The present invention relates to novel polymers
especially cationic polyurethanes of elastic nature
and also to their use in cosmetic or pharmaceutical
compositions and to the cosmetic or pharmaceutical
compositions thus obtained.
The formation of deposits and films with elastic
properties has always been a subject of considerable
research in cosmetics. The reason for this is that most
of the areas of the human body liable to receive
cosmetic deposits such as the skin the lips the
hair the eyelashes and the nails are subject to large
mechanical stresses and deformations. Cosmetic films
and deposits must be able to withstand these stresses
and to follow these deformations without breaking.
The use of polyurethanes in cosmetics has been known
for a long time and is described for example in
patents WO 94/13724 and EP 619111.
However the polyurethanes described in the said
documents have glass transition temperatures (Tg)
greater than room temperature (20°C) which means that
at room temperature they are in vitreous form and form
brittle films which are unacceptable for cosmetic use.
Admittedly physiologically acceptable polymers with
low glass transition temperatures exist for instance
acrylic polymers but these polymers generally form
very tacky deposits which is a drawback in the
majority of cosmetic applications.
Physiologically acceptable polyurethanes that form nontacky
non-brittle films capable of plastic and elastic
deformations are moreover known from patent application
WO 02/32978. These advantageous viscoelastic properties
are due to the presence in the polymer of long
macromolecular units of relatively low glass transition
temperature which at room temperature are not in
vitreous form.
The polymers described especially comprise
macromolecular units of polyether type in particular
polytetramethylehe oxide {PTMO} or alternatively of
(ethylene-butylene.) copolymer type.
Mention may also be made of patent US 3 388 087 which
describes polyurethanes comprising polypropylene glycol
ether or polybutylene glycol ether units.
These polymers comprise hygroscopic units which is
detrimental to the cosmetic quality of the polymer
applied to the hair the polymer is then too
hydrophilie is tacky and is sparingly water-resistant.
The aim of the present invention is to propose
physiologically acceptable polymers especially
polyurethanes with improved film-forming and
viscoelastic properties.
Polymers especially of polyurethane type that make it
possible to obtain a cosmetic composition with better
humidity and/or water resistance and thus sufficient
resistance over time of the styling nature are also
sought.
This aim is especially achieved by means of the use of
quite specific polymers obtained from polyolefins and
which have a hydrophobic nature such that the styling
products especially hair gels sprays and/or foams
comprising them make it possible to give the hair hold
while at the same time conserving sufficient resistance
over time of this styling.
This is particularly advantageous during the production
of styling with "strands" (tufts).
One subject of the present invention is a polyurethane
consisting essentially of:
(al) at least one cationic or eationizable unit derived
from at least one tertiary or quaternary amine
containing at least two reactive functions containing
labile hydrogen
(a2) at least one nonionic unit derived from at least
one polyolefin containing at least two reactive
functions containing labile hydrogen the said
polyolefin comprising at least 10 mo 1ft of units
comprising at least one C=C (carbon-carbon) double
bond relative to the total amount of units forming the
said polyolefin
(b) at least one unit derived from a compound
comprising at least two isocyanate functions.
The invention also relates to a composition comprising
at least one such pplyurethane in a physiologically
acceptable medium.
The polymer according to the invention is preferably of
elastic nature this means that the said polymer is a
macromolecular material that rapidly returns to its
initial form and dimensions after a low stress that has
produced a large deformation has ceased.
By virtue of its cationic/cationizable nature the
polymer according to the invention moreover has the
advantage of having excellent affinity for keratin
substrates such as the hair the nails and the horny
layer of the epidermis to which keratin gives a
negative charge.
The use of the polymer according to the invention in
lakes and styling compositions makes it possible to
improve the flexibility of the styling i.e. to obtain
more natural and more durable resistance of the hair
than that obtained with the fixing polymers of the
prior art.
Finally the polymers are not tacky which facilities
their use in cosmetics.
Furthermore the compositions comprising a polymer
according to the invention have better water resistance
by virtue of the use of olefin copolymers of
hydrophobic nature.
The polymer according to the invention may be obtained
by polyeondensation of compounds bearing reactive
functions containing labile hydrogen with compounds
comprising at least two isocyanate functions.
The term "reactive functions containing labile
hydrogen" means functions capable after loss of a
hydrogen atom of forming covalent bonds with the
isocyanate functions of compounds comprising at least
two isocyanate functions. Examples of such functions
that may be mentioned include hydroxyl primary amine
or secondary amine groups or thiol groups.
Depending on the nature of the reactive functions
bearing the labile hydrogen {-OH -NH2 -NHR or -SH)
the polyeondensation leads respectively to
polyurethanes polyureas or polythiourethanes. Thus
the polymers used in the invention may be urethane/urea
and/or thiourethane copolymers. All these polymers are
combined in the present patent application for the
sake of simplicity under the term "polyurethanes".
The cationic or cationizable polyurethane according to
the invention thus comprises at least one cationic or
cationizable unit (al) resulting from at least one
tertiary or quaternary amine containing at least two
reactive functions containing labile hydrogen.
The term "cationic or cationizable unit" means for the
purposes of the present invention any unit which
either by its intrinsic chemical nature or as a
function of the medium and/or the pH in which it is
present will be in cationic form.
The tertiary amine is preferably protonatable at a pH
chosen between pH 1 and pH 12. The term "protonatable"
means that the said tertiary amine function may be at
least partially neutralized with a neutralizer or as a
function of the medium in which it is formulated.
When the tertiary or quaternary amines forming the
units (al) bear more than two functions containing
labile hydrogen the polyurethane obtained has a
branched structure.
However preferably the tertiary or quaternary amines
forming the units (al) contain only two reactive
functions containing labile hydrogen and the
polyurethanes obtained via polycondensation
consequently have an essentially linear structure.
It is obviously also possible to use a mixture of
difunctional amines containing or otherwise a small
proportion of amines bearing more than two reactive
functions containing labile hydrogen.
The tertiary or quaternary amines forming the cationic
or cationizable units (al) are preferably chosen from
compounds corresponding to one of the following
formulae:
each Ra independently of each other/ represents a
linear or branched divalent Gi-Cg alkylene group or
alternatively a C3-C6 cycloalkylene or arylene or
mixtures thereof these groups possibly being
substituted with one or more halogen atoms and/or
comprising one or more heteroatoms cho&en from 0 N P
and S each Rb represents independently of each other
linear or branched Cj-C6 alkyl group or alternatively cycloalkyl or aryl or mixtures thereof these
groups possibly being substituted with one or more
halogen atoms arid/or comprising one or more heteroatoms
chosen from 0 N P and S
each R'b represents H or a linear or branched Cj-Ce
alkyl group or alternatively a Ca-Ce cycloalkyl or
aryl or mixtures thereof these groups possibly being
substituted with one or more halogen atoms and/or
comprising one or more heteroatoms chosen from 0 N P
and S
m and p are independently of each other equal to 0
or 1 preferably m = 1 and p = 1
each X represents independently of each other an
oxygen or sulfur atom or a group NH or NRe in which Rc
represents a alkyl group and
A" represents a physiologically acceptable counterion
and especially a halide such as chloride or bromide.
Preferably the amines are of formula:
Preferably Ra is a linear or branched divalent Ci-Ce
alkylene group especially methylene or ethylene.
