, and mixtures thereof. This
alkylpolyglucoside may be used as a mixture with a coemulsifier, more especially
with a fatty alcohol and especially a fatty alcohol containing the same fatty chain
as that of the alkylpolyglucoside, i.e. comprising from 14 to 24 carbon atoms and
containing a branched and/or unsaturated chain, for example isostearyl alcohol
when the alkylpolyglucoside is isostearyl glucoside, and oleyl alcohol when the
alkylpolyglucoside is oleyl glucoside, optionally in the form of a self-emulsifying
composition, as described, for example, in document WO-A-92/06778. Use may
be made, for example, of the mixture of isostearyl glucoside and isostearyl alcohol,
sold under the name Montanov WO 18 by the company SEPPIC, and also the
mixture octyldodecanol and octyldodecyl xyloside sold under the name Fludanov
20X by the company SEPPIC.
Mention may also be made of succinic-terminated polyolefins, for instance
esterified succinic-terminated polyisobutylenes and salts thereof, especially the
diethanolamine salts, such as the commercial products sold under the names
Lubrizol 2724, Lubrizol 2722 and Lubrizol 5603 by the company Lubrizol or the
commercial product Chemcinnate 2000.
The total amount of emulsifiers in the composition will preferably be, in the
composition according to the invention, in active material contents ranging from
1% to 8% by weight and more particularly from 2% to 6% by weight relative to the
total weight of the composition.
FATTY PHASE
The compositions according to the invention may contain at least one waterimmiscible
organic liquid phase, known as a fatty phase. This phase generally
comprises one or more hydrophobic compounds that make the said phase waterimmiscible.
The said phase is liquid (in the absence of structuring agent) at room
temperature (20-25°C). Preferentially, the water-immiscible organic-liquid organic
phase in accordance with the invention generally comprises at least one volatile oil
and/or non-volatile oil and optionally at least one structuring agent.
The term "oil" means a fatty substance that is liquid at room temperature (25°C)
and atmospheric pressure (760 mmHg, i.e. 105 Pa). The oil may be volatile or
non-volatile.
For the purposes of the invention, the term "volatile oil" means an oil that is
capable of evaporating on contact with the skin or the keratin fibre in less than one
hour, at room temperature and atmospheric pressure. The volatile oils of the
invention are volatile cosmetic oils, which are liquid at room temperature, having a
non-zero vapour pressure, at room temperature and atmospheric pressure,
ranging in particular from 0.1 3 Pa to 40 000 Pa ( 10 3 to 300 mmHg), in particular
ranging from 1.3 Pa to 13 000 Pa (0.01 to 100 mmHg) and more particularly
ranging from 1.3 Pa to 1300 Pa (0.01 to 10 mmHg).
The term "non-volatile oil" means an oil that remains on the skin or the keratin fibre
at room temperature and atmospheric pressure for at least several hours, and that
especially has a vapour pressure of less than 10 3 mmHg (0.13 Pa).
The oil may be chosen from any physiologically acceptable oil and in particular
cosmetically acceptable oil, especially mineral, animal, plant or synthetic oils; in
particular volatile or nonvolatile hydrocarbon-based oils and/or silicone oils and/or
fluoro oils, and mixtures thereof.
More precisely, the term "hydrocarbon-based oil" means an oil mainly comprising
carbon and hydrogen atoms and optionally one or more functions chosen from
hydroxyl, ester, ether and carboxylic functions. Generally, the oil has a viscosity of
from 0.5 to 100 000 mPa.s, preferably from 50 to 50 000 mPa.s and more
preferably from 100 to 300 000 mPa.s.
As examples of volatile oils that may be used in the invention, mention may be
made of:
- volatile hydrocarbon-based oils chosen from hydrocarbon-based oils containing
from 8 to 16 carbon atoms, and especially Cs-Ci6 isoalkanes of petroleum origin
(also known as isoparaffins), for instance isododecane (also known as 2,2,4,4,6-
pentamethylheptane), isodecane and isohexadecane, for example the oils sold
under the trade names Isopar or Permethyl, branched Cs-Ci6 esters and isohexyl
neopentanoate, and mixtures thereof. Other volatile hydrocarbon-based oils, for
instance petroleum distillates, especially those sold under the name Shell Solt by
the company Shell, may also be used; volatile linear alkanes, such as those
described in patent application DE1 0 2008 0 12 457 from the company Cognis.
- volatile silicones, for instance volatile linear or cyclic silicone oils, especially
those with a viscosity < 8 centistokes (8x1 0 6 m2/s) and especially containing from
2 to 7 silicon atoms, these silicones optionally comprising alkyl or alkoxy groups
containing from 1 to 10 carbon atoms. As volatile silicone oils that may be used in
the invention, mention may be made especially of octamethylcyclotetrasiloxane,
decamethylcyclopentasiloxane, dodecamethylcyclohexasiloxane,
heptamethylhexyltrisiloxane, heptamethyloctyltrisiloxane, hexamethyldisiloxane,
octamethyltrisiloxane, decamethyltetrasiloxane and dodecamethylpentasiloxane;
- and mixtures thereof.
Mention may also be made of linear volatile alkyltrisiloxane oils of general formula
(I):
in which R represents an alkyl group containing from 2 to 4 carbon atoms, of which
one or more hydrogen atoms may be substituted with a fluorine or chlorine atom.
Among the oils of general formula (I) that may be mentioned are:
3-butyl-1 , 1 , 1 ,3,5,5,5-heptamethyltrisiloxane,
3-propyl-1 , 1 , 1 ,3,5,5,5-heptamethyltrisiloxane, and
3-ethyl-1 , 1 , 1 ,3,5,5,5-heptamethyltrisiloxane,
corresponding to the oils of formula (I) for which R is, respectively, a butyl group, a
propyl group or an ethyl group.
As examples of nonvolatile oils that may be used in the invention, mention may be
made of:
- hydrocarbon-based oils of animal origin, such as perhydrosqualene;
- hydrocarbon-based plant oils such as liquid triglycerides of fatty acids of 4 to 24
carbon atoms, for instance heptanoic or octanoic acid triglycerides, or wheatgerm
oil, olive oil, sweet almond oil, palm oil, rapeseed oil, cottonseed oil, alfalfa oil,
poppy oil, pumpkin oil, marrow oil, blackcurrant oil, evening primrose oil, millet oil,
barley oil, quinoa oil, rye oil, safflower oil, candlenut oil, passion flower oil, musk
rose oil, sunflower oil, corn oil, soybean oil, grapeseed oil, sesame seed oil,
hazelnut oil, apricot oil, macadamia oil, castor oil, avocado oil, caprylic/capric acid
triglycerides, for instance those sold by the company Stearineries Dubois or those
sold under the names Miglyol 8 10, 8 12 and 8 18 by the company Sasol, jojoba oil
and shea butter oil,
- linear or branched hydrocarbons, of mineral or synthetic origin, such as liquid
paraffins and derivatives thereof, petroleum jelly, polydecenes, polybutenes,
hydrogenated polyisobutene such as Parleam, and squalane,
- synthetic ethers containing from 10 to 40 carbon atoms;
- synthetic esters, especially of fatty acids, for instance the oils of formula
R1COOR2 in which R represents a linear or branched higher fatty acid residue
containing from 1 to 40 carbon atoms and R2 represents a hydrocarbon-based
chain, which is especially branched, containing from 1 to 40 carbon atoms, with R
+ R2 > 10, for instance purcellin oil (cetostearyl octanoate), isononyl isononanoate,
isopropyl myristate, isopropyl palmitate, C12-C15 alkyl benzoates, hexyl laurate,
diisopropyl adipate, isononyl isononanoate, 2-ethylhexyl palmitate, 2-octyldodecyl
stearate, 2-octyldodecyl erucate, isostearyl isostearate or tridecyl trimellitate;
alcohol or polyalcohol octanoates, decanoates or ricinoleates, for instance
propylene glycol dioctanoate; hydroxylated esters, for instance isostearyl lactate,
octyl hydroxystearate, octyldodecyl hydroxystearate, diisostearyl malate, triisocetyl
citrate, and fatty alcohol heptanoates, octanoates or decanoates; polyol esters, for
instance propylene glycol dioctanoate, neopentyl glycol diheptanoate or diethylene
glycol diisononanoate; and pentaerythritol esters, for instance pentaerythrityl
tetraisostearate,
- fatty alcohols that are liquid at room temperature, containing a branched and/or
unsaturated carbon-based chain containing from 12 to 26 carbon atoms, for
instance octyldodecanol, isostearyl alcohol, 2-butyloctanol, 2-hexyldecanol, 2-
undecylpentadecanol o oleyl alcohol,
- higher fatty acids such as oleic acid, linoleic acid or linolenic acid;
- carbonates;
- acetates;
- citrates;
- fluoro oils that are optionally partially hydrocarbon-based and/or silicone-based,
for instance fluorosilicone oils, fluoro polyethers and fluorosilicones as described in
document EP-A-847 752;
- silicone oils, for instance linear or cyclic non-volatile polydimethylsiloxanes
(PDMS); polydimethylsiloxanes comprising alkyl, alkoxy or phenyl groups, which
are pendant or at the end of a silicone chain, these groups containing from 2 to 24
carbon atoms; phenyl silicones, for instance phenyl trimethicones, phenyl
dimethicones, phenyl trimethylsiloxy diphenyl siloxanes, diphenyl dimethicones,
diphenyl methyldiphenyl trisiloxanes and 2-phenylethyl trimethylsiloxy silicates,
and
mixtures thereof.
