U.S. patent application number 12/746428 was filed with the patent office on 2010-10-14 for cosmetic method using a composition comprising a siloxane resin and a mineral filler.
This patent application is currently assigned to L'Oreal. Invention is credited to Florence Dop.
Application Number | 20100260700 12/746428 |
Document ID | / |
Family ID | 40566065 |
Filed Date | 2010-10-14 |
United States Patent
Application |
20100260700 |
Kind Code |
A1 |
Dop; Florence |
October 14, 2010 |
COSMETIC METHOD USING A COMPOSITION COMPRISING A SILOXANE RESIN AND
A MINERAL FILLER
Abstract
The invention relates to a cosmetic method for making up and/or
caring for keratinous substances, in particular the skin,
comprising the application, to said keratinous substances, of a
cosmetic composition comprising a siloxane resin and an inorganic
filler. The invention relates in particular to compositions for
caring for or making up said keratinous substances.
Inventors: |
Dop; Florence; (Villiers Le
Bacle, 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.: |
12/746428 |
Filed: |
December 5, 2008 |
PCT Filed: |
December 5, 2008 |
PCT NO: |
PCT/FR08/52235 |
371 Date: |
June 4, 2010 |
Related U.S. Patent Documents
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Application
Number |
Filing Date |
Patent Number |
|
|
60992357 |
Dec 5, 2007 |
|
|
|
Current U.S.
Class: |
424/78.03 ;
401/196 |
Current CPC
Class: |
A61K 8/891 20130101;
A61Q 1/10 20130101; A61K 2800/88 20130101; A61K 8/31 20130101; A61K
2800/591 20130101; A61Q 1/02 20130101; A45D 33/00 20130101; A61Q
1/06 20130101 |
Class at
Publication: |
424/78.03 ;
401/196 |
International
Class: |
A61K 8/891 20060101
A61K008/891; A61Q 1/12 20060101 A61Q001/12; A61Q 19/00 20060101
A61Q019/00; A45D 40/26 20060101 A45D040/26 |
Claims
1-15. (canceled)
16. A cosmetic method for making up and/or caring, comprising
applying to a keratinous substance a composition comprising, in a
physiologically acceptable medium: i) a siloxane resin comprising
the 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 having 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 zero and 0.3, c being greater
than zero, d being between 0.05 and 0.6, a+b+c+d=1, provided that
more than 40 mol % of the R.sup.3 groups of the siloxane resin are
propyl groups, and ii) at least one inorganic filler.
17. The cosmetic method for making up and/or caring according to
claim 16, wherein the siloxane resin present in said composition
comprises the units: (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 with
R.sup.1 and R.sup.3 independently representing an alkyl group
having from 1 to 8 carbon atoms; a being between 0.05 and 0.5, c
being greater than zero, d being between 0.05 and 0.6, a+c+d=1,
provided that more than 40 mol % of the R.sup.3 groups of the
siloxane resin are propyl groups.
18. The method according to claim 16, wherein said siloxane resin
is obtained by a process comprising reacting: A) an MQ resin
comprising at least 80 mol % of (R.sup.1.sub.3SiO.sub.1/2).sub.a
and (SiO.sub.4/2).sub.d units, R.sup.1 representing a methyl group,
a and d being greater than zero, the ratio a/d being between 0.5
and 1.5; and B) a propyl T resin comprising at least 80 mol % of
(R.sup.3SiO.sub.3/2).sub.c units, R.sup.3 representing a propyl
group, c being greater than zero, where the A/B ratio by weight is
between 95:5 and 15:85.
19. The method according to claim 16, wherein said composition
comprises an amount of siloxane resin, by weight of dry active
material, ranging from 0.5 to 60% by weight, with respect to the
total weight of the composition.
20. The method according to claim 16, wherein said composition is
provided in the form of powders, of anhydrous dispersions or of
emulsions.
21. The method according to claim 16, wherein the inorganic filler
present in said composition is selected from the group consisting
of talc, mica, silica, kaolin, boron nitride, precipitated calcium
carbonate, magnesium carbonate, basic magnesium carbonate,
hydroxyapatite, hollow silica microspheres, glass or ceramic
microcapsules, clay, quartz, natural diamond powder and mixtures
thereof.
22. The method according to claim 16, wherein the inorganic filler
present in said composition is chosen from talc and silica.
23. The method according to claim 16, wherein said composition
additionally comprises at least one other inorganic or organic
filler.
24. The method according to claim 23, wherein said other filler is
inorganic and is optionally used in combination with at least one
organic filler.
25. The method according to claim 23, wherein the composition
comprises an organic filler, and said organic filler is a powder
formed of a material selected from the group consisting of
polyamide, acrylic polymer, cellulose, poly-.beta.-alanine,
polyethylene, tetrafluoroethylene polymer, lauroyl lysine, starch,
hollow polymeric microspheres, acrylic acid copolymer, silicone
resin microbeads, polyorganosiloxane elastomer particles, and metal
soaps derived from organic carboxylic acids having from 8 to 22
carbon atoms.
26. The method according to claim 23, wherein the composition
comprises an organic filler, and said organic filler comprises a
polyamide powder.
27. The method according to claim 16, wherein the inorganic filler
is present in the composition in a content ranging from 0.01 to 50%
by weight, with respect to the total weight of the composition.