Preferably Rb ia a linear or branched Ci-C6 alkyl
group especially a methyl ethyl n-butyl isobutyl or
tert-butyl group.
Preferably X = 0.
Even more preferentially the amines are of formula:
in which Ra is a linear or branched divalent Ci-Cg
alkylene group especially methylene or ethylene and
Rb is a linear or branched Ci-Cg alkyl group especially
a methyl ethyl n-butyl isobutyl or tert-butyl group.
As tertiary amines that are particularly preferred
mention may be made of N-methyldiethanolamine and
N-tert-butyldiethanolamine.
The protonatable tertiary amines may be totally or
partially neutralized with a neutralizer of organic
acid type comprising at least one carboxylic sulfonic
and/or phosphonic acid function or with a mineral acid.
Examples of preferred acids that may be mentioned
include hydrochloric acid sulfuric acid acetic acid
propionic acid citric acid gluconic acid tartaric
acid lactic acidr phosphoric acid benzoic acid
stearic acid oleio acid 2-ethylcaproic acid behenic
acid and betaine hydrochloride and a mixture thereof.
The cationic polyurethane according to the invention
also comprises at least one nonionic unit (a2)
resulting from at least one polyolefin containing at
least two reactive functions containing labile
hydrogen the said polyolefin comprising at least
10 mol% of units comprising at least one OC double
bond (residual) relative to the total amount of units
forming the said pe-lyolefin.
Preferably the polyolefin(s) is (are) nonionic.
Preferably the reactive functions containing labile
hydrogen are located at the ends of the polyolefin. The
said reactive functions containing labile hydrogen are
especially hydroxides. Preferentially the number of
hydroxide units is close to or even equal to 2.
More preferably the polyolefin(s) forming the unit
(a2) is chosen from olefin homppolyroers and/or
copolymers bearing at their ends reactive functions
containing labile hydrogen and having a glass
transition temperature (Tg) measured by differential
thermal analysis (DSC differential scanning
calorimetry) according to ASTM standard D3418-97 of
less than 10°C.
The polyurethane according to the invention comprises
several units (a2) resulting from several identical or
different polyolefins. (polyolefin mixtures) however
in this case each of the polyolefins comprises at
least 10 moll of units comprising at least one C=C
double bond.
The term "unit comprising a C=C double bond" means a
unit comprising at least one residual C=C double bond
preferably only one double bond it may be for
example a unit derived from the polymerization of a
butadiene or isoprene unit all isomeric forms included
(cis or trans 12- or 14-).
The polyolefin according to the invention may be an
olefin homopolymer. Examples that may be mentioned
include 12-butadiene 14-butadiene or isoprene
homopolymers and especially:
12-polybutadienes: -[CH2-CH(CH=CH2)-]n
poly(cis-14-isoprenes):
poly(trans-14-isoprenes):
The polyolefin according to the invention may also be a
copolymer of different olefins (olefin copolymer)
provided that the final polyolefin comprises at least
10 mol% of units comprising at least one C=C double
bond.
In a first embodiment the said polyolefin may consist
exclusively of units comprising at least one C=C double
bond. Examples that may be mentioned include
copolymers especially statistical copolymers
comprising 12-butadiene units and/or 14-butadiene
units in its cis and/or trans forms and/or is.oprene
units especially cis-14-isoprene and trans-14-
isoprene as a mixture. Mention may be made especially
of (12-butadiene/l4-butadiene) statistical
copolymers.
Preferably the polyolefins may be statistical and with
hydroxyl end groups and correspond to the following
structure:
in which:
m n and p being mole fractions between 0 and 1 and
m+n+p=l
especially m between 0.1 and 0.8 or even 0.15 and 0.7
p between 0.1 and 0.8 or even 0.15 and 0.7 and q
between 0.05 and 0.5 or even 0.1 and 0.4
n is an integer between 10 and 100 especially between
15 and 50
x - 0 or 1 and
X = divalent carbon-based radical especially linear
cyclic or branched alkylene containing 1 to 10 carbon
atoms especially methylene ethylene propylene or
isopropylene.
They may preferably have a number-average molecular
mass Mn of between 400 and 50 000 preferably between
500 and 30 000 better still between 1000 and 15 000
and even better still between 1500 and 12 000.
Mention may be made more particularly of:
polybutadienes with hydroxyl end groups such as the
polymers of structure:
with m = 0.6 p=0.2 and q = 0.2 (mole fractions) and
n = 25.
Mention may be made in particular of the commercial
products Poly bd R20LM and Poly bd R45HTLO from
Sartomer
polybutadienes. with primary hydroxyl end groups such
as the polymers that may be represented by the
following structure:
HO— CH—CHj OH
which are statistical copolymers especially of 14-cisbutadiene
and of 14-trans-butadiene with m = 0.17
0.65 and q = 0.18 (mole fractions) and n is such
that the number-average molecular weight Mn is between
1000 and 10 000 and especially between 2000 and
6000 (g.mol'1) .
Mention may be made in particular of the commercial
products Krasol LBH-P 2000 3000 or 5000 from Sartomer
- polybutadienes with secondary hydroxyl end groups
such as the polymers that may be represented by the
following structure:
CH—CHS
OH
which are statistical copolymers of 14-cis-butadiene
and of 14-trans-butadiene with in = 0.17 p = 0.65 and
q = 0.18 (mole fractions)r and n is such that the
number-average molecular weight Mn is between 1000 and
12 000 and especially between 2000 and 10 000 (g.mol"1) .
Mention may be made in particular of the commercial
products Krasol LBH 2000 3000 5000 or 10 000 from
Sartomer.
In a second embodiment the said polyolefin may also
comprise additional units not comprising a C=C double
bond.
However these additional units are present in a
maximum amount of 90 mol% given that the final
polyolefin should comprise at least 10 mol% of units
comprising at least one C=C double bond.
These additional blefin units may be chosen especially
from ethylene -(CH2-CH2)n- propylene - (CH2-CH2-CH2)n- or
isopropylene -(CHaCHfCHj) )n- units and/or butylene
units of formula:
and also mixtures thereof.
The olefin homopolymers o.r copolymers as defined above
may undergo after polymerization a partial
hydrogenation of the residual double bonds. This
hydrogenation cannot in any way be total.
Specifically the polyolefins that may be used to form
the units (a2) according to the invention should
necessarily comprise at least 10 mol% of units
comprising at least one C=C double bond (residual)
relative to the total amount of units forming the said
polyolefin.
They preferably comprise at least 20 mol% especially
at least 40 mol% or even at least 5.0 mol%
preferentially at least 80 mol% and most particularly
100 mo.1% of units comprising at least one C=C double
bond especially comprising only one C=C double bond.
This content of units comprising at least one C=C
double bond may especially be determined via the usual
techniques especially via NMR or iodine assay.
Preferably the polyolefin(s) forming the nonionic
units £a2) have a number-average molecular mass (Mn) of
between 400 and 50 000 preferably between 500 and
30 000 better still between 1000 and 15 000 and even
better still between 1500 and 12 000.