STRUCTURING AGENT
The compositions according to the invention comprising a fatty phase may also
contain at least one agent for structuring the said fatty phase, which may
preferably be chosen from waxes, pasty compounds, and mineral or organic
lipophilic gelling agents, and mixtures thereof.
It is understood that the amount of these compounds may be adjusted by a person
skilled in the art so as not to harm the desired effect in the context of the present
invention.
Wax(es)
The wax is in general a lipophilic compound that is solid at room temperature
(25°C), with a solid/liquid reversible change of state, having a melting point of
greater than or equal to 30°C, which may be up to 200°C and in particular up to
120°C.
In particular, the waxes that are suitable for the invention may have a melting point
of greater than or equal to 45°C and in particular greater than or equal to 55°C.
For the purposes of the invention, the melting point corresponds to the
temperature of the most endothermic peak observed on thermal analysis (DSC) as
described in standard ISO 11357-3; 1999. The melting point of the wax may be
measured using a differential scanning calorimeter (DSC), for example the
calorimeter sold under the name MDSC 2920 by the company TA Instruments.
The measuring protocol is as follows:
A sample of 5 mg of wax placed in a crucible is subjected to a first temperature
rise ranging from -20°C to 100°C, at a heating rate of 10°C/minute, it is then
cooled from 100°C to -20°C at a cooling rate of 10°C/minute and is finally
subjected to a second temperature increase ranging from -20°C to 100°C at a
heating rate of 5°C/minute. During the second temperature increase, the variation
of the difference in power absorbed by the empty crucible and by the crucible
containing the sample of wax is measured as a function of the temperature. The
melting point of the compound is the temperature value corresponding to the top of
the peak of the curve representing the variation in the difference in power
absorbed as a function of the temperature.
The waxes that may be used in the compositions according to the invention are
chosen from waxes that are solid at room temperature of animal, plant, mineral or
synthetic origin, and mixtures thereof.
As illustrations of waxes that are suitable for the invention, mention may be made
especially of hydrocarbon-based waxes, for instance beeswax, lanolin wax,
Chinese insect waxes, rice bran wax, carnauba wax, candelilla wax, ouricury wax,
esparto grass wax, berry wax, shellac wax, Japan wax and sumach wax; montan
wax, orange wax and lemon wax, refined sunflower wax sold under the name
Sunflower Wax by Koster Keunen, microcrystalline waxes, paraffins and ozokerite;
polyethylene waxes, the waxes obtained by Fischer-Tropsch synthesis and waxy
copolymers, and also esters thereof.
Mention may also be made of waxes obtained by catalytic hydrogenation of animal
or plant oils containing linear or branched C8-C32 fatty chains. Among these waxes
that may especially be mentioned are isomerized jojoba oil such as the transisomerized
partially hydrogenated jojoba oil manufactured or sold by the company
Desert Whale under the commercial reference lso-Jojoba-50®, hydrogenated
sunflower oil, hydrogenated castor oil, hydrogenated coconut oil, hydrogenated
lanolin oil and bis(1 , 1 ,1-trimethylolpropane) tetrastearate sold under the name
Hest 2T-4S® by the company Heterene.
Mention may also be made of silicone waxes (C3o-4 5 alkyl dimethicone) and fluoro
waxes.
The waxes obtained by hydrogenation of castor oil esterified with cetyl alcohol,
sold under the names Phytowax ricin 16L64® and 22L73® by the company
Sophim, may also be used. Such waxes are described in patent application FR-A-
2 792 190.
A wax that may be used is a C2o-C4o alkyl (hydroxystearyloxy)stearate (the alkyl
group containing from 20 to 40 carbon atoms), alone or as a mixture.
Such a wax is especially sold under the names Kester Wax K 82 P®,
Hydroxypolyester K 82 P® and Kester Wax K 80 P® by the company Koster
Keunen.
As microwaxes that may be used in the compositions according to the invention,
mention may be made especially of carnauba microwaxes, such as the product
sold under the name MicroCare 350® by the company Micro Powders, synthetic
microwaxes, such as the product sold under the name MicroEase 114S® by the
company Micro Powders, microwaxes consisting of a mixture of carnauba wax and
polyethylene wax, such as the products sold under the names Micro Care 300®
and 3 10® by the company Micro Powders, microwaxes consisting of a mixture of
carnauba wax and of synthetic wax, such as the product sold under the name
Micro Care 325® by the company Micro Powders, polyethylene microwaxes, such
as the products sold under the names Micropoly 200®, 220®, 220L® and 250S®
by the company Micro Powders, the commercial products Performalene 400,
Polyethylene and Performalene 500-L Polyethylene from New Phase
Technologies, Performalene 655, Polyethylene or paraffin waxes, for instance the
wax having the INCI name Microcrystalline Wax and Synthetic Wax and sold
under the trade name Microlease by the company Sochibo; polytetrafluoroethylene
microwaxes such as those sold under the names Microslip 5 19® and 519 L® by
the company Micro Powders.
The composition according to the invention may preferably comprise a content of
wax(es) ranging from 3% to 20% by weight relative to the total weight of the
composition, in particular from 5% to 15% and more particularly from 6% to 15%
thereof.
According to one particular form of the invention, in the context of anhydrous solid
compositions in stick form, use will be made of polyethylene microwaxes in the
form of crystallites with an aspect ratio at least equal to 2, and with a melting point
ranging from 70 to 110°C and preferably from 70 to 100°C, so as to reduce or
even eliminate the presence of strata in the solid composition.
These crystallites in needle form and especially the dimensions thereof may be
characterized visually according to the following method.
The wax is deposited on a microscope slide, which is placed on a hotplate. The
slide and the wax are heated to a temperature generally at least 5°C higher than
the melting point of the wax or of the mixture of waxes under consideration. At the
end of melting, the liquid thus obtained and the microscope slide are allowed to
cool to solidify. Observation of the crystallites is performed using a Leica
DMLB1 00 optical microscope, with an objective lens selected as a function of the
size of the objects to be viewed, and under polarized light. The dimensions of the
crystallites are measured using image analysis software such as that sold by the
company Microvision.
The crystallite polyethylene waxes in accordance with the invention preferably
have an average length ranging from 5 to 10 miti . The term "average length"
denotes the dimension given by statistical granulometric distribution of half the
population, which is written as D50.
Use will be made more particularly of a mixture of the waxes Performalene 400
Polyethylene and Performalene 500-L Polyethylene from New Phase
Technologies.
Pasty compounds
For the purposes of the present invention, the term "pasty compound" is intended
to denote a lipophilic fatty compound that undergoes a reversible solid/liquid
change of state, which has in solid form an anisotropic crystal organization, and
that comprises, at a temperature of 23°C, a liquid fraction and a solid fraction.
The pasty compound is preferably chosen from synthetic compounds and
compounds of plant origin. A pasty compound may be obtained by the synthesis
from starting materials of plant origin.
The pasty compound may be advantageously chosen from:
- lanolin and derivatives thereof,
- polymeric or non-polymeric silicone compounds,
- polymeric or non-polymeric fluoro compounds,
- vinyl polymers, especially:
- olefin homopolymers,
- olefin copolymers,
- hydrogenated diene homopolymers and copolymers,
- linear or branched oligomers, homopolymers or copolymers of alkyl
(meth)acrylates preferably containing a C8-C30 alkyl group,
- oligomers, homopolymers and copolymers of vinyl esters containing C8-C30 alkyl
groups,
- oligomers, homopolymers and copolymers of vinyl ethers containing C8-C30 alkyl
groups,
- liposoluble polyethers resulting from the polyetherification between one or more
C2-C100 and preferably C2-C5odiols,
- esters,
- mixtures thereof.
