U.S. patent application number 12/746282 was filed with the patent office on 2010-12-09 for cosmetic makeup and/or care process using a siloxane resin and a film-forming polymer.
This patent application is currently assigned to L'Oreal. Invention is credited to Claudia Barba.
Application Number | 20100310489 12/746282 |
Document ID | / |
Family ID | 40566065 |
Filed Date | 2010-12-09 |
United States Patent
Application |
20100310489 |
Kind Code |
A1 |
Barba; Claudia |
December 9, 2010 |
COSMETIC MAKEUP AND/OR CARE PROCESS USING A SILOXANE RESIN AND A
FILM-FORMING POLYMER
Abstract
The present invention relates to a process for making up and/or
caring for keratin materials, in which a composition is applied to
the keratin materials, and especially to the lips, this composition
containing, in a physiologically acceptable medium: a) a siloxane
resin comprising the following units: (i)
(R.sup.1.sub.3SiO.sub.1/2).sub.a (ii)
(R.sup.2.sub.2SiO.sub.2/2).sub.b (iii) (R.sup.3SiO.sub.3/2).sub.c
and (iv) (SiO.sub.4/2).sub.d with R.sup.1, R.sup.2 and R.sup.3
independently representing an alkyl group containing from 1 to 8
carbon atoms, an aryl group, a carbinol group or an amino group, a
being between 0.05 and 0.5, b being between 0 and 0.3, c being
greater than 0, d being between 0.05 and 0.6, a+b+c+d=1, on
condition that more than 40 mol % of the groups R.sup.3 of the
siloxane resin are propyl groups, and b) at least one liquid fatty
phase, and c) at least one film-forming polymer chosen from the
group comprising: a film-forming block ethylenic polymer,
comprising at least a first block and at least a second block, is
characterized in that the first block is obtained from at least one
acrylate monomer of formula CH.sub.2.dbd.CH--COOR.sub.2 in which
R.sub.2 represents a C.sub.4 to C.sub.12 cycloalkyl group and at
least one methacrylate monomer of formula
CH.sub.2.dbd.C(CH.sub.3)--COOR.sub.2 in which R'.sub.2 represents a
C.sub.4 to C.sub.12 cycloalkyl group, and characterized in that the
second block is obtained from an acrylic acid monomer and from at
least one monomer with a glass transition temperature of less than
or equal to 20.degree. C., a vinyl polymer comprising at least one
carbosiloxane dendrimer-based unit, a dispersion of acrylic or
vinyl radical homopolymer or copolymer particles dispersed in the
said liquid fatty phase.
Inventors: |
Barba; Claudia; (Paris,
FR) |
Correspondence
Address: |
OBLON, SPIVAK, MCCLELLAND MAIER & NEUSTADT, L.L.P.
1940 DUKE STREET
ALEXANDRIA
VA
22314
US
|
Assignee: |
L'Oreal
Paris
FR
|
Family ID: |
40566065 |
Appl. No.: |
12/746282 |
Filed: |
December 5, 2008 |
PCT Filed: |
December 5, 2008 |
PCT NO: |
PCT/FR08/52228 |
371 Date: |
August 24, 2010 |
Related U.S. Patent Documents
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Application
Number |
Filing Date |
Patent Number |
|
|
60992357 |
Dec 5, 2007 |
|
|
|
Current U.S.
Class: |
424/70.121 |
Current CPC
Class: |
A61Q 1/10 20130101; A61K
2800/591 20130101; A61K 2800/88 20130101; A61Q 1/06 20130101; A45D
33/00 20130101; A61K 8/31 20130101; A61K 8/891 20130101; A61Q 1/02
20130101 |
Class at
Publication: |
424/70.121 |
International
Class: |
A61K 8/90 20060101
A61K008/90; A61Q 5/00 20060101 A61Q005/00 |
Claims
1. A process for making up and/or caring for keratin materials,
comprising: applying to the keratin materials a composition,
comprising in a physiologically acceptable medium: a) a siloxane
resin comprising the following units: (i)
(R.sup.1.sub.3SiO.sub.1/2).sub.a (ii)
(R.sup.2.sub.2SiO.sub.2/2).sub.b (iii) (R.sup.3SiO.sub.3/2).sub.c
and (iv) (SiO.sub.4/2).sub.d wherein R.sup.1, R.sup.2 and R.sup.3
are each independently an alkyl group containing from 1 to 8 carbon
atoms, an aryl group, a carbinol group or an amino group, a is
between 0.05 and 0.5, b is between 0 and 0.3, c is greater than 0,
d is between 0.05 and 0.6, a+b+c+d=1, with the proviso that more
than 40 mol % of the groups R.sup.3 of the siloxane resin are
propyl groups, and b) at least one liquid fatty phase, and c) at
least one film-forming polymer chosen from the group comprising: a
film-forming block ethylenic polymer, comprising at least a first
block and at least a second block, wherein the first block is
obtained from at least one acrylate monomer of formula
CH.sub.2.dbd.CH--COOR.sub.2 R.sub.2 represents a C.sub.4 to
C.sub.12 cycloalkyl group and at least one methacrylate monomer of
formula CH.sub.2.dbd.C(CH.sub.3)--COOR'.sub.2 wherein R'.sub.2
represents a C.sub.4 to C.sub.12 cycloalkyl group, and the second
block is obtained from an acrylic acid monomer and from at least
one monomer with a glass transition temperature of less than or
equal to 20.degree. C., a vinyl polymer comprising at least one
carbosiloxane dendrimer-based unit, a dispersion of acrylic or
vinyl radical homopolymer or copolymer particles dispersed in the
said liquid fatty phase.
2. The process for making up and/or caring for keratin materials
according to claim 1, wherein the said siloxane resin comprises:
(i) (R.sup.1.sub.3SiO.sub.1/2).sub.a (iii)
(R.sup.3SiO.sub.3/2).sub.c and (iv) (SiO.sub.4/2).sub.d wherein
R.sup.1 and R.sup.3 each independently is an alkyl group containing
from 1 to 8 carbon atoms, a is between 0.05 and 0.5 , c is greater
than zero, d is between 0.05 and 0.6, a+b+c+d=1, with the proviso
that more than 40 mol % of the groups R.sup.3 of the siloxane resin
are propyl groups.
3. The process for making up and/or caring for keratin materials
according to claim 1 wherein the said siloxane resin is obtained
via a process comprising reaction between: A) an MQ resin
comprising at least 80 mol % of units
(R.sup.1.sub.3SiO.sub.1/2).sub.a and (SiO.sub.4/2).sub.d wherein
R.sup.1 is a methyl group, a and d are greater than zero, a ratio
a/d is between 0.5 and 1.5; and B) a T propyl resin comprising at
least 80 mol % of units (R.sup.3SiO.sub.3/2).sub.c, wherein R.sup.3
is a propyl group, c is greater than zero, in which a mass ratio
A/B is between 95/5 and 15/85 .
4. The process for making up and/or caring for keratin materials
according to claim 1, wherein the film-forming block ethylenic
polymer comprises an intermediate block comprising at least one
constituent monomer of the first block and at least one constituent
monomer of the second block, and a polydispersity index of the
film-forming block ethylenic polymer is greater than 2.
5. The process for making up and/or caring for keratin materials
according to claim 1, wherein, the second block of the film-forming
block ethylenic polymer is obtained from polymerization of acrylic
acid and isobutyl acrylate, and the first block is obtained from
polymerization of isobornyl acrylate and isobornyl
methacrylate.
6. The process for making up and/or caring for keratin materials
according to claim 1, wherein the vinyl polymer comprises at least
one carbosiloxane dendrimer of formula (I): ##STR00034## wherein Z
is a divalent organic group, p is 0 or 1, R.sup.1 is an aryl or
alkyl group of 1 to 10 carbon atoms and X.sup.i is a silylalkyl
group of formula (II): ##STR00035## wherein R.sup.1 is an aryl or
alkyl group of 1 to 10 carbon atoms, R.sup.2 is an alkylene group
of 1 to 10 carbon atoms, R.sup.3 is an alkyl group of 1 to 10
carbon atoms, and X.sup.i+1 is a group selected from the group
consisting of hydrogen atoms, aryl groups and alkyl groups
containing up to 10 carbon atoms, and silylalkyl groups the index i
is an integer from 1 to 10 indicating the generation of the
silylalkyl group starting in each carbosiloxane dendritic structure
with a value of 1 for the group X.sup.i in formula (I) and the
index a.sup.i is an integer from 0 to 3.
7. The process for making up and/or caring for keratin materials
according to claim 1, wherein the dispersion of homopolymer or
copolymer particles comprises polymer particles in dispersion
selected from acrylic polymers or copolymers which are insoluble in
water-soluble alcohols.
8. The process for making up and/or caring for keratin materials
according to claim 1, wherein a content of the film-forming polymer
is from 0.1% to 60% by weight of film-forming polymer solids.
9. The process for making up and/or caring for keratin materials
according to claim 1, wherein a total solids content of the
siloxane resin is from 1% to 80% by weight relative to the total
weight of the composition.
10. The process for making up and/or caring for keratin materials
claim 1, wherein the composition comprises less than 3% by weight
of water relative to the total weight of the composition.
11. The process for making up and/or caring for keratin materials
according to claim 1, wherein the composition further comprises at
least one structuring agent selected from the group consisting of
thickeners, organogelling agents, waxes, pasty fatty substances and
gums.
12. The process for making up and/or caring for keratin materials
according to claim 1, wherein the composition further comprises at
least one other oil, which is non-volatile.
13. The process for making up and/or caring for keratin materials
according to claim 1, wherein the composition further comprises at
least one dyestuff and/or at least one filler.
14. A composition for making up and/or caring for keratin
materials, comprising, in a physiologically acceptable medium: a) a
siloxane resin comprising the following units: (i)
(R.sup.1.sub.3SiO.sub.1/2).sub.a (ii)
(R.sup.2.sub.2SiO.sub.2/2).sub.b (iii) (R.sup.3SiO.sub.3/2).sub.c
and (iv) (SiO.sub.4/2).sub.d (i) (R.sup.1.sub.3SiO.sub.1/2).sub.a
(ii) (R.sup.2.sub.2SiO.sub.2/2).sub.b (iii)
(R.sup.3SiO.sub.3/2).sub.c and (iv) (SiO.sub.4/2).sub.d wherein
R.sup.1, R.sup.2 and R.sup.3 are each independently an alkyl group
containing from 1 to 8 carbon atoms, an aryl group, a carbinol
group or an amino group, a is between 0.05 and 0.5, b is between 0
and 0.3, c is greater than 0, d is between 0.05 and 0.6, a+b+c+d=1,
with the proviso that more than 40 mol % of the groups R.sup.3 of
the siloxane resin are propyl groups, and b) at least one liquid
fatty phase, and c) at least one film-forming polymer chosen from
the group comprising: a film-forming block ethylenic polymer,
comprising at least a first block and at least a second block,
wherein the first block is obtained from at least one acrylate
monomer of formula CH.sub.2.dbd.CH--COOR.sub.2 R.sub.2 represents a
C.sub.4 to C.sub.12 cycloalkyl group and at least one methacrylate
monomer of formula CH.sub.2.dbd.C(CH.sub.3)--COOR'.sub.2 in which
wherein R'.sub.2 represents a C.sub.4 to C.sub.12 cycloalkyl group,
and the second block is obtained from an acrylic acid monomer and
from at least one monomer with a glass transition temperature of
less than or equal to 20.degree. C., a vinyl polymer comprising at
least one carbosiloxane dendrimer-based unit, a dispersion of
acrylic or vinyl radical homopolymer or copolymer particles
dispersed in the said liquid fatty phase.
15. A product for making up and/or caring for keratin materials,
comprising a first composition and a second composition conditioned
in separate containers, wherein the first composition comprises, in
a physiologically acceptable medium: a) a siloxane resin comprising
the following units: (i) (R.sup.1.sub.3SiO.sub.1/2).sub.a (ii)
(R.sup.2.sub.2SiO.sub.2/2).sub.b (iii) (R.sup.3SiO.sub.3/2).sub.c
and (iv) (SiO.sub.4/2).sub.d wherein R.sup.1, R.sup.2 and R.sup.3
are each independently an alkyl group containing from 1 to 8 carbon
atoms, an aryl group, a carbinol group or an amino group, a is
between 0.05 and 0.5, b is between 0 and 0.3, c is greater than 0,
d is between 0.05 and 0.6, a+b+c+d=1, with the proviso that more
than 40 mol % of the groups R.sup.3 of the siloxane resin are
propyl groups, and b) at least one liquid fatty phase, and c) at
least one film-forming polymer selected from the group consisting
of: a film-forming block ethylenic polymer, comprising at least a
first block and at least a second block, wherein the first block is
obtained from at least one acrylate monomer of formula
CH.sub.2.dbd.CH--COOR.sub.2 R.sub.2 represents a C.sub.4 to
C.sub.12 cycloalkyl group and at least one methacrylate monomer of
formula CH.sub.2.dbd.C(CH.sub.3)--COOR'.sub.2 wherein R'.sub.2
represents a C.sub.4 to C.sub.12 cycloalkyl group, and the second
block is obtained from an acrylic acid monomer and from at least
one monomer with a glass transition temperature of less than or
equal to 20.degree. C.; a vinyl polymer comprising at least one
carbosiloxane dendrimer-based unit; and a dispersion of acrylic or
vinyl radical homopolymer or copolymer particles dispersed in the
said liquid fatty phase; and the second composition, which is
different from the first, comprises at least one fatty substance.
Description
[0001] The invention relates to a cosmetic composition for keratin
materials, especially the skin, the hair and the nails. The
invention relates in particular to makeup compositions for keratin
materials.
[0002] One of the objects of the patent application is to produce
makeup compositions for keratin materials (skin, mucous membranes,
fibre, eyelashes and integuments) that allow the application of a
total transfer-resistant film with good staying power.
[0003] In the field of lipsticks and makeup in general, formulators
are in search of compositions that have good staying-power
properties, to satisfy consumers' expectations. These compositions
should also be transfer-resistant, while at the same time offering
good comfort properties.
[0004] Formulators are thus in search of starting materials and/or
systems for obtaining compositions whose application is
characterized by improved staying power and a good level of
comfort. The term "comfort" means the comfort on application, i.e.
a composition that is easy to apply in terms of glidance and of
amount applied, without, however, the applied film being too thick
and/or tacky. The term "comfort" also means the comfort after
application, so that the user does not experience any tautness or
drying out, in particular.
[0005] It is known to those skilled in the art to use polymers to
obtain these staying-power properties in the course of the day.
[0006] These polymers are of very diverse chemical nature and are
conveyed either in a fatty phase or in an aqueous phase.
[0007] Examples that may be mentioned include silicone resins,
especially of MQ type, polyacrylates, latices, etc.
[0008] Although these polymers do indeed afford staying-power
properties, in particular transfer resistance, they are usually
accompanied by discomfort either during the application of the
product (difficult spreading, tackiness, etc.) or during the day
(tautness, mask effect, etc.).
[0009] It is thus necessary to search for a technical solution for
obtaining these staying-power properties while at the same time
maintaining comfortable use.
[0010] These objects, and others, are achieved by means of a
composition containing, in a physiologically acceptable medium, a)
a siloxane resin comprising the following units:
[0011] (i) (R.sup.1.sub.3SiO.sub.1/2).sub.a
[0012] (ii) (R.sup.2.sub.2SiO.sub.2/2).sub.b
[0013] (iii)(R.sup.3SiO.sub.3/2).sub.c and
[0014] (iv) (SiO.sub.4/2).sub.d
with
[0015] R.sup.1, R.sup.2 and R.sup.3 independently representing an
alkyl group containing from 1 to 8 carbon atoms, an aryl group, a
carbinol group or an amino group,
[0016] a being between 0.05 and 0.5,
[0017] b being between 0 and 0.3,
[0018] c being greater than 0,
[0019] d being between 0.05 and 0.6,
[0020] a+b+c+d=1,
[0021] on condition that more than 40 mol % of the groups R.sup.2
of the siloxane resin are propyl groups, b) at least one liquid
fatty phase and c) at least one film-forming polymer chosen from
the group comprising: [0022] a film-forming block ethylenic
polymer, which preferably comprises at least a first block and at
least a second block with different glass transition temperatures
(Tg), the said first and second blocks being linked together via an
intermediate block comprising at least one constituent monomer of
the first block and at least one constituent monomer of the second
block, [0023] a vinyl polymer comprising at least one carbosiloxane
dendrimer-based unit, [0024] a dispersion of acrylic or vinyl
radical homopolymer or copolymer particles dispersed in the said
liquid fatty phase.
[0025] Preferably, the block ethylenic film-forming polymer,
comprising at least a first block and at least a second block, is
characterized in that the first block is obtained from at least one
acrylate monomer of formula CH.sub.2.dbd.CH--COOR.sub.2 in which
R.sub.2 represents a C.sub.4 to C.sub.12 cycloalkyl group and at
least one methacrylate monomer of formula
CH.sub.2.dbd.C(CH.sub.3)--COOR.sub.2 in which R'.sub.2 represents a
C.sub.4 to C.sub.12 cycloalkyl group, and characterized in that the
second block is obtained from an acrylic acid monomer and from at
least one monomer with a glass transition temperature of less than
or equal to 20.degree. C. Such polymers and the process for
preparing them are described, for example, in document EP 1 882
709.
[0026] Preferably, the siloxane resin comprises the following
units:
[0027] (i) (R.sup.1.sub.3SiO.sub.1/2).sub.a
[0028] (iii) (R.sup.3SiO.sub.3/2).sub.c and
[0029] (iv) (SiO.sub.4/2).sub.d
with
[0030] R.sup.1 and R.sup.3 independently representing an alkyl
group containing from 1 to 8 carbon atoms, R.sup.1 preferably being
a methyl group and R.sup.3 preferably being a propyl group,
[0031] a being between 0.05 and 0.5 and preferably between 0.15 and
0.4,
[0032] c being greater than zero, preferably between 0.15 and
0.4,
[0033] d being between 0.05 and 0.6, preferably between 0.2 and 0.6
or alternatively between 0.2 and 0.55,
[0034] a+b+c+d=1,
[0035] on condition that more than 40 mol % of the groups R.sup.3
of the siloxane resin are propyl groups.
[0036] The siloxane resins that may be used according to the
invention may be obtained via a process comprising the reaction of:
[0037] A) an MQ resin comprising at least 80 mol % of units
(R.sup.1.sub.3SiO.sub.1/2).sub.a and (SiO.sub.4/2).sub.d [0038]
R.sup.1 representing an alkyl group containing from 1 to 8 carbon
atoms, an aryl group, a carbinol group or an amino group, [0039] a
and d being greater than zero, [0040] the ratio a/d being between
0.5 and 1.5; [0041] and [0042] B) a propyl resin T comprising at
least 80 mol % of units (R.sup.3SiO.sub.3/2).sub.c, [0043] R.sup.3
representing an alkyl group containing from 1 to 8 carbon atoms, an
aryl group, a carbinol group or an amino group, [0044] c being
greater than zero, [0045] on condition that at least 40 mol % of
the groups R.sup.3 are propyl groups, in which the mass ratio A/B
is between 95/5 and 15/85 and preferably the mass ratio A/B is
30/70.
[0046] Advantageously, the mass ratio A/B is between 95/5 and
15/85. Preferably, the ratio A/B is less than or equal to 70/30.
These preferred ratios have proven to afford comfortable deposits
due to the absence of percolation of the rigid particles of MQ
resin in the deposit.
[0047] The compositions according to the invention may be in
various forms, especially in the form of a powder, an anhydrous
dispersion, a water/oil, water/wax, oil/water, multiple or
wax/water emulsion, or a gel.
[0048] The compositions according to the invention are found to
have very good staying-power and transfer-resistance properties
while at the same time maintaining a comfortable deposit,
especially when it is applied to the lips.
[0049] The resins that may be used according to the invention are
especially those described in patent application WO 2005/075 542,
the content of which is incorporated herein by reference.
[0050] According to a first embodiment, the composition according
to the invention is liquid.
[0051] According to a second embodiment, the composition according
to the invention is solid.
[0052] The term "solid" characterizes the state of the composition
at room temperature (25.degree. C.) and at atmospheric pressure
(760 mmHg).
[0053] Preferably, the composition according to the invention has,
when it is solid, a hardness of between 30 and 300 g, or even from
50 to 200 g.
[0054] Protocol for Measuring the Shear:
[0055] The measurement is performed according to the following
protocol:
[0056] A sample of the composition under consideration is hot-cast
into a stick mould 12.7 mm in diameter. The mould is then cooled in
a freezer for about one hour. The stick of lipstick is then stored
at 20.degree. C.
[0057] The hardness of the samples is measured after an interval of
24 hours.
[0058] The hardness of the samples of compositions of the
invention, expressed in grams, is measured using a DFGS2 tensile
testing machine sold by the company Indelco-Chatillon.
[0059] The hardness corresponds to the maximum shear force exerted
by a rigid tungsten wire 250 .mu.m in diameter, advancing at a rate
of 100 mm/minute.
[0060] The technique described above is usually referred to as the
"cheese wire" method.
[0061] Preferably, the composition according to the invention
comprises less than 3% and better still less than 1% by weight of
water relative to the total weight of the composition. More
preferably, the composition is totally anhydrous. The term
"anhydrous" especially means that water is preferably not
deliberately added to the composition, but may be present in trace
amount in the various compounds used in the composition.
[0062] According to another aspect, the present invention relates
to a makeup and/or care process in which the composition as defined
previously is applied to keratin materials, and especially to the
lips.
[0063] Film-Forming Polymer:
[0064] In the present invention, the term "film-forming polymer"
means a polymer that is capable, by itself or in the presence of an
auxiliary film-forming agent, of forming a macroscopically
continuous film that adheres to keratin materials, and preferably a
cohesive film, better still a film whose cohesion and mechanical
properties are such that the said film can be isolated and
manipulated individually, for example when the said film is
prepared by pouring onto a non-stick surface such as a
Teflon-coated or silicone-coated surface.
[0065] Block Ethylenic Polymer
[0066] According to a first embodiment of the invention, the
film-forming polymer present in the composition according to the
invention is a film-forming block ethylenic polymer (which is
preferably essentially linear), which preferably comprises at least
a first block and at least a second block with different glass
transition temperatures (Tg), the said first and second blocks
being linked together via an intermediate block comprising at least
one constituent monomer of the first block and at least one
constituent monomer of the second block.
[0067] The term "at least one block" means one or more blocks.
[0068] The term "block polymer" means a polymer comprising at least
two different blocks and preferably at least three different
blocks.
[0069] Advantageously, the first and second blocks of the block
polymer are advantageously mutually incompatible.
[0070] Such polymers are described, for example, in documents EP 1
411 069 or WO 04/028 488. Patent application EP 1 411 069 describes
the possibility of preparing block polymers from acrylate monomers
or methacrylate monomers.