Preferably the polyolefina that may be used in the
context of the invention are:
homopolymers such as 14-polybutadiene and 12-
polybutadiene
copolymers of structure:
with
m n and p being mole fractions between 0 and 1 and
rtH-n+p=l
especially m between 0.1 and 0.8 or even 0.15 and 0.7
p between 0.1 arid 0.8 or even 0.15 and 0.7 and q
between 0.05 and 0.5 or even 0.1 and 0.4
n is an integer between 10 and 100. and especially
between 15 and 50
x = 0 or 1 and
X = divalent carbon-based radical especially linear
cyclic or branched alkylene containing 1 to 10 carbon
atoms especially methylene ethylene propylene or
isopropylene.
The cationic polyurethane according to the invention
also comprises at least one unit (b) resulting from at
least one compound comprising at least two isocyanate
functions.
It may obviously be a mixture of several compounds
comprising at. least two isocyanate functions.
The compounds comprising at least two isocyanate
functions may be chosen from diisocyanates or mixtures
of a diisocyanate and a polyisocyanate comprising more
than two isocyanate functions the said polyisocyanate
preferably representing 0.1% to 40% of the weight of
the said mixture especially 0.5% to 35% by weight or
even 1% to 30% by weight relative to the weight of the
said mixture.
The compounds comprising at least two isocyanate
functions may preferably be chosen from conjugated or
non-conjugated aromatic or non-aromatic cyclic
aliphatic diisocyanat.es. They may be chosen especially
from methylenediphenyl diisocyanate methylenecyclohexane
diisocyanate isophorone diisocyanate
toluene diisocyanate naphthalene diisocyanate
14-butane diisocyanate and 16-hexane diisocyanate
and a mixture thereof preferably isophorone
diisocyanate.
Preferentially the polyurethane according to the
invention consists essentially of:
in which:
Ra is a linear or branched divalent Ci-C6 alkylene
group especially methylene or ethylene
Rb is a linear or branched Ci-C6 alkyl group especially
a methyl ethyl n-butyl isobutyl or tert-butyl group
and X = 0
at least one nonionic unit resulting from polyolefins
chosen from 14-polybutadiene and 12-polybutadiene
homopolymers or eopolymers of structure:
m n and p being mole fractions between 0 and 1 and
m+n+p=l
especially m between 0.1 and 0.8 or even 0.15 and 0.7
p between 0.1 and 0.8 or even 0.15 and 0.7 and q
between 0.05 and 0.5 or even 0.1 and 0.4
n is an integer between 10 and 100 and especially
between 15 and 5.0
x •= 0 or 1 and
X = divalent carbon-based radical especially linear
cyclic or branched alkylene containing 1 to 10 carbon
atoms especially methylene ethylene propylene or
isopropylene
- at least one unit resulting from aliphatic
diisocyanates.
Even more preferentially the polyurethanes according
to the invention consist essentially of:
- at least one cationic unit resulting from amines of
formula:
in which Ra is a linear or branched divalent Ci-Ce
alkylene group/ especially methylene or ethylene and
Rb is a linear or branched Ci-Ce alkyl group especially
a methyl ethyl n-butyl isob.utyl or tert-butyl group
and more particularly N-methyldiethanolamine and
N-tert-butyldiethanolamine
- at least one nonionic unit resulting from polyolefins
of structure:
with
m n and p being mole fractions between 0 and 1 and
m-fn+p=l
especially m between 0.1 and 0.8 or even 0.15 and 0.7
p between 0.1 and 0.8 or even 0.15 and 0.7 and q
between 0.05 and 0.5 or even 0.1 and 0.4
n is an integer between 10 and 100 and especially
between 15 and 50
x = 0 or 1 and
X = divalent carbon-based radical especially linear
cyclic or branched alkylene containing 1 to 1.0 carbon
atoms especially methylene ethylene propylene or
isopropylene
- at least one unit resulting from diisocyanates chosen
from methylenecyclohexane diisocyanate isophorone
diisocyanate 14-butane diisocyanate and 16-hexane
diisocyanate and a mixture thereof preferably
isophorone diisocyanate.
The polyurethane according to the invention consists
essentially of units (al) (a2) and (b) as defined
above which implies that it does not comprise
additional units other than these.
The physical parameter that best characterizes the
viscoelastic properties of the cationic polyurethane
according to the invention is its instantaneous strain
recovery Ri.
The cationic polyurethane of the present invention
preferably has an instantaneous recovery (Ri) measured
under the conditions indicated below before the
examples of between 5% and 95% in particular between
20% and 90% and ideally between 50% and 85% especially
between 55% and 05%
The viscosity of the polyurethane according to the
invention measured at .10% in tetrahydrofuran (THF) at
25°C with a Brookfield viscometer needle module is
generally between 1 and 1000 cps preferably between 1
and 100 cps and better still between 2 and 80 cps. polyurethane is characterized in non-neutralized form.
The polyurethane according to the present invention
preferably has at least two glass transition
temperatures (Tg) at least one of which is preferably
less than 10°C preferably less than 0°C and better
still less than -10°C and at least one other is
preferably greater than or equal to room temperature
(20°C).
The instantaneous recovery and consequently the
viscoelastic properties of the polyurethane according
to the invention depend on the nature and the amount of
the various units (al) (a2) and (b).
The fraction of cationic units (al) should preferably
be sufficient to give the polymers their positive
charge responsible for their good affinity for keratin
substrates.
The nonionie unit(s) (a2) should preferably represent
weight fraction sufficient for the polyurethanes to
have at least one glass transition temperature of less
than 10°C and not to form brittle films.
Preferably the amines forming the cationic or
cationizable units (al) represent from 0.1% to 50%
preferably from 1% to 30% and better still from 5% to
20% by weight relative to the total weight of the
final polyurethane.
Preferably the polyolefins forming the nonionie units
(a2) represent from 30% to 99% by weight preferably
from 50% to 90% and better still from 60% to 80% by
weight relative to the total weight of the final
polyurethane.
Preferably the compounds comprising at least two
isocyanate functions forming the units (b) are
present in an essentially stoichiometric amount
relative to the sum of the tertiary/quaternary amines
forming the units (al) and of the polyolefins forming
the units (a2)
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 labile hydrogen. A person skilled in the art
will know how to select a possible molar excess of one
or the other type of function to adjust the molar mass
to the desired value.
Thus preferably the compounds comprising at least two
isocyanate functions forming the units (b) represent to 60% by weight especially 5% to 50% by weight and
better still 15% to 35$ by weight relative to the
total weight of the final polyurethane.
In order to form the polyureth.ane according to the
invention the following are preferably used:
20 mol% to 55 mol% especially 25 mol% to 50 mol% or
even from 30 mol% to 47 mol% o.f tertiary and/or
quaternary amine(s) capable of forming the units (al)
1 mol% to 30 mol% especially 2 mol% to 25 mol% or
even from 3 mol$ to 20 mol% of polyolefin(s) capable of
forming the units (a2) and
30 mol% to 65 mol% especially 35 mol% to 60 mol% or
even from 45 mol% to 55 mol% of compound(s) comprising
at least two isocyanate functions capable of forming
the units (b).
Preferentially the mole ratio between (b) and
(al) + (a2) is close to 1 and especially between 0.9 and
1.1.
The cationic or cationizable polyurethane of elastic
nature according to the invention finds a most
particular application in cosmetics and
Pharmaceuticals. Thus it may be incorporated into many
cosmetic compositions in which it will improve the
cosmetic properties especially in terms of styling.