Among the esters, the following are especially preferred:
- esters of a glycerol oligomer, especially diglycerol esters, in particular
condensates of adipic acid and of glycerol, for which some of the hydroxyl groups
of the glycerols have reacted with a mixture of fatty acids such as stearic acid,
capric acid, stearic acid and isostearic acid, and 12-hydroxystearic acid, especially
such as those sold under the brand name Softisan 649 by the company Sasol,
- the arachidyl propionate sold under the brand name Waxenol 801 by Alzo,
- phytosterol esters,
- fatty acid triglycerides and derivatives thereof,
- pentaerythritol esters,
- non-crosslinked polyesters resulting from polycondensation between a linear or
branched C4-C5o dicarboxylic acid or polycarboxylic acid and a C2-C50 diol or
polyol,
- aliphatic esters of an ester, resulting from the esterification of an aliphatic
hydroxycarboxylic acid ester with an aliphatic carboxylic acid,
- polyesters resulting from the esterification, with a polycarboxylic acid, of an
aliphatic hydroxycarboxylic acid ester, the said ester comprising at least two
hydroxyl groups, such as the products Risocast DA-H® and Risocast DA-L®,
- esters of a diol dimer and of a diacid dimer, where appropriate esterified on their
free alcohol or acid function(s) with acid or alcohol radicals, such as Plandool-G,
- mixtures thereof.
Among the pasty compounds of plant origin that will preferably be chosen is a
mixture of oxyethylenated (5 OE) oxypropylenated (5 OP) soybean sterols and
pentaerythritol, sold under the reference Lanolide by the company Vevy.
Lipophilic gelling agents
Mineral gelling agents
Mineral lipophilic gelling agents that may be mentioned include optionally modified
clays, for instance hectorites modified with a C10-C22 ammonium chloride, for
instance hectorite modified with distearyldimethylammonium chloride, for instance
the product sold under the name Bentone 38V® by the company Elementis.
Mention may also be made of fumed silica optionally subjected to a hydrophobic
surface treatment, the particle size of which is less than 1 miti . Specifically, it is
possible to chemically modify the surface of the silica, by chemical reaction
generating a reduced number of silanol groups present at the surface of the silica.
It is especially possible to substitute silanol groups with hydrophobic groups: a
hydrophobic silica is then obtained. The hydrophobic groups may be
trimethylsiloxyl groups, which are obtained especially by treating fumed silica in
the presence of hexamethyldisilazane. Silicas thus treated are known as "silica
silylate" according to the CTFA (8th Edition, 2000). They are sold, for example,
under the references Aerosil R81 2® by the company Degussa, Cab-O-Sil TS-
530® by the company Cabot, dimethylsilyloxyl or polydimethylsiloxane groups,
which are obtained especially by treating fumed silica in the presence of
polydimethylsiloxane or dimethyldichlorosilane. Silicas thus treated are known as
"silica dimethyl silylate" according to the CTFA (8th Edition, 2000). They are sold,
for example, under the references Aerosil R972® and Aerosil R974® by the
company Degussa, and Cab-O-Sil TS-61 0® and Cab-O-Sil TS-720® by the
company Cabot.
The hydrophobic fumed silica preferably has a particle size that may be
nanometric to micrometric, for example ranging from about 5 to 200 nm.
Organic gelling agents
The polymeric organic lipophilic gelling agents are, for example, partially or totally
crosslinked elastomeric organopolysiloxanes of three-dimensional structure, for
instance those sold under the names KSG6®, KSG1 6® and KSG1 8® from Shin-
Etsu, Trefil E-505C® or Trefil E-506C® from Dow Corning, Gransil SR-CYC®, SR
DMF1 0®, SR-DC556®, SR 5CYC gel®, SR DMF 10 gel® and SR DC 556 gel®
from Grant Industries and SF 1204® and JK 113® from General Electric;
ethylcellulose, for instance the product sold under the name Ethocel® by Dow
Chemical; galactomannans comprising from one to six and in particular from two
to four hydroxyl groups per saccharide, substituted with a saturated or unsaturated
alkyl chain, for instance guar gum alkylated with C 1 to C6, and in particular C 1 to
C3, alkyl chains, and mixtures thereof. Block copolymers of "diblock", "triblock" or
"radial" type, of the polystyrene/polyisoprene or polystyrene/polybutadiene type,
such as the products sold under the name Luvitol HSB® by the company BASF, of
the polystyrene/copoly(ethylene-propylene) type, such as the products sold under
the name Kraton® by the company Shell Chemical Co., or of the
polystyrene/copoly(ethylene-butylene) type, and mixtures of triblock and radial
(star) copolymers in isododecane, such as those sold by the company Penreco
under the name Versagel®, for instance the mixture of butylene/ethylene/styrene
triblock copolymer and of ethylene/propylene/styrene star copolymer in
isododecane (Versagel M 5960).
Lipophilic gelling agents that may also be mentioned include polymers with a
weight-average molecular mass of less than 100 000, comprising a) a polymer
backbone with hydrocarbon-based repeating units containing at least one
heteroatom, and optionally b) at least one optionally functional ized pendent fatty
chain and/or terminal fatty chain, containing from 6 to 120 carbon atoms and being
linked to these hydrocarbon-based units, as described in patent applications WOA-
02/056 847 and WO-A-02/47619, in particular polyamide resins (especially
comprising alkyl groups containing from 12 to 22 carbon atoms) such as those
described in US-A-5 783 657.
Among the lipophilic gelling agents that may be used in the compositions
according to the invention, mention may also be made of fatty acid esters of
dextrin, such as dextrin palmitates, especially the products sold under the name
Rheopearl TL® or Rheopearl KL® by the company Chiba Flour.
Silicone polyamides of the polyorganosiloxane type may also be used, such as
those described in documents US-A-5 874 069, US-A-5 9 19 441 , US-A-6 051 2 16
and US-A-5 981 680.
These silicone polymers may belong to the following two families:
- polyorganosiloxanes comprising at least two groups capable of establishing
hydrogen interactions, these two groups being in the chain of the polymer, and/or
- polyorganosiloxanes comprising at least two groups capable of establishing
hydrogen interactions, these two groups being located on grafts or branches.
MOISTURE ABSORBERS
It is also possible to add moisture absorbers, for instance perlites and preferably
expanded perlites.
The perlites that may be used according to the invention are generally
aluminosilicates of volcanic origin and have as the composition:
70.0-75.0% by weight of silica SiO2
12.0-1 5.0% by weight of oxide of aluminium oxide AI2O3
3.0-5.0% of sodium oxide Na2O
3.0-5.0% of potassium oxide K2O
0.5-2% of iron oxide Fe2O3 -
0.2-0.7% of magnesium oxide MgO
0.5-1 .5% of calcium oxide CaO
0.05-0.15% of titanium oxide TiO2
The perlite is ground, dried and then calibrated in a first step. The product
obtained, known as perlite ore, is grey-coloured and has a size of about 100 miti .
The perlite ore is then expanded ( 1000°C/2 seconds) to give more or less white
particles. When the temperature reaches 850-900°C, the water trapped in the
structure of the material evaporates and brings about the expansion of the material
relative to its original volume. The expanded perlite particles in accordance with
the invention may be obtained via the expansion process described in patent US 5
002 698.
Preferably, the perlite particles used are ground: in this case, they are known as
Expanded Milled Perlite (EMP). They preferably have a particle size defined by a
median diameter D50 ranging from 0.5 to 50 miti and preferably from 0.5 to 40 miti .
Preferably, the perlite particles used have an untamped apparent density at 25°C
ranging from 10 to 400 kg/m3 (standard DIN 53468) and preferably from 10 to 300
kg/m3.
Preferably, the expanded perlite particles according to the invention have a waterabsorbing
capacity, measured at the wet point, ranging from 200% to 1500% and
preferably from 250% to 800%.
The wet point corresponds to the amount of water that needs to be added to 1 g of
particle in order to obtain a homogeneous paste. This method is derived directly
from that of the oil uptake applied to solvents. The measurements are taken in the
same manner by means of the wet point and the flow point, which have,
respectively, the following definition:
wet point: mass expressed in grams per 100 g of product corresponding to the
production of a homogeneous paste during the addition of a solvent to a powder;
flow point: mass expressed in grams per 100 g of product at and above which the
amount of solvent is greater than the capacity of the powder to retain it. This is
reflected by the production of a more or less homogeneous mixture that flows on a
glass plate.