[0071] Preferably, according to this embodiment, the film-forming
polymer present in the composition according to the invention is a
block polymer, comprising at least a first block and at least a
second block, characterized in that the first block is obtained
from at least one acrylate monomer of formula
CH.sub.2.dbd.CH--COOR.sub.2 in which R.sub.2 represents a C.sub.4
to C.sub.12 cycloalkyl group, and from at least one methacrylate
monomer of formula CH.sub.2.dbd.C(CH.sub.3)--COOR.sub.2 in which
R'.sub.2 represents a C.sub.4 to C.sub.12 cycloalkyl group, and
characterized in that the second block is obtained from an acrylic
acid monomer and from at least one monomer with a glass transition
temperature of less than or equal to 20.degree. C. Such polymers
and the process for preparing them are described, for example, in
document EP 1 882 709.
[0072] The first block and the second block of the polymer of the
invention may be advantageously mutually incompatible.
[0073] The term "mutually incompatible blocks" means that the blend
formed from a polymer corresponding to the first block and from a
polymer corresponding to the second block is not miscible in the
polymerization solvent that is the majority amount by weight of the
block polymer, at room temperature (25.degree. C.) and atmospheric
pressure (10.sup.5 Pa), for a polymer blend content of greater than
or equal to 5% by weight, relative to the total weight of the blend
and of the said polymerization solvent, it being understood that:
[0074] i) the said polymers are present in the blend in a content
such that the respective weight ratio ranges from 10/90 to 90/10,
and that [0075] ii) each of the polymers corresponding to the first
and second blocks has an average (weight-average or number-average)
molecular mass equal to that of the block polymer .+-.15%.
[0076] In the case of a mixture of polymerization solvents, and
should two or more solvents be present in identical mass
proportions, the said polymer blend is immiscible in at least one
of them.
[0077] Needless to say, in the case of a polymerization performed
in a single solvent, this solvent is the majority solvent.
[0078] The said first and second blocks may be advantageously
linked together via an intermediate block comprising at least one
constituent monomer of the first block and at least one constituent
monomer of the second block.
[0079] The intermediate block is a block comprising at least one
constituent monomer of the first block and at least one constituent
monomer of the second block of the polymer, which enables these
blocks to be "compatibilized".
[0080] Advantageously, the intermediate block comprising at least
one constituent monomer of the first block and at least one
constituent monomer of the second block of the polymer is a random
polymer.
[0081] Preferably, the intermediate block is derived essentially
from constituent monomers of the first block and of the second
block.
[0082] The term "essentially" means at least 85%, preferably at
least 90%, better still 95% and even better still 100%.
[0083] Advantageously, the intermediate block has a glass
transition temperature Tg that is between the glass transition
temperatures of the first and second blocks.
[0084] The block polymer according to the invention is
advantageously a film-forming block ethylenic polymer.
[0085] The term "ethylenic polymer" means a polymer obtained by
polymerization of ethylenically unsaturated monomers.
[0086] The term "film-forming polymer" means a polymer that is
capable of forming, by itself or in the presence of a film-forming
auxiliary agent, a continuous film that adheres to a support,
especially to keratin materials.
[0087] Preferentially, the polymer used in the composition
according to the invention comprises no silicon atoms in its
backbone. The term "backbone" means the main chain of the polymer,
as opposed to the pendent side chains.
[0088] Preferably, the polymer according to the invention is not
water-soluble, i.e. the polymer is not soluble in water or in a
mixture of water and of linear or branched lower monoalcohols
containing from 2 to 5 carbon atoms, for instance ethanol,
isopropanol or n-propanol, without pH modification, at an active
material content of at least 1% by weight, at room temperature
(25.degree. C.).
[0089] Preferably, the polymer according to the invention is not an
elastomer.
[0090] The term "non-elastomeric polymer" means a polymer which,
when it is subjected to a constraint intended to pull it (for
example by 30% relative to its initial length), does not return to
a length substantially identical to its initial length when the
constraint ceases.
[0091] More specifically, the term "non-elastomeric polymer"
denotes a polymer with an instantaneous recovery R.sub.i<50% and
a delayed recovery R.sub.2h<70% after having been subjected to a
30% elongation. Preferably, R.sub.i is <30% and
R.sub.2h<50%.
[0092] More specifically, the non-elastomeric nature of the polymer
is determined according to the following protocol:
[0093] A polymer film is prepared by pouring a solution of the
polymer in a Teflon-coated mould, followed by drying for 7 days in
an environment conditioned at 23.+-.5.degree. C. and 50.+-.10%
relative humidity.
[0094] A film about 100 .mu.m thick is thus obtained, from which
are cut rectangular specimens (for example using a punch) 15 mm
wide and 80 mm long.
[0095] This sample is subjected to a tensile stress using a machine
sold under the reference Zwick, under the same temperature and
humidity conditions as for the drying.
[0096] The specimens are pulled at a speed of 50 mm/min and the
distance between the jaws is 50 mm, which corresponds to the
initial length (l.sub.0) of the specimen.
[0097] The instantaneous recovery R.sub.i is determined in the
following manner: [0098] the specimen is pulled by 30%
(.epsilon..sub.max), i.e. about 0.3 times its initial length
(1.sub.0) [0099] the constraint is released by applying a return
speed equal to the tensile speed, i.e. 50 mm/min, and the residual
elongation of the specimen is measured as a percentage, after
returning to zero constraint (.epsilon..sub.i).
[0100] The percentage instantaneous recovery (R.sub.i) is given by
the following formula:
R.sub.i=(.epsilon..sub.max-.epsilon..sub.i)/(.epsilon..sub.max).times.10-
0
[0101] To determine the delayed recovery, the percentage residual
elongation of the specimen (.epsilon..sub.2h) is measured after 2
hours (2 hours after returning to zero stress load).
[0102] The percentage delayed recovery (R.sub.2h) is given by the
following formula:
R.sub.2h=(.epsilon..sub.max-.epsilon..sub.2h)/(.epsilon..sub.max).times.-
100
[0103] Purely as a guide, a polymer according to one embodiment of
the invention has an instantaneous recovery R.sub.i of 10% and a
delayed recovery R.sub.2h of 30%.
[0104] The polydispersity index of the polymer of the invention is
advantageously greater than 2.
[0105] The polydispersity index I of the polymer is equal to the
ratio of the weight-average mass Mw to the number-average mass
Mn.
[0106] The weight-average molar mass (Mw) and number-average molar
mass (Mn) are determined by gel permeation liquid chromatography
(THF solvent, calibration curve established with linear polystyrene
standards, refractometric detector).
[0107] The weight-average mass (Mw) of the polymer according to the
invention is preferably less than or equal to 300 000; it ranges,
for example, from 35 000 to 200 000 and better still from 45 000 to
150 000 g/mol.
[0108] The number-average mass (Mn) of the polymer according to the
invention is preferably less than or equal to 70 000; it ranges,
for example, from 10 000 to 60 000 and better still from 12 000 to
50 000 g/mol.
[0109] Preferably, the polydispersity index of the polymer
according to the invention is advantageously greater than 2, for
example ranging from 2 to 9, preferably greater than or equal to
2.5, for example ranging from 2.5 to 8, and better still greater
than or equal to 2.8, especially from 2.8 to 6.
[0110] The block polymer of the invention comprises at least a
first block and at least a second block.
[0111] The first block is advantageously obtained from at least one
acrylate monomer of formula CH.sub.2.dbd.CH--COOR.sub.2 and from at
least one methacrylate monomer of formula
CH.sub.2.dbd.C(CH.sub.3)--COOR.sub.2 in which R.sub.2 represents a
C.sub.4 to C.sub.12 cycloalkyl group. The monomers and the
proportions thereof are preferably chosen such that the glass
transition temperature of the first block is greater than
20.degree. C.
[0112] The second block is advantageously obtained from an acrylic
acid monomer and from at least one monomer with a glass transition
temperature of less than or equal to 20.degree. C.
[0113] The monomers and the proportions thereof are preferably
chosen such that the glass transition temperature of the second
block is less than or equal to 20.degree. C.
[0114] The glass transition temperatures indicated for the first
and second blocks may be theoretical Tg values determined from the
theoretical Tg values of the constituent monomers of each of the
blocks, which may be found in a reference manual such as the
Polymer Handbook, 3rd Edition, 1989, John Wiley, according to the
following relationship, known as Fox's law:
1 / Tg = i ( .omega. _ i / Tg i ) , ##EQU00001##
.omega..sub.i being the mass fraction of the monomer i in the block
under consideration and Tg.sub.i being the glass transition
temperature of the homopolymer of the monomer i.
[0115] Unless otherwise indicated, the Tg values indicated for the
first and second blocks in the present patent application are
theoretical Tg values.
[0116] The difference between the glass transition temperatures of
the first and second blocks is generally greater than 10.degree.
C., preferably greater than 20.degree. C. and better still greater
than 30.degree. C.
[0117] In the present invention, the expression: "between . . . and
. . . " is intended to denote a range of values for which the
limits mentioned are excluded, and "from . . . to . . . " and
"ranging from . . . to . . . " are intended to denote a range of
values for which the limits are included.
[0118] First Block
[0119] The first block preferably has a Tg of greater than
20.degree. C., for example a Tg ranging from 20 to 170.degree. C.
and preferably greater than or equal to 50.degree. C., for example
ranging from 50.degree. C. to 160.degree. C., especially ranging
from 90.degree. C. to 130.degree. C.
[0120] According to one embodiment, the first block is obtained
from at least one acrylate monomer of formula
CH.sub.2.dbd.CH--COOR.sub.2 in which R.sub.2 represents a C.sub.4
to C.sub.12 cycloalkyl group, and from at least one methacrylate
monomer of formula CH.sub.2.dbd.C(CH.sub.3)--COOR'.sub.2 in which
R'.sub.2 represents a C.sub.4 to C.sub.12 cycloalkyl group.
[0121] The first block may be obtained exclusively from the said
acrylate monomer and from the said methacrylate monomer.
[0122] The acrylate monomer and the methacrylate monomer are
preferably in mass proportions of between 30/70 and 70/30,
preferably between 40/50 and 50/40 and especially of the order of
50/50.
[0123] The proportion of the first block advantageously ranges from
20% to 90%, better still from 30% to 80% and even better still from
60% to 80% by weight of the polymer.
[0124] According to one embodiment, the first block is obtained by
polymerization of isobornyl methacrylate and isobornyl
acrylate.
[0125] The first block may also comprise: [0126] (meth)acrylic
acid, preferably acrylic acid, [0127] tert-butyl acrylate, [0128]
the methacrylates of formula CH.sub.2.dbd.C(CH.sub.3)--COOR.sub.1,
in which R.sub.1 represents a linear or branched unsubstituted
alkyl group containing from 1 to 4 carbon atoms, such as a methyl,
ethyl, propyl or isobutyl group, [0129] the (meth)acrylamides of
formula:
##STR00001##
[0129] in which R.sub.7 and R.sub.8, which may be identical or
different, each represent a hydrogen atom or a linear or branched
C.sub.1 to C.sub.12 alkyl group, such as an n-butyl, t-butyl,
isopropyl, isohexyl, isooctyl or isononyl group; or R.sub.7
represents H and R.sub.8 represents a 1,1-dimethyl-3-oxobutyl
group, and R' denotes H or methyl. Examples of monomers that may be
mentioned include N-butylacrylamide, N-t-butylacrylamide,
N-isopropylacrylamide, N,N-dimethylacrylamide and
N,N-dibutylacrylamide, [0130] and mixtures thereof.
[0131] Second Block
[0132] The second block advantageously has a glass transition
temperature Tg of less than or equal to 20.degree. C., for example
a Tg ranging from -100 to 20.degree. C., preferably less than or
equal to 15.degree. C., especially ranging from -80.degree. C. to
15.degree. C. and better still less than or equal to 10.degree. C.,
for example ranging from -100.degree. C. to 10.degree. C.,
especially ranging from -30.degree. C. to 10.degree. C.
[0133] The second block is obtained from an acrylic acid monomer
and from another monomer with a Tg of less than or equal to
20.degree. C.
[0134] The monomer with a Tg of less than or equal to 20.degree. C.
is preferably chosen from the following monomers: [0135] the
acrylates of formula CH.sub.2.dbd.CH--COOR.sub.3, R.sub.3
representing a linear or branched, unsubstituted C.sub.1-C.sub.12
alkyl group, with the exception of a tert-butyl group, in which is
(are) optionally intercalated one or more heteroatoms chosen from
O, N and S; [0136] the methacrylates of formula
CH.sub.2.dbd.C(CH.sub.3)--COOR.sub.4, R.sub.4 representing a linear
or branched, unsubstituted C.sub.6-C.sub.12 alkyl group, in which
is (are) optionally intercalated one or more heteroatoms chosen
from O, N and S; [0137] vinyl esters of formula
R.sub.5--CO--O--CH.dbd.CH.sub.2, in which R.sub.5 represents a
linear or branched C.sub.4-C.sub.12 alkyl group; [0138]
(C.sub.4-C.sub.12 alkyl) vinyl ethers; [0139] N--(C.sub.4-C.sub.12
alkyl)acrylamides, such as N-octylacrylamide; [0140] and mixtures
thereof.
[0141] The preferred monomers with a Tg of less than or equal to
20.degree. C. are isobutyl acrylate and 2-ethylhexyl acrylate, or
mixtures thereof in all proportions.
[0142] Each of the first and second blocks may contain in minor
proportion at least one constituent monomer of the other block.
[0143] Thus, the first block may contain at least one constituent
monomer of the second block, and vice versa.
[0144] Each of the first and/or second blocks may comprise, in
addition to the monomers indicated above, one or more other
monomers known as additional monomers, which are different from the
main monomers mentioned above.
[0145] The nature and amount of this or these additional monomer(s)
are chosen such that the block in which they are present has the
desired glass transition temperature.
[0146] This additional monomer is chosen, for example, from: [0147]
ethylenically unsaturated monomers comprising at least one tertiary
amine function, for instance 2-vinylpyridine, 4-vinylpyridine,
dimethylaminoethyl methacrylate, diethylaminoethyl methacrylate and
dimethylaminopropylmethacrylamide, and salts thereof, [0148]
methacrylates of formula CH.sub.2.dbd.C(CH.sub.3)--COOR.sub.6, in
which R.sub.6 represents a linear or branched alkyl group
containing from 1 to 4 carbon atoms, such as a methyl, ethyl,
propyl or isobutyl group, the said alkyl group being substituted
with one or more substituents chosen from hydroxyl groups (for
instance 2-hydroxypropyl methacrylate and 2-hydroxyethyl
methacrylate) and halogen atoms (Cl, Br, I or F), such as
trifluoroethyl methacrylate, [0149] methacrylates of formula
CH.sub.2.dbd.C(CH.sub.3)--COOR.sub.9,
[0150] R.sub.9 representing a linear or branched C.sub.6 to
C.sub.12 alkyl group in which one or more heteroatoms chosen from
O, N and S is (are) optionally intercalated, the said alkyl group
being substituted with one or more substituents chosen from
hydroxyl groups and halogen atoms (Cl, Br, I or F); [0151]
acrylates of formula CH.sub.2.dbd.CHCOOR.sub.10,
[0152] R.sub.10 representing a linear or branched C.sub.1 to
C.sub.12 alkyl group substituted with one or more substituents
chosen from hydroxyl groups and halogen atoms (Cl, Br, I or F),
such as 2-hydroxypropyl acrylate and 2-hydroxyethyl acrylate, or
R.sub.10 represents a C.sub.1 to C.sub.12 alkyl-O-POE
(polyoxyethylene) with repetition of the oxyethylene unit 5 to 30
times, for example methoxy-POE, or R.sub.10 represents a
polyoxyethylenated group comprising from 5 to 30 ethylene oxide
units.
[0153] The additional monomer may represent 0.5% to 30% by weight
relative to the weight of the polymer. According to one embodiment,
the polymer of the invention does not contain any additional
monomer.
[0154] Preferably, the polymer of the invention comprises at least
one of the isobornyl acrylate and isobornyl methacrylate monomers
in the first block and isobutyl acrylate and acrylic acid monomers
in the second block.
[0155] Preferably, the polymer comprises at least one of the
isobornyl acrylate and isobornyl methacrylate monomers in
equivalent weight proportion in the first block and isobutyl
acrylate and acrylic acid monomers in the second block.
[0156] Preferably, the polymer comprises at least isobornyl
acrylate and isobornyl methacrylate monomers in equivalent weight
proportion in the first block, and isobutyl acrylate and acrylic
acid monomers in the second block, the first block representing 70%
of the weight of the polymer.
[0157] Preferably, the polymer comprises at least isobornyl
acrylate and isobornyl methacrylate monomers in equivalent weight
proportion in the first block, and isobutyl acrylate and acrylic
acid monomers in the second block, the block with a Tg of greater
than 20.degree. C. representing 70% of the weight of the polymer,
and acrylic acid representing 5% of the weight of the polymer.
[0158] Vinyl Polymer Grafted with a Carbosiloxane Dendrimer
[0159] According to a second embodiment of the invention, the
film-forming polymer present in the composition according to the
invention is a vinyl polymer comprising at least one carbosiloxane
dendrimer-based unit.
[0160] The vinyl polymer may especially have a backbone and at
least one side chain, which comprises a carbosiloxane dendrimer
structure. The term "carbosiloxane dendrimer structure" in the
context of the present invention represents a structure with
branched groups of high molecular masses with high regularity in
the radial direction starting from the simple backbone. Such
carbosiloxane dendrimer structures are described in the form of a
highly branched siloxane-silylalkylene copolymer in the laid-open
Japanese patent application Kokai 9-171 154.
[0161] The vinyl polymer contains carbosiloxane dendrimer-based
units that may be represented by the following general formula:
##STR00002##
[0162] in which R.sup.1 represents an aryl group or an alkyl group
containing from 1 to 10 carbon atoms, and X' represents a
silylalkyl group which, when i=1, is represented by the
formula:
##STR00003##
[0163] in which R.sup.1 is the same as defined above, R.sup.2
represents an alkylene group containing from 2 to 10 carbon atoms,
R.sup.3 represents an alkyl group containing from 1 to 10 carbon
atoms, X.sup.i+1 represents a hydrogen atom, an alkyl group
containing from 1 to 10 carbon atoms, an aryl group or the
silylalkyl group defined above with i=i+1; i is an integer from 1
to 10 which represents the generation of the said silylalkyl group,
and a.sup.i is an integer from 0 to 3; Y represents an organic
group that may be polymerized using radicals chosen from the group
consisting of an organic group that contains a methacrylic group or
an acrylic group and that is represented by the formulae:
##STR00004##
[0164] in which R.sup.4 represents a hydrogen atom or an alkyl
group, R.sup.5 represents an alkylene group containing from 1 to 10
carbon atoms, such as a methylene group, an ethylene group, a
propylene group or a butylene group, the methylene group and the
propylene group being preferred; and
[0165] an organic group that contains a styryl group and that is
represented by the formula:
##STR00005##
[0166] in which R.sup.6 represents a hydrogen atom or an alkyl
group, R.sup.7 represents an alkyl group containing from 1 to 10
carbon atoms, such as a methyl group, an ethyl group, a propyl
group or a butyl group, the methyl group being preferred, R.sup.8
represents an alkylene group containing from 1 to 10 carbon atoms,
such as a methylene group, an ethylene group, a propylene group or
a butylene group, the ethylene group being preferred, b is an
integer from 0 to 4, and c is 0 or 1 such that if c is 0,
--(R.sup.8).sub.c-- represents a bond,
[0167] R.sup.1 represents an aryl group or an alkyl group
containing from 1 to 10 carbon atoms, in which the alkyl group is
preferably represented by a methyl group, an ethyl group, a propyl
group, a butyl group, a pentyl group, an isopropyl group, an
isobutyl group, a cyclopentyl group or a cyclohexyl group, and in
which the aryl group is preferably represented by a phenyl group
and a naphthyl group, in which the methyl and phenyl groups are
more particularly preferred, and the methyl group is preferred
among all.
[0168] The vinyl polymer that contains a carbosiloxane dendrimer
structure may be the product of polymerization of
[0169] (A) from 0 to 99.9 parts by weight of a monomer of vinyl
type; and
[0170] (B) from 100 to 0.1 parts by weight of a carbosiloxane
dendrimer containing an organic group that may be polymerized using
radicals, represented by the general formula:
##STR00006##
[0171] in which Y represents an organic group that may be
polymerized using radicals, R.sup.1 represents an aryl group or an
alkyl group containing from 1 to 10 carbon atoms, and X.sup.1
represents a silylalkyl group which, when i=1, is represented by
the formula:
##STR00007##
[0172] in which R.sup.1 is the same as defined above, R.sup.2
represents an alkylene group containing from 2 to 10 carbon atoms,
R.sup.3 represents an alkyl group containing from 1 to 10 carbon
atoms, X.sup.i+1 represents a hydrogen atom, an alkyl group
containing from 1 to 10 carbon atoms, an aryl group, or the
silylalkyl group defined above with i=i+1; i is an integer from 1
to 10 that represents the generation of the said silylalkyl group,
and a.sup.i is an integer from 0 to 3; in which the said organic
group that may be polymerized with radicals contained in the
component (B) is chosen from the group consisting of an organic
group that contains a methacrylic group or an acrylic group and
that is represented by the formulae:
##STR00008##
[0173] in which R.sup.4 represents a hydrogen atom or an alkyl
group, R.sup.5 represents an alkylene group containing from 1 to 10
carbon atoms; and
[0174] an organic group that contains a styryl group and that is
represented by the formula:
##STR00009##
[0175] in which R.sup.6 represents a hydrogen atom or an alkyl
group, R.sup.7 represents an alkyl group containing from 1 to
carbon atoms, R.sup.8 represents an alkylene group containing from
1 to 10 carbon atoms, b is an integer from 0 to 4, and c is 0 or 1.
When c is 0, --(R.sup.8).sub.c-represents a bond.
[0176] The monomer of vinyl type that is the component (A) in the
vinyl polymer is a monomer of vinyl type that contains a
radical-polymerizable vinyl group. There is no particular
limitation as regards the type of such a monomer. The following are
examples of this type of vinyl monomer: methyl methacrylate, ethyl
methacrylate, n-propyl methacrylate, isopropyl methacrylate or a
methacrylate of a lower alkyl analogue; glycidyl methacrylate;
n-butyl methacrylate, isobutyl methacrylate, tert-butyl
methacrylate, n-hexyl methacrylate, methacrylic acid, cyclohexyl
methacrylate, 2-ethylhexyl methacrylate, octyl methacrylate, lauryl
methacrylate, stearyl methacrylate or a higher-analogue
methacrylate; vinyl acetate, vinyl propionate or a vinyl ester of a
lower fatty acid analogue; vinyl caproate, vinyl 2-ethylhexoate,
vinyl laurate, vinyl stearate or an ester of a higher fatty acid
analogue; styrene, vinyltoluene, benzyl methacrylate, phenoxyethyl
methacrylate, vinyl-pyrrolidone or similar vinylaromatic monomers;
methacrylamide, N-methylolmethacrylamide,
N-methoxy-methylmethacrylamide, isobutoxymethoxymethacrylamide,
N,N-dimethylmethacrylamide or similar monomers of vinyl type
containing amide groups; hydroxyethyl methacrylate, hydroxypropyl
methacrylate or similar monomers of vinyl type containing hydroxyl
groups; methacrylic acid, itaconic acid, crotonic acid, fumaric
acid, maleic acid or similar monomers of vinyl type containing a
carboxylic acid group; tetrahydrofurfuryl methacrylate, butoxyethyl
methacrylate, ethoxydiethylene glycol methacrylate, polyethylene
glycol methacrylate, polypropylene glycol monomethacrylate,
hydroxybutyl vinyl ether, cetyl vinyl ether, 2-ethylhexyl vinyl
ether or a similar monomer of vinyl type with ether bonds;
methacryloxypropyl-trimethoxysilane, polydimethylsiloxane
containing a methacrylic group on one of its molecular ends,
polydimethylsiloxane containing a styryl group on one of its
molecular ends, or a similar silicone compound containing
unsaturated groups; butadiene; vinyl chloride; vinylidene chloride;
methacrylonitrile; dibutyl fumarate; anhydrous maleic acid;
anhydrous succinic acid; methacryl glycidyl ether; an organic salt
of an amine, an ammonium salt, and an alkali metal salt of
methacrylic acid, of itaconic acid, of crotonic acid, of maleic
acid or of fumaric acid; a radical-polymerizable unsaturated
monomer containing a sulfonic acid group such as a styrenesulfonic
acid group; a quaternary ammonium salt derived from methacrylic
acid, such as 2-hydroxy-3-methacryloxypropyltrimethylammonium
chloride; and a methacrylic acid ester of an alcohol containing a
tertiary amine group, such as a methacrylic acid ester of
diethylamine.