The amount of polyurethane present in the compositions
obviously depends on the type of composition and on the
desired properties and may vary within a very wide
range generally of between 0.1% and 90% by weight
preferably between 1% and 50% by weight especially
between 2% and 25% by weight or even between 5% and
15% by weight and better still between 6% and 10% by
weight relative to the weight of the final cosmetic or
pharmaceutical composition.
Thus when the polyurethane according to the invention
is intended to be incorporated into hair compositions
such as hair lacquers its content is preferably
between 0.1% and 25% by weight especially between 1%
and 20% by weight better still between 2% and 15% by
weight or even between 4% and 8% by weight relative
to the weight of the final composition.
When it is intended to be incorporated into styling
compositions it preferably represents 0.5% to 20% by
weight especially between 1% and 15% by weight better
still between 2% and 10% by weight or even between 5%
and 8% by weight relative to the weight of the
composition.
When it is intended to be incorporated into
compositions of shampoo type it preferably represents
0.1% to 20% by weight especially 0.5% to 15% by
weight better still between 1% and 10% by weight or
even between 2% and 5% by weight relative to the
weight of the composition.
The compositions according to the invention may be in
any galenical form conventionally used for topical
application and especially in the form of an aqueous
alcoholic or aqueous-alcoholic solution or suspension
an oily solution or suspension a solution or
dispersion of the lotion or serum type an emulsion of
liquid or semi-liquid consistency of the milk type
obtained by dispersing a fatty phase in an aqueous
phase (0/W) or conversely (W/0) a suspension or
emulsion of soft consistency of the (0/W) or (W/0)
cream type an aqueous or anhydrous gel an ointment a
loose or compacted powder to be used in its native form
or to be incorporated into an excipient or any other
cosmetic form.
The cosmetic or pharmaceutical compositions according
to the invention comprise besides the said polymers a
physiologically acceptable and especially a
cosmetically or pharmaceutically acceptable medium
especially a dermatologically acceptable medium i.e. a
medium that is compatible with cutaneous tissue for
instance facial or bodily skin and keratin materials
such as the hair the eyelashes the eyebrows and the
nails.
Preferably the physiologically acceptable medium
comprises a solvent medium or a dispersion of polymers
according to the invention which may comprise at least
one compound chosen from water alcohols polyols
esters carbon-based oils silicone oils and
fluorosilicone oils and mixtures thereof.
Preferably the physiologically acceptable medium of
the compositions according to the invention may
comprise water or a mixture of water and of hydrophilic
organic solvent(s) for instance alcohols and
especially linear or branched Gi-Cg monoalcohols for
instance ethanol tert-butanol n-butanol isopropanol
n-propanol or 2-butoxyethanol and polyols for
instance glycerol diglycerol ethylene glycol
propylene glycol sorbitol pentylene glycol and
polyethylene glycols or alternatively polyol or glycol
ethers especially of C2 such as diethylene glycol
mono-ethyl ether and monomethyl ether and hydrophilic
C2-C4 aldehydes.
The composition according to the invention may also
comprise at least one cosmetieally acceptable adjuvant
conventionally used in cosmetic compositions intended
to be applied to keratin fibres.
Cosmetieally acceptable adjuvants that may be mentioned
in particular include gelling agents and/or thickeners
associative or non-associative polymers anionic
nonionic cationic and/or amphoteric surfactants propenetrating
agents emulsifiers fragrances preserving
agents fillers sunscreens dyestuffs proteins
vitamins provitamins fixing or non-fixing anionic
nonionic cationic or amphoteric polymers
moisturizers emollients softeners mineral plant or
synthetic oils hydrophilic or lipophilic active
agents for instance ceramides and pseudoceramides
antifoams antiperspirants free-radical scavengers
bactericidal agents and anti-dandruff agents.
A person skilled in the art will take care to select
the optional additives and the amount thereof such that
they do not harm the properties of the compositions of
the present invention.
Preferably the composition according to the invention
may be in the form of a thickened or non-thickened
lotion a thickened or non-thickened cream a gel a
mousse or any other suitable form. It may optionally be
packaged in a pump-dispenser bottle or in an aerosol
container.
The cosmetic composition according to the invention may
be in the form of a care cleansing and/or makeup
product for bodily or facial skin the lips the
eyelashes the nails and the hair an antisun product
or self-tanning product a body hygiene product or a
hair product especially a product for caring for
cleansing styling or colouring the hair.
It especially finds a particularly advantageous
application in the field of haircare especially for
holding the hairstyle or for shaping the hair or
alternatively for cleansing the hair. The hair
compositions are preferably shampoos hair
conditioners styling or care gels care lotions or
creams conditioners hairsetting lotions blow-drying
lotions and fixing and styling compositions such as
lacquers or sprays. The lotions may be packaged in
various forms especially in vaporizers or pumpdispenser
bottles or in aerosol containers in order to
allow application of the composition in vaporized form
or in the form of a mousse.
It may especially be in the form of a hair colouring
product or in the form of a permanent-waving relaxing
or bleaching composition or alternatively in the form
of rinse-out compositions to be applied before or
after dyeing bleaching permanent-waving or relaxing
the hair or alternatively between the two steps of a
permanent-waving or hair-relaxing operation.
The composition according to the invention may also be
in the form of a care composition especially a
moisturizing composition for the skin the lips and/or
the integuments or in the form of a skin cleansing
composition for example a. makeup-removing product or a
bath or shower gel.
It may also be in the form of an uncoloured care
product intended for treating the skin and especially
for moisturizing it making it smooth depigmenting it
nourishing it protecting it against solar rays or
giving it a specific treatment.
It may also be in the form of a body hygiene
composition especially in the form of a deodorant or
antiperspirant product or alternatively in the form of
a hair-removing composition.
It may also be in the form of a makeup product in
particular a coloured makeup product for bodily or
facial skin or for the hair in particular a
foundation optionally having care properties a
blusher a makeup rouge an eyeshadow a concealer
product an eyeliner a lip makeup product for
instance a lipstick/ optionally having care properties
a lip gloss lip pencils a makeup product for the
integuments for instance the nails or the eyelashes
in particular in the form of a mascara cake or for the
eyebrows and the hair a temporary tattoo product for
bodily skin.
Advantageously the composition according to the
invention is a hair composition for styling the hair
and may be in the form of a gel a mousse or a spray.
A subject of the invention is also a cosmetic treatment
process especially for making up earing for
cleansing colouring or shaping keratin materials
especially bodily or facial skinr the nails head hair
bodily hair and/of the eyelashes comprising the
application to the said materials of a cosmetic
composition as defined above.
Preferably it is a cosmetic treatment process for
shaping and/or holding the hair comprising the
application of a composition according to the invention
to the said hair optionally followed by a rinsing
step.
The invention is illustrated in greater detail in the
examples that follow.
Determination of the molar masses
The weight-average (Mw) and number-average (Mn) molar
masses are determined by gel permeation liquid
i chromatography or GPC (THF solvent calibration curve
established with linear polystyrene standards
refractomeric detector).
The dispersity index is calculated in the following
i manner: Ip = Mw/Mn
The GPC is performed with Styragel HR4/7.8 x 300 mm
columns sold by Waters WAT044225.
i The detection is performed with a Waters 410
refractometer.