The wet point and the flow point are measured according to the following protocol:
Protocol for measuring the water absorption
1) Materials used
Glass plate (25 x 25 mm)
Spatula (wooden and partly metallic handle, 15 x 2.7 mm)
Silk-bristled brush
Balance
2) Procedure
The glass plate is placed on the balance and 1 g of perlite particles is weighed out.
The beaker containing the solvent and the sampling pipette is placed on the
balance. The solvent is gradually added to the powder, the whole being regularly
blended (every 3 to 4 drops) with the spatula.
The mass of solvent needed to obtain the wet point is noted. Further solvent is
added and the mass required to reach the flow point is noted. The average of
three tests is determined.
The expanded perlite particles sold under the trade names Optimat 1430 OR or
Optimat 2550 by the company World Minerals will be used in particular.
DEODORANTS
The deodorant active agents may be bacteriostatic agents or bactericides that act
on underarm odour microorganisms, such as 2,4,4'-trichloro-2'-hydroxydiphenyl
ether (©Triclosan), 2,4-dichloro-2'-hydroxydiphenyl ether, 3',4',5'-
trichlorosalicylanilide, 1-(3',4'-dichlorophenyl)-3-(4'-chlorophenyl)urea
(©Triclocarban) or 3,7,1 1-trimethyldodeca-2, 5,1 0-trienol (©Farnesol); quaternary
ammonium salts such as cetyltrimethylammonium salts, cetylpyridinium salts,
DPTA ( 1 ,3-diaminopropanetetraacetic acid), 1,2-decanediol (Symclariol from the
company Symrise), glycerol derivatives, for instance caprylic/capric glycerides
(Capmul MCM from Abitec), glyceryl caprylate or caprate (Dermosoft GMCY and
Dermosoft GMC, respectively from Straetmans), Polyglyceryl-2 caprate
(Dermosoft DGMC from Straetmans), and biguanide derivatives, for instance
polyhexamethylene biguanide salts. - chlorhexidine and salts thereof; 4-phenyl-
4,4-dimethyl-2-butanol (Symdeo MPP from Symrise).
Among the deodorant active agents in accordance with the invention, mention may
also be made of - zinc salts, for instance zinc salicylate, zinc gluconate, zinc
pidolate; zinc sulfate, zinc chloride, zinc lactate, zinc phenolsulfonate; salicylic acid
and derivatives thereof such as 5-n-octanoylsalicylic acid.
The deodorant active agents may be odour absorbers such as zinc ricinoleate,
sodium bicarbonate; metallic or non-metallic zeolites, cyclodextrins or alum.
It may also be a chelating agent such as Dissolvine GL-47-S from Akzo Nobel,
EDTA; DPTA.
It may also be a polyol such as glycerol or propane-1 ,3-diol (Zemea Propane diol
sold by Dupont Tate and Lyle Bioproducts).
Alternatively, it may be an enzyme inhibitor such as triethyl citrate.
In the event of incompatibility or to stabilize them, some of the agents mentioned
above may be incorporated into spherules, especially ionic or nonionic vesicles
and/or nanoparticles (capsules and/or spheres).
The deodorant agents may preferably be present in the compositions according to
the invention in weight concentrations ranging from 0.01 % to 15% by weight
relative to the total weight of the composition.
ORGANIC POWDER
According to one particular form of the invention, the compositions according to
the invention will also contain an organic powder.
In the present patent application, the term "organic powder" means any solid that
is insoluble in the medium at room temperature (25°C).
As organic powders that may be used in the composition of the invention,
examples that may be mentioned include polyamide particles and especially those
sold under the name Orgasol by the company Atochem; nylon-6,6 fibres,
especially the polyamide fibres sold by Etablissements P Bonte under the name
Polyamide 0.9 Dtex 0.3 mm (INCI name: Nylon-6,6 or Polyamide 6,6) with a mean
diameter of 6 miti , a weight of about 0.9 dtex and a length ranging from 0.3 mm to
1.5 mm; polyethylene powders; microspheres based on acrylic copolymers, such
as those made of ethylene glycol dimethacrylate/lauryl methacrylate copolymer,
sold by the company Dow Corning under the name Polytrap; polymethyl
methacrylate microspheres, sold under the name Microsphere M-1 00 by the
Company Matsumoto or under the name Covabead LH85 by the Company
Wackher; hollow polymethyl methacrylate microspheres (particle size: 6.5-1 0.5
miti ) sold under the name Ganzpearl GMP 0800 by Ganz Chemical; methyl
methacrylate/ethylene glycol dimethacrylate copolymer microbeads (size: 6.5-1 0.5
miti ) sold under the name Ganzpearl GMP 0820 by Ganz Chemical or
Microsponge 5640 by the company Amcol Health & Beauty Solutions; ethyleneacrylate
copolymer powders, such as those sold under the name Flobeads by the
company Sumitomo Seika Chemicals; expanded powders such as hollow
microspheres and especially microspheres formed from a terpolymer of vinylidene
chloride, acrylonitrile and methacrylate and sold under the name Expancel by the
company Kemanord Plast under the references 551 DE 12 (particle size of about
12 m and mass per unit volume of 40 kg/m3) , 551 DE 20 (particle size of about
30 miti and mass per unit volume of 65 kg/m3) , 551 DE 50 (particle size of about
40 miti ) , or the microspheres sold under the name Micropearl F 80 ED by the
company Matsumoto; powders of natural organic materials such as starch
powders, especially of crosslinked or non-crossl inked corn, wheat or rice starch,
such as the powders of starch crosslinked with octenylsuccinic anhydride, sold
under the name Dry-Flo by the company National Starch; silicone resin
microbeads such as those sold under the name Tospearl by the company Toshiba
Silicone, especially Tospearl 240; amino acid powders such as the lauroyllysine
powder sold under the name Amihope LL-1 1 by the company Ajinomoto; particles
of wax microdispersion, which preferably have mean sizes of less than 1 miti and
especially ranging from 0.02 miti to 1 miti , and which are formed essentially from a
wax or a mixture of waxes, such as the products sold under the name Aquacer by
the company Byk Cera, and especially: Aquacer 520 (mixture of synthetic and
natural waxes), Aquacer 514 or 5 13 (polyethylene wax), Aquacer 5 11 (polymeric
wax), or such as the products sold under the name Jonwax 120 by the company
Johnson Polymer (mixture of polyethylene wax and paraffin wax) and under the
name Ceraflour 961 by the company Byk Cera (micronized modified polyethylene
wax); and mixtures thereof.
ADDITIVES
The cosmetic compositions according to the invention may also comprise cosmetic
adjuvants chosen from softeners, antioxidants, opacifiers, stabilizers, moisturizers,
vitamins, bactericides, preserving agents, polymers, fragrances, thickeners or
suspension agents, propellants or any other ingredient usually used in cosmetics
for this type of application.
Needless to say, a person skilled in the art will take care to select this or these
optional additional compounds such that the advantageous properties intrinsically
associated with the cosmetic composition in accordance with the invention are not,
or are not substantially, adversely affected by the envisaged addition(s).
THICKENERS AND SUSPENSION AGENTS
The thickeners may be chosen from carboxyvinyl polymers, such as Carbopols
(Carbomers) and the Pemulens (acrylate/Cio-C3o alkyl acrylate copolymer);
polyacrylamides, for instance the crosslinked copolymers sold under the names
Sepigel 305 (CTFA name: polyacrylamide /Ci3-i 4 isoparaffin/Laureth 7) or Simulgel
600 (CTFA name: acrylamide/sodium acryloyldimethyltaurate
copolymer/isohexadecane/polysorbate 80) by the company SEPPIC; 2-
acrylamido-2-methylpropanesulfonic acid polymers and copolymers, optionally
crosslinked and/or neutralized, for instance poly(2-acrylamido-2-
methylpropanesulfonic acid) sold by the company Hoechst under the trade name
Hostacerin AMPS (CTFA name: ammonium polyacryloyldimethyl taurate or
Simulgel 800 sold by the company SEPPIC (CTFA name: sodium
polyacryolyldimethyltaurate/polysorbate 80/sorbitan oleate); copolymers of 2-
acrylamido-2-methylpropanesulfonic acid and of hydroxyethyl acrylate, for
instance Simulgel NS and Sepinov EMT 10 sold by the company SEPPIC;
cellulose derivatives such as hydroxyethylcellulose or cetylhydroxyethylcellulose;
polysaccharides and especially gums such as xanthan gum and hydroxypropyl
guar gums; silicas, for instance Bentone Gel MIO sold by the company NL
Industries or Veegum Ultra sold by the company Polyplastic.