[0177] Multifunctional monomers of vinyl type may also be used. The
following represent examples of such compounds: trimethylolpropane
trimethacrylate, pentaerythrityl trimethacrylate, ethylene glycol
dimethacrylate, tetraethylene glycol dimethacrylate, polyethylene
glycol dimethacrylate, 1,4-butanediol dimethacrylate,
1,6-hexanediol dimethacrylate, neopentyl glycol dimethacrylate,
trimethylolpropane-trioxyethyl methacrylate,
tris(2-hydroxyethyl)-isocyanurate dimethacrylate,
tris(2-hydroxyethyl)-isocyanurate trimethacrylate,
polydimethylsiloxane capped with styryl groups containing
divinylbenzene groups on both ends, or similar silicone compounds
containing unsaturated groups.
[0178] The carbosiloxane dendrimer, which is the component (B), is
represented by the following formula:
##STR00010##
[0179] The following represent the preferred examples of
radical-polymerizable organic group Y: an acryloxymethyl group, a
3-acryloxypropyl group, a methacryloxymethyl group, a
3-methacryloxypropyl group, a 4-vinylphenyl group, a 3-vinylphenyl
group, a 4-(2-propenyl)phenyl group, a 3-(2-propenyl)phenyl group,
a 2-(4-vinylphenyl)ethyl group, a 2-(3-vinyl-phenyl)ethyl group, a
vinyl group, an allyl group, a methallyl group and a 5-hexenyl
group.
[0180] R.sup.1 represents an alkyl group or an aryl group
containing from 1 to 10 carbon atoms, in which the alkyl group may
be a methyl group, an ethyl group, a propyl group, a butyl group, a
pentyl group, an isopropyl group, an isobutyl group, a cyclopentyl
group or a cyclohexyl group; and the aryl group may be a phenyl
group or a naphthyl group. The methyl and phenyl groups are
particularly preferred, the methyl group being preferred among all.
X.sup.1 represents a silylalkyl group that is represented by the
following formula, when i is equal to 1:
##STR00011##
[0181] in which R.sup.2 represents an alkylene group containing
from 2 to 10 carbon atoms, such as an ethylene group, a propylene
group, a butylene group, a hexylene group or a similar linear
alkylene group; a methylmethylene group, a methylethylene group, a
1-methylpentylene group, a 1,4-dimethylbutylene group or a similar
branched alkylene group. The ethylene, methylethylene, hexylene,
1-methylpentylene and 1,4-dimethylbutylene groups are preferred
among all. R.sup.3 represents an alkyl group containing from 1 to
10 carbon atoms, such as methyl, ethyl, propyl, butyl and isopropyl
groups. R.sup.1 is the same as defined above. X.sup.i+1 represents
a hydrogen atom, an alkyl group containing from 1 to 10 carbon
atoms, an aryl group or the silylalkyl group with i=i+1. a.sup.i is
an integer from 0 to 3, and i is an integer from 1 to 10 that
indicates the generation number, which represents the number of
repetitions of the silylalkyl group.
[0182] For example, when the generation number is equal to 1, the
carbosiloxane dendrimer may be represented by the first general
formula shown below, in which Y, R.sup.1, R.sup.2 and R.sup.3 are
the same as defined above, R.sup.12 represents a hydrogen atom or
is identical to R.sup.1; a.sup.1 is identical to a.sup.i.
Preferably, the mean total number of groups OR.sup.3 in a molecule
is within the range from 0 to 7. When the generation number is
equal to 2, the carbosiloxane dendrimer may be represented by the
second general formula shown below, in which Y, R.sup.1, R.sup.2,
R.sup.3 and R.sup.12 are the same as defined above; a.sup.1 and
a.sup.2 represent the a.sup.i of the indicated generation.
Preferably, the mean total number of groups OR.sup.3 in a molecule
is within the range from 0 to 25. When the generation number is
equal to 3, the carbosiloxane dendrimer is represented by the third
general formula shown below, in which Y, R.sup.2, R.sup.3 and
R.sup.12 are the same as defined above; a.sup.1, a.sup.2 and
a.sup.3 represent the a.sup.i of the indicated generation.
Preferably, the total mean number of groups OR.sup.3 in a molecule
is within the range from 0 to 79.
##STR00012##
[0183] A carbosiloxane dendrimer that contains a
radical-polymerizable organic group may be represented by the
following mean structural formulae:
##STR00013## ##STR00014##
[0184] The carbosiloxane dendrimer may be manufactured according to
the process for manufacturing a branched silalkylene siloxane
described in Japanese patent application Hei 9-171 154. For
example, it may be produced by subjecting an organosilicon compound
containing a hydrogen atom linked to a silicon atom, represented by
the following general formula:
##STR00015##
[0185] and an organosilicon compound containing an alkenyl group,
to a hydrosilylation reaction. In the above formula, the
organosilicon compound may be represented by
3-methacryloxypropyltris(dimethyl-siloxy)silane,
3-acryloxypropyltris(dimethylsiloxy)-silane and
4-vinylphenyltris(dimethylsiloxy)silane. The organosilicon compound
that contains an alkenyl group may be represented by
vinyltris(trimethylsiloxy)silane,
vinyltris(dimethylphenylsiloxy)silane, and
5-hexenyl-tris(trimethylsiloxy)silane. The hydrosilylation reaction
is performed in the presence of a chloroplatinic acid, a complex of
vinylsiloxane and of platinum, or a similar transition metal
catalyst.
[0186] In the vinyl polymer that contains a dendrimer structure,
the polymerization ratio between the components (A) and (B), in
terms of the weight ratio between (A) and (B), may be within the
range from 0/100 to 99.9/0.1 and preferably within the range from
1/99 to 99/1. A ratio between the components (A) and (B) of 0/100
means that the compound becomes a homopolymer of component (B).
[0187] The vinyl polymer contains a carbosiloxane dendrimer
structure and this polymer may be obtained by copolymerization of
the components (A) and (B), or by polymerization of the component
(B) alone. The polymerization may be a free-radical polymerization
or an ionic polymerization, but free-radical polymerization is
preferred. The polymerization may be performed by bringing about a
reaction between the components (A) and (B) in a solution for a
period of from 3 to 20 hours in the presence of a radical initiator
at a temperature of from 50.degree. C. to 150.degree. C. A suitable
solvent for this purpose is hexane, octane, decane, cyclohexane or
a similar aliphatic hydrocarbon; benzene, toluene, xylene or a
similar aromatic hydrocarbon; diethyl ether, dibutyl ether,
tetrahydrofuran, dioxane or similar ethers; acetone, methyl ethyl
ketone, methyl isobutyl ketone, diisobutyl ketone or similar
ketones; methyl acetate, ethyl acetate, butyl acetate, isobutyl
acetate or similar esters; methanol, ethanol, isopropanol, butanol
or similar alcohols; octamethylcyclotetrasiloxane,
decamethylcyclopentasiloxane, hexamethyldisiloxane,
octamethyltrisiloxane or a similar organosiloxane oligomer. A
radical initiator may be any compound known in the art for standard
free-radical polymerization reactions. The specific examples of
such radical initiators are 2,2'-azobis(isobutyronitrile),
2,2'-azobis(2-methylbutyronitrile),
2,2'-azobis(2,4-dimethylvaleronitrile) or similar compounds of
azobis type; benzoyl peroxide, lauroyl peroxide, tert-butyl
peroxybenzoate, tert-butyl peroxy-2-ethylhexanoate or a similar
organic peroxide. These radical initiators may be used alone or in
a combination of two or more. The radical initiators may be used in
an amount of from 0.1 to 5 parts by weight per 100 parts by weight
of the components (A) and (B). A chain-transfer agent may be added.
The chain-transfer agent may be 2-mercaptoethanol, butyl mercaptan,
n-dodecyl mercaptan, 3-mercaptopropyltrimethoxysilane, a
polydimethyl-siloxane containing a mercaptopropyl group or a
similar compound of mercapto type; methylene chloride, chloroform,
carbon tetrachloride, butyl bromide, 3-chloropropyltrimethoxysilane
or a similar halogenated compound. In the manufacture of the
polymer of vinyl type, after the polymerization, the residual
unreacted vinyl monomer may be removed under conditions of heating
under vacuum.
[0188] To facilitate the preparation of the mixture of the starting
material of cosmetic products, the number-average molecular mass of
the vinyl polymer containing a carbosiloxane dendrimer may be
chosen within the range between 3000 and 2 000 000 and preferably
between 5000 and 800 000. It may be a liquid, a gum, a paste, a
solid, a powder or any other form. The preferred forms are
solutions consisting of the dilution of a dispersion or of a powder
in solvents.
[0189] The vinyl polymer may be a dispersion of a polymer of vinyl
type having a carbosiloxane dendrimer structure in its side
molecular chain, in a liquid such as a silicone oil, an organic
oil, an alcohol or water.
[0190] The vinyl polymer having a carbosiloxane dendrimer structure
in its side molecular chain, in this embodiment, is the same as
that described above. The liquid may be a silicone oil, an organic
oil, an alcohol or water. The silicone oil may be a
dimethylpolysiloxane with the two molecular ends capped with
trimethylsiloxy groups, a copolymer of methylphenylsiloxane and of
dimethylsiloxane having the two molecular ends capped with
trimethylsiloxy groups, a copolymer of
methyl-3,3,3-trifluoropropylsiloxane and of dimethylsiloxane having
the two molecular ends capped with trimethylsiloxy groups, or
similar unreactive linear silicone oils, and also
hexamethyl-cyclotrisiloxane, octamethylcyclotetrasiloxane,
decamethylcyclopentasiloxane, dodecamethylcyclo-hexasiloxane or a
similar cyclic compound. In addition to the unreactive silicone
oils, modified polysiloxanes containing functional groups such as
silanol groups, amino groups and polyether groups on the ends or
within the side molecular chains may be used.
[0191] The organic oils may be liquid paraffin, isoparaffin, hexyl
laurate, isopropyl myristate, myristyl myristate, cetyl myristate,
2-octyldodecyl myristate; isopropyl palmitate, 2-ethylhexyl
palmitate, butyl stearate, decyl oleate, 2-octyldodecyl oleate,
myristyl lactate, cetyl lactate, lanolin acetate, stearyl alcohol,
cetostearyl alcohol, oleyl alcohol, avocado oil, almond oil, olive
oil, cocoa oil, jojoba oil, gum oil, sunflower oil, soybean oil,
camellia oil, squalane, castor oil, mink oil, cottonseed oil,
coconut oil, egg yolk oil, beef tallow, lard, polypropylene glycol
monooleate, neopentyl glycol 2-ethylhexanoate or a similar glycol
ester oil; triglyceryl isostearate, the triglyceride of a fatty
acid of coconut oil, or a similar oil of a polyhydric alcohol
ester; polyoxyethylene lauryl ether, polyoxypropylene cetyl ether
or a similar polyoxyalkylene ether.
[0192] The alcohol may be any type that is suitable for use in
combination with a cosmetic product starting material. For example,
it may be methanol, ethanol, butanol, isopropanol or similar lower
alcohols. A solution or a dispersion of the alcohol should have a
viscosity within the range from 10 to 10.sup.9 mPa at 25.degree. C.
To improve the sensory use properties in a cosmetic product, the
viscosity should be within the range from 100 to 5.times.10.sup.8
mPas.
[0193] The solutions and dispersions may be readily prepared by
mixing the vinyl polymer having a carbosiloxane dendrimer structure
with a silicone oil, an organic oil, an alcohol or water. The
liquids may be present in the step of polymerization of the polymer
of vinyl type having a carbosiloxane dendrimer structure. In this
case, the unreacted residual vinyl monomer should be completely
removed by heat treatment of the solution or dispersion under
atmospheric pressure or reduced pressure. In the case of a
dispersion, the dispersity of the polymer of vinyl type may be
improved by adding a surfactant. Such an agent may be
hexyl-benzenesulfonic acid, octylbenzenesulfonic acid,
decylbenzenesulfonic acid, dodecylbenzenesulfonic acid,
cetylbenzenesulfonic acid, myristylbenzenesulfonic acid or anionic
surfactants of the sodium salts of these acids;
octyltrimethylammonium hydroxide, dodecyltrimethylammonium
hydroxide, hexadecyltrimethyl-ammonium hydroxide,
octyldimethylbenzylammonium hydroxide, decyldimethylbenzylammonium
hydroxide, dioctadecyldimethylammonium hydroxide, beef
tallow-trimethylammonium hydroxide, coconut oil-trimethylammonium
hydroxide, or a similar cationic surfactant; a polyoxyalkylene
alkyl ether, a polyoxyalkylenealkylphenol, a polyoxyalkylene alkyl
ester, the sorbitol ester of polyoxyalkylene, polyethylene glycol,
polypropylene glycol, an ethylene oxide additive of diethylene
glycol trimethylnonanol, and nonionic surfactants of polyester
type, and also mixtures. In addition, the solvents and dispersions
may be combined with iron oxide suitable for use with cosmetic
products, or a similar pigment, and also zinc oxide, titanium
oxide, silicon oxide, mica, talc or similar mineral oxides in
powder form. In the dispersion, a mean particle diameter of the
polymer of vinyl type may be within a range of between 0.001 and
100 microns and preferably between 0.01 and 50 microns. The reason
for this is that, outside the recommended range, a cosmetic product
mixed with the emulsion will not have a nice enough feel on the
skin or to the touch, or sufficient spreading properties or a
pleasant feel.
[0194] The vinyl polymer contained in the dispersion or the
solution may have a concentration in the range between 0.1% and 95%
by weight and preferably between 5% and 85% by weight. However, to
facilitate the handling and the preparation of the mixture, the
range should preferably be between 10% and 75% by weight.
[0195] The vinyl polymer may be one of the polymers described in
the examples of patent application EP 0 963 751 or, for example,
the product TIB-4-200 sold by Dow Corning.
[0196] According to one embodiment, the vinyl polymer also
comprises at least one organofluorine group.
[0197] Structures in which the polymerized vinyl units constitute
the backbone and carbosiloxane dendritic structures and also
organofluorine groups are attached to side chains are particularly
preferred.
[0198] The organofluorine groups may be obtained by replacing with
fluorine atoms all or some of the hydrogen atoms of methyl, ethyl,
propyl, isopropyl, butyl, isobutyl, tert-butyl, pentyl, neopentyl,
hexyl, cyclohexyl, heptyl, octyl, nonyl, decyl, undecyl, dodecyl,
tridecyl, tetradecyl, hexadecyl and octadecyl groups and other
alkyl groups of 1 to 20 carbon atoms, and also alkyloxyalkylene
groups of 6 to 22 carbon atoms.
[0199] The groups represented by the formula:
--(CH.sub.2).sub.x--(CF.sub.2).sub.y--R.sup.13 are suggested as
examples of fluoroalkyl groups obtained by substituting fluorine
atoms for hydrogen atoms of alkyl groups. In the formula, the index
"x" is 0, 1, 2 or 3 and "y" is an integer from 1 to 20. R.sup.13 is
an atom or a group chosen from a hydrogen atom, a fluorine atom,
--CH(CF.sub.3).sub.2-- and CF(CF.sub.3).sub.2. Such
fluorine-substituted alkyl groups are exemplified by linear or
branched polyfluoroalkyl or perfluoroalkyl groups represented by
the formulae presented below.
[0200] --CF.sub.3, --C.sub.2F.sub.5, -nC.sub.3F.sub.7, --CF
(CF.sub.3).sub.2, -nC.sub.4F.sub.9,
CF.sub.2CF(CF.sub.3).sub.2,-nC.sub.5F.sub.11, -nC.sub.6F.sub.13,
-nC.sub.8F.sub.17, --CH.sub.2CF.sub.3, --CH(CF.sub.3).sub.2,
CH.sub.2CH(CF.sub.3).sub.2--CH.sub.2(CF.sub.2).sub.2F,
--CH.sub.2(CF.sub.2).sub.3F, --CH.sub.2(CF.sub.2).sub.4F,
--CH.sub.2(CF.sub.2).sub.6F, --CH.sub.2(CF.sub.2).sub.8F,
--CH.sub.2CH.sub.2CF.sub.3, --CH.sub.2CH.sub.2(CF.sub.2).sub.2F,
--CH.sub.2CH.sub.2(CF.sub.2).sub.3F,
--CH.sub.2CH.sub.2(CF.sub.2).sub.4F,
--CH.sub.2CH.sub.2(CF.sub.2).sub.6F,
--CH.sub.2CH.sub.2(CF.sub.2).sub.8F,
--CH.sub.2CH.sub.2(CF.sub.2).sub.10F,
--CH.sub.2CH.sub.2(CF.sub.2).sub.12F,
--CH.sub.2CH.sub.2(CF.sub.2).sub.14F,
--CH.sub.2CH.sub.2(CF.sub.2).sub.16F,
--CH.sub.2CH.sub.2CH.sub.2CF.sub.3,
--CH.sub.2CH.sub.2CH.sub.2(CF.sub.2).sub.2F,
--CH.sub.2CH.sub.2CH.sub.2(CF.sub.2).sub.2H,
--CH.sub.2(CF.sub.2).sub.4H, and
--CH.sub.2CH.sub.2(CF.sub.2).sub.3H.
[0201] The groups represented by --CH.sub.2CH.sub.2--
(CF.sub.2).sub.m--CFR.sup.14--[OCF.sub.2CF
(CF.sub.3)].sub.n--OC.sub.3F.sub.7 are suggested as
fluoroalkyloxyfluoroalkylene groups obtained by substituting
fluorine atoms for hydrogen atoms of alkyloxyalkylene groups. In
the formula, the index "m" is 0 or 1, "n" is 0, 1, 2, 3, 4 or 5,
and R.sup.14 is a fluorine atom CF.sub.3. Such
fluoroalkyloxyfluoroalkylene groups are exemplified by the
perfluoroalkyloxy-fluoroalkylene groups represented by the formulae
presented below:
--CH.sub.2CH.sub.2CF(CF.sub.3)--[OCF.sub.2CF(CF.sub.3)].sub.n--OC.sub.3F-
.sub.7,
--CH.sub.2CH.sub.2CF.sub.2CF.sub.2--[OCF.sub.2CF(CF.sub.3)].sub.n--
-OC.sub.3F.sub.7.
[0202] The number-average molecular weight of the vinyl polymer
used in the present invention may be between 3000 and 2 000 000 and
more preferably between 5000 and 800 000.
[0203] This type of fluorinated vinyl polymer may be obtained by
addition [0204] of a vinyl monomer (B) not containing any
organofluorine groups in the molecule [0205] to a vinyl monomer
containing organofluorine groups in the molecule (A), and [0206] a
carbosiloxane dendrimer (C) containing radical-polymerizable
organic groups represented by the general formula (III):
##STR00016##
[0207] in which Y is a radical-polymerizable organic group and
R.sup.1 and X.sup.i are as above, and by subjecting them to a
copolymerization.
[0208] The vinyl monomers (A) containing organofluorine groups in
the molecule are preferably monomers represented by the general
formula: --(CH.sub.2).dbd.CR.sup.15COOR.sup.f. In the formula,
R.sup.15 is a hydrogen atom or a methyl group and R.sup.f is an
organofluorine group exemplified by the fluoroalkyl and
fluoroalkyloxyfluoroalkylene groups described above. The compounds
represented by the formulae presented below are suggested as
specific examples of the component (A). In the formulae presented
below "z" is an integer from 1 to 4.
[0209] CH.sub.2.dbd.CCH.sub.3COO--CF.sub.3.
CH.sub.2.dbd.CCH.sub.3COO--C.sub.2F.sub.5.
CH.sub.2.dbd.CCH.sub.3COO-nC.sub.3F.sub.7 CH.sub.2
CCH.sub.3COO--CF(CF.sub.3).sub.2.
CH.sub.2.dbd.CCH.sub.3COO-nC.sub.4F.sub.9.
CH.sub.2.dbd.CCH.sub.3COO--CF.sub.2CF (CF.sub.3).sub.2.
CH.sub.2.dbd.CCH.sub.3COO-nC.sub.5F.sub.11.
CH.sub.2.dbd.CCH.sub.3COO-nC.sub.6F.sub.13.
CH.sub.2.dbd.CCH.sub.3COO-nC.sub.8F.sub.17.
CH.sub.2.dbd.CCH.sub.3COO--CH.sub.2CF.sub.3.
CH.sub.2.dbd.CCH.sub.3COO--CH(CF.sub.3).sub.2.
CH.sub.2.dbd.CCH.sub.3COO--CH.sub.2CH(CF.sub.3).sub.2.
CH.sub.2.dbd.CCH.sub.3COO--CH.sub.2(CF.sub.2).sub.2F.
CH.sub.2.dbd.CCH.sub.3COO--CH.sub.2(CF.sub.2).sub.3F.
CH.sub.2.dbd.CCH.sub.3COO--CH.sub.2(CF.sub.2).sub.4F.
CH.sub.2.dbd.CCH.sub.3COO--CH.sub.2(CF.sub.2).sub.6F.
CH.sub.2.dbd.CCH.sub.3COO--CH.sub.2(CF.sub.2).sub.8F.
CH.sub.2.dbd.CCH.sub.3COO--CH.sub.2CH.sub.2CF.sub.3.
CH.sub.2.dbd.CCH.sub.3COO--CH.sub.2CH.sub.2(CF.sub.2).sub.2F.
CH.sub.2.dbd.CCH.sub.3COO--CH.sub.2CH.sub.2(CF.sub.2).sub.3F.
CH.sub.2.dbd.CCH.sub.3COO--CH.sub.2CH.sub.2(CF.sub.2).sub.4F.
CH.sub.2.dbd.CCH.sub.3COO--CH.sub.2CH.sub.2(CF.sub.2).sub.6F.