The eluent is THF (tetrahydrofuran) at a flow rate of
1 ml/minute.
i
The volume injected is 50 microlitres at 25°C.
The calibration is performed using polystyrene
standards.
i
Determination of the instantaneous recovery Ri
The physical parameter that best characterizes the
viscoelastic properties of the polyurethane according
i to the invention is its instantaneous strain recovery.
This recovery is determined by means of a creep test
under tension which consists in rapidly stretching a
sample to a predetermined degree of elongation
> followed by releasing the stress and measuring the
length of the sample.
The creep test used for the characterization of the
polyurethane according to the invention is performed in
the following manner:
A polyurethane film with a thickness of 500 ± 50 mm
cut into strips of 80 mm x 15 mm is used as sample.
This copolymer film is obtained by drying at a
temperature of 22 ± 2°C and at a relative humidity of
50+5% of solution or dispersion at 3% by weight of
the said polyurethane in water and/or ethanol.
Each strip is fixed between two jaws 50 ± 1 mm apart
and is stretched at a speed of 20 mm/minute (under the
above temperature and relative humidity conditions) to
an elongation of 50% (Bmax) i.e. up to 1.5 times its
initial length. The stress is then released by imposing
a return speed equal to the tension speed i.e.
20 mm/minute and the elongation of the sample
(expressed as a % relative to the initial length) is
measured immediately after returning to zero load
The instantaneous recovery is calculated using the
The hydrophobicity of the polymer is measured on filmsvia determination of the contact angles or drop angle.
When a drop of liquid is placed on a flat solid
surface the angle between the tangent to the drop at
the point of contact and the solid surface is known as
the contact angle (9) . It takes into account the
amplitude of a liquid to spread out on a surface and
depends on the interactions between the liquid and the
solid.
Measurement of this angle gives us several types of
information:
- if water is used as liquid for measuring "the contact
angle the hydrophobia nature (low surface energy) or
hydrophilic nature {high surface energy) of the surface
may be deduced. Thus the greater the contact angle
the more hydrophobia the surface
measurement of the hysteresis between the angle at
the leading edge of the drop and at the trailing edge
of the drop gives information regarding the physical
inhomogeneity (roughness) or chemical inhomogeneity of
the surface.
Example 1
he following are introduced into a 1 litre reactor:
69.7 g of (12.9 mol%) of Polybd R45 HT10 from
Sartomer which is a polybutadiene resin containing
hydroxyl end groups
8.15 g (355 raol%) of N-methyldiethanolamine (NMDEA)
0.025 g of dibutyltin dilaurate (DBTL) and
100 g of methyl ethyl ketone (MEK).
The medium is homogenized by stirring and with heating
to 70°C. When the medium is homogeneous 22.1 g
(51.6 mol%) of isophbrone diisocyanate (IPDI) are added
and the mixture is refluxed for 8 hours.
After 8 hours an infrared analysis of the reaction
medium shows a weak residual NCO band at 2250 cm"1. 10 g
of ethanol and 130 g of methyl ethyl ketone are added
and the mixture is then allowed to return to room
temperature.
A polymer solution with a final dry extract of 28% is
obtained.
177 g of the above polymer solution at 28% in MEK is
introduced into a 1 litre reactor and is then diluted
with 105 g of THF (tetrahydrofuran) . The solution is
heated to 70°C and 90 mol% of the amine functions are
then neutralized by introducing 30.8 g of IN HC1. 250 g
of water are then added and the organic solvents are
distilled off under vacuum to obtain an opaque aqueous
gel with a dry extract of 15.3%.
Example 2
A/
The following are introduced into a 1 litre reactor:
70 g (11.4 mol%) of Krasol LBH-P 3000 which is a
polybutadiene containing primary hydroxyl end groups
of Mn = 3200
8.8 g (38.6 mol%) of N-methyldiethanolamine (NMDEA)
0.025 g of dibutyltin dilaurate (DETL) and
100 g of methyl ethyl ketone (MEK).
The medium is homogenized with stirring and by heating
to 70°C. When the medium is homogeneous 21.2 g (49.9%)
of isophorone diisocyanate are added and the mixture is
refluxed for 8 hours.
After 8 hours an infrared analysis of the reaction
medium shows no more trace of residual NCO at 2250 cm'1.
10 g of ethanol and 150 g of MEK are added and the
mixture is then allowed to return to room temperature.
ft polymer solution with a final dry extract of 28% is
btained.
180 g of the above polymer solution at 28% in MEK are
introduced into a 1 litre reactor. The solution is
heated to 70°C and 90 mol% of the amine functions are
then neutralized by introducing 33.2 g of IN HC1. 87 g
of water and 70 g of ethanol are then added to
homogenize the medium. The dilution is completed with
370 g of water and the mixture is then homogenized by
adding 110 g of THF. The organic solvents are distilled
off under vacuum to obtain an opaque aqueous gel with a
dry extract of 10.9%..
The instantaneous recovery (.Rj) is Ri = 75.5%.
Example 3

The following are introduced into a 1 litre reactor:
70.9 g (7.9 mol%) of Krasol LBH 5000 which is a
polybutadiene containing secondary hydroxyl end groups
of Mn = 3000
9.1 g {42.3 mol%) of N-methyldiethanolamine (NMDEA)
0.025 g of dibutyltin dilaurate (DBTL) and
100 g of methyl ethyl ketone (MEK).
The medium is homogenized with stirring and by heating
to 70DC. When the medium is homogeneous 20 g
(49.8 mol%) of isophorone diisocyanate are introduced
and the medium is refluxed for 8 hours.
After 8 hours an infrared analysis of the reaction
medium shows no more trace of residual NCO at 2250 cirf1.
10 g of ethanol and 150 g of MEK are added and the
mixture is then allowed to return to room temperature.
The polymer in solution with a final dry extract of
28% is obtained.
175 g of solution of the above polymer at 2.8% in MEK
are introduced into a 1 litre reactor. The solution is
diluted with 100 g of THF and then heated to 70°C.
90 mol% of the amine functions are neutralized by
introducing 34.4 g of IN HC1. 250 g of water and then
150 g of ethanol are then added to homogenize the
medium. The organic solvents are then distilled off
under vacuum to obtain an opaque white aqueous
dispersion with a dry extract of 17.6% and a pH = Example 4
The following are introduced into a 1 litre reactor:
- 70.5 g (4 mol%) of Krasol LBH 10 000 which is a
polybutadiene containing secondary hydroxyl end groups
of Mn - about 10 000
- 9.8 g (46.2 mol%) of N-methyldiethanolamine (NMDEA)
- 0.025 g of dibutyltin dilaurate (DBTL) and
- 100 g of methyl ethyl ketone (MEK).
The medium is homogenized with stirring and by heating
to 70°C. When the medium is homogeneous 19.7 g
(49.8 raol%] of isophorone diisocyanate are introduced
and the medium is refluxed for 8 hours.
After 8 hours an infrared analysis of the reaction
medium shows no more trace of residual NCO at 2250 cm'1.
10 g of ethanol and 150 g of MEK are added and the
mixture is then allowed to return to room temperature.
The polymer in solution with a final dry extract of
29% is obtained.