The thickeners may also be cationic, for instance Polyquaternium-37 sold under
the name Salcare SC95 (Polyquaternium-37 (and) Mineral Oil (and) PPG-1
Trideceth-6) or Salcare SC96 (Polyquaternium-37 (and) Propylene Glycol
Dicaprylate/Dicaprate (and) PPG-1 Trideceth-6) or other crosslinked cationic
polymers, for instance those of the CTFA name Ethyl Acrylate/Dimethylaminoethyl
Methacrylate Cationic Copolymer In Emulsion.
SUSPENSION AGENTS
In order to improve the homogeneity of the product, it is also possible to use one
or more suspension agents preferably chosen from hydrophobic modified
montmorillonite clays such as hydrophobic modified bentonites or hectorites.
Examples that may be mentioned include the product Stearalkonium Bentonite
(CTFA name) (product of reaction of bentonite and the quaternary ammonium
stearalkonium chloride) such as the commercial product sold under the name
Tixogel MP 250 by the company Sud Chemie Rheologicals, United Catalysts Inc.
or the product Disteardimonium Hectorite (CTFA name) (product of reaction of
hectorite and distearyldimonium chloride) sold under the name Bentone 38 or
Bentone Gel by the company Elementis Specialities.
Other suspension agents may be used, in the present case in hydrophilic media
(aqueous and/or ethanolic). They may be cellulose, xanthan, guar, starch, locust
bean or agar derivatives.
The suspension agents are preferably present in amounts ranging from 0.1 % to
5% by weight and more preferentially from 0.2% to 2% by weight relative to the
total weight of the composition.
The amounts of these various constituents that may be present in the cosmetic
composition according to the invention are those conventionally used in
compositions for treating perspiration.
AEROSOLS
The compositions according to the invention may also be pressurized and may be
conditioned in an aerosol device formed by:
(A) a container comprising an antiperspirant composition as defined previously,
(B) at least one propellant and a means for dispensing the said aerosol
composition.
The propellants generally used in products of this type and that are well known to
those skilled in the art are, for instance, dimethyl ether (DME); volatile
hydrocarbons such as n-butane, propane, isobutane and mixtures thereof,
optionally with at least one chlorohydrocarbon and/or fluorohydrocarbon; among
these derivatives, mention may be made of the compounds sold by the company
DuPont de Nemours under the names Freon® and Dymel®, and in particular
monofluorotrichloromethane, difluorodichloromethane, tetrafluorodichloroethane
and 1, 1 -difluoroethane sold especially under the trade name Dymel 152 A by the
company DuPont. Carbon dioxide, nitrous oxide, nitrogen or compressed air may
also be used as propellant.
The compositions containing perlite particles as defined previously and the
propellant(s) may be in the same compartment or in different compartments in the
aerosol container. According to the invention, the concentration of propellant
generally ranges from 5% to 95% by weight of pressurized composition, and more
preferentially from 50% to 85% by weight relative to the total weight of the
pressurized composition.
The dispensing means, which forms a part of the aerosol device, is generally
formed by a dispensing valve controlled by a dispensing head, which itself
comprises a nozzle via which the aerosol composition is vaporized. The container
containing the pressurized composition may be opaque or transparent. It may be
made of glass, a polymer or a metal, optionally coated with a protective varnish
coat.
Example 1: Antiperspirant stick
Procedure:
The cyclopentasiloxane is heated to 65°C. The other ingredients are added one by
one, while keeping the temperature at 65-70°C. The whole is homogenized
(transparent solution) for 15 minutes. The product is cooled to about 55°C (a few
degrees Celsius above the thickening point of the mixture) and is poured into
sticks. The sticks are placed at 4°C for 30 minutes.
Example 2: Antiperspirant emulsion (roll-on)
Phase Ingredients Amounts
in weight %
Procedure:
Phases (B) and (C) are separately heated to 70°C. (B) and (C) are mixed together
by Turrax blending for 5 minutes, and the mixture is then cooled to 55°C with
continued stirring. Phase A is then added slowly with stirring. The mixture is
homogenized for 1 to 3 minutes. It is cooled to 35°C with stirring.
Example 3: Antiperspirant vaporizer (PIT emulsion)
Procedure:
Poly(vinylpyridine) from Aldrich is dissolved in water, and Emulgade CM is added
to the mixture with moderate stirring.
Example 4 : Antiperspirant aerosol
Stearalkonium Bentonite 0.5
(Tixogel MP 250 - Sud Chemie)
Poly(4-vinylpyridine-co-styrene 10%) Aldrich 5
neutralized 100% HCI
C 12-1 5 alkyl benzoate 3
(Finsolv TN - Witco)
Triethyl citrate 1
(Citroflex 2; Morflex)
Isopropyl palmitate 1
Cyclopentasiloxane 9.5
(DC 245 Fluid from Dow Corning)
Isobutane (propellant) 80
Examples of synthesis of flocculant polymers comprising as side chain nonquaternary
amine groups and at least one hydrophobic nonionic monomer
Polymer 1: copolymer (NMDEA -PEG 200-IPDI) (weight%: 20/20.22/59.78)
neutralized HCI
The monomers and solvents below are introduced into a thermostatically
controlled reactor equipped with a mechanical stirring system and a condenser:
- 1 mol of a mixture of monomers of diol type, i.e. a mixture of Nmethyldiethanolamine
(0.62 mol) and of PEG-200 (0.38 mol),
and
- an amount of methyl ethyl ketone such that the concentration of monomers of
diol type is equal to 75% by weight.
The mixture is heated with stirring to a temperature of 70°C, followed by dropwise
addition with stirring, over a period of about 2 hours, of a small molar access, i.e.
1.03 mol, of isophorone diisocyanate. During this addition, an increase in
temperature up to the reflux point of the solvent is observed. Samples are
withdrawn at regular intervals and the IR absorption spectrum is plotted to monitor
the disappearance of the band corresponding to the isocyanate functions (2260
cm 1) . When the absorption band of the -NCO functions no longer decreases,
which is generally the case after about 5 hours, the reaction mixture is allowed to
cool to room temperature and is then diluted with acetone to a polymer
concentration of about 40% by weight. 20 cm3 of ethanol are then added to the
mixture obtained in order to destroy the residual -NCO functions, and stirring is
continued at room temperature until all these -NCO functions have disappeared,
i.e. until the disappearance of the IR absorption band at 2260 cm 1 . 2M
hydrochloric acid solution is then added in an amount such that the amine groups
are neutralized to the desired proportion. The various organic solvents (methyl
ethyl ketone, acetone and ethanol) are then removed by distillation under vacuum
at a temperature of 40°C. After removal of the organic phase, an amount of water
sufficient to obtain a final polymer concentration in the water of about 25% by
weight is added to the aqueous polymer solution.
Polymers 2 to 5 are synthesized according to a similar procedure, replacing the
methyl ethyl ketone with THF for the polymers based on Krasol LBH P 2000.
Polymer 2 : copolymer (NMDEA -PEG 100 000 g/mol - IPDI) (weight%:
20/37.4/42.6) neutralized HCI
Polymer 3 : copolymer (NMDEA -Krasol LBH P 2000 - IPDI) (weight%:
19.1/40.7/40.2) neutralized HCI
Polymer 4 : copolymer (NMDEA -Krasol LBH P 2000 - IPDI) (weight%:
11.6/60/28.4) neutralized HCI
Polymer 5: copolymer (NMDEA -Krasol LBH P 2000 - IPDI) (weight%:
15.5/50/34.5) neutralized HCI
Polymer 6 : copolymer (PEG 10 000 g/mol - Desmodur W - 2-
dimethylaminoethanol quaternized with dodecyl(2-
hydroxyethyl)dimethylammonium) bromide (weight% 95.5/2/0.5/2)
A 500 ml reactor equipped with a central mechanical stirrer, a thermometer,
a condenser and a nitrogen inlet is charged with 0.01 mol of PEG 10 000 g/mol +
0.0006 mol of tin 2-ethylhexanoate + 100 cm3 of tetrahydrofuran (THF). The
mixture is stirred at room temperature to obtain a homogeneous solution, followed
by dropwise addition of 0.02 mol of methylenedicyclohexyl 4,4'-diisocyanate
(Desmodur W 2) while remaining at room temperature. The mixture is then heated
to the reflux temperature of the solvent (66°C) over about 30 minutes, and is left at
this temperature for about 5 hours. 0.02 mol of N-methyldiethanolamine is then
introduced and the mixture is left to react for 2 hours at 66°C (the disappearance
of the NCO band of the isocyanate is monitored by IR), followed by addition of
0.02 mol of methylenedicyclohexyl 4,4'-diisocyanate, which is left to react for 3
hours (the disappearance of the NCO band of the isocyanate is also monitored by
IR) and finally 0.02 mol of dodecanol. The mixture is left for a further 3 hours at
reflux temperature of the solvent.