CH.sub.2.dbd.CCH.sub.3COO--CH.sub.2CH.sub.2(CF.sub.2).sub.8F.
CH.sub.2.dbd.CCH.sub.3COO--CH.sub.2CH.sub.2(CF.sub.2).sub.10F.
CH.sub.2.dbd.CCH.sub.3COO--CH.sub.2CH.sub.2(CF.sub.2).sub.12F.
CH.sub.2.dbd.CCH.sub.3COO--CH.sub.2CH.sub.2(CF.sub.2).sub.14F.
CH.sub.2.dbd.CCH.sub.3COO--CH.sub.2CH.sub.2(CF.sub.2).sub.16F.
CH.sub.2.dbd.CCH.sub.3COO--CH.sub.2CH.sub.2CH.sub.2CF.sub.3.
CH.sub.2.dbd.CCH.sub.3COO--CH.sub.2CH.sub.2CH.sub.2(CF.sub.2).sub.2F.
CH.sub.2 CCH.sub.3COO--CH.sub.2CH.sub.2CH.sub.2(CF.sub.2).sub.2H.
CH.sub.2.dbd.CCH.sub.3COO--CH.sub.2(CF.sub.2).sub.4H.
CH.sub.2.dbd.CCH.sub.3COO--CH.sub.2CH.sub.2(CF.sub.2).sub.3H.
CH.sub.2.dbd.CCH.sub.3COO--CH.sub.2CH.sub.2CF
(CF.sub.3)--[OCF.sub.2CF(CF.sub.3)].sub.z--OC.sub.3F.sub.7.
CH.sub.2.dbd.CCH.sub.3COO--CH.sub.2CH.sub.2CF.sub.2CF.sub.2[OCF.sub.2CF
(CF.sub.3)].sub.z--OC.sub.3F.sub.7. CH.sub.2.dbd.CHCOO--CF.sub.3.
CH.sub.2.dbd.CHCOO--C.sub.2F.sub.5.
CH.sub.2.dbd.CHCOO-nC.sub.3F.sub.7. CH.sub.2.dbd.CHCOO--CF
(CF.sub.3).sub.2. CH.sub.2.dbd.CHCOO-nC.sub.4F.sub.9.
CH.sub.2.dbd.CHCOO--CF.sub.2CF (CF.sub.3).sub.2.
CH.sub.2.dbd.CHCOO-nC.sub.5F.sub.11.
CH.sub.2.dbd.CHCOO-nC.sub.6F.sub.13.
CH.sub.2.dbd.CHCOO-nC.sub.8F.sub.17.
CH.sub.2.dbd.CHCOO--CH.sub.2CF.sub.3.
CH.sub.2.dbd.CHCOO--CH(CF.sub.3).sub.2.
CH.sub.2.dbd.CHCOO--CH.sub.2CH(CF.sub.3).sub.2.
CH.sub.2.dbd.CHCOO--CH.sub.2(CF.sub.2).sub.2F.
CH.sub.2.dbd.CHCOO--CH.sub.2(CF.sub.2).sub.3F.
CH.sub.2.dbd.CHCOO--CH.sub.2(CF.sub.2).sub.4F.
CH.sub.2.dbd.CHCOO--CH.sub.2(CF.sub.2).sub.6F.
CH.sub.2.dbd.CHCOO--CH.sub.2(CF.sub.2).sub.8F.
CH.sub.2.dbd.CHCOO--CH.sub.2CH.sub.2CF.sub.3.
CH.sub.2.dbd.CHCOO--CH.sub.2CH.sub.2(CF.sub.2).sub.2F.
CH.sub.2.dbd.CHCOO--CH.sub.2CH.sub.2(CF.sub.2).sub.3F.
CH.sub.2.dbd.CHCOO--CH.sub.2CH.sub.2(CF.sub.2).sub.4F.
CH.sub.2.dbd.CHCOO--CH.sub.2CH.sub.2(CF.sub.2).sub.6F.
CH.sub.2.dbd.CHCOO--CH.sub.2CH.sub.2(CF.sub.2).
CH.sub.2.dbd.CHCOO--CH.sub.2CH.sub.2(CF.sub.2).sub.10F.
CH.sub.2.dbd.CHCOO--CH.sub.2CH.sub.2(CF.sub.2).sub.12F.
CH.sub.2.dbd.CHCOO--CH.sub.2CH.sub.2(CF.sub.2).sub.14F.
CH.sub.2.dbd.CHCOO--CH.sub.2CH.sub.2(CF.sub.2).sub.16F.
CH.sub.2.dbd.CHCOO--CH.sub.2CH.sub.2CH.sub.2CF.sub.3.
CH.sub.2.dbd.CHCOO--CH.sub.2CH.sub.2CH.sub.2(CF.sub.2).sub.2F.
CH.sub.2.dbd.CHCOO--CH.sub.2CH.sub.2CH.sub.2(CF).sub.2H.
CH.sub.2.dbd.CHCOO--CH.sub.2(CF.sub.2).sub.4H.
CH.sub.2.dbd.CHCOO--CH.sub.2CH.sub.2(CF.sub.2).sub.3H.
CH.sub.2.dbd.CHCOO--CH.sub.2CH.sub.2CF(CF.sub.3)--[OCF.sub.2CF(CF.sub.3)]-
.sub.z--OC.sub.3F.sub.7.
CH.sub.2.dbd.CHCOO--CH.sub.2CH.sub.2CF.sub.2CF.sub.2--[OCF.sub.2CF
(CF.sub.3)].sub.z--OC.sub.3F.sub.7.
[0210] Among these, the vinyl polymers represented by the formulae
presented below are preferable:
[0211] CH.sub.2.dbd.CHCOO--CH.sub.2CH.sub.2(CF.sub.2).sub.6F.
CH.sub.2.dbd.CHCOO--CH.sub.2CH.sub.2(CF.sub.2)
CH.sub.2.dbd.CCH.sub.3COO--CH.sub.2CH.sub.2(CF.sub.2).sub.6F.
CH.sub.2.dbd.CCH.sub.3COO--CH.sub.2CH.sub.2(CF.sub.2).sub.8F.
CH.sub.2.dbd.CHCOO--CH.sub.2CF.sub.3.
CH.sub.2.dbd.CCH.sub.3COO--CH.sub.2CF.sub.3
[0212] The vinyl polymers represented by the formulae presented
below are particularly preferable.
[0213] CH.sub.2.dbd.CHCOO--CH.sub.2CF.sub.3.
CH.sub.2.dbd.CCH.sub.3COO--CH.sub.2CF.sub.3.
[0214] The vinyl monomers (B) not containing any organofluorine
groups in the molecule may be any monomer containing
radical-polymerizable vinyl groups illustrated, for example, by
methyl acrylate, methyl methacrylate, ethyl acrylate, ethyl
methacrylate, n-propyl acrylate, n-propyl methacrylate, isopropyl
acrylate, isopropyl methacrylate, and other lower alkyl acrylates
or methacrylates; glycidyl acrylate, glycidyl methacrylate; n-butyl
acrylate, n-butyl methacrylate, isobutyl acrylate, isobutyl
methacrylate, tert-butyl acrylate, tert-butyl methacrylate, n-hexyl
acrylate, n-hexyl methacrylate, n-hexyl acrylate, n-hexyl
methacrylate, cyclohexyl acrylate, cyclohexyl methacrylate,
2-ethylhexyl acrylate, 2-ethylhexyl methacrylate, octyl acrylate,
octyl methacrylate, lauryl acrylate, lauryl methacrylate, stearyl
acrylate, stearyl methacrylate, and other higher acrylates and
methacrylates; vinyl acetate, vinyl propionate and other lower
fatty acid vinyl esters; vinyl butyrate, vinyl caproate, vinyl
2-ethylhexanoate, vinyl laurate, vinyl stearate, and other higher
fatty acid esters; styrene, vinyltoluene, benzyl acrylate, benzyl
methacrylate, phenoxyethyl acrylate, phenoxyethyl methacrylate,
vinylpyrrolidone, and other vinylaromatic monomers;
dimethylaminoethyl acrylate, dimethylaminoethyl methacrylate,
diethylaminoethyl acrylate, diethylaminoethyl methacrylate, and
other aminovinyl monomers, acrylamide, methacrylamide,
N-methylolacrylamide, N-methylolmethacrylamide,
N-methoxymethylacrylamide, N-methoxymethyl-methacrylamide,
isobutoxymethoxyacrylamide, isobutoxymethoxymethacrylamide,
N,N-dimethylacrylamide, N,N-dimethylmethacrylamide, and other
vinylamide monomers; hydroxyethyl acrylate, hydroxyethyl
methacrylate, acrylic acid hydroxypropyl alcohol, methacrylic acid
hydroxypropyl alcohol, and other hydroxyvinyl monomers; acrylic
acid, methacrylic acid, itaconic acid, crotonic acid, fumaric acid,
maleic acid, and other vinylcarboxylic acid monomers;
tetra-hydrofurfuryl acrylate, tetrahydrofurfuryl methacrylate,
butoxyethyl acrylate, butoxyethyl methacrylate, ethoxydiethylene
glycol acrylate, ethoxy-diethylene glycol methacrylate,
polyethylene glycol acrylate, polyethylene glycol methacrylate,
polypropylene glycol monoacrylate, polypropylene glycol
monomethacrylate, hydroxybutyl vinyl ether, cetyl vinyl ether,
2-ethylhexyl vinyl ether, and other vinyl monomers containing an
ether bond; acryloxypropyl-trimethoxysilane,
methacryloxypropyltrimethoxysilane, polydimethylsiloxanes
containing acryl or methacryl groups at one of the ends,
polydimethylsiloxanes containing alkenylaryl groups at one of the
ends and other silicone compounds containing unsaturated groups;
butadiene; vinyl chloride; vinylidene chloride, acrylonitrile,
methacrylonitrile; dibutyl fumarate; maleic anhydride;
dodecylsuccinic anhydride; acryl glycidyl ether, methacryl glycidyl
ether, 3,4-epoxy-cyclohexylmethyl acrylate,
3,4-epoxycyclohexylmethyl methacrylate, alkali metal salts,
ammonium salts and organic amine salts of acrylic acid, of
methacrylic acid, of itaconic acid, of crotonic acid, of fumaric
acid, of maleic acid and of other radical-polymerizable unsaturated
carboxylic acids, radical-polymerizable unsaturated monomers
containing sulfonic acid groups, such as styrene sulfonic acid and
also the alkali metal salts thereof, the ammonium salts thereof and
the organic amine salts thereof; the quaternary ammonium salts
derived from acrylic acid or methacrylic acid, such as
2-hydroxy-3-methacryloxypropyltrimethylammonium chloride,
methacrylic acid esters of a tertiary amine alcohol, such as the
diethylamine ester of methacrylic acid and quaternary ammonium
salts thereof.
[0215] In addition, it is also possible to use as vinyl monomers
(B) the polyfunctional vinyl monomers illustrated, for example, by
trimethylolpropane triacrylate, trimethylolpropane trimethacrylate,
pentaerythrityl triacrylate, pentaerythrityl trimethacrylate,
ethylene glycol diacrylate, ethylene glycol dimethacrylate,
tetraethylene glycol diacrylate, tetraethylene glycol
dimethacrylate, polyethylene glycol diacrylate, polyethylene glycol
dimethacrylate, 1,4-butanediol diacrylate, 1,4-butanediol
dimethacrylate, 1,6-hexanediol diacrylate, 1,6-hexane-diol
dimethacrylate, neopentyl glycol diacrylate, neopentyl glycol
dimethacrylate, trimethylolpropane-trioxyethyl acrylate,
trimethylolpropanetrioxyethyl methacrylate,
tris(2-hydroxyethyl)isocyanurate diacrylate,
tris(2-hydroxyethyl)isocyanurate dimethacrylate,
tris(2-hydroxyethyl)isocyanurate triacrylate,
tris(2-hydroxyethyl)isocyanurate trimethacrylate,
polydimethylsiloxane in which the two ends of the molecular chain
are blocked with alkenylaryl groups, and other silicone compounds
containing unsaturated groups.
[0216] As regards the ratio mentioned above in which the component
(A) and the component (B) are copolymerized, the weight ratio of
compound (A) to compound (B) should be within the range from
0.1:99.9 to 100:0 and preferably within the range 1:99 to
100:0.
[0217] The carbosiloxane dendrimer (C) is represented by the
general formula (III) indicated above. In formula (III), Y is a
radical-polymerizable organic group, the type of which is not
subject to any special limitations provided that it is an organic
group capable of undergoing a radical addition reaction. Organic
groups containing acryl and methacryl, organic groups containing
alkenylaryl, or alkenyl groups of 2 to 10 carbon atoms represented
by the general formulae presented below are suggested as specific
examples.
##STR00017##
[0218] In the formulae, R.sup.4 and R.sup.6 are hydrogen atoms or
methyl groups, R.sup.5 and R.sup.8 are alkylene groups of 1 to 10
carbon atoms, and R.sup.7 is an alkyl group of 1 to 10 carbon
atoms. The index "b" is an integer from 0 to 4 and "c" is 0 or 1.
Acryloxymethyl, 3-acryloxypropyl, methacryloxymethyl,
3-methacryloxypropyl, 4-vinylphenyl, 3-vinylphenyl,
4-(2-propenyl)phenyl, 3-(2-propenyl)phenyl, 2-(4-vinylphenyl)ethyl,
2-(3-vinylphenyl)enyl, vinyl, allyl, methallyl, and 5-hexenyl are
suggested as examples of such radical-polymerizable organic groups.
The index "i" in formula (II), which is an integer from 1 to 10, is
the number of generations of the said silylalkyl group, in other
words the number of times that the silylalkyl group is repeated.
Thus, the carbosiloxane dendrimer of this component with a
generation number of 1 is represented by the general formula:
##STR00018##
[0219] (in which Y, R.sup.1, R.sup.2 and R.sup.3 are as above and
R.sup.12 is a hydrogen atom or such as R.sup.1 described above. The
index "a.sup.1" is an integer from 0 to 3, the total mean of
"a.sup.1" per molecule being from 0 to 7). The carbosiloxane
dendrimers of this component with a generation number of 2 are
represented by the general formula:
##STR00019##
[0220] (in which Y, R.sup.1, R.sup.2, R.sup.3 and R.sup.12 are as
above and the indices "a.sup.1" and "a.sup.2" are integers from 0
to 3, the total mean of "a.sup.1" and of "a.sup.2" per molecule
being from 0 to 25).
[0221] The carbosiloxane dendrimers of this component with a
generation number of 3 are represented by the general formula:
##STR00020##
[0222] (in which Y, R.sup.1, R.sup.2, R.sup.3 and R.sup.12 are as
above and the indices "a.sup.1" and "a.sup.2" and "a.sup.3" are
integers from 0 to 3, the total mean of "a.sup.1", "a.sup.2" and
"a.sup.3" per molecule being from 0 to 79).
[0223] The component (C) is illustrated by carbosiloxane dendrimers
represented by formulae of mean composition represented below.
##STR00021## ##STR00022##
[0224] The carbosiloxane dendrimers of the component (C) may be
prepared using the process for preparing siloxane/silylalkylene
branched copolymers described in document EP 1 055 674. For
example, they may be prepared by subjecting organic alkenyl
silicones and silicone compounds comprising hydrogen atoms linked
to silicon, represented by the general formula:
##STR00023##
[0225] (in which R.sup.1 and Y are as above) to a hydrosilylation
reaction. For example,
3-methacryloxypropyltris(dimethylsiloxy)silane,
3-acryloxypropyltris(dimethylsiloxy)silane and
4-vinylphenyltris(dimethylsiloxy)silane are used as silicon
compounds represented by the above formula.
Vinyltris(trimethylsiloxy)silane,
vinyltris(dimethyl-phenylsiloxy)silane and
5-hexenyltris(trimethylsiloxy)-silane are used as organosilicon
alkenyl compounds. In addition, it is preferable to perform the
hydrosilylation reaction in the presence of a transition metal
catalyst such as chloroplatinic acid and the platinum/vinylsiloxane
complex.
[0226] The copolymerization ratio of the component (C), in terms of
its weight ratio relative to the total weight of compounds (A) and
(B) should be within the range from 0.1:99.9 to 99.9:0.1,
preferably within the range from 1:99 to 99:1 and even more
preferably within the range from 5:95 to 95:5.
[0227] Amino groups may be introduced into the side chains of the
vinyl polymer using, included in the component (B), vinyl monomers
containing amino groups, such as dimethylaminoethyl acrylate,
dimethylaminoethyl methacrylate, diethylaminoethyl acrylate and
diethyl-aminoethyl methacrylate, followed by performing a
modification with potassium acetate monochloride, ammonium acetate
monochloride, the aminomethylpropanol salt of monochloroacetic
acid, the triethanolamine salt of monobromoacetic acid, sodium
monochloropropionate, and other alkali metal salts of halogenated
fatty acids; otherwise, carboxylic acid groups may be introduced
into the side chains of the vinyl polymer using, included in the
component (B), vinyl monomers containing carboxylic acids, such as
acrylic acid, methacrylic acid, itaconic acid, crotonic acid,
fumaric acid and maleic acid, and the like, followed by
neutralizing the product with triethylamine, diethylamine,
triethanolamine and other amines.
[0228] The fluorinated vinyl polymer may be one of the polymers
described in the examples of patent application WO 03/045337 or,
for example, the product TIB-4-100 sold by Dow Corning.
[0229] The vinyl polymer may be present in a content ranging from
0.1% to 70% by weight, relative to the total weight of the
composition, preferably ranging from 0.5% to 50% by weight,
preferentially ranging from 1% to 40% by weight and more preferably
ranging from 5% to 15% by weight.
[0230] The vinyl polymer may be present in the composition in a
proportion of at least 3% by weight in the composition, preferably
between 5% and 25% by weight, more preferably between 5% and 15% by
weight and especially about 10% by weight.
[0231] Polymer in Dispersion
[0232] According to a third embodiment of the invention, the
film-forming polymer present in the composition according to the
invention is a dispersion of homopolymer particles or of acrylic or
vinyl radical copolymers dispersed in the liquid fatty phase of the
composition.
[0233] According to the invention, the polymer in the form of
particles dispersed in the volatile liquid fatty phase is a solid
that is insoluble in the liquid fatty phase of the composition even
at its softening point, unlike a wax even of polymeric origin,
which is itself soluble in the liquid organic phase (or fatty
phase) at its melting point.
[0234] The composition according to the invention advantageously
comprises at least one stable dispersion of generally spherical
polymer particles of one or more polymers, in a volatile liquid
fatty phase. These dispersions may especially be in the form of
polymer nanoparticles in stable dispersion in the said liquid
organic phase. The nanoparticles preferably have a mean size of
between 5 and 800 nm and better still between and 500 nm. However,
it is possible to obtain polymer particles ranging up to 1 .mu.m in
size.
[0235] Preferably, the polymer particles in dispersion are
insoluble in water-soluble alcohols, for instance ethanol.
[0236] The polymers in dispersion that may be used in the
composition of the invention preferably have a molecular weight of
about from 2000 to 10 000 000 g/mol and a Tg of from -100.degree.
C. to 300.degree. C., better still from -50.degree. C. to
100.degree. C. and preferably from -10.degree. C. to 50.degree.
C.
[0237] It is possible to use film-forming polymers preferably
having a low Tg, of less than or equal to skin temperature and
especially less than or equal to 40.degree. C.
[0238] Preferably, the polymer used is film-forming, i.e. it is
capable of forming an isolable film, by itself or in combination
with a plasticizer. It is, however, possible to use a
non-film-forming polymer.
[0239] The term "non-film-forming polymer" means a polymer that is
incapable of forming an isolable film by itself. This polymer can,
in combination with a non-volatile compound of the oil type, form a
continuous, uniform deposit on the skin and/or the lips.
[0240] Among the film-forming polymers that may be mentioned are
acrylic or vinyl free-radical homopolymers or copolymers,
preferably with a Tg of less than or equal to 40.degree. C. and
especially ranging from -10.degree. C. to 30.degree. C., used alone
or as a mixture.
[0241] Among the non-film-forming polymers that may be mentioned
are optionally crosslinked vinyl or acrylic free-radical
homopolymers or copolymers preferably with a Tg of greater than
40.degree. C. and especially ranging from 45.degree. C. to
150.degree. C., used alone or as a mixture.
[0242] The term "free-radical polymer" means a polymer obtained by
polymerization of unsaturated and especially ethylenic monomers,
each monomer being capable of homopolymerizing (unlike
polycondensates). The free-radical polymers may especially be vinyl
polymers or copolymers, especially acrylic polymers.
[0243] The acrylic polymers may result from the polymerization of
ethylenically unsaturated monomers containing at least one acid
group and/or esters of these acid monomers and/or amides of these
acids.
[0244] Monomers bearing an acid group that may be used include
.alpha.,.beta.-ethylenic unsaturated carboxylic acids such as
acrylic acid, (meth)acrylic acid, crotonic acid, maleic acid or
itaconic acid. (Meth)acrylic acid and crotonic acid are preferably
used, and more preferably (meth)acrylic acid.
[0245] The acid monomer esters are advantageously chosen from
(meth)acrylic acid esters (also known as (meth)acrylates), for
instance alkyl (meth)acrylates, in particular of a C.sub.1-C.sub.20
and preferably C.sub.1-C.sub.8 alkyl, aryl (meth)acrylates, in
particular of a C.sub.6-C.sub.10 aryl, and hydroxyalkyl
(meth)acrylates, in particular of a C.sub.2-C.sub.6 hydroxyalkyl.
Alkyl (meth)acrylates that may be mentioned include methyl, ethyl,
butyl, isobutyl, 2-ethylhexyl and lauryl (meth)acrylate.
Hydroxyalkyl (meth)acrylates that may be mentioned include
hydroxyethyl (meth)acrylate and 2-hydroxypropyl (meth)acrylate.
Aryl (meth)acrylates that may be mentioned include benzyl or phenyl
acrylate.
[0246] The (meth)acrylic acid esters that are particularly
preferred are the alkyl (meth)acrylates.
[0247] Free-radical polymers that are preferably used include
copolymers of (meth)acrylic acid and of alkyl (meth)acrylate,
especially of a C.sub.1-C.sub.4 alkyl. Methyl acrylates optionally
copolymerized with acrylic acid may more preferentially be
used.
[0248] Amides of the acid monomers that may be mentioned include
(meth)acrylamides, especially N-alkyl(meth)-acrylamides, in
particular of a C.sub.2-C.sub.12 alkyl, such as N-ethylacrylamide,
N-t-butylacrylamide and N-octylacrylamide;
N-di(C.sub.1-C.sub.4)alkyl(meth)acrylamides.
[0249] The acrylic polymers may also result from the polymerization
of ethylenically unsaturated monomers containing at least one amine
group, in free form or in partially or totally neutralized form, or
alternatively in partially or totally quaternized form. Such
monomers may be, for example, dimethylaminoethyl (meth)acrylate,
dimethylaminoethyl(meth)acrylamide, vinylamine, vinylpyridine or
diallyldimethylammonium chloride.