171 g of solution of the above polymer at 29% in MEK
are introduced into a 1 litre reactor. 100. g of THF are
added and the solution is heated to 7.0.°C. 90 mol% of
the amine fractions are neutralized by introducing 37 g
of IN H.C1. 250 g of water are then added. The organic
solvents are distilled off under vacuum to obtain an
opaque white aqueous dispersion with a dry extract of
17.6%.
Example 5
A/
The following are introduced into a 1 litre reactor:
- 67.9 g (16 mol%) of Krasol LBH-P 2000 which is a
polybutadiene containing primary hydroxyl end groups
of Mn = 2100
- 8.7 g (34.4 rnol%) of N-methyldiethanolamine (NMDEA)
- 0.025 g of dibutyltin dilaurate (DBTL) and
- 100 g of methyl ethyl Icetone (MEK) .
The medium is homogenized with stirring and by heating
to 70°C. When the medium is homogeneous 23.4 g
(49.6 mol%) of isophorone diisocyanate are introduced
and the medium is refluxed for 8 hours.
After 8 hours an infrared analysis of the reaction
medium shows the absence of NCO band at 2250 cm"1. 10 g
of ethanol and 150 g of THF are added and the reaction
medium is then allowed to return to room temperature.
The polymer in solution with a final dry extract of
25.5% is obtained.
B/
196 g of solution of the above polymer at 25.5% in the
MEK/THF mixture are introduced into a 1 litre reactor.
The solution is heated to 70°C and 90 mol% of the amine
functions are then neutralized by introducing 32.9 g of
IN HC1. 300 g of water are then added and the reaction
medium is then evaporated under vacuum to obtain an
opalescent dispersion with a dry extract of 14.4% and
of pH = 4.5.
The instantaneous recovery (Ri) is Ri = 72%.
Mass: typ - 48 900 g/irvol Mn = 31 100 g/nol Mw - 56 800 g/mol
38 g of dry polymer obtained by evaporation of the
solvents and drying of the solution prepared in step A
are introduced into a 1 litre reactor and dissolved in
38 g of MEK by heating to 70°C. 40 mol% of the amine
functions are neutralized by adding 11 g of IN HC1.
77 g of water are then added and the MEK is evaporated
off under vacuum. A fluid opalescent latex (dispersion)
is then obtained.
Example 6
The synthesis is identical to that of Example 5 except
that 0.01% of catalyst is used instead of 0.025%.
The following are introduced into a 1 litre reactor:
- 203.7 g of Krasol LBH-P 2000
- 26.1 g of N-methyldiethanol amine (NMDEA)
- 0.03 g of dibutyltin dilaurate (DBTL) and
- 300 g of methyl ethyl ketone (MEK) .
The medium is homogenized with stirring and by heating
to 70°C. When the medium is homogeneous 70.2 g of
isophorone diisocyanate are added and the mixture is
refluxed for 8 hours.
After 8 hours an infrared analysis of the reaction
medium shows the absence of an NCO band at 2250 cm l.
30 g of ethanol are added and the reaction medium is
then allowed to return to room temperature.
The polymer in solution/ with a final dry extract of
53.5% is obtained.
Mass: Mp = 58 300 g/inol Mn - 37 500 g/mol Mw = 70 700 g/mol
B187 g of 53.5% solution of the polyme± prepared in step
A are introduced into a 1 litre reactor 13 g of MEK
are added to obtain a solution with .a dry extract of
50% and the solution is then heated to 70°C. 40 mol%
of the amine functions are neutralized by adding 29.2 g
of IN HC1. 204 g of water are then added and the MEK is
evaporated off under vacuum. An opalescent dispersion
with a dry extract of 30.1% is thus obtained.
The instantaneous recovery (Rj.) is Ri = 72%.
C/
58.9 g of 53.5% solution of the polymer prepared in
step A above are introduced into a 1 litre reactor 8 g
of MEK are added to obtain a solution with a dry
extract of 50%. The solution is heated to 70 °C and
90 mol% of the amine functions are then neutralized by
introducing 38.7 g of IN HC1. 295 g of water are then
added and the MEK is then evaporated off under vacuum.
A fluid opalescent latex with a dry extract of 14.8% is
thus obtained.
The instantaneous recovery (Ri) is Ri = 73%.
D/
20 g of the polymer obtained in step A above are
introduced into a 500 ml three-necked flask and diluted
to 20% in MEK. 207.3 g of iodomethane (Mel) are added
and the mixture is stirred at room temperature for
24 hours. After 24 hours the medium has gelled and
turned yellow.
200 g of the MEK/Mel mixture are distilled off by
heating to 100&C. 200 g of MEK are then added and a
further 200 g of solvent are: distilled off to remove
the traces of residual iodomethane.
162 q of water are then added with stirring and a twophase
medium is recovered which is evaporated under
vacuum.
A white latex with a dry extract of 13.1% and of
pH = 55 is obtained.
The instantaneous recovery (Ri) is Ri ~ 75%.
Mass: Mp = 58 30Q g/mol Mn = 37 500 g/mol Mw = 70 700 g/mol
Ip = 1.9
Comparative Example 7
A comparative polymer is prepared according to
The following are introduced into a 1 litre reactor:
70 g (12.5 mol%) of PTMO (polytetrainethylene oxide)
of Mn - 2900
8.6 g (37.5 mol%) of N-methyldiethanolamine. (NMDEA)
0.025 g of dibutyltin dilaurate (DBTL) and
100 g of methyl ethyl ketone (MEK)-
The medium is homogenized with stirring and by heating
to 70°C. When the medium is homogeneous 21.4 g
(50 mol%) of isophorone diisocyanate are added and the
mixture is refluxed for 8 hours.
After 8 hoursr an infrared analysis of the reaction
medium shows the absence of an NCO band at 2250 cm"1.
10 g of ethanol are added and the reaction medium is
then allowed to return to room temperature.
The polymer in solution with a final dry extract of
50% is obtained.
200 g of solution of the above polymer with a dry
extract of 50% are introduced into a 1 litre reactor.
The solution is heated to 70°C and 90 mol% of the amine
functions are then neutralized by introducing 64.9 g of
IN HC1. 400 g of water are then added and the reaction
medium is then evaporated under vacuum to obtain an
opalescent dispersion with a dry extract of 20%.
The following three polymers are compared:
Comparative
Preparation of the films:
The polymer dispersions of Examples 5B 5C and 7B are
diluted to 13% with HPL.C water. 2 ml of dispersion
then placed on 1 cm x 5 cm glass plates. The films are
left to dry at ambient temperature and humidity (20°C)
for 24 hours.
Measurement of the contact angles:
Machine brand: GBX
Machine name: DGD Fast 160 Contact 'Angle Meter
Parameters: Method: Manual 2 photos at 100 ms drop
volume 3.5 ul vertical displacement: 95
Liquid used: water
The measurements are performed on the left and right
angles of the drop several measurements are taken so
as to obtain a mean value.
The contact angle values measured are given in the
table below.
The comparative polymer is markedly more hydrophilic
than the polymers according to the invention. The
incorporation of a polybutadiene segment thus makes
possible to render the material more hydrophobic and
more water resistant.
Moreover it is found that the deposit placed on a lock
of hair ('"strand") onto which the comparative polymer
7B has been applied (as a lotion impregnation drying
under a hood) is less water resistant than that
obtained with polymers 5B or 5C.