The polymer is then quaternized by addition of 0.022 mol of dimethyl sulfate. The
reaction medium becomes opaque, and heating is maintained at 66°C for 48
hours. The mixture is then allowed to cool to room temperature. The polyurethane
is purified by precipitation from petroleum ether, filtered off and dried under
vacuum at 55°C to a constant weight.
Example 5: Antiperspirant stick
Procedure:
The cyclopentasiloxane is heated to 65°C. The other ingredients are added one by
one, while keeping the temperature at 65-70°C. The whole is homogenized for 15
minutes. The product is cooled to about 55°C (a few degrees Celsius above the
thickening point of the mixture) and is poured into sticks. The sticks are placed at
4°C for 30 minutes.
Example 6: Antiperspirant emulsion (roll-on)
Procedure:
Phases (B) and (C) are separately heated to 70°C. (B) and (C) are mixed together
by Turrax blending for 5 minutes, and the mixture is then cooled to 55°C with
paddle stirring. Phase A is then added slowly with stirring. The mixture is
homogenized for 1 to 3 minutes. The mixture is cooled to 35°C with stirring.
Example 7: Antiperspirant vaporizer (Phase-Inversion Technique Emulsion)
Procedure:
Polymer 2 is dissolved in water, and Emulgade CM is added to the mixture with
moderate stirring.
Examples of synthesis of polyurethane flocculant polymers
Polymer 1': copolymer (NMDEA -PEG 200-IPDI) (weight%: 20/20.22/59.78)
neutralized HCI
The monomers and solvents below are introduced into a thermostatically
controlled reactor equipped with a mechanical stirring system and a condenser:
- 1 mol of a mixture of monomers of diol type, i.e. a mixture of Nmethyldiethanolamine
(0.62 mol) and of PEG-200 (0.38 mol),
and
- an amount of methyl ethyl ketone such that the concentration of monomers of
diol type is equal to 75% by weight.
The mixture is heated with stirring to a temperature of 70°C, followed by dropwise
addition with stirring, over a period of about 2 hours, of a small molar access, i.e.
1.03 mol, of isophorone diisocyanate. During this addition, an increase in
temperature up to the reflux point of the solvent is observed. Samples are
withdrawn at regular intervals and the IR absorption spectrum is plotted to monitor
the disappearance of the band corresponding to the isocyanate functions (2260
cm 1) . When the absorption band of the -NCO functions no longer decreases,
which is generally the case after about 5 hours, the reaction mixture is allowed to
cool to room temperature and is then diluted with acetone to a polymer
concentration of about 40% by weight. 20 cm3 of ethanol are then added to the
mixture obtained in order to destroy the residual -NCO functions, and stirring is
continued at room temperature until all these -NCO functions have disappeared,
i.e. until the disappearance of the IR absorption band at 2260 cm 1 . 2M
hydrochloric acid solution is then added in an amount such that the amine groups
are neutralized to the desired proportion. The various organic solvents (methyl
ethyl ketone, acetone and ethanol) are then removed by distillation under vacuum
at a temperature of 40°C. After removal of the organic phase, an amount of water
sufficient to obtain a final polymer concentration in the water of about 25% by
weight is added to the aqueous polymer solution.
Polymers 2 to 5 are synthesized according to a similar procedure, replacing the
methyl ethyl ketone with THF for the polymers based on Krasol LBH P 2000.
Polymer 2': copolymer (NMDEA -PEG 100 000 g/mol - IPDI) (weight%:
20/37.4/42.6) neutralized HCI
Polymer 3': copolymer (NMDEA -Krasol LBH P 2000 - IPDI) (weight%:
9.1/40.7/40.2) neutralized HCI
Polymer 4': copolymer (NMDEA -Krasol LBH P 2000 - IPDI) (weight%:
11.6/60/28.4) neutralized HCI
Polymer 5': copolymer (NMDEA -Krasol LBH P 2000 - IPDI) (weight%:
15.5/50/34.5) neutralized HCI
Polymer 6': copolymer (PEG 10 000 g/mol - Desmodur W - 2-
dimethylaminoethanol quaternized with dodecyl(2-
hydroxyethyl)dimethylammonium) bromide (weight% 95.5/2/0.5/2)
A 500 ml reactor equipped with a central mechanical stirrer, a thermometer,
a condenser and a nitrogen inlet is charged with 0.01 mol of PEG 10 000 g/mol +
0.0006 mol of tin 2-ethylhexanoate + 100 cm3 of tetrahydrofuran (THF). The
mixture is stirred at room temperature to obtain a homogeneous solution, followed
by dropwise addition of 0.02 mol of methylenedicyclohexyl 4,4'-diisocyanate
(Desmodur W 2) while remaining at room temperature. The mixture is then heated
to the reflux temperature of the solvent (66°C) over about 30 minutes, and is left at
this temperature for about 5 hours. 0.02 mol of N-methyldiethanolamine is then
introduced and the mixture is left to react for 2 hours at 66°C (the disappearance
of the NCO band of the isocyanate is monitored by IR), followed by addition of
0.02 mol of methylenedicyclohexyl 4,4'-diisocyanate, which is left to react for 3
hours (the disappearance of the NCO band of the isocyanate is also monitored by
IR) and finally 0.02 mol of dodecanol. The mixture is left for a further 3 hours at
reflux temperature of the solvent.
The polymer is then quaternized by addition of 0.022 mol of dimethyl sulfate. The
reaction medium becomes opaque, and heating is maintained at 66°C for 48
hours. The mixture is then allowed to cool to room temperature. The polyurethane
is purified by precipitation from petroleum ether, filtered off and dried under
vacuum at 55°C to a constant weight.
Example 8: Antiperspirant stick
Ingredients Amounts
in weight %
Cyclopentasiloxane 33
(DC 245 Fluid from Dow
Corning)
PPG-14 butyl ether 10
(Ucon Fluid AP - Amerchol)
Hydrogenated castor oil 4
(Cutina HR Pulver - Cognis)
Talc 2
Polymer 6' 20
Stearyl alcohol 14
PEG-8 distearate 2
(Stearineries Dubois)
C 12-1 5 alkyl benzoate 15
(Finsolv TN - Witco)
Procedure:
The cyclopentasiloxane is heated to 65°C. The other ingredients are added one by
one, while keeping the temperature at 65-70°C. The whole is homogenized
(transparent solution) for 15 minutes. The product is cooled to about 55°C (a few
degrees Celsius above the thickening point of the mixture) and is poured into
sticks. The sticks are placed at 4°C for 30 minutes.
Example 9: Antiperspirant stick
Procedure:
The cyclopentasiloxane is heated to 65°C. The other ingredients are added one by
one, while keeping the temperature at 65-70°C. The whole is homogenized
(transparent solution) for 15 minutes. The product is cooled to about 55°C (a few
degrees Celsius above the thickening point of the mixture) and is poured into
sticks. The sticks are placed at 4°C for 30 minutes.
Example 10: Antiperspirant emulsion (roll-on)
Procedure:
Phases (B) and (C) are separately heated to 70°C. (B) and (C) are mixed together
by Turrax blending for 5 minutes, and the mixture is then cooled to 55°C with
paddle stirring. Phase A is then added slowly with stirring. The mixture is
homogenized for 1 to 3 minutes. The mixture is cooled to 35°C with stirring.
Example 11: Antiperspirant emulsion (roll-on)
Procedure:
Phases (B) and (C) are separately heated to 70°C. (B) and (C) are mixed together
by Turrax blending for 5 minutes, and the mixture is then cooled to 55°C with
paddle stirring. Phase A is then added slowly with stirring. The mixture is
homogenized for 1 to 3 minutes. The mixture is cooled to 35°C with stirring.
Example 12 : Antiperspirant vaporizer (Emulsion obtained by phase
inversion)
Procedure:
Polymer 5 is dissolved in water, and Emulgade CM is added to the mixture with
moderate stirring.