[0250] The vinyl polymers may also result from the
homopolymerization or copolymerization of at least one monomer
chosen from vinyl esters and styrene monomers. In particular, these
monomers may be polymerized with acid monomers and/or esters
thereof and/or amides thereof, such as those mentioned previously.
Examples of vinyl esters that may be mentioned include vinyl
acetate, vinyl propionate, vinyl neodecanoate, vinyl pivalate,
vinyl benzoate and vinyl t-butylbenzoate. Styrene monomers that may
be mentioned include styrene and .alpha.-methylstyrene.
[0251] The list of monomers given is not limiting, and it is
possible to use any monomer known to those skilled in the art
included in the categories of acrylic and vinyl monomers (including
monomers modified with a silicone chain).
[0252] As other vinyl monomers that may be used, mention may also
be made of: [0253] N-vinylpyrrolidone, vinylcaprolactam,
vinyl-N--(C.sub.1-C.sub.6)alkylpyrroles, vinyloxazoles,
vinylthiazoles, vinylpyrimidines and vinylimidazoles, [0254]
olefins such as ethylene, propylene, butylene, isoprene or
butadiene.
[0255] The vinyl polymer may be crosslinked with one or more
difunctional monomers especially comprising at least two ethylenic
unsaturations, such as ethylene glycol di(meth)acrylate or diallyl
phthalate.
[0256] The polymer(s) in dispersion in the organic liquid phase may
represent, as solids, from 5% to 40%, preferably from 5% to 35% and
better still from 8% to 30% of the weight of the composition.
[0257] It is preferably chosen to use a dispersion of film-forming
polymer particles, the particles being dispersed in a volatile
oil.
[0258] According to one embodiment, the composition contains a
stabilizer that is solid at room temperature. The polymer particles
are preferably surface-stabilized by means of a stabilizer that may
be a block polymer, a grafted polymer and/or a random polymer,
alone or as a mixture. The stabilization may take place by any
known means, and in particular by direct addition of the block
polymer, grafted polymer and/or random polymer during the
polymerization.
[0259] The stabilizer is preferably also present in the mixture
before polymerization. However, it is also possible to add it
continuously, especially when the monomers are also added
continuously.
[0260] 2-30% by weight and preferably 5-20% by weight of stabilizer
may be used relative to the initial monomer mixture.
[0261] Among the grafted polymers that may be mentioned are
silicone polymers grafted with a hydrocarbon-based chain;
hydrocarbon-based polymers grafted with a silicone chain.
[0262] Thus, grafted-block or block copolymers comprising at least
one block of polyorganosiloxane type and at least one block of a
free-radical polymer, for instance grafted copolymers of
acrylic/silicone type, may thus be used, which may be used
especially when the non-aqueous medium is silicone-based.
[0263] It is also possible to use grafted-block or block copolymers
comprising at least one block of polyorganosiloxane type and at
least one block of a polyether. The polyorganosiloxane block may
especially be a polydimethylsiloxane or a
poly(C.sub.2-C.sub.18)alkylmethyl-siloxane; the polyether block may
be a poly(C.sub.2-C.sub.10-alkylene, in particular polyoxyethylene
and/or polyoxy-propylene. In particular, dimethicone copolyols or
(C.sub.2-C.sub.18)alkyldimethicone copolyols such as those sold
under the name Dow Corning 3225C by the company Dow Corning, and
lauryl methicones such as those sold under the name Dow Corning
Q2-5200 by the company Dow Corning, may be used.
[0264] Grafted-block or block copolymers that may also be mentioned
include those comprising at least one block resulting from the
polymerization of at least one ethylenic monomer containing one or
more optionally conjugated ethylenic bonds, for instance ethylene
or dienes such as butadiene and isoprene, and of at least one block
of a vinyl polymer and better still a styrene polymer. When the
ethylenic monomer comprises several optionally conjugated ethylenic
bonds, the residual ethylenic unsaturations after the
polymerization are generally hydrogenated. Thus, in a known manner,
the polymerization of isoprene leads, after hydrogenation, to the
formation of an ethylene-propylene block, and the polymerization of
butadiene leads, after hydrogenation, to the formation of an
ethylene-butylene block. Among these polymers that may be mentioned
are block copolymers, especially of "diblock" or "triblock" type
such as polystyrene/polyisoprene (SI), polystyrene/polybutadiene
(SB) such as those sold under the name Luvitol HSB by BASF, of the
type such as polystyrene/copoly(ethylene-propylene) (SEP) such as
those sold under the name Kraton by Shell Chemical Co. or of the
type such as polystyrene/copoly(ethylene-butylene) (SEB). Kraton
G1650 (SEBS), Kraton G1651 (SEBS), Kraton G1652 (SEBS), Kraton
G1657X (SEBS), Kraton G1701X (SEP), Kraton G1702X (SEP), Kraton
G1726X (SEW, Kraton D-1101 (SBS), Kraton D-1102 (SBS) and Kraton
D-1107 (SIS) may be used in particular. The polymers are generally
known as hydrogenated or non-hydrogenated diene copolymers.
[0265] Gelled Permethyl 99A-750, 99A-753-59 and 99A-753-(mixture of
triblock and of star polymer), Versagel 5960 from Penreco
(triblock+star polymer); OS129880, OS129881 and OS84383 from
Lubrizol (styrene/(meth)acrylate copolymer) may also be used.
[0266] As grafted-block or block copolymers comprising at least one
block resulting from the polymerization of at least one ethylenic
monomer containing one or more ethylenic bonds and of at least one
block of an acrylic polymer, mention may be made of poly(methyl
(meth)acrylate)/polyisobutylene diblock or triblock copolymers or
grafted copolymers containing a poly(methyl(meth)acrylate) skeleton
and polyisobutylene grafts.
[0267] As grafted-block or block copolymers comprising at least one
block resulting from the polymerization of at least one ethylenic
monomer containing one or more ethylenic bonds and of at least one
block of a polyether such as a C.sub.2-C.sub.18 polyalkylene
(especially polyethylene and/or polyoxypropylene), mention may be
made of polyoxyethylene/polybutadiene or
polyoxyethylene/polyisobutylene diblock or triblock copolymers.
[0268] Copolymers based on alkyl acrylates or (meth)acrylates
derived from C.sub.1-C.sub.4 alcohols and on alkyl acrylates or
(meth)acrylates derived from C.sub.8-C.sub.30 alcohols may thus be
used. Mention may be made in particular of stearyl
(meth)acrylate/methyl (meth)acrylate copolymer.
[0269] When the liquid synthesis solvent comprises at least one
silicone oil, the stabilizer is preferably chosen from the group
consisting of grafted-block or block copolymers comprising at least
one block of polyorganosiloxane type and at least one block of a
free-radical polymer or of a polyether or of a polyester, for
instance polyoxypropylene and/or polyoxyethylene blocks.
[0270] When the liquid organic phase does not comprise any silicone
oil, the stabilizer is preferably chosen from the group formed by:
[0271] (a) grafted-block or block copolymers comprising at least
one block of polyorganosiloxane type and at least one block of a
free-radical polymer or of a polyether or a polyester, [0272] (b)
copolymers of alkyl acrylates or (meth)acrylates derived from
C.sub.1-C.sub.4 alcohols and of alkyl acrylates or (meth)acrylates
derived from C.sub.8-C.sub.30 alcohols, [0273] (c) grafted-block or
block copolymers comprising at least one block resulting from the
polymerization of at least one ethylenic monomer containing
conjugated ethylenic bonds,
[0274] and at least one block of a vinyl or acrylic polymer or of a
polyether or of a polyester, or mixtures thereof.
[0275] Diblock polymers are preferably used as stabilizer.
[0276] When the polymer has a glass transition temperature that is
too high for the intended application, a plasticizer may be
combined therewith. The plasticizer may be chosen from the
plasticizers usually used in the field of application and
especially from compounds liable to be solvents for the polymer.
Coalescers may also be used in order to aid the polymer to form a
continuous and homogeneous deposit.
[0277] The coalescers or plasticizers that may be used in the
invention are especially those mentioned in document FR-A-2 782
917.
[0278] The composition may contain a polymer plasticizer, so as to
lower the Tg of the polymer film and to improve the adhesion of the
polymer film to its support, in particular to keratin materials.
The plasticizer especially lowers the glass transition temperature
of the polymer by at least 2, 3 or 4.degree. C. and preferably from
5.degree. C. to 20.degree. C. In one preferred embodiment, the
plasticizer especially lowers the glass transition temperature of
the polymer by at least 2, 3 or 4.degree. C. and preferably from
5.degree. C. to 20.degree. C., when the plasticizer represents not
more than 10% by weight of the polymer.
[0279] According to one embodiment, the compound may be chosen from
esters of at least one carboxylic acid comprising 1 to 7 carbon
atoms and of a polyol comprising at least four hydroxyl groups.
[0280] The polyol according to the invention may be a saccharide or
a saccharide-based polyol, such as erythritol, xylitol or sorbitol.
The polymer may be a monosaccharide or a polysaccharide comprising
1 to 10 saccharides, preferably from 1 to 4 and more preferably or
2 saccharides. The polyol may be chosen from erythritol, xylitol,
sorbitol, glucose and sucrose.
[0281] The polyol according to the invention is preferably a
disaccharide. Among the disaccharides that may be mentioned are
sucrose (.alpha.-D-glucopyranosyl-(1-2)-.beta.-D-fructofuranose),
lactose (.beta.-D-galactopyranosyl-(1-4)-.beta.-D-glucopyranose)
and maltose
(.alpha.-D-glucopyranosyl-(1-4)-.beta.-D-glucopyranose).
[0282] The plasticizer may be formed from a polyol substituted with
at least two different monocarboxylic acids, or with at least three
different monocarboxylic acids. The acid is preferably a
monocarboxylic acid chosen in particular from acids comprising 1 to
7 carbon atoms and preferably 1 to 5 carbon atoms, for example
acetic acid, n-propanoic acid, isopropanoic acid, n-butanoic acid,
isobutanoic acid, tert-butanoic acid, n-pentanoic acid and benzoic
acid.
[0283] According to one preferred embodiment, the ester is sucrose
diacetate hexakis(2-methylpropanoate).
[0284] Synthesis Solvent for the Polymer Particles
[0285] The polymer dispersion may be manufactured as described in
document EP-A-749 747.
[0286] A mixture comprising the initial monomers and also a
free-radical initiator is prepared. This mixture is dissolved in a
solvent referred to hereinbelow in the present description as the
"synthesis solvent". When the fatty phase is a non-volatile oil,
the polymerization may be performed in an apolar organic solvent
(synthesis solvent), followed by adding the non-volatile oil (which
should be miscible with the said synthesis solvent) and selectively
distilling off the synthesis solvent.
[0287] A synthesis solvent which is such that the initial monomers
and the free-radical initiator are soluble therein, and the polymer
particles obtained are insoluble therein, so that they precipitate
during their formation, is chosen. In particular, the synthesis
solvent may be chosen from alkanes such as heptane, isododecane and
cyclohexane.
[0288] When the fatty phase chosen is a volatile oil, the
polymerization may be performed directly in the said oil, which
thus also acts as synthesis solvent. The monomers should also be
soluble therein, as should the free-radical initiator, and the
polymer obtained should be insoluble therein.
[0289] The monomers are preferably present in the synthesis
solvent, before polymerization, in a proportion of 5-201 by weight
of the reaction mixture. The total amount of monomers may be
present in the solvent before the start of the reaction, or part of
the monomers may be added gradually as the polymerization reaction
proceeds.
[0290] The free-radical initiator may especially be
azobisisobutyronitrile or tert-butylperoxy-2-ethyl hexanoate.
[0291] The volatile phase of the composition may be formed from or
comprise the synthesis solvent for the dispersed polymer
particles.
[0292] Additional Polymer:
[0293] The compositions according to the invention may contain,
besides the film-forming polymers described previously, an
additional film-forming or non-film-forming polymer.
[0294] The composition may comprise an aqueous phase and the
additional polymer may be present in this aqueous phase. In this
case, the polymer will preferably be a polymer in dispersion or an
amphiphilic or associative polymer.
[0295] The term "polymer in dispersion" means the water-insoluble
polymers present in the form of particles of variable size. The
polymer may or may not be crosslinked. The size of the polymer
particles is typically between 25 and 500 nanometres and preferably
between 50 and 200 nanometres. The following polymers in aqueous
dispersion may be used: Ultrasol 2075 from Ganz Chemical, Daitosol
5000 AD from Daito Kasei, Avalure UR 450 from Noveon, DynamX from
National Starch, Syntran 5760 from Interpolymer, Acusol OP 301 and
from Rohm & Haas, and Neocryl A 1090 from Avecia.
[0296] The acrylic dispersions sold under the names Neocryl
XK-90.RTM., Neocryl A-1070.RTM., Neocryl A-1090.RTM., Neocryl
BT-62.RTM., Neocryl A-1079.RTM. and Neocryl A-523.RTM. by the
company Avecia-Neoresins, Dow Latex 432.RTM. by the company Dow
Chemical, Daitosol 5000 AD.RTM. or Daitosol 5000 SJ.RTM. by the
company Daito Kasey Kogyo; Syntran 5760.RTM. by the company
Interpolymer, Soltex OPT by the company Rohm & Haas, aqueous
dispersions of acrylic or styrene/acrylic polymers sold under the
brand name Joncryl.RTM. by the company Johnson Polymer, or the
aqueous dispersions of polyurethane sold under the names Neorez
R-981.RTM. and Neorez R-974.RTM. by the company Avecia-Neoresins,
Avalure UR-405.RTM., Avalure UR-410.RTM., Avalure UR-425.RTM.,
Avalure UR-450.RTM., Sancure 875.RTM., Sancure 861.RTM., Sancure
878.RTM. and Sancure 2060.RTM. by the company Goodrich, Impranil
85.RTM. by the company Bayer and Aquamere H-1511.RTM. by the
company Hydromer; the sulfopolyesters sold under the brand name
Eastman AQ.RTM. by the company Eastman Chemical Products, and vinyl
dispersions, for instance Mexomer PAM.RTM. from the company Chimex,
and mixtures thereof, are other examples of aqueous dispersions of
water-dispersible film-forming polymer particles.
[0297] The term "amphiphilic or associative polymers" means
polymers comprising one or more hydrophilic parts that make them
partially water-soluble and one or more hydrophobic parts via which
the polymers associate or interact. The following associative
polymers may be used: Nuvis FX 1100 from Elementis, Aculyn 22,
Aculyn 44 and Aculyn 46 from Rohm & Haas, Viscophobe DB 1000
from Amerchol. Diblock copolymers formed from a hydrophilic block
(polyacrylate or polyethylene glycol) and from a hydrophobic block
(polystyrene or polysiloxane) may also be used.
[0298] Polymers that are soluble in an aqueous phase containing
monodisperse particles may be avoided, since they may cause
aggregation of the monodisperse particles. The film-forming polymer
may thus be insoluble in such an aqueous phase.
[0299] The composition may comprise an oily phase and the
film-forming polymer may be present in this oily phase. The polymer
may then be in dispersion or in solution. Microgels (for example
KSG) may be used, as may polymers of the type PS-PA or
styrene-based copolymers (Kraton, Regalite).
[0300] As examples of lipodispersible non-aqueous film-forming
polymer dispersions in the form of non-aqueous dispersions of
polymer particles in one or more silicone and/or hydrocarbon-based
oils, which may be surface-stabilized with at least one stabilizer,
especially a block, grafted or random polymer, mention may be made
of acrylic dispersions in isododecane, for instance Mexomer PAP
from the company Chimex, and dispersions of particles of a grafted
ethylenic polymer, preferably an acrylic polymer, in a liquid fatty
phase, the ethylenic polymer advantageously being dispersed in the
absence of additional stabilizer at the surface of the particles as
described especially in document WO 04/055 081.
[0301] Among the additional film-forming polymers that may be used
in the composition of the present invention, mention may be made of
synthetic polymers, of free-radical type or of polycondensate type,
and polymers of natural origin, and mixtures thereof.
[0302] The expression "free-radical film-forming polymer" means a
polymer obtained by polymerization of unsaturated and especially
ethylenically unsaturated monomers, each monomer being capable of
homopolymerizing (unlike polycondensates).
[0303] The film-forming polymers of free-radical type may be, in
particular, vinyl polymers or copolymers, in particular acrylic
polymers.
[0304] The vinyl film-forming polymers may result from the
polymerization of ethylenically unsaturated monomers containing at
least one acidic group and/or esters of these acidic monomers
and/or amides of these acidic monomers.
[0305] Monomers bearing an acidic group which may be used are
.alpha.,.beta.-ethylenic unsaturated carboxylic acids such as
acrylic acid, methacrylic acid, crotonic acid, maleic acid or
itaconic acid. (Meth)acrylic acid and crotonic acid are preferably
used, and more preferably (meth)acrylic acid.
[0306] The esters of acidic monomers are advantageously chosen from
(meth)acrylic acid esters (also known as (meth)acrylates),
especially (meth)acrylates of an alkyl, in particular of a
C.sub.1-C.sub.30 and preferably C.sub.1-C.sub.20 alkyl,
(meth)acrylates of an aryl, in particular of a C.sub.6-C.sub.10
aryl, and (meth)acrylates of a hydroxyalkyl, in particular of a
C.sub.2-C.sub.6 hydroxyalkyl.
[0307] Among the alkyl (meth)acrylates that may be mentioned are
methyl methacrylate, ethyl methacrylate, butyl methacrylate,
isobutyl methacrylate, 2-ethylhexyl methacrylate, lauryl
methacrylate and cyclohexyl methacrylate.
[0308] Among the hydroxyalkyl (meth)acrylates that may be mentioned
are hydroxyethyl acrylate, 2-hydroxypropyl acrylate, hydroxyethyl
methacrylate and 2-hydroxypropyl methacrylate.
[0309] Among the aryl (meth)acrylates that may be mentioned are
benzyl acrylate and phenyl acrylate.
[0310] The (meth)acrylic acid esters that are particularly
preferred are the alkyl (meth)acrylates.
[0311] According to the present invention, the alkyl group of the
esters may be either fluorinated or perfluorinated, i.e. some or
all of the hydrogen atoms of the alkyl group are substituted with
fluorine atoms.
[0312] Examples of amides of the acid monomers that may be
mentioned are (meth)acrylamides, and especially
N-alkyl(meth)acrylamides, in particular of a C.sub.2-C.sub.12
alkyl. Among the N-alkyl(meth)acrylamides that may be mentioned are
N-ethylacrylamide, N-t-butylacrylamide, N-t-octylacrylamide and
N-undecylacrylamide.
[0313] The vinyl film-forming polymers may also result from the
homopolymerization or copolymerization of monomers chosen from
vinyl esters and styrene monomers. In particular, these monomers
may be polymerized with acid monomers and/or esters thereof and/or
amides thereof, such as those mentioned above.
[0314] Examples of vinyl esters that may be mentioned are vinyl
acetate, vinyl neodecanoate, vinyl pivalate, vinyl benzoate and
vinyl t-butylbenzoate.
[0315] Styrene monomers that may be mentioned are styrene and
.alpha.-methylstyrene.
[0316] Among the film-forming polycondensates that may be mentioned
are polyurethanes, polyesters, polyester-amides, polyamides,
epoxyester resins and polyureas.
[0317] The polyurethanes may be chosen from anionic, cationic,
nonionic and amphoteric polyurethanes, polyurethane-acrylics,
polyurethane-polyvinyl-pyrrolidones, polyester-polyurethanes,
polyether-polyurethanes, polyureas and polyurea-polyurethanes, and
mixtures thereof.
[0318] The polyesters may be obtained, in a known manner, by
polycondensation of dicarboxylic acids with polyols, in particular
diols.
[0319] The dicarboxylic acid may be aliphatic, alicyclic or
aromatic. Examples of such acids that may be mentioned are: oxalic
acid, malonic acid, dimethylmalonic acid, succinic acid, glutaric
acid, adipic acid, pimelic acid, 2,2-dimethylglutaric acid, azelaic
acid, suberic acid, sebacic acid, fumaric acid, maleic acid,
itaconic acid, phthalic acid, dodecanedioic acid,
1,3-cyclohexanedicarboxylic acid, 1,4-cyclohexanedicarboxylic acid,
isophthalic acid, terephthalic acid, 2,5-norbornanedicarboxylic
acid, diglycolic acid, thiodipropionic acid,
2,5-naphthalene-dicarboxylic acid or 2,6-naphthalenedicarboxylic
acid. These dicarboxylic acid monomers may be used alone or as a
combination of at least two dicarboxylic acid monomers. Among these
monomers, the ones preferentially chosen are phthalic acid,
isophthalic acid and terephthalic acid.
[0320] The diol may be chosen from aliphatic, alicyclic and
aromatic diols. The diol used is preferably chosen from: ethylene
glycol, diethylene glycol, triethylene glycol, 1,3-propanediol,
cyclohexanedimethanol and 4-butanediol. Other polyols that may be
used are glycerol, pentaerythritol, sorbitol and
trimethylol-propane.
[0321] The polyesteramides may be obtained in a manner analogous to
that of the polyesters, by polycondensation of diacids with
diamines or amino alcohols. Diamines that may be used are
ethylenediamine, hexamethylenediamine and meta- or
para-phenylenediamine. An amino alcohol that may be used is
monoethanolamine.
[0322] The polyester may also comprise at least one monomer bearing
at least one group --SO.sub.3M, with M representing a hydrogen
atom, an ammonium ion NH.sub.4.sup.+ or a metal ion such as, for
example, an Na.sup.+, Li.sup.+, K.sup.+, Mg.sup.2+, Ca.sup.2+,
Cu.sup.2+, Fe.sup.2+ or Fe.sup.3+ ion. A difunctional aromatic
monomer comprising such a group --SO.sub.3M may be used in
particular.
[0323] The aromatic nucleus of the difunctional aromatic monomer
also bearing a group --SO.sub.3M as described above may be chosen,
for example, from benzene, naphthalene, anthracene, biphenyl,
oxybiphenyl, sulfonylbiphenyl and methylenebiphenyl nuclei. As
examples of difunctional aromatic monomers also bearing a group
--SO.sub.3M, mention may be made of: sulfoisophthalic acid,
sulfoterephthalic acid, sulfophthalic acid,
4-sulfonaphthalene-2,7-dicarboxylic acid.
[0324] According to one example of a composition according to the
invention, the film-forming polymer may be a polymer dissolved in a
liquid fatty phase comprising organic solvents or oils (the
film-forming polymer is thus said to be a liposoluble polymer). The
liquid fatty phase preferably comprises a volatile oil, optionally
mixed with a non-volatile oil.
[0325] Examples of liposoluble polymers that may be mentioned are
copolymers of vinyl ester (the vinyl group being directly linked to
the oxygen atom of the ester group and the vinyl ester containing a
saturated, linear or branched hydrocarbon-based radical of 1 to 19
carbon atoms, linked to the carbonyl of the ester group) and of at
least one other monomer which may be a vinyl ester (other than the
vinyl ester already present), an .alpha.-olefin (containing from 8
to 28 carbon atoms), an alkyl vinyl ether (in which the alkyl group
comprises from 2 to 18 carbon atoms) or an allylic or methallylic
ester (containing a saturated, linear or branched hydrocarbon-based
radical of 1 to 19 carbon atoms, linked to the carbonyl of the
ester group).