The comparative polymer 7B forms a tacky strand
whereas polymers 5B and 5C according to the invention
give non-tacky strands.
Example 8
A hair composition of lacquer type is prepared
comprising:
polymer of Example 1 6% AM (active material
demineralized water qs 100%
dimethyl ether: 35 g of gas per 65 g of 6% polymer
dispersion
Example 9
A hair composition of styling mousse type is prepared
comprising:
polymer of Example 1 6% AM (active material}
deraineralized water qs 100%
isobutane/propane/butane mixture: 5 g of gas per 95
of the 6% polymer dispersion.

1. Polyurethane consisting essentially of:
(al) at least one cationic or cationizable unit derived
from at least one tertiary or quaternary amine
containing at least two reactive functions containing
labile hydrogen
(a2) at least one nbnionic unit derived from at least
one polyolefin containing at least two reactive
functions containing labile hydrogen the said
polyolefin comprising at least 10 mol% of units
comprising at least one C=C double bond relative to
the total amount of units forming the said polyolefin
(b) at least one unit derived from a compound
comprising at least two isocyanate functions.
2. Polyurethane according to Claim I in which the
amines forming the units (al) are chosen from the
compounds of formulae:
which:
each Ra independently of each other represents a
linear or branched divalent d-C6 alkylene group or
alternatively a C3-C6 cycloalkylene or arylene or
mixtures thereof these groups possibly being
substituted with one or more halogen atoms and/or
comprising one or more heteroatoms cho.sen from 0 N
each Rb represents independently of each other a
linear or branched Ci-Cs alkyl group/ or alternatively a
cycloalkyl or aryl or mixtures thereof these
groups possibly being substituted with one or more
halogen atoms and/or comprising one or more heteroatoms
chosen from 0 N P and S
each R'b represents H or a linear or branched alkyl group or alternatively a cycloalkyl or
aryl or mixtures thereof these groups possibly being
substituted with one or more halogen atoms and/or
comprising one or more heteroatoms chosen from 0 N P
and S
m and p are independently of each other equal to 0
or 1} preferably m = 1 and p = 1
each X represents independently of each other an
oxygen or sulfur atom or a group NE( or NRC in which Rc
represents a Ci-Ce alkyl group and
- A" represents a physiologically acceptable counterion
and especially a halide such as chloride or bromide.
3. Polyurethane according to either of the preceding
claims in which the amines are:- of formula:

- Ra is a linear or branched divalent Ci-Cg alkylene
group especially methylene or ethylene and/or
- Rb is a linear or branched Ci-C6 alkyl group
especially a methyl ethyl n-butyl isobutyl or
tert -butyl group and/or
- X - 0.
4. Polyurethane according to. one of the preceding
claims in which the amine.s are of formula:
in which Ra is a linear or branched divalent Gi-Cg
alkylene group especially methylene or ethylene and
Rb is a linear or branched Ci-C$ allcyl group especially
a methyl ethyl n-butyl isobutyl or tert-butyl group.
5. Polyurethane according to one of the preceding
claims in which the amines are chosen from Nmethyldiethanolamine
and N-tert-butyldiethanolamine.
6. Polyurethane according to one of the preceding
claims in which the polyolefin containing at least two
reactive functions containing labile hydrogen forming
the nonionic units {a2j is an olefin homopolymer.
7 . Polyurethane according to Claim 6 in which the
homopolymer is chosen from 12-butadiene 1 4-butadiene
and isoprene homopolymers and especially 14-
polybutadienes in their cis and trans forms 12-
polybutadienes poly (cis-1 4-isoprenes) and
poly (trans-l4-isoprenes} .
8. Polyurethane according to one of Claims 1 to 5 in
which the polyolefin containing at least two reactive
functions containing labile hydrogen forming the
nonionic units (a2) is an olefin copolymer consisting
exclusively of units comprising at least one C=C double
bond.
9. Polyurethane according to Claim 8 in which the
polyolefin is chosen from copblymers especially
statistical copolymers comprising 12-butadiene units
and/or 14-butadiene units in its cis and/or trans
forms and/or isoprene units especially cis-14-
isoprene and trans-14-isoprene as a mixture.
10. Polyurethane according to either of Claims 8 and
9 in which the polyolefin is a (12-butadiene/
14-butadiene) statistical copolymer.
11. Polyurethane according to either of Claims 8 and
9 in which the polyolefin is statistical and
corresponds to the following structure:
in which:
m n and p being mole fractions between 0 and 1 and
m+n+p=l
especially m between 0.1 and 0.8 or even 0.15 and 0.7
p between 0.1 and 0.8 or even 0.15 and 0.7 and q
between 0.05 and 0.5 or even 0.1 and 0.4
n is an integer between 10 and 100 especially between
15 and SO
x = 0 or 1 and
X = divalent carbon-based radical especially linear
cyclic or branched alkylene containing 1 to 10 carbon
atoms especially methylene ethylene propylene or
isopropylene.
12. Polyurethane according to Claim 11 in which the
polyolefin is chosen from:
polybutadienes with hydroxyl end groups such as the
polymers of structure:
Jn
with m=06 p = q ~ 0.2 and n = 25
polybutadienes with primary hydroxyl end groups such
as the polymers of structure:
with m = 0.17 p = 0.65 and q = 0.18- and n is such
that the number-average molecular weight Mn is between
1000 and 10 000 and especially between 2000 and 6000
polybutadienes with secondary hydroxyl end groups
such as the polymers of the following structure:
with m = 0.17 p = 0.65 and q = 0.18 and n is such that
the number-average molecular weight Mn is between 1000
and 12 000 and especially between 2000 and 10 000.
13 Polyurethane according to one o.f Claims 1 to 5 in
which the polyolefin containing at least two reactive
functions containing labile hydrogen forming the
nonionic units (a2) is a copolymer also comprising
additional units not comprising a C=C double bond
present in a maximum amount of 90 mol%.
14. Polyurethane according to Claim 13 in which the
additional units are chosen from ethylene -(CH2-CH2)n-
propylene -(CH2-CH2-CH2) B- or isopropylene
- (CH2CH(CH3) )„- units and/or butylene units of formula:
1.5. Polyurethane according to one of the preceding
claims in which the polyolefins that may be used to
form the units (a2) comprise at least 20 mol%
especially at least 40 mol% or even at least 50 11101%
preferentially at least 80 mol% and most particularly
100 mol% of units comprising at least one C=C double
bond relative to the total amount of units forming the
said polyolefin.
16. Polyurethane according to one of the preceding
claims in which the polyolefins that may be used are
chosen from:
- homopolymers such as 14-polybtatadiene and 12-
polybutadiene
- copolymers of structure:
m n and p being mole fractions between 0 and 1 and
especially m between 0.1 and 0.8 or even 0.15 and 0.7
p between 0.1 and 0.8 or even 0.15 and 0.7 and q
between 0.05 and 0.5 or even 0.1 and 0.4
n is an integer between 10 and 100 and especially
between 15 and 50
x = 0 or I and
X = divalent carbon-based radical especially linear
cyclic or branched alXylene containing 1 to 10 carbon
atoms especially methylene ethylene propylene or
isopropylene.