Example 12 : Antiperspirant aerosol
Ingredients Amounts in
weight %
Stearalkonium Bentonite 0.5
(Tixogel MP 250 - Sud
Chemie)
Polymer 2' 5
C 12-1 5 alkyl benzoate 3
(Finsolv TN - Witco)
Triethyl citrate 1
(Citroflex 2; Morflex)
Isopropyl palmitate 1
Cyclopentasiloxane 9.5
(DC 245 Fluid from Dow
Corning)
Isobutane (propellant) 80

CLAIMS
1. Cosmetic use of a flocculant polymer chosen from:
(i) flocculant polymers comprising as side chain non-quaternized pyridine groups
directly or indirectly linked to the main chain;
(ii) flocculant polymers comprising as side chain non-quaternary amine groups
borne by a side substituent directly linked to the main chain; the said polymer
comprising at least one non-quaternary cationic monomer and at least one
hydrophobic nonionic monomer;
(iii) cationic polyurethane flocculant polymers; as antiperspirant active agent.
2. Use according to Claim 1, in which the flocculant polymer is contained in a
composition comprising a cosmetically acceptable medium, in particular not
containing any antiperspirant aluminium and/or zirconium salts.
3. Use according to Claim 1 or 2, in which the flocculant polymer of paragraph i) is
chosen from homopolymers or copolymers comprising at least one monomer (A)
to (F) defined below:
B) (C) (D) (E) (F)
where:
X =O, or NH
Ri represents a hydrogen atom or an alkyl group containing from 1 to 3 carbon
atoms, preferably methyl;
A is a linear or branched C1-C6 and preferably C2-C3 alkyl group; a Ci-C4
hydroxyalkyl group, preferably monohydroxyalkyl;
4. Use according to Claim 3, in which the pyridine monomers (A) to (F) are chosen
from 2-vinylpyridine; 4-vinylpyridine; N-(4-pyridyl)propylmethacrylamide and N-4-
(pyridyl)ethyl methacrylate.
5. Use according to Claim 3 or 4, in which the flocculant polymer may also
comprise:
- units consisting of at least one additional cationic monomer preferably chosen
from benzyl dimethylaminoethylacrylate chloride (DMAEA-BCQ),
acryloyloxyethyltrimethylammonium chloride (AETAC),
methacryloyloxyethyltrimethylammonium methosulfate (METAMS) and
methylaminoethyl methacrylate;
- units consisting of at least one anionic monomer preferably chosen from maleic
anhydride, acrylic acid, methacrylic acid, crotonic acid, itaconic acid, fumaric acid,
maleic acid, 2-carboxyethyl acrylate (CH2=CH-C(O)-O-(CH 2)2-COOH);
styrenesulfonic acid, 2-acrylamido-2-methylpropanesulfonic acid, vinylbenzoic
acid, vinylphosphoric acid and sulfopropyl (meth)acrylate, and salts thereof;
- units consisting of at least one nonionic monomer preferably chosen from methyl
methacrylate, methyl acrylate, ethyl methacrylate, ethyl acrylate, propyl acrylate,
isopropyl acrylate, tetrahydrofurfuryl methacrylates, butyl methacrylate, 2-
ethylhexyl acrylate, stearyl methacrylate, acrolein, tetrahydrofurfuryl acrylate, 2-
hydroxyethyl methacrylate, 2-hydroxyethyl acrylate, ethoxyethyl methacrylate,
ethoxyethyl acrylate, N-isopropylacrylamide, N-isopropylmethacrylamide, N,Ndimethylacrylamide,
N,N-dimethylmethacrylamide, vinyl acetate, methyl vinyl
ether, ethyl vinyl ether, vinylpyrrolidone, vinylcaprolactam, N-vinylacetamide,
hydroxypropyl acrylate, N-vinyllactam, acrylamide, N-methylacrylamide, N,Ndimethylacrylamide,
N-methyl-N-vinylacetamide, N-vinylformamide, N-methyl-Nvinylformamide,
vinyl alcohol (copolymerized in the form of vinyl acetate and then
hydrolysed).
6. Use according to any one of Claims 3 to 5, in which the flocculant polymer of
paragraph i) is chosen from:
- poly(2-vinylpyridine) homopolymers;
- poly(4- or 2-vinylpyridine)-co-styrene copolymers;
- poly(4- or 2-vinylpyridine)-co-butyl methacrylate copolymers;
- poly(4- or 2-vinylpyridine) crosslinked with divinylbenzene;
- diblock polymers comprising a polyethylene glycol (PEG) or polyisobutylene
block and a poly(4- or 2-vinylpyridine) block;
- poly(4-vinylpyhdinium) p-toluenesulfonate;
- poly(4-vinylpyridine hydrochloride) 2% crosslinked with divinylbenzene.
7. Use according to Claim 1 or 2, in which, in the flocculant polymer of paragraph
ii), the non-quaternary cationic monomer is chosen from those of formula (I) below,
or a salt thereof:
in which:
Rii is a hydrogen atom or a linear or branched hydrocarbon-based radical, of the
type CpH2p+ i , with p being an integer between 1 and 12 inclusive (in particular, R
may represent a methyl, ethyl, propyl or butyl radical (preferably, Rn represents
hydrogen or a methyl radical));
- Zi is a divalent group chosen from -COO-, -CONH-, -CONCH3-, -OCOor
-O-, -SO2- -CO-O-CO- or -CO-CH2-CO-, (preferably Z is chosen from COO and
CONH);
- x = 0 or 1, preferably 1;
Ri2 is a saturated or unsaturated, optionally aromatic, linear, branched or cyclic
carbon-based divalent radical of 1 to 30 carbon atoms, which may comprise 1 to
18 heteroatoms chosen from O, N, S, F, Si and P; the heteroatom(s) may be
intercalated in the chain of the said radical .
the said radical R12 may be substituted with one or more groups comprising them
such as hydroxyl or a group NH2, NHR' or NR'R" with R' and R", which may be
identical or different, representing a linear or branched C1-C22 alkyl, especially
methyl or ethyl;
R12 may also be an alkylene radical such as methylene, ethylene, propylene, nbutylene,
isobutylene, tert-butylene, n-hexylene, n-octylene, n-dodecylene, noctadecylene,
n-tetradecylene or n-docosanylene); a phenylene radical - H -
(ortho, meta or para), optionally substituted with a C1-C12 alkyl radical optionally
comprising 1 to 25 heteroatoms chosen from N, O, S, F, Si and/or P; or
alternatively a benzylene radical -C6H -CH2- , optionally substituted with a C1-C12
alkyl radical optionally comprising 1 to 25 heteroatoms chosen from O, N, S, F, Si
and P;
R12 may also be a radical of formula -CH2-O-CO-O-, CH2-CH2-O-CO-O-, -CH2-COO-,
-CH2-CH2-CO-O-, -[(CH2)5-CO-O] n- , -CH2-CH(CH 3)-O-, -(CH2)2-O-, -CH2-OCO-
NH-, -CH2-CH2-O-CO-NH-; -CH2-NH-CO-NH- or -CH2-CH2-NH-CO-NH-, -CH2-
CHOH-, -CH2-CH2-CHOH-, -CH2-CH2-CH(NH 2)-, -CH2-CH(NH 2)-, -CH2-CH2-
CH(NHR')-, -CH2-CH(NHR'")-, -CH2-CH2-CH(NR'"R"")-, -CH2-CH(NR'"R"")-, -CH2-
CH2-CH2-NR'"-, -CH2-CH2-CH2-O-; -CH2-CH2-CHR'-O- with FT and R""
representing a linear or branched C1-C22 alkyl optionally comprising 1 to 12
heteroatoms chosen from O, N, S, F, Si and P;
R12 may be a mixture of these radicals;
m is 0 or 1;
X is
a) either a guanidino or amidino group having the following formul
Guanidino Amidino
b) or a group of formula -N(Ri 3)(Ri 4) or
-P(Ri 3)(Ri ) with Ri3 and Ri4 representing, independently of each other:
(i) a hydrogen atom;
(ii) a linear, branched or cyclic, saturated or unsaturated, optionally
aromatic alkyl group, comprising from 1 to 18 carbon atoms, which may
comprise 1 to 10 heteroatoms chosen from O, N, S, F, Si and P;
(iii) Ri3 and Ri 4 may form, with the nitrogen or phosphorus atom, a first
saturated or unsaturated, optionally aromatic ring comprising in total 5,
6, 7 or 8 atoms, and especially 4, 5 or 6 carbon atoms and/or 2 to 4
heteroatoms chosen from O, S and N; the said first ring possibly being
fused with one or more other saturated or unsaturated, optionally
aromatic rings, each comprising 5, 6 or 7 atoms, and especially 4, 5, 6
or 7 carbon atoms and/or 2 to 4 heteroatoms chosen from O, S and N;
c) a group R'3-N-R'4 in which R'3 and R4 form, with the nitrogen atom, a saturated
ring comprising in total 5, 6, 7 or 8 atoms, and especially 4, 5 or 6 carbon atoms
and/or 2 to 4 heteroatoms chosen from O, S and N; the said ring possibly being
fused with one or more other saturated rings, each comprising 5, 6 or 7 atoms,
and especially 4, 5, 6, 7 or 8 carbon atoms and/or 2 to 4 heteroatoms chosen from
O, S and N.