[0326] These copolymers may be crosslinked with the aid of
crosslinking agents, which may be either of the vinyl type or of
the allylic or methallylic type, such as tetraallyloxyethane,
divinylbenzene, divinyl octane-dioate, divinyl dodecanedioate and
divinyl octadecane-dioate.
[0327] Examples of these copolymers that may be mentioned are the
following copolymers: vinyl acetate/allyl stearate, vinyl
acetate/vinyl laurate, vinyl acetate/vinyl stearate, vinyl
acetate/octadecene, vinyl acetate/octadecyl vinyl ether, vinyl
propionate/allyl laurate, vinyl propionate/vinyl laurate, vinyl
stearate/1-octadecene, vinyl acetate/1-dodecene, vinyl
stearate/ethyl vinyl ether, vinyl propionate/cetyl vinyl ether,
vinyl stearate/allyl acetate, vinyl 2,2-dimethyloctanoate/vinyl
laurate, allyl 2,2-dimethylpentanoate/vinyl laurate, vinyl
dimethylpropionate/vinyl stearate, allyl dimethylpropionate/vinyl
stearate, vinyl propionate/vinyl stearate, crosslinked with 0.2%
divinylbenzene, vinyl dimethylpropionate/vinyl laurate, crosslinked
with 0.2% divinylbenzene, vinyl acetate/octadecyl vinyl ether,
crosslinked with 0.2% tetraallyloxyethane, vinyl acetate/allyl
stearate, crosslinked with 0.2% divinyl-benzene, vinyl
acetate/1-octadecene, crosslinked with 0.2% divinylbenzene, and
allyl propionate/allyl stearate, crosslinked with 0.26
divinylbenzene.
[0328] Examples of liposoluble film-forming polymers that may be
mentioned include copolymers of a vinyl ester and of at least one
other monomer that may be a vinyl ester, especially vinyl
neodecanoate, vinyl benzoate and vinyl t-butylbenzoate, an
.alpha.-olefin, an alkyl vinyl ether or an allylic or methallylic
ester.
[0329] Examples of liposoluble film-forming polymers that may also
be mentioned are liposoluble copolymers, and in particular those
resulting from the copolymerization of vinyl esters containing from
9 to 22 carbon atoms or of alkyl acrylates or methacrylates, and
alkyl radicals containing from 10 to 20 carbon atoms.
[0330] Such liposoluble copolymers may be chosen from copolymers of
polyvinyl stearate, polyvinyl stearate crosslinked with the aid of
divinylbenzene, of diallyl ether or of diallyl phthalate,
polystearyl (meth)acrylate, polyvinyl laurate and polylauryl
(meth)acrylate, it being possible for these poly(meth)acrylates to
be crosslinked with the aid of ethylene glycol dimethacrylate or
tetraethylene glycol dimethacrylate.
[0331] The liposoluble copolymers defined above are known and are
described in particular in patent application FR-A-2 232 303; they
may have a weight-average molecular weight ranging from 2000 to 500
000 and preferably from 4000 to 200 000.
[0332] As liposoluble film-forming polymers that may be used in the
invention, mention may also be made of polyalkylenes and in
particular copolymers of C.sub.2-C.sub.20 alkenes, such as
polybutene, alkylcelluloses with a linear or branched, saturated or
unsaturated C.sub.1-C.sub.8 alkyl radical, for instance
ethylcellulose and propylcellulose, copolymers of vinylpyrrolidone
(VP) and in particular copolymers of vinylpyrrolidone and of
C.sub.2 to C.sub.40 and better still C.sub.3 to C.sub.20 alkene. As
examples of VP copolymers which may be used in the invention,
mention may be made of the copolymers of VP/vinyl acetate, VP/ethyl
methacrylate, butylated polyvinyl-pyrrolidone (PVP), VP/ethyl
methacrylate/methacrylic acid, VP/eicosene, VP/hexadecene,
VP/triacontene, VP/styrene or VP/acrylic acid/lauryl
methacrylate.
[0333] Mention may also be made of silicone resins, which are
generally soluble or swellable in silicone oils, which are
crosslinked polyorganosiloxane polymers. The nomenclature of
silicone resins is known under the name "MDTQ", the resin being
described as a function of the various siloxane monomer units it
comprises, each of the letters "MDTQ" characterizing a type of
unit.
[0334] Examples of commercially available polymethyl-silsesquioxane
resins that may be mentioned include those sold by the company
Wacker under the reference Resin MK, such as Belsil PMS MK, or by
the company Shin-Etsu under the reference KR-220L.
[0335] Examples of commercially available polypropyl-silsesquioxane
resins that may be mentioned include those sold under the reference
DC670 by the company Dow Corning.
[0336] Siloxysilicate resins that may be mentioned include
trimethyl siloxysilicate (TMS) resins such as those sold under the
reference SR 1000 by the company General Electric or under the
reference TMS 803 by the company Wacker. Mention may also be made
of the trimethyl siloxysilicate resins sold in a solvent such as
cyclomethicone, sold under the name KF-7312J by the company
Shin-Etsu, and DC 749 and DC 593 by the company Dow Corning.
[0337] In the case of skin makeup or care compositions, the
combination of a resin according to the invention with a trimethyl
siloxysilicate resin or a polypropylsilsesquioxane resin makes it
possible to improve the durability of the transfer resistance.
[0338] Mention may also be made of silicone resin copolymers such
as those mentioned above with polydimethylsiloxanes, for instance
the pressure-sensitive adhesive copolymers sold by the company Dow
Corning under the reference Bio-PSA and described in document U.S.
Pat. No. 5,162,410, or the silicone copolymers derived from the
reaction of a silicone resin, such as those described above, and of
a diorganosiloxane, as described in document WO 2004/073 626.
[0339] The film-forming polymer may be chosen from block or random
polymers and/or copolymers especially comprising polyurethanes,
polyacrylics, silicones, fluoro polymers, butyl rubbers, ethylene
copolymers, natural gums and polyvinyl alcohols, and mixtures
thereof. The monomers of the block or random copolymers comprising
at least one combination of monomers whose resulting polymer has a
glass transition temperature of less than room temperature
(25.degree. C.) may be chosen especially from butadiene, ethylene,
propylene, acrylic, methacrylic, isoprene, isobutene and a
silicone, and mixtures thereof.
[0340] The film-forming polymer may also be present in the first
and/or second composition in the form of particles dispersed in an
aqueous phase or in a non-aqueous solvent phase, which is generally
known as a latex or pseudolatex. The techniques for preparing these
dispersions are well known to those skilled in the art.
[0341] The composition according to the invention may comprise a
plasticizer that promotes the formation of a film with the
film-forming polymer. Such a plasticizer may be chosen from any
compound known to those skilled in the art as being capable of
satisfying the desired function.
[0342] As other examples of film-forming systems that may be used
in the compositions according to the invention, mention may be made
of systems in which the film is formed in situ at the time of
application of the composition or of a mixture of compositions
containing two silicone compounds that react together when they are
placed in contact. Such systems are described especially in patent
application WO 2007/071 706, the content of which is incorporated
herein by reference. Systems of this type are also described in
patent applications US 2007/142 575 and US 2007/142 599, the
content of which is also incorporated herein by reference.
[0343] Other Polymers:
[0344] The compositions according to the invention may contain an
elastomer, especially a polyglycerolated silicone elastomer. By way
of example, use is made of an elastomeric crosslinked
organopolysiloxane that may be obtained by a crosslinking addition
reaction of a diorganopolysiloxane containing at least one hydrogen
bonded to silicon and of polyglycerolated compounds containing
ethylenically unsaturated groups, especially in the presence of a
platinum catalyst.
[0345] Polyglycerolated silicone elastomers that may be used
include those sold under the names KSG-710, KSG-810, KSG-820,
KSG-830 and KSG-840 by the company Shin-Etsu.
[0346] The compositions according to the invention may also
comprise an additional emulsifying silicone elastomer.
[0347] By way of example, use may be made of polyoxyalkylenated
elastomers as described especially in U.S. Pat. No. 5,236,986, U.S.
Pat. No. 5,412,004, U.S. Pat. No. 5,837,793 and U.S. Pat. No.
5,811,487, the content of which is incorporated by reference.
[0348] Polyoxyalkylenated silicone elastomers that may be used
include those sold under the names KSG-21, KSG-20, KSG-30, KSG-31,
KSG-32, KSG-33, KSG-210, KSG-310, KSG-320, KSG-330, KSG-340 and
X-226146 by the company Shin-Etsu, and DC9010 and DC9011 by the
company Dow Corning.
[0349] When they are in combination with the resins according to
the invention, these particular elastomers may make it possible to
improve the transfer-resistance and comfort (suppleness) properties
of the compositions comprising them.
[0350] The compositions according to the invention may also
comprise a non-emulsifying elastomer.
[0351] Non-emulsifying elastomers are especially described in
patent applications JP-A-61-194 009, EP-A-242 219, EP-A-285 886 and
EP-A-765 656, the content of which is incorporated by
reference.
[0352] Spherical non-emulsifying elastomers that may be used
include those sold under the names DC9040, DC9041, DC9509, DC9505
and DC9506 by the company Dow Corning.
[0353] The spherical non-emulsifying silicone elastomer may also be
in the form of an elastomeric crosslinked organopolysiloxane powder
coated with silicone resin, especially with silsesquioxane resin,
as described, for example, in U.S. Pat. No. 5,538,793, the content
of which is incorporated by reference. Such elastomers are sold
under the names KSP-100, KSP-101, KSP-102, KSP-103, KSP-104 and
KSP-105 by the company Shin-Etsu.
[0354] Other elastomeric crosslinked organopolysiloxanes in the
form of spherical powders may be powders of a hybrid silicone
functionalized with fluoroalkyl groups, sold especially under the
name KSP-200 by the company Shin-Etsu; powders of a hybrid silicone
functionalized with phenyl groups, sold especially under the name
KSP-300 by the company Shin-Etsu.
[0355] Silicone elastomers bearing a group MQ, such as those sold
by the company Wacker under the names Belsil RG100, Belsil RPG33
and, preferentially, RG80, may also be used in the compositions
according to the invention. These particular elastomers, when they
are in combination with the resins according to the invention, may
make it possible to improve the transfer-resistance properties of
the compositions comprising them.
[0356] The Oils:
[0357] The composition according to the invention comprises at
least one liquid fatty phase comprising at least one oil.
[0358] The oil may be chosen from hydrocarbon-based oils, silicone
oils and fluoro oils.
[0359] The oil may be chosen from volatile oils and non-volatile
oils, and mixtures thereof.
[0360] The term "hydrocarbon-based oil" means an oil formed
essentially from, or even consisting of, carbon and hydrogen atoms,
and possibly oxygen and nitrogen atoms, and containing no silicon
or fluorine atoms; it may contain ester, ether, amine or amide
groups.
[0361] The term "silicone oil" means an oil containing at least one
silicon atom, and especially containing Si--O groups.
[0362] The term "fluoro oil" means an oil containing at least one
fluorine atom.
[0363] The composition according to the invention may comprise at
least one volatile oil.
[0364] The term "volatile oil" means an oil (or non-aqueous medium)
capable of evaporating on contact with the skin in less than one
hour, at room temperature and atmospheric pressure. The volatile
oil is a volatile cosmetic oil, which is liquid at room
temperature, especially having a non-zero vapour pressure, at room
temperature and atmospheric pressure, in particular having a vapour
pressure ranging from 0.13 Pa to 40 000 Pa (10.sup.-3 to 300 mmHg),
preferably ranging from 1.3 Pa to 13 000 Pa (0.01 to 100 mmHg) and
preferentially ranging from 1.3 Pa to 1300 Pa (0.01 to 10
mmHg).
[0365] In addition, the volatile oil generally has a boiling point,
measured at atmospheric pressure, ranging from 150.degree. C. to
260.degree. C. and preferably ranging from 170.degree. C. to
250.degree. C.
[0366] The composition according to the invention may comprise a
volatile hydrocarbon-based oil chosen especially from
hydrocarbon-based oils with a flash point ranging from 40.degree.
C. to 102.degree. C., preferably ranging from 40.degree. C. to
55.degree. C. and preferentially ranging from 40.degree. C. to
50.degree. C.
[0367] Volatile hydrocarbon-based oils that may be mentioned
include volatile hydrocarbon-based oils containing from 8 to 16
carbon atoms and mixtures thereof, and especially branched
C.sub.8-C.sub.16 alkanes, for instance C.sub.8-C.sub.16 isoalkanes
(also known as isoparaffins), isododecane, isodecane, isohexadecane
and, for example, the oils sold under the trade name Isopar or
Permethyl, branched C.sub.8-C.sub.16 esters, for instance isohexyl
neopentanoate, and mixtures thereof. Preferably, the volatile
hydrocarbon-based oil is chosen from volatile hydrocarbon-based
oils containing from 8 to 16 carbon atoms, and mixtures thereof, in
particular from isododecane, isodecane and isohexadecane, and is
especially isododecane.
[0368] For skin makeup products, especially foundations and
lipsticks, linear hydrocarbon-based volatile oils containing from 8
to 16 carbon atoms will advantageously be used.
[0369] Volatile silicone oils that may be mentioned include linear
or cyclic silicones 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, heptamethyl-hexyltrisiloxane,
heptamethyloctyltrisiloxane, octamethyltrisiloxane and
decamethyltetrasiloxane, and mixtures thereof.
[0370] The volatile oil may be present in the composition according
to the invention in a content ranging from 0.1% to 90% by weight,
preferably ranging from 1% to 70% by weight and preferentially
ranging from 5% to 50% by weight, relative to the total weight of
the composition.
[0371] The composition according to the invention may comprise at
least one non-volatile oil.
[0372] Non-volatile hydrocarbon-based oils that may be used include
liquid paraffin (or petroleum jelly), squalane, hydrogenated
polyisobutylene (Parleam oil), perhydrosqualene, mink oil, turtle
oil, soybean oil, sweet almond oil, beauty-leaf oil, palm oil,
grapeseed oil, sesame seed oil, corn oil, arara oil, rapeseed oil,
sunflower oil, cottonseed oil, apricot oil, castor oil, avocado
oil, jojoba oil, olive oil or cereal germ oil; linoleic acid, oleic
acid, lauric acid or stearic acid esters; fatty esters, especially
of C.sub.12-C.sub.36, such as isopropyl myristate, isopropyl
palmitate, butyl stearate, hexyl laurate, diisopropyl adipate,
isononyl isononanoate, 2-ethylhexyl palmitate, 2-hexyldecyl
laurate, 2-octyldecyl palmitate, 2-octyldodecyl myristate or
lactate, bis(2-ethylhexyl) succinate, diisostearyl malate, and
glyceryl or diglyceryl triisostearate; behenic acid, oleic acid,
linoleic acid, linolenic acid or isostearic acid; higher fatty
alcohols, especially of C.sub.16-C.sub.22, such as cetanol, oleyl
alcohol, linoleyl alcohol, linolenyl alcohol, isostearyl alcohol or
octyldodecanol; and mixtures thereof.
[0373] The non-volatile oil may be present in a content ranging
from 0.1% to 70% by weight, preferably ranging from 0.5% to 60% by
weight and preferentially ranging from 1% to 50% by weight relative
to the total weight of the non-volatile liquid fatty phase.
[0374] For skin makeup products, especially foundations and
lipsticks, volatile or non-volatile linear silicone oils will
advantageously be used. The combination of a resin according to the
invention and of a linear silicone oil may especially improve the
transfer resistance.
[0375] For skin makeup products, especially lipsticks, phenyl
silicone oils will advantageously be used. The combination of a
resin according to the invention and of a phenyl silicone oil may
especially improve the gloss and comfort and reduce the tacky
sensation.
[0376] Structuring Agents:
[0377] The composition according to the invention may comprise a
structuring agent.
[0378] The term "structuring agent" means a compound capable of
increasing the viscosity of the composition. The structuring agent
makes it possible especially to obtain a composition that can have
a texture ranging from fluid to solid textures.
[0379] The structuring agent may be present in the composition in a
content ranging from 0.05% to 40% by weight, preferably ranging
from 0.1% to 30% by weight and preferentially ranging from 0.1% to
25% by weight, relative to the total weight of the composition.
[0380] The structuring agent may be chosen especially from
thickeners (oily-medium thickeners; aqueous-medium thickeners),
organogelling agents, waxes, pasty compounds and gums.
[0381] The aqueous-medium thickener may be chosen from: [0382]
hydrophilic clays, [0383] hydrophilic fumed silica, [0384]
water-soluble cellulose-based thickeners, [0385] guar gum, xanthan
gum, carob gum, scleroglucan gum, gellan gum, rhamsan gum, karaya
gum or carrageenan gum, [0386] alginates, maltodextrins, starch and
its derivatives, and hyaluronic acid and its salts, [0387] the
polyglyceryl (meth)acrylate polymers sold under the names
"Hispagel" or "Lubragel" by the companies Hispano Quimica or
Guardian, [0388] polyvinylpyrrolidone, [0389] polyvinyl alcohol,
[0390] crosslinked acrylamide polymers and copolymers, such as
those sold under the names PAS 5161 or Bozepol C by the company
Hoechst, Sepigel 305 by the company SEPPIC by the company Allied
Colloid, or alternatively [0391] the crosslinked
methacryloyloxyethyltrimethyl-ammonium chloride homopolymers sold
under the name "Salcare SC95" by the company Allied Colloid, [0392]
associative polymers and especially associative polyurethanes.
[0393] Such thickeners are described especially in patent
application EP-A-1 400 234, the content of which is incorporated by
reference.
[0394] The oily-medium thickener may be chosen from: [0395]
carboxylate silicones, [0396] saccharide silicones, [0397]
organophilic clays; [0398] hydrophobic fumed silicas; [0399] alkyl
guar gums (with a C.sub.1-C.sub.6 alkyl group), such as those
described in EP-A-708 114; [0400] hydrophobic celluloses, [0401]
oil-gelling polymers, for instance triblock polymers or star
polymers resulting from the polymerization or copolymerization of
at least one monomer containing an ethylenic group, for instance
the polymers sold under the name Kraton; [0402] polymers with a
weight-average molecular mass of less than 100 000, comprising a) a
polymer skeleton containing hydrocarbon-based repeating units
containing at least one heteroatom, and optionally b) at least one
pendent fatty chain and/or at least one terminal fatty chain, which
are optionally functionalized, containing from 6 to 120 carbon
atoms and being linked to these hydrocarbon-based units, as
described in patent applications WO-A-02/056847 and WO-A-02/47619,
the content of which is incorporated by reference; in particular,
polyamide resins (especially comprising alkyl groups containing
from 12 to 22 carbon atoms) such as those described in U.S. Pat.
No. 5,783,657, the content of which is incorporated by reference;
[0403] the silicone-based polyamide resins as described in patent
application EP-A-1 266 647 and in the French patent application
filed under the number 0 216 039, the content of which is
incorporated by reference.
[0404] Such thickeners are especially described in patent
application EP-A-1 400 234, the content of which is incorporated by
reference.
[0405] The organogelling agents may be chosen from those described
in patent application WO-A-03/105 788, the content of which is
incorporated by reference.
[0406] In particular, it may be advantageous to combine the resins
according to the invention with particular organogelling agents,
and especially:
[0407] the bis-urea derivatives of general formula (I):
##STR00024##
in which:
[0408] A is a group of formula:
##STR00025##
[0409] with R' being a linear or branched C.sub.1 to C.sub.4 alkyl
radical and the *s symbolizing the points of attachment of the
group A to each of the two nitrogen atoms of the rest of the
compound of general formula (I), and [0410] R is a saturated or
unsaturated, non-cyclic, mono-branched C.sub.6 to C.sub.16 alkyl
radical whose hydrocarbon-based chain is optionally interrupted
with 1 to 3 heteroatoms chosen from O, S and N, or
[0411] a salt or isomer thereof, described especially in patent
application FR-A-2 892 303,
[0412] the silicone bis-urea derivatives of general formula (I), or
a salt and/or isomer thereof:
##STR00026##
in which: [0413] A is a group of formula (II):
##STR00027##
[0414] with R.sub.1 being a linear or branched C.sub.1-C.sub.4
alkyl radical, and the *s symbolizing the points of attachment of
the group A to each of the two nitrogen atoms of the rest of the
compound of general formula (I), and [0415] R and R', which may be
identical or different, are chosen from: [0416] i) the radicals of
formula (III):
##STR00028##
[0417] in which: [0418] L is a single bond or a divalent
carbon-based radical, especially a linear, branched and/or cyclic,
saturated or unsaturated hydrocarbon-based radical (alkylene),
containing 1 to 18 carbon atoms, and possibly comprising 1 to 4
heteroatoms chosen from N, O and S; [0419] R.sub.a is:
[0420] a) a carbon-based radical, especially a linear, branched
and/or cyclic, saturated or unsaturated hydrocarbon-based radical
(alkyl), containing 1 to 18 carbon atoms, and possibly comprising 1
to 8 heteroatoms chosen from N, O, Si and S; or
[0421] b) a silicone radical of formula:
##STR00029##
[0422] with n being between 0 and 100, especially between 1 and 80,
or even 2 to 20;
[0423] and R.sub.2 to R.sub.6 being, independently of each other,
carbon-based radicals, especially linear or branched
hydrocarbon-based radicals (alkyl) containing 1 to 12 and
especially 1 to 6 carbon atoms, and possibly comprising 1 to 4
heteroatoms, especially O; [0424] R.sub.b and R.sub.c are,
independently of each other, chosen from:
[0425] a) carbon-based radicals, especially linear, branched and/or
cyclic, saturated or unsaturated hydrocarbon-based radicals
(alkyl), containing 1 to 18 carbon atoms, and possibly comprising 1
to 4 heteroatoms chosen from N, O, Si and S;
[0426] b) the radicals of formula:
##STR00030##
[0427] with n being between 0 and 100, especially between 1 and 80,
or even 2 to 20;
[0428] and R'.sub.2 to R'.sub.6 being, independently of each other,
carbon-based radicals, especially linear or branched
hydrocarbon-based radicals (alkyl), containing 1 to 12 and
especially 1 to 6 carbon atoms, and possibly comprising 1 to 4
heteroatoms, especially O; and [0429] ii) linear, branched and/or
cyclic, saturated or unsaturated C.sub.1-C.sub.30 alkyl radicals,
optionally comprising 1 to 3 heteroatoms chosen from O, S, F and
N;
[0430] it being understood that at least one of the radicals R
and/or R' is of formula (III), such as those described in patent
application FR-A-2 900 819,
[0431] the bis-urea derivatives described in patent application
FR-A-2 899 4476.
[0432] Wax(es)
[0433] The composition may comprise at least one solid fatty
substance chosen from waxes, as structuring agent.
[0434] The wax under consideration in the context of the present
invention is generally a lipophilic compound that is solid at room
temperature (25.degree. C.), with a solid/liquid reversible change
of state, having a melting point of greater than or equal to
30.degree. C., which may be up to 200.degree. C. and in particular
up to 120.degree. C.