17. Polyurethane according to one of the preceding
claims in which the polyolefin(s) forming the nonionic
units (a2) have a number-average molecular mass (Mn) of
between 400 and 50 000 preferably between 500 and
3Q 000 better still between 1000 and 15 000 and even
better still between 1500 and 12 000.
18. Polyurethane according to one of the preceding
claims in which the compound comprising at least two
isoeyanate functions is chosen from diisocyanates or
mixtures of a diisocyanate and of a polyisocyanate
comprising more than two isoeyanate functions the said
polyisocyanate preferably representing 0.1% to 40% of
the weight of the said mixture especially 0.5% to 35%
by weight or even 1% to 30% by weight relative to the
weight of the said mixture.
19. Polyurethane according to one of the preceding
claims in which the compound comprising at least two
isoeyanate functions is chosen from conjugated or nonconjugated
aromatic or nOn-arbmatic cyclic aliphatic
diisocyanates.
20. Polyurethane according to one of the preceding
claims in which the compound comprising at least two
isoeyanate functions is chosen from methylenediphenyl
diisocyanate methylenecyclohexane diisocyanate
isophorone diisocyanate toluene diisocyanate
naphthalene diisocyanate 14-butane diisocyanate and
16-hexane diisocyanate and a mixture thereof
preferably isophorone diisocyanate.
21. Polyurethane according to one of the preceding
claims consisting essentially of:
in which:
Ra is a linear or branched divalent Ci-C6 alkylene
group especially methylene or ethylene
Rb is a linear or branched Ci-Cg alkyl group especially
a methyl ethyl n-butyl isobutyl or tert-butyl group
and X = 0
- at least one nonionic unit resulting from polyolefins
chosen from 14-polybutadiene and 12-polybutadiene
homopolymers or copolymers of structure:
m n and p being mole fractions between 0 and 1 and
m-f n+p=l
especially m between 0.1 and 0.8 or even 0.15 and 0.7
p between 0.1 and Q.8f or even 0.15 and 0.7 and q
between 0.05 and 0.5 or even 0.1 and 0.4
n is an integer between 10 and 100 and especially
between 15 and 50
x = 0 or 1 and
X - divalent carbon-based radical especially linear
cyclic or branched alkylene containing 1 to 10 carbon
atoms especially methylene ethylene propylene or
is.opropylene
- at least one unit resulting from aliphatic
diisocyanates.
22. Polyurethane according to one of the preceding
claims consisting essentially of:
- at least one. cationie unit resulting from amines
in which Ra is a linear or branched divalent C:-C6
alkylene group especially methylene or ethylene and
Rb is a linear or branched Ci-Cg alkyl group especially
a methyl ethyl n-butyl isobutyl or tert -butyl group
and more particularly N-methyldiethanolamine and
N-tert-butyldiethanolamine
- at least one nonionic unit resulting from polyolefins
of structure:
with
m n and p being mole fractions between 0 and 1 and
m+n-f-p=l
especially m between 0.1 and 0.8 or even 0.15 and 0.7
p between 0.1 and 0.8 or even 0.15 and 0.7 and q
between 0.05 and 0.5 or even 0.1 and 0.4
n is an integer between 10 and 100 and especially
between 15 and 50
x• = 0 or 1 and
X = divalent carbon-based radical especially linear
cyclic or branched alkylene containing 1 to 10 carbon
atoms especially methylene ethylene propylene or
isopropylene
- at least one unit resulting from diisocyanates chosen
from methylenecyelohexarie diisocyanate isophorone
diisocyanate 14-butane diisocyanate and 16-hexane
diisocyanate and a mixture thereof preferably
isophorone diisocyanate.
23. Polyurethane according to one of the preceding
claims in which:
- the amines forming the cationic or cationizable (al) represent from 0.1% to 50% preferably from 1% to
30% and better still from 5% to 20% by weight relative
to the total weight of the final polyurethane and/or
- the polyolefins forming the nonionic units (a2)
represent from 30% to 99% by weight preferably from
50% to 90% and better still from 60% to 80% by weight
relative to the total weight of the final polyurethane
and/or
- the compounds comprising at least two isocyanate
functions forming the units (b) represent from 1% to
60% by weight especially 5% to 50% by weight and
better still 15% to 35% by weight relative to the
total weight of the final polyurethane.
24. Cosmetic or pharmaceutical composition comprising
in a physiologically acceptable medium at least one
polyurethane as defined in one of the preceding claims.
25. Composition according to Claim 24 in which the
polyurethane is present in an amount of between 0.1%
and 90% by weight preferably between 1% and 50% by
weight especially between 2% and 25% by weight or
even between 5% and 15% by weight and better still
between 6% and 10% by weight relative to the weight of
the composition.
26. Composition according to either of Claims 24 and
25 in which the physiologically acceptable medium
comprises at least one compound chosen from water
alcohols polyols polyol or glycol ethers hydrophilic
C'2-C^ aldehydes esters carbon-based oils silicons
oils fluorosilicone oils gelling agents and/or
thickeners such as anionic nonionic or cationic
associative or non-associative polymers anionic
nonionic cationic and/or amphoteric surfactants propenetrating
agents emulsifiers fragrances preserving
agents fillers sunscreens silicone.s dyestuffs
proteins vitamins provitamins fixing or non-fixing
anionic nonionic cationic or amphoteric polymers
moisturizers emollients softeners mineral plant or
synthetic oils hydrophilic or lipophilic active
agents for instance ceramides and pseudoceramides
antifoams antiperapirants free-radical scavengers
bactericidal agents and anti-dandruff agents and also
mixtures thereof.
27. Composition according to one of Claims 24 to 26
which is in the form of a product for caring for
cleansing and/or making up bodily or facial skin the
lips the eyelashes the nails and the hair an antisun
or self-tanning product a body hygiene product a hair
product especially for caring for cleansing styling
or colouring the hair.
28. Composition according to one of Claims 24 to 27
which is in the form of a half composition especially
for holding the hairstyle or for shaping the hair.
29. Composition according to one of Claims 24 to 27
which is in the form of a hair composition of hair
lacquer type and in which the polyurethane is present
in a content of between 0.1% and 25% by weight
especially between 1% and 20% by weight better still
between 2% and 15% by weight or even between 4% and 8%
by weight relative to the weight of the composition.
30. Composition according to one of Claims 24 to 27
which is in the form of a styling composition in which
the polyurethane is present in a content of from 0.5%
to 20% by weight especially between 1% and 15% by
weight better still between 2% and 10% by weight or
even between 5% and 8% by weight relative to the
weight of the composition.
31. Composition according to one of Claims 24 to 27
which is in the form of a hair composition of shampoo
type in which the polyurethane is present in a content
of from 0.1% to 20 by weight especially 0.5% to 15%
by weight better still between 1% and 10% by weight or
even between 2% and 5% by weight relative to the
weight of the composition.
32. Cosmetic treatment process especially for making
up caring for cleansing colouring or shaping keratin
materials especially bodily or facial skin the nails
head hair bodily hair and/or the eyelashes comprising
the application to the said materials of a cosmetic
composition as defined in one of Claims 24 to 31.
33. Cosmetic treatment process for shaping and/or
holding the hair comprising the application of a
cosmetic composition as defined in one of Claims 24 to
31 to the said hair optionally followed by a rinsing
step.