8. Use according to Claim 7, in which the non-quaternary amine cationic
monomers of formula (I) are chosen from the following monomers:
and preferably chosen from dimethylaminopropyl(meth)acrylamide,
dimethylaminoethyl(meth)acrylamide, diethylaminoethyl (meth)acrylate,
dimethylaminoethyl (meth)acrylate, vinylimidazole and morpholinoethyl
(meth)acrylate, and mixtures thereof.
9. Use according to Claim 7 or 8, in which the non-quaternary amine cationic
monomers of formula (I) are present in a proportion of from 5% to 80% by weight
relative to the weight of the final polymer, especially from 7% to 30% by weight
and preferably from 10% to 20% by weight.
10. Use according to any one of Claims 7 to 9, in which the flocculant polymer of
paragraph ii) comprises units consisting of at least one hydrophobic nonionic
monomer preferably chosen from those of formula ( Ila) or (Mb) below:
1 a )
R2
HC C
(lib)
C = 0
X'
R1
in which:
X' represents an oxygen atom or a group NH, and
R1 represents a linear, branched, cycloaliphatic or aromatic C2-C60 hydrocarbonbased
group, which may contain one or more atoms chosen from O, S and P; ; the
said group may further contain at least a polyoxyalkylenated chain ;
R2 represents a hydrogen atom or a methyl group.
11. Use according to Claim 10, in which the nonionic monomers of formula ( Ila) or
(Mb) are present in a proportion of from 10% to 95% by weight relative to the
weight of the final polymer, especially from 20% to 90% by weight and preferably
from 30% to 85% by weight.
12. Use according to any one of Claims 7 to 11, in which the flocculant polymer of
paragraph ii) may also comprise:
- units consisting of at least one hydrophobic nonionic monomer preferably chosen
from vinyl monomers bearing a silicone side chain, chlorotrifluoroethylene,
tetrafluoroethylene, and vinyl, allylic or (meth)acrylic monomers bearing a
perhalogenated, in particular perfluoro, hydrocarbon-based side chain, such as
perfluorohexyl (meth)acrylate or perfluorooctyl (meth)acrylate. These monomers
will preferably be present in small amounts relative to the weight of the final
polymer;
- units consisting of at least one anionic monomer preferably chosen from maleic
anhydride, acrylic acid, methacrylic acid, crotonic acid, itaconic acid, fumaric acid,
maleic acid, 2-carboxyethyl acrylate (CH2=CH-C(O)-O-(CH 2 ) 2-COOH);
styrenesulfonic acid, 2-acrylamido-2-methylpropanesulfonic acid, vinylbenzoic
acid, vinylphosphoric acid and sulfopropyl (meth)acrylate, and salts thereof.
13. Use according to any one of Claims 7 to 11, in which the flocculant polymer of
paragraph ii) is chosen from the following polymers:
• copolymers of butyl acrylate and of dimethylaminoethyl methacrylate,
• copolymers of butyl acrylate and of dimethylaminopropylmethacrylamide, and
• copolymers of 2-ethylhexyl acrylate and of dimethylaminopropylmethacrylamide.
14. Use according to any one of Claims 1 to 3, in which the flocculant cationic
polyurethane polymer is chosen from:
- polyurethanes of type ( 1) comprising a tertiary or quaternary amine function as
pendent functions on the main chain, and
- polyurethanes of type (2) necessarily comprising a tertiary or quaternary amine
function at the end of the main chain and optionally tertiary or quaternary amine
functions as pendent functions on the main chain.
15. Use according to Claim 14, in which the cationic polyurethanes of type ( 1 )
comprise at least:
(a1 ) cationic units derived from at least one tertiary or quaternary amine bearing at
least two reactive functions containing labile hydrogen, and
(a2) nonionic units derived from oligomers or from nonionic polymers bearing at
their ends reactive functions containing labile hydrogen, and
(a3) nonionic units derived from nonionic monomer compounds containing at least
two functions containing labile hydrogen, and
(b) units derived from at least one diisocyanate.
16. Use according to Claim 14, in which the cationic polyurethanes of type (2)
comprise at least:
(a2) nonionic units derived from oligomers or from nonionic polymers bearing at
their ends reactive functions containing labile hydrogen, and
(a3) nonionic units derived from nonionic monomer compounds containing at least
two functions containing labile hydrogen, and
(a4) units consisting of at least one tertiary amine and containing only one function
containing labile hydrogen; the tertiary amine function possibly being quaternized,
and
(b) units derived from at least one diisocyanate, and
(a1 ) optionally cationic units derived from at least one tertiary or quaternary amine
bearing at least two reactive functions containing labile hydrogen.
17. Use according to Claim 15 or 16, in which the tertiary or quaternary amines
forming the cationic units (a1 ) are chosen from:
(i) compounds corresponding to one of the following formulae:
in which each Ra independently represents a linear or branched C 1-C6 alkylene,
C3-C6 cycloalkylene or arylene group, all possibly being substituted with one or
more halogen atoms and comprising one or more heteroatoms chosen from O, N,
P and S, each Rb independently represents a C 1-C6 alkyl, C3-C6 cycloalkyl or aryl
group, all possibly being substituted with one or more halogen atoms and
comprising one or more heteroatoms chosen from O, N, P and S, each X
independently represents an oxygen or sulfur atom or a group NH or NRc, in
which Rc represents a C 1-C6 alkyl group, and A represents a physiologically
acceptable counterion.
(ii) polymers containing tertiary and/or quaternary amine functions, bearing at their
ends reactive functions containing labile hydrogen and more preferentially chosen
from N-methyldiethanolamine and N-tert-butyldiethanolamine, and polyesters
derived from the polycondensation of N-methyldiethanolamine and of adipic acid.
18. Use according to any one of Claims 15 to 17, in which the units (a2) are
derived from nonionic polymers bearing at their ends reactive functions containing
labile hydrogen and preferably having a glass transition temperature (Tg) of less
than 10°C; the said units preferably being chosen from polyethers, polyesters,
polysiloxanes, copolymers of ethylene and butylene, polycarbonates and fluoro
polymers, and more particularly polyethers and even more particularly
poly(tetramethylene oxide) and hydrogenated or non-hydrogenated polymers of
ethylene and butylene.
19. Use according to any one of Claims 15 to 18, in which the units (a3) are
compounds of formula: HX-R2-XH in which each X independently represents an
oxygen or sulfur atom or a group NH or NRc, in which Rc represents a C 1-C6 alkyl
group and more particularly each X is an oxygen atom, and are preferably
neopentyl glycol, hexaethylene glycol or aminoethanol derivatives.
20. Use according to any one of Clainns 15 to 19, in which the units (a4) are
chosen from diamines comprising on the same molecule a tertiary amine unit and
a primary or secondary amine unit, chosen in particular from N,N-di methyl - 1 ,4-
butanediamine, N,N-dimethyl-1 ,3-propanediamine, N,N-diethyl-1 ,3-
propanediamine, N,N-dibutyl-1 ,3-propanediamine, N,N-dimethyl-1 ,2-
propanediamine, N,N-dimethyl-1 ,2-ethanediamine, N,N-diethyl-1 ,2-ethanediamine.
2 1. Use according to any one of Claims 15 to 20, in which the diisocyanates
forming the units (b) include aliphatic, alicyclic or aromatic diisocyanates and are
preferably chosen from methylenediphenyl diisocyanate, methylenecyclohexane
diisocyanate, isophorone diisocyanate, toluene diisocyanate, naphthalene 10-
diisocyanate, butane diisocyanate and hexyl diisocyanate.
22. Use according to any one of Claims 15 to 2 1, in which the units (a1 ) represent
from 1% to 90% and preferably from 5% to 60% by weight, the units (a2) from
10% to 80% and preferably from 40% to 70% by weight, the units (a3) from 0 to
50% by weight and preferably from 0 to 30% by weight, and the units (a4) from 0
to 10% and preferably from 0 to 5% by weight of the total polymer.
23. Cosmetic process for treating perspiration, which consists in applying to the
surface of the skin a composition comprising, in a cosmetically acceptable
medium, at least one flocculant polymer as defined in any one of Claims 1 to 22,
not containing any antiperspirant aluminium and/or zirconium salts.