[0435] In particular, the waxes that are suitable for the invention
may have a melting point of greater than or equal to 45.degree. C.
and in particular greater than or equal to 55.degree. C.
[0436] For the purposes of the invention, the melting point
corresponds to the temperature of the most endothermic peak
observed by 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.
[0437] The measuring protocol is as follows:
[0438] A sample of 5 mg of wax placed in a crucible is subjected to
a first temperature rise ranging from -20.degree. C. to 100.degree.
C., at a heating rate of 10.degree. C./minute, it is then cooled
from 100.degree. C. to -20.degree. C. at a cooling rate of
10.degree. C./minute and is finally subjected to a second
temperature increase ranging from -20.degree. C. to 100.degree. C.
at a heating rate of 5.degree. 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 absorbed power as a function of the
temperature.
[0439] 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.
[0440] 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, microcrystalline waxes, paraffins
and ozokerite; polyethylene waxes, the waxes obtained by
Fischer-Tropsch synthesis and waxy copolymers, and also esters
thereof.
[0441] Mention may also be made of waxes obtained by catalytic
hydrogenation of animal or plant oils containing linear or branched
C.sub.8-C.sub.32 fatty chains. Among these waxes that may
especially be mentioned are isomerized jojoba oil such as the
trans-isomerized partially hydrogenated jojoba oil manufactured or
sold by the company Desert Whale under the commercial reference
Iso-Jojoba-50.RTM., hydrogenated sunflower oil, hydrogenated castor
oil, hydrogenated coconut oil, hydrogenated lanolin oil and
bis(1,1,1-trimethylol-propane) tetrastearate sold under the name
Hest 2T-4S.RTM. by the company Heterene.
[0442] Mention may also be made of silicone waxes (C.sub.30-45
alkyl dimethicone) and fluoro waxes.
[0443] The waxes obtained by hydrogenation of castor oil esterified
with cetyl alcohol, sold under the names Phytowax ricin 16L64.RTM.
and 22L73.RTM. by the company Sophim, may also be used. Such waxes
are described in patent application FR-A-2 792 190.
[0444] A wax that may be used is a C.sub.20-C.sub.40 alkyl
(hydroxystearyloxy)stearate (the alkyl group containing from 20 to
40 carbon atoms), alone or as a mixture.
[0445] Such a wax is especially sold under the names Kester Wax K
82 P.RTM., Hydroxypolyester K 82 P.RTM., Kester Wax K 80 P.RTM. and
Kester Wax K 82H.RTM. by the company Koster Keunen.
[0446] 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.RTM. by the company Micro Powders, synthetic microwaxes, such
as the product sold under the name MicroEase 114S.RTM. 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.RTM. and 310.RTM. 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.RTM. by the company Micro Powders, polyethylene microwaxes,
such as the products sold under the names Micropoly 200.RTM.,
220.RTM., 220L.RTM. and 250S.RTM. by the company Micro Powders, and
polytetrafluoroethylene microwaxes, such as the products sold under
the names Microslip 519.RTM. and 519 L.RTM. by the company Micro
Powders.
[0447] The composition according to the invention may have a wax
content ranging from 0.1% to 50% by weight and better still from 1%
to 30% by weight relative to the total weight of the
composition.
[0448] Pasty Compounds
[0449] The composition according to the invention may comprise at
least one pasty compound as structuring agent. Pasty fatty
substances are considered as solid fatty substances for the
purposes of the present invention.
[0450] For the purposes of the present invention, the term "pasty"
means a lipophilic fatty compound that undergoes a reversible
solid/liquid change of state and that comprises in the solid state
an anisotropic crystal organization, and comprises, at a
temperature of 23.degree. C., a liquid fraction and a solid
fraction.
[0451] In other words, the starting melting point of the pasty
compound is less than 23.degree. C. The liquid fraction of the
pasty compound measured at 23.degree. C. may represent 9% to 97% by
weight of the compound. This liquid fraction at 23.degree. C.
preferably represents between 15% and 85% and more preferably
between 40% and 85% by weight.
[0452] The liquid fraction by weight of the pasty compound at
23.degree. C. is equal to the ratio of the heat of fusion consumed
at 23.degree. C. to the heat of fusion of the pasty compound.
[0453] The heat of fusion of the pasty compound is the heat
consumed by the compound to change from the solid state to the
liquid state. The pasty compound is said to be in the solid state
when all of its mass is in solid form. The pasty compound is said
to be in the liquid state when all of its mass is in liquid
form.
[0454] The heat of fusion of the pasty compound is equal to the
area under the curve of the thermogram obtained using a
differential scanning calorimeter (DSC), such as the calorimeter
sold under the name MDSC 2920 by the company TA Instrument, with a
temperature rise of 5 or 10.degree. C. per minute, according to
standard ISO 11357-3:1999. The heat of fusion of the pasty compound
is the amount of energy required to make the compound change from
the solid state to the liquid state. It is expressed in J/g.
[0455] The heat of fusion consumed at 23.degree. C. is the amount
of energy absorbed by the sample to change from the solid state to
the state that it has at 23.degree. C., constituted of a liquid
fraction and a solid fraction.
[0456] The liquid fraction of the pasty compound, measured at
32.degree. C., preferably represents from 30% to 100% by weight of
the compound, preferably from 50% to 100% and more preferably from
60% to 100% by weight of the compound. When the liquid fraction of
the pasty compound measured at 32.degree. C. is equal to 100%, the
temperature of the end of the melting range of the pasty compound
is less than or equal to 32.degree. C.
[0457] The liquid fraction of the pasty compound measured at
32.degree. C. is equal to the ratio of the heat of fusion consumed
at 32.degree. C. to the heat of fusion of the pasty compound. The
heat of fusion consumed at 32.degree. C. is calculated in the same
manner as the heat of fusion consumed at 23.degree. C.
[0458] The pasty compound is preferably chosen from synthetic
compounds and compounds of plant origin. A pasty compound may be
obtained by synthesis from starting materials of plant origin.
[0459] The pasty compound may advantageously be chosen from: [0460]
i) lanolin and derivatives thereof, [0461] ii) polymer or
non-polymer silicone compounds, [0462] iii) polymer or non-polymer
fluoro compounds, [0463] iv) vinyl polymers, especially: [0464] v)
olefin homopolymers [0465] vi) olefin copolymers [0466] vii)
hydrogenated diene homopolymers and copolymers [0467] viii) linear
or branched oligomers, which are homopolymers or copolymers of
alkyl (meth)acrylates preferably containing a C.sub.8-C.sub.30
alkyl group [0468] ix) oligomers, which are homopolymers and
copolymers of vinyl esters containing C.sub.8-C.sub.30 alkyl groups
[0469] x) oligomers, which are homopolymers and copolymers of vinyl
ethers containing C.sub.8-C.sub.30 alkyl groups, [0470] xi)
liposoluble polyethers resulting from the polyetherification
between one or more C.sub.2-C.sub.100 and preferably
C.sub.2-C.sub.50 diols, [0471] xii) esters, [0472] xiii) and
mixtures thereof.
[0473] Among the esters that are especially preferred are: [0474]
xiv) 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 the product sold under the brand name Softisan 649 by the
company Sasol, [0475] xv) arachidyl propionate sold under the brand
name Waxenol 801 by Alzo, [0476] xvi) phytosterol esters, [0477]
xvii) fatty acid triglycerides and derivatives thereof, [0478]
xviii) pentaerythritol esters, [0479] xix) non-crosslinked
polyesters resulting from polycondensation between a linear or
branched C.sub.4-C.sub.50 dicarboxylic acid or polycarboxylic acid
and a C.sub.2-C.sub.50 diol or polyol, [0480] xx) aliphatic esters
of an ester resulting from the esterification of an aliphatic
hydroxycarboxylic acid with an aliphatic carboxylic acid, [0481]
xxi) polyesters resulting from the esterification, with a
polycarboxylic acid, of an ester of an aliphatic hydroxycarboxylic
acid, the said ester comprising at least two hydroxyl groups, such
as the products Risocast DA-H.RTM. and Risocast DA-L.RTM., [0482]
xxii) 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, [0483] xxiii)
and mixtures thereof.
[0484] Among the pasty compounds of plant origin, a mixture of
soybean sterols and of oxyethylenated (5 EO) oxypropylenated (5 PO)
pentaerythritol, sold under the reference Lanolide by the company
Vevy, will preferably be chosen.
[0485] Preferably, the composition comprises a total content of
pasty fatty substances ranging from 0.5% to 50% by weight,
preferably from 1% to 40% by weight and better still from 5% to 30%
by weight relative to the weight of the composition.
[0486] The gums are generally polydimethylsiloxanes (PDMS) of high
molecular weight or cellulose gums or polysaccharides.
[0487] Surfactants
[0488] The composition according to the invention may comprise at
least one surfactant.
[0489] The surfactant may be lipophilic and/or hydrophilic, used
alone or in combination.
[0490] The surfactant may be chosen from nonionic, anionic,
cationic and amphoteric surfactants.
[0491] The nonionic surfactant may be chosen from: [0492] a
C.sub.8-C.sub.22 alkyl dimethicone copolyol, i.e. an
oxypropylenated and/or oxyethylenated polymethyl
(C.sub.8-C.sub.22)alkyl dimethyl methyl siloxane.
[0493] The C.sub.8-C.sub.22 alkyl dimethicone copolyol is
advantageously a compound of formula (I) below:
##STR00031##
in which: [0494] PE represents (--C.sub.2H.sub.4O).sub.x--
(C.sub.3H.sub.6O).sub.y--R, R being chosen from a hydrogen atom and
an alkyl radical of 1 to 4 carbon atoms, x ranging from 0 to 100
and y ranging from 0 to 80, x and y not simultaneously being 0
[0495] m ranging from 1 to 40 [0496] n ranging from 10 to 200
[0497] o ranging from 1 to 100 [0498] p ranging from 7 to 21 [0499]
q ranging from 0 to 4
[0500] and preferably:
[0501] R.dbd.H
[0502] m=1 to 10
[0503] n=10 to 100
[0504] o=1 to 30
[0505] p=15
[0506] q=3.
[0507] A C.sub.8-C.sub.22 alkyl dimethicone copolyol that may be
mentioned is cetyl dimethicone copolyol, for instance the product
sold under the name Abil EM-90 by the company Goldschmidt. [0508] a
dimethicone copolyol, i.e. an oxypropylenated and/or oxyethylenated
polydimethyl methyl siloxane. It contains no alkyl groups with a
chain length of more than 8 carbon atoms, especially
C.sub.8-C.sub.22.
[0509] Dimethicone copolyols that may be used include those
corresponding to formula (II) below:
##STR00032##
[0510] in which:
[0511] R.sub.1, R.sub.2 and R.sub.3, independently of each other,
represent a C.sub.1-C.sub.6 alkyl radical or a radical
--(CH.sub.2).sub.X--(OCH.sub.2CH.sub.2).sub.y--(OCH.sub.2CH.sub.2CH.sub.2-
).sub.z--OR.sub.4, at least one radical R.sub.1, R.sub.2 or R.sub.3
not being an alkyl radical; R.sub.4 being a hydrogen, a
C.sub.1-C.sub.2 alkyl radical or a C.sub.2-C.sub.4 acyl
radical;
[0512] A is an integer ranging from 0 to 200;
[0513] B is an integer ranging from 0 to 50; on condition that A
and B are not simultaneously equal to zero;
[0514] x is an integer ranging from 1 to 6;
[0515] y is an integer ranging from 1 to 30;
[0516] z is an integer ranging from 0 to 5.
[0517] According to one preferred embodiment of the invention, in
the compound of formula (II), R.sub.1.dbd.R.sub.3=methyl radical, x
is an integer ranging from 2 to 6 and y is an integer ranging from
4 to 30. R.sub.4 is in particular a hydrogen.
[0518] Examples of compounds of formula (II) that may be mentioned
include the compounds of formula (III):
##STR00033##
[0519] in which A is an integer ranging from 20 to 105, B is an
integer ranging from 2 to 10 and y is an integer ranging from 10 to
20.
[0520] Examples of silicone compounds of formula (II) that may also
be mentioned include the compounds of formula (IV):
HO--(CH.sub.2CH.sub.2O).sub.y--(CH.sub.2).sub.3-[(CH.sub.3).sub.2SiO].su-
b.A'-[(CH.sub.3).sub.2Si]-(CH.sub.2).sub.3--(OCH.sub.2CH.sub.2).sub.y--OH
(Iv)
[0521] in which A' and y are integers ranging from 10 to 20.
[0522] Dimethicone copolyols that may be used include those sold
under the names DC 5329, DC 7439-146, DC 2-5695 and Q4-3667 by the
company Dow Corning; KF-6013, KF-6015, KF-6016 and KF-6017 by the
company Shin-Etsu.
[0523] The compounds DC 5329, DC 7439-146 and DC2-5695 are
compounds of formula (III) in which, respectively, A is 22, B is 2
and y is 12; A is 103, B is 10 and y is 12; A is 27, B is 3 and y
is 12.
[0524] Nonionic surfactants that may also be mentioned include
fatty acid esters of polyols, for instance sorbitol or glyceryl
mono-, di-, tri- or sesqui-oleates or stearates, glyceryl or
polyethylene glycol laurates; fatty acid esters of polyethylene
glycol (polyethylene glycol monostearate or monolaurate);
polyoxyethylenated fatty acid esters (stearate or oleate) of
sorbitol; polyoxyethylenated alkyl (lauryl, cetyl, stearyl or
octyl)ethers.
[0525] Anionic surfactants that may be mentioned include
carboxylates (sodium 2-(2-hydroxyalkyloxy)acetate)), amino acid
derivatives (N-acylglutamates, N-acylglycinates or
acylsarcosinates), alkyl sulfates, alkyl ether sulfates and
oxyethylenated derivatives thereof, sulfonates, isethionates and
N-acylisethionates, taurates and N-acyl N-methyltaurates,
sulfosuccinates, alkylsulfoacetates, phosphates and alkyl
phosphates, polypeptides, anionic derivatives of alkyl
polyglycoside (acyl-D-galactoside uronate), and fatty acid soaps,
and mixtures thereof.
[0526] Amphoteric and zwitterionic surfactants that may be used
include betaines, N-alkylamidobetaines and derivatives thereof,
glycine derivatives, sultaines, alkyl polyaminocarboxylates and
alkylamphoacetates, and mixtures thereof.
[0527] Such surfactants are described especially in patent
application WO-A-02/056 854, the content of which is incorporated
by reference.
[0528] The surfactant may be present in the composition according
to the invention in a content ranging from 0.1% to 10% by weight,
preferably ranging from 0.5% to 8% by weight and preferentially
ranging from 0.5% to 7% by weight, relative to the total weight of
the composition.
[0529] Dyestuffs:
[0530] The composition according to the invention may comprise at
least one dyestuff.
[0531] The dyestuff may be chosen from pulverulent dyestuffs
(especially pigments and nacres) and water-soluble dyestuffs.
[0532] The term "pigments" should be understood as meaning white or
coloured, mineral or organic particles of any form, which are
insoluble in the physiological medium, and which are intended to
colour the composition.
[0533] The term "nacres" should be understood as meaning iridescent
particles of any form, produced especially by certain molluscs in
their shell, or else synthesized.
[0534] The pigments may be white or coloured, and mineral and/or
organic. Among the mineral pigments that may be mentioned are
titanium dioxide, optionally surface-treated, zirconium oxide or
cerium oxide, and also zinc oxide, iron oxide (black, yellow or
red) or chromium oxide, manganese violet, ultramarine blue,
chromium hydrate and ferric blue, and metal powders, for instance
aluminium powder or copper powder.
[0535] Among the organic pigments that may be mentioned are carbon
black, pigments of D & C type, and lakes based on cochineal
carmine or on barium, strontium, calcium or aluminium.
[0536] Mention may also be made of pigments with an effect, such as
particles comprising a natural or synthetic, organic or mineral
substrate, for example glass, acrylic resins, polyester,
polyurethane, polyethylene terephthalate, ceramics or aluminas, the
said substrate being uncoated or coated with metallic substances,
for instance aluminium, gold, silver, platinum, copper or bronze,
or with metal oxides, for instance titanium dioxide, iron oxide or
chromium oxide, and mixtures thereof.
[0537] The nacreous pigments may be chosen from white nacreous
pigments such as mica coated with titanium or with bismuth
oxychloride, coloured nacreous pigments such as titanium mica
coated with iron oxides, titanium mica coated especially with
ferric blue or with chromium oxide, titanium mica coated with an
organic pigment of the abovementioned type, and also nacreous
pigments based on bismuth oxychloride. Interference pigments,
especially liquid-crystal or multilayer interference pigments, may
also be used.
[0538] The term "alkyl" mentioned in the compounds cited above
especially denotes an alkyl group containing from 1 to 30 carbon
atoms and preferably containing from 5 to 16 carbon atoms.
[0539] Hydrophobic-treated pigments are described especially in
patent application EP-A-1 086 683.
[0540] The water-soluble dyes are, for example, beetroot juice or
methylene blue.
[0541] The synthetic or natural liposoluble dyes are, for example,
DC Red 17, DC Red 21, DC Red 27, DC Green 6, DC Yellow 11, DC
Violet 2, DC Orange 5, Sudan red, carotenes (.beta.-carotene,
lycopene), xanthophylls (capsanthin, capsorubin, lutein), palm oil,
Sudan brown, quinoline yellow, annatto and curcumin.
[0542] The dyestuffs, in particular the pigments treated with a
hydrophobic agent, may be present in the composition in a content
ranging from 0.1% to 50% by weight, preferably ranging from 0.5% to
30% by weight and preferentially ranging from 1% to 20% by weight,
relative to the total weight of the composition.
[0543] Fillers:
[0544] The composition according to the invention may comprise at
least one filler.
[0545] For the purposes of the present invention, the term "filler"
denotes solid particles of any form, which are in an insoluble form
and dispersed in the medium of the composition, even at
temperatures that may be up to the melting point of all the fatty
substances of the composition.
[0546] Generally, the fillers used according to the invention are
colourless or white, namely non-pigmentary, i.e. they are not used
to give a particular colour or shade to the composition according
to the invention, even though their use may inherently lead to such
a result. These fillers serve especially to modify the rheology or
texture of the composition.
[0547] In this respect, they are different from nacres, organic
pigmentary materials, for instance carbon black, pigments of
D&C type, and lakes based on cochineal carmine or on barium,
strontium, calcium or aluminium, and inorganic pigmentary
materials, for instance titanium dioxide, zirconium oxide or cerium
oxide, and also iron oxides (black, yellow or red), chromium oxide,
manganese violet, ultramarine blue, chromium hydrate and ferric
blue, which are, themselves, used to give a shade and coloration to
the compositions incorporating them.
[0548] For the purposes of the invention, such compounds are not
covered by the definition of fillers, which thus covers
non-pigmentary fillers, which may be organic or inorganic.
[0549] The non-pigmentary fillers used in the compositions
according to the present invention may be of lamellar, globular or
spherical form, of fibre type, or of any intermediate form between
these defined forms.
[0550] The size of the particles, i.e. their granulometry, is
chosen so as to ensure the good dispersion of the fillers in the
composition according to the invention. The granulometry of the
particles may be distributed within the range from 5 .mu.m to 10 nm
and in particular from 10 .mu.m to 10 nm.
[0551] The fillers according to the invention may or may not be
surface-coated, in particular surface-treated with silicones, amino
acids, fluoro derivatives or any other substance that promotes the
dispersion and compatibility of the filler in the composition.
[0552] Mineral Fillers
[0553] For the purposes of the present invention, the terms
"mineral" and "inorganic" are used interchangeably.
[0554] Among the non-pigmentary mineral fillers that may be used in
the compositions according to the invention, mention may be made of
talc, mica, silica, perlite, which is especially commercially
available from the company World Minerals Europe under the trade
name Perlite P1430, Perlite P2550 or Perlite P204, kaolin,
precipitated calcium carbonate, magnesium carbonate, magnesium
hydrogen carbonate, hydroxyapatite, boron nitride, hollow silica
microspheres (Silica Beads.RTM. from Maprecos), and glass or
ceramic microcapsules, and mixtures thereof.
[0555] According to one embodiment, the cosmetic composition
according to the invention comprises at least one non-pigmentary
mineral filler chosen from the group comprising kaolin, talc,
silica, perlite and clay, and mixtures thereof.
[0556] Organic Fillers
[0557] Among the organic fillers that may be mentioned are
polyamide powder (Orgasol.RTM. Nylon.RTM. from Atochem),
poly-.beta.-alanine powder and polyethylene powder, lauroyllysine,
starch, tetrafluoroethylene polymer powders (Teflon.RTM.), hollow
polymer microspheres such as those of polyvinylidene
chloride/acrylonitrile, for instance Expancel.RTM. (Nobel
Industrie) or of acrylic acid copolymer (such as Polytrap (Dow
Corning)), acrylate copolymers, PMMA, 12-hydroxystearic acid
oligomer stearate and silicone resin microbeads (for example
Tospearls.RTM. from Toshiba), magnesium carbonate, magnesium
hydrogen carbonate, and metal soaps derived from organic carboxylic
acids containing from 8 to 22 carbon atoms and preferably from 12
to 18 carbon atoms, for example zinc stearate, magnesium stearate,
lithium stearate, zinc laurate or magnesium myristate, and mixtures
thereof.
[0558] For the purposes of the present invention, the organic
fillers are different from the pigments.
[0559] They may also be particles comprising a copolymer, the said
copolymer comprising trimethylol hexyl lactone. In particular, it
may be a hexamethylene diisocyanate/trimethylol hexyl lactone
copolymer. Such particles are especially commercially available,
for example under the name Plastic Powder D-400.RTM. or Plastic
Powder D-800.RTM. from the company Toshiki.
[0560] According to one embodiment, a composition of the invention
may comprise at least one filler chosen from talc, silica, starch,
clay, kaolin and perlite, and mixtures thereof.
[0561] One or more dispersants may be used, where appropriate, to
protect the dispersed fillers or particles against aggregation or
flocculation. They may be added independently of the solid fillers
or particles or in the form of a colloidal dispersion of
particles.
[0562] The concentration of dispersants is chosen so as to obtain
satisfactory dispersion of the solid particles (without
flocculation).
[0563] This dispersant may be a surfactant, an oligomer, a polymer
or a mixture of several thereof, bearing one or more
functionalities with strong affinity for the surface of the
particles to be dispersed. In particular, poly(12-hydroxystearic
acid) esters are used, such as poly(12-hydroxystearic acid)
stearate with a molecular weight of about 750 g/mol, such as the
product sold under the name Solsperse 21 000.RTM. by the company
Avecia, esters of poly(12-hydroxystearic acid) with polyols such as
glycerol or diglycerol, such as polyglyceryl-2
dipolyhydroxystearate (CTFA name) sold under the reference Dehymuls
PGPH.RTM. by the company Henkel (or diglyceryl
poly(12-hydroxystearate)), or alternatively poly(12-hydroxystearic
acid), such as the product sold under the reference Arlacel P100 by
the company Uniqema, and mixtures thereof.
[0564] As other dispersants that may be used in the composition of
the invention, mention may be made of quaternary ammonium
derivatives of polycondensate fatty acids, for instance Solsperse
17 000.RTM. sold by the company Avecia, and mixtures of
polydimethylsiloxane/oxypropylene such as those sold by the company
Dow Corning under the references DC2-5185 and DC2-5225 C.
[0565] A composition of the invention should be cosmetically or
dermatologically acceptable, i.e. it should contain a non-toxic
physiologically acceptable medium that can be applied to human
lips. For the purposes of the invention, the term "cosmetically
acceptable" refers to a composition of pleasant appearance, odour
and feel.
[0566] The composition according to the invention may also contain
ingredients commonly used in cosmetics, such as vitamins,
thickeners, trace elements, softeners, sequestrants, fragrances,
acidifying agents, basifying agents, preserving agents, sunscreens,
surfactants, antioxidants, hair-loss counteractants, antidandruff
agents and propellants, or mixtures thereof.
[0567] Needless to say, a person skilled in the art will take care
to select this or these optional additional compounds, and/or the
amount thereof, such that the advantageous properties of the
corresponding composition according to the invention are not, or
are not substantially, adversely impaired by the envisaged
addition.
[0568] According to another aspect, the invention also relates to a
cosmetic assembly comprising:
[0569] i) a container delimiting at least one compartment, the said
container being closed by a closing member; and
[0570] ii) a composition placed inside the said compartment, the
composition being in accordance with the invention.
[0571] The container may be in any adequate form. It may especially
be in the form of a bottle, a tube, a jar, a case, a box, a sachet
or a carton.
[0572] The closing member may be in the form of a removable
stopper, a lid, a cap, a tear-off strip or a capsule, especially of
the type comprising a body attached to the container and a cover
cap articulated on the body. It may also be in the form of a member
for selectively closing the container, especially a pump, a valve
or a flap valve.
[0573] The container may be combined with an applicator, especially
in the form of a brush comprising an arrangement of bristles
maintained by a twisted wire. Such a twisted brush is described
especially in U.S. Pat. No. 4,887,622. It may also be in the form
of a comb comprising a plurality of application members, obtained
especially by moulding. Such combs are described, for example, in
patent FR 2 796 529. The applicator may be in the form of a fine
brush, as described, for example, in patent FR 2 722 380. The
applicator may be in the form of a block of foam or of elastomer, a
felt or a spatula. The applicator may be free (tuft or sponge) or
securely fastened to a rod borne by the closing member, as
described, for example, in U.S. Pat. No. 5,492,426. The applicator
may be securely fastened to the container, as described, for
example, in patent FR 2 761 959.
[0574] The product may be contained directly in the container, or
indirectly. By way of example, the product may be arranged on an
impregnated support, especially in the form of a wipe or a pad, and
arranged (individually or in plurality) in a box or in a sachet.
Such a support incorporating the product is described, for example,
in patent application WO 01/03538.
[0575] The closing member may be coupled to the container by
screwing. Alternatively, the coupling between the closing member
and the container is done other than by screwing, especially via a
bayonet mechanism, by click-fastening, gripping, welding, bonding
or by magnetic attraction. The term "click-fastening" in particular
means any system involving the crossing of a bead or cord of
material by elastic deformation of a portion, especially of the
closing member, followed by return to the elastically unconstrained
position of the said portion after the crossing of the bead or
cord.
[0576] The container may be at least partially made of
thermoplastic material. Examples of thermoplastic materials that
may be mentioned include polypropylene or polyethylene.
[0577] Alternatively, the container is made of non-thermoplastic
material, especially glass or metal (or alloy).
[0578] The container may have rigid walls or deformable walls,
especially in the form of a tube or a tubular bottle.
[0579] The container may comprise means for distributing or
facilitating the distribution of the composition. By way of
example, the container may have deformable walls so as to allow the
composition to exit in response to a positive pressure inside the
container, this positive pressure being caused by elastic (or
non-elastic) squeezing of the walls of the container.
Alternatively, especially when the product is in the form of a
stick, the product may be driven out by a piston mechanism. Still
in the case of a stick, especially of makeup product (lipstick,
foundation, etc.), the container may comprise a mechanism,
especially a rack mechanism, a threaded-rod mechanism or a helical
groove mechanism, and may be capable of moving a stick in the
direction of the said aperture. Such a mechanism is described, for
example, in patent FR 2 806 273 or in patent FR 2 775 566. Such a
mechanism for a liquid product is described in patent FR 2 727
609.
[0580] The container may be formed from a carton with a base
delimiting at least one housing containing the composition, and a
lid, especially articulated on the base, and capable of at least
partially covering the said base. Such a carton is described, for
example, in patent application WO 03/018423 or in patent FR 2 791
042.
[0581] The container may be equipped with a drainer arranged in the
region of the aperture of the container. Such a drainer makes it
possible to wipe the applicator and possibly the rod to which it
may be securely fastened. Such a drainer is described, for example,
in patent FR 2 792 618.
[0582] The composition may be at atmospheric pressure inside the
container (at room temperature) or pressurized, especially by means
of a propellent gas (aerosol). In the latter case, the container is
equipped with a valve (of the type used for aerosols).
[0583] Protocol for Measuring the Transfer:
[0584] The transfer index of the deposit obtained with the
composition according to the invention is determined according to
the measuring protocol described below.
[0585] A support (40 mm.times.70 mm rectangle) consisting of an
acrylic coating (hypoallergenic acrylic adhesive on polyethylene
film sold under the name Blenderme ref. FH5000-55113 by the company
3M Sante) bonded onto a layer of polyethylene foam that is adhesive
on the side opposite the one to which the adhesive plaster is fixed
(foam layer sold under the name RE 40.times.70EP3 from the company
Joint Technique Lyonnais Ind.) is prepared.
[0586] The colour L*.sub.0a*.sub.0b*.sub.0 of the support, on the
acrylic coating side, is measured using a Minolta CR300
colorimeter.
[0587] The support thus prepared is preheated on a hotplate
maintained at a temperature of 40.degree. C. so that the surface of
the support is maintained at a temperature of 33.degree.
C..+-.1.degree. C.
[0588] While leaving the support on the hotplate, the composition
is applied to the entire non-adhesive surface of the support (i.e.
to the surface of the acrylic coating), spreading it out with a
brush to obtain a deposit of the composition of about 15 .mu.m, and
this deposit is then left to dry for 10 minutes.
[0589] After drying, the colour L*a*b* of the film thus obtained is
measured.
[0590] The colour difference .DELTA.E1 between the colour of the
film relative to the colour of the naked support is then determined
via the following relationship:
.DELTA.E1= {square root over
((L*-L.sub.0*).sup.2+(a*-a.sub.0*).sup.2+(b*-b.sub.0*).sup.2)}{square
root over
((L*-L.sub.0*).sup.2+(a*-a.sub.0*).sup.2+(b*-b.sub.0*).sup.2)}{-
square root over
((L*-L.sub.0*).sup.2+(a*-a.sub.0*).sup.2+(b*-b.sub.0*).sup.2)}
[0591] The support is then bonded via its adhesive face (adhesive
face of the foam layer) to an anvil 20 mm in diameter and equipped
with a screw pitch. A sample of the support/deposit assembly is
then cut out using a sample punch 18 mm in diameter. The anvil is
then screwed onto a press (Statif Manuel Imada SV-2 from the
company Someco) equipped with a tensile testing machine (Imada
DPS-20 from the company Someco).
[0592] A strip 33 mm wide and 29.7 cm long is drawn on a sheet of
white photocopier paper with a basis weight of 80 g/m.sup.2, a
first line is marked 2 cm from the edge of the sheet, and a second
line is then marked 5 cm from the edge of the sheet, the first and
second lines thus delimiting a box on the strip; next, a first mark
and a second mark located in the strip at reference points 8 cm and
16 cm, respectively, from the second mark, are applied. 20 .mu.l of
water are placed on the first mark and 10 .mu.l of refined
sunflower oil (sold by the company Lesieur) are placed on the
second mark.
[0593] The white paper is placed on the base of the press and the
sample placed on the box of the strip of paper is then pressed at a
pressure of about 300 g/cm.sup.2 exerted for 30 seconds. The press
is then opened and the sample is again placed just after the second
mark (i.e. next to the box), a pressure of about 300 g/cm.sup.2 is
again exerted, and the paper is displaced, in a rectilinear manner
as soon as the contact is made, at a speed of 1 cm/s over the
entire length of the strip such that the sample passes through the
water and oil deposits.
[0594] After removing the sample, some of the deposit has
transferred onto the paper. The colour L*', a*', b*' of the deposit
remaining on the sample is then measured.
[0595] The colour difference .DELTA.E2 between the colour of the
deposit remaining on the sample relative to the colour of the naked
support is then determined via the following relationship:
.DELTA.E2= {square root over
((L*'-L.sub.0*).sup.2+(a*'-a.sub.0*).sup.2+(b*'-b.sub.0*).sup.2)}{square
root over
((L*'-L.sub.0*).sup.2+(a*'-a.sub.0*).sup.2+(b*'-b.sub.0*).sup.2-
)}{square root over
((L*'-L.sub.0*).sup.2+(a*'-a.sub.0*).sup.2+(b*'-b.sub.0*).sup.2)}
[0596] The transfer index of the composition, expressed as a
percentage, is equal to the ratio:
100.times..DELTA.E2/.DELTA.E1
[0597] The measurement is performed on 6 supports in succession and
the transfer index corresponds to the mean of the six measurements
obtained with the six supports.
[0598] The present invention also relates to a cosmetic product for
making up and/or caring for keratin materials, comprising at least
two compositions that can be applied successively to keratin
materials, especially to the lips.
[0599] The present invention also relates to a process for making
up the face and the body using these two compositions. They are
preferably applied successively to the keratin materials: the first
composition and then the second composition.
[0600] These two compositions are conventionally known as a topcoat
and a basecoat.
[0601] Thus, according to this embodiment, the invention relates to
a product (also known as a kit) for making up and/or caring for
keratin materials, especially the lips, comprising a first
composition and a second composition conditioned in separate
containers,
[0602] the first composition containing, in a physiologically
acceptable medium:
[0603] a) a siloxane resin comprising the following units:
[0604] (i) (R.sup.1.sub.3SiO.sub.1/2).sub.a
[0605] (ii) (R.sup.2.sub.2SiO.sub.2/2).sub.b
[0606] (iii) (R.sup.3SiO.sub.3/2).sub.c and
[0607] (iv) (SiO.sub.4/2).sub.d
with
[0608] R.sup.1, R.sup.2 and R.sup.3 independently representing an
alkyl group containing from 1 to 8 carbon atoms, an aryl group, a
carbinol group or an amino group,
[0609] a being between 0.05 and 0.5,
[0610] b being between 0 and 0.3,
[0611] c being greater than 0,
[0612] d being between 0.05 and 0.6,
[0613] a+b+c+d=1,
[0614] on condition that more than 40 mol % of the groups R.sup.3
of the siloxane resin are propyl groups, and
[0615] b) at least one liquid fatty phase, and
[0616] c) at least one film-forming polymer chosen from the group
comprising: [0617] a film-forming block ethylenic polymer,
comprising at least a first block and at least a second block, is
characterized in that the first block is obtained from at least one
acrylate monomer of formula CH.sub.2.dbd.CH--COOR.sub.2 in which
R.sub.2 represents a C.sub.4 to C.sub.12 cycloalkyl group and at
least one methacrylate monomer of formula
CH.sub.2.dbd.C(CH.sub.3)--COOR.sub.2 in which R'.sub.2 represents a
C.sub.4 to C.sub.12 cycloalkyl group, and characterized in that the
second block is obtained from an acrylic acid monomer and from at
least one monomer with a glass transition temperature of less than
or equal to 20.degree. C., [0618] a vinyl polymer comprising at
least one carbosiloxane dendrimer-based unit, [0619] a dispersion
of acrylic or vinyl radical homopolymer or copolymer particles
dispersed in the said liquid fatty phase,
[0620] and the second composition, which is different from the
first, comprising at least one fatty substance.
[0621] The fatty substance of the second composition is preferably
chosen from waxes and non-volatile oils.
[0622] According to one preferred embodiment, the second
composition comprises at least one wax and at least one
non-volatile oil.
[0623] Advantageously, the wax is a sunflower wax.
[0624] Preferably, the non-volatile oil is an oil such as
caprylic/capric acid triglycerides.
[0625] The presence of a second composition applied over the first
composition onto the keratin materials can especially improve the
gloss and/or comfort properties.
[0626] The content of all the patents or patent applications cited
previously is incorporated by reference into the present patent
application.
[0627] In the patent application, unless specifically mentioned
otherwise, the contents are expressed on a weight basis relative to
the total weight of the composition.
[0628] The invention is illustrated in greater detail by the
examples described below, which are given as non-limiting
illustrations. The percentages are weight percentages.
EXAMPLE 1
Preparation of the Siloxane Resins
[0629] The following resins are used:
[0630] MQ resin=an MQ resin of formula M.sub.0.43Q.sub.0.57 and of
M.sub.n=3230 dissolved in xylene to a proportion of 70.8% by weight
of solids. The MQ resin was manufactured according to the
techniques described by Daudt in U.S. Pat. No. 2,676,182.
[0631] T Propyl resin=a propyl silsesquioxane resin at 74.8% by
weight in toluene. The propyl silsesquioxane resin was obtained by
hydrolysis of propyltrichlorosilane.
[0632] Preparation of the MQT.sup.Pr Resins
[0633] An MQ resin, a T propyl resin, xylene and 1M KOH in water in
the proportions presented in Table 1 are introduced into a 3-necked
flask equipped with a stirrer, a temperature probe and Dean-Stark
apparatus mounted with a condenser. Xylene is pre-introduced into
the Dean-Stark apparatus so as to ensure maintenance of a level of
solids of 50% in the reactor. The mixture in the reactor is
refluxed (between 100 and 140.degree. C.) for at least 3 hours. Any
water formed in the reaction mixture is continuously removed and
trapped in the form of an azeotrope in the Dean-Stark apparatus.
After refluxing for 3 hours, the water is removed from the
apparatus and heating is continued for a further 30 minutes. After
cooling the mixture, an excess of acetic acid is added to
neutralize the KOH in the mixture. The mixture is then filtered to
remove the salts formed, by passing it through a filter under
pressure. Solvent exchange is performed by heating the mixture in a
rotary evaporator under vacuum. After removing the majority of the
xylene, decamethylcyclopentasiloxane (or isododecane) is added
while continuing to remove any residual aromatic solvent. The
structures of the resulting siloxane resins are characterized by
.sup.29Si NMR and GPC, and the results are summarized in Table 2
below.
TABLE-US-00001 TABLE 1 Weight Weight Weight Weight Mass ratio % of
% of T Weight % of % of of MQ/T.sup.Pr MQ propyl % of 1M acetic
Example # resins added resin resin xylene KOH acid 1-a (85:15) 59.4
10.5 29.1 0.9 0.2 1-b (50:50) 34.9 34.8 29.1 0.9 0.2 1-c (30:70)
20.9 48.8 29.2 0.9 0.2 1-d (95:5) 67.1 3.5 28.3 0.9 0.2 1-e (100:0)
69.3 0 28.8 0.9 0.2
TABLE-US-00002 TABLE 2 Resin structure Weight according to NMR % of
Example # characterization OH Mn Mw Mw/Mn MQ resin
M.sup.0.43Q.sup.0.57 3230 1516 4.7 T Propyl T.sup.Pr.sub.1.0 7.0
3470 11 400 3.3 resin 1-a M.sub.0.374Q.sub.0.529:T.sup.Pr.sub.0.097
1.4 5880 271 000 46.1 1-b M.sub.0.248Q.sub.0.341:T.sup.Pr.sub.0.412
2.1 6640 3 860 000 581.3 1-c
M.sub.0.162Q.sub.0.217:T.sup.Pr.sub.0.621 1.5 7600 25 300 000 3329
1-d M.sub.0.419Q.sub.0.5485:T.sup.Pr.sub.0.03 1.5 1-e MQ 1.7 5200
28 900 5.6
EXAMPLE 2
Preparation of a Poly(Isobornyl Acrylate/Isobornyl
Methacrylate/Isobutyl Acrylate/Acrylic Acid) Polymer
[0634] 300 g of isododecane are introduced into a 1-litre reactor
and the temperature is then raised so as to pass from room
temperature (25.degree. C.) to 90.degree. C. over 1 hour.
[0635] 105 g of isobornyl methacrylate (manufactured by Arkema),
105 g of isobornyl acrylate (manufactured by Arkema) and 1.8 g of
2,5-bis(2-ethylhexanoylperoxy)-2,5-dimethylhexane (Trigonox.RTM.
141 from Akzo Nobel) are then added, at 90.degree. C. and over 1
hour.
[0636] The mixture is maintained at 90.degree. C. for 1 hour 30
minutes.
[0637] 75 g of isobutyl acrylate (manufactured by Fluka), g of
acrylic acid and 1.2 g of
2,5-bis(2-ethylhexanoylperoxy)-2,5-dimethylhexane are then
introduced into the preceding mixture, still at 90.degree. C. and
over 30 minutes.
[0638] The mixture is maintained at 90.degree. C. for 3 hours, and
is then cooled.
[0639] A solution containing 50% polymer active material in
isododecane is obtained.
[0640] A polymer comprising a first poly(isobornyl
acrylate/isobornyl methacrylate) rigid block with a Tg of
110.degree. C., a second poly(isobutyl acrylate/acrylic acid)
flexible block with a Tg of -9.degree. C. and an intermediate
block, which is an isobornyl acrylate/isobornyl
methacrylate/isobutyl acrylate/acrylic acid random polymer, is
obtained.
EXAMPLES 3 AND 4
Liquid Lipsticks
[0641] Compositions 3 and 4 below were prepared:
TABLE-US-00003 Composition Composition 4 3 comparative Weight
Weight percentages percentages Compounds % % 2-Octyldodecanol 9.43
8.23 Refined plant perhydrosqualene 5.05 4.21 (Phytosqualan from
Sophim) Brilliant yellow FCF aluminium lake on 2.58 2.58 alumina
(42/58) (CI: 15985:1 + 77002) Brilliant blue FCF aluminium lake on
0.16 0.16 alumina (12/88) (CI: 42090:2 + 77002) Calcium salt of
Lithol B Red 0.59 0.59 Rutile titanium oxide treated with 2.74 2.74
alumina/silica/trimethylolpropane (CI: 77891) Black iron oxide (CI:
77499) 0.32 0.32 Mixture of isopropyl, isobutyl and n- 0.65 0.65
butyl p-hydroxybenzoates (40/30/30) (Liquapar Oil from ISP)
Polyphenyltrimethylsiloxydiphenylsiloxane 25.03 25.03 (viscosity:
1000 cSt-MW: 3000 - g/mol) (Belsil PDM 1000 from Wacker)
Mica-titanium dioxide-brown iron oxide 2 2 (77/21/4) (size: 16-128
microns) Fragrance 0.3 0.3 Polybutylene (monoolefins/isoparaffins)
10.65 10.65 (MW: 920) (Indopol H 100 from Ineos) Poly(isobornyl
methacrylate-co-isobornyl 30 37.04 acrylate-co-isobutyl
acrylate-co-acrylic acid) as prepared in Example 2 above (50% of
polymer in 50% of isododecane) MQ-T propyl resin (30:70) in
isododecane 5.1 -- as prepared in Example 1 above, from Dow Corning
Hydrophilic fumed silica (Aerosil 200 0.5 0.5 from Evonik Degussa)
Hydrophobic fumed silica, surface-treated 5 5 with dimethylsilane
(Aerosil 972 from Evonik Degussa) Total: 100 100
[0642] Procedure: [0643] a. The fillers and pigments optionally
present are ground in part of the oily phase. [0644] b. The rest of
the liposoluble ingredients are then mixed together at a
temperature of about 100.degree. C. The ground mixture is then
added to the oily phase. [0645] c. The mixture is stirred with a
Rayneri blender for 45 minutes, and the siloxane resin is added at
room temperature. [0646] d. The formulation is poured into
isododecane-leaktight heating bags.
[0647] Composition 3 according to the invention contains 15%
polymer (weight of solids) prepared according to Example 2 and 3.5%
(weight of solids) of siloxane resin prepared according to Example
1-C), i.e. in total 18.5% of film-forming polymer.
[0648] Comparative composition 4 contains 18.5% of polymer (weight
of solids) prepared according to Example 2.
[0649] Comparative composition 4 is very viscous and tacky and is
very thick on application. It is uncomfortable on the lips since
the film formed is very thick and tacky.
[0650] Composition 3 according to the invention is much more
pleasant (slippery) on application and it forms a much finer and
more comfortable deposit.
EXAMPLES 5 AND 6
Liquid Lipsticks
[0651] The following lipstick formulation was prepared (same
procedure as that described previously).
TABLE-US-00004 Composition 5 according to the Comparative invention
(Weight composition 6 Compounds percentages %) (Weight percentages
%) Butyl acrylate copolymer containing 31.25 37.5 dendritic
silicone side chains: [tris(trimethylsiloxy)siloxyethyldimethyl-
siloxy]silylpropyl methacrylate in isododecane: 40/60 (Dow Corning
FA 4002 ID Silicone Acrylate from Dow Corning) MQ-T propyl resin
(30/70) in isododecane as 4 -- prepared in Example 1-C above, from
Dow Corning Isododecane from Ineos 1.3 -- Refined plant
perhydrosqualene 12.02 12.02 (Phytosqualan from Sophim)
Octyldodecanol 14.2 13.62 Polybutene (Indopol H 100 from Ineos)
10.65 10.65 Isopropyl paraben (and) isobutyl paraben 0.65 0.65
(and) butyl paraben (Liquapar Oil from ISP) Red 7 (Unipure Red LC
3079 OR from LCW 0.23 0.23 (Sensient)) Iron oxides (Sunpuro Black
Iron Oxide C33- 0.05 0.05 7001 from Sun) Mica (and) titanium
dioxide (and) iron 1 1 oxides (Cloisonne Sparkle Gold 222 J from
Engelhard) Calcium aluminium borosilicate (and) silver 2.5 2.5
(Metashine ME 2040 PS from NError! Hyperlink reference not valid.)
Trimethylsiloxyphenyl Dimethicone (Belsil 16.65 16.3 PDM 1000 from
Wacker) Silica Dimethyl Silylate Aerosil R 972 from 5 5 EError!
Hyperlink reference not valid. Silica (Aerosil 200 from EError!
Hyperlink 0.5 0.5 reference not valid.) Total 100 100
[0652] The staying power of compositions 5 and 6 is evaluated
according to the transfer index measurement protocol described
above. The results obtained are as follows:
[0653] The two compositions 5 and 6 have substantially the same
solids content of film-forming polymer (siloxane resin vinyl
polymer containing carbosiloxane dendrimer-based units).
[0654] For composition 5 according to the invention containing a
vinyl polymer comprising at least one carbosiloxane dendrimer-based
unit and an MQ-T propyl siloxane resin, a transfer index value of
31.81.+-.7.87 is measured.
[0655] For comparative composition 6 containing no siloxane resin,
a transfer index value of 18.32.+-.0.56 is measured.
* * * * *