28. A composition for making up and/or caring for the skin capable
of being employed in a method as claimed in claim 16, comprising,
in a physiologically acceptable medium: i) at least one siloxane
resin comprising the 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 having 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 zero and 0.3, c being greater than zero, d being between
0.05 and 0.6, a+b+c+d=1, provided that more than 40 mol % of the
R.sup.3 groups of the siloxane resin are propyl groups, and ii) at
least one inorganic filler selected from the group consisting of
talc, mica, silica, kaolin, boron nitride, precipitated calcium
carbonate, magnesium carbonate, basic magnesium carbonate,
hydroxyapatite, hollow silica microspheres, glass or ceramic
microcapsules, clay, quartz, natural diamond powder and mixtures
thereof.
29. A cosmetic combination comprising: a container delimiting at
least one compartment, said container being closed by a closing
element; and a composition positioned inside said compartment, the
composition being defined as claimed in the preceding claim.
30. The cosmetic combination according to claim 29, additionally
comprising an applicator in the form of a pad of foam or elastomer,
of a felt-tipped pen or of a spatula.
31. The method according to claim 17, wherein said siloxane resin
is obtained by a process comprising reacting: A) an MQ resin
comprising at least 80 mol % of (R.sup.1.sub.3SiO.sub.1/2).sub.a
and (SiO.sub.4/2).sub.d units, R.sup.1 representing a methyl group,
a and d being greater than zero, the ratio aid being between 0.5
and 1.5; and B) a propyl T resin comprising at least 80 mol % of
(R.sup.3SiO.sub.3/2).sub.c units, R.sup.3 representing a propyl
group, c being greater than zero, where the A/B ratio by weight is
between 95:5 and 15:85.
32. The method according to claim 23, wherein the organic filler is
a powder formed of an acrylic polymer selected from the group
consisting of polymethyl methacrylate, of poly(methyl
methacrylate/ethylene glycol dimethacrylate), of poly(allyl
methacrylate/ethylene glycol dimethacrylate) or of ethylene glycol
dimethacrylate/lauryl methacrylate copolymer.
33. The method according to claim 23, wherein the organic filler is
a polyorganosiloxane elastomer particle obtained by polymerization
of organopolysiloxane having at least two hydrogen atoms each
bonded to a silicon atom and of an organopolysiloxane comprising at
least two groups possessing ethylenic unsaturation, in the presence
of a platinum catalyst.
34. The method according to claim 23, wherein the organic filler is
a powder formed of a metal soap derived from organic carboxylic
acids having from 8 to 22 selected from the group consisting of
zinc stearate, magnesium stearate, lithium stearate, zinc laurate
and magnesium myristate.
35. The method according to claim 23, wherein the composition
comprises an organic filler and the organic filler and the
inorganic filler are present in the composition in a content
ranging from 0.01 to 50% by weight with respect to the total weight
of the composition.
36. The method of claim 16, wherein the keratinous substance is
skin.
Description
[0001] The invention relates to a cosmetic method for making up
and/or caring for keratinous substances, in particular the skin,
comprising the application to said keratinous substances of a
cosmetic composition comprising a siloxane resin and an inorganic
filler. The invention relates in particular to compositions for
caring for or making up said keratinous substances.
[0002] It is known to use makeup products in order to contribute
color and mattness to the skin. The makeup resulting from these
makeup products is expected to last all day.
[0003] A makeup product must also be comfortable. Comfortable is
understood to mean a product which glides over the skin, without a
rubbing feeling, when the product is applied to the skin, but also
a product which confers a soft touch on said skin.
[0004] It is known to a person skilled in the art to confer comfort
properties on a makeup product, such as is described above, by
formulating these products with fillers.
[0005] It is also known to a person skilled in the art to confer
properties of hold of a makeup by formulating these products with
silicone resins, polyacrylates or latexes, which have, however, a
tendency to provide a feeling of discomfort after application, with
a tacky feel.
[0006] The aim of the present invention is thus to provide a makeup
method which makes it possible to obtain satisfactory properties of
hold of the makeup while at the same time retaining the comfort
during and after application.
[0007] This aim and others are achieved by the present invention
which describes in particular a cosmetic method for making up
and/or caring for keratinous substances, comprising the
application, to said keratinous substances, in particular to the
skin, of a composition comprising, in a physiologically acceptable
medium: [0008] i) a siloxane resin comprising the units: [0009]
(R.sup.1.sub.3SiO.sub.1/2).sub.a [0010] (ii)
(R.sup.2.sub.2SiO.sub.2/2).sub.b [0011] (iii)
(R.sup.3SiO.sub.3/2).sub.c and [0012] (iv) (SiO.sub.4/2).sub.d with
[0013] R.sup.1, R.sup.2 and R.sup.3 independently representing an
alkyl group having from 1 to 8 carbon atoms, an aryl group, a
carbinol group or an amino group, [0014] a being between 0.05 and
0.5, [0015] b being between zero and 0.3, [0016] c being greater
than zero, [0017] d being between 0.05 and 0.6,
[0017] a+b+c+d=1,
provided that more than 40 mol % of the R.sup.3 groups of the
siloxane resin are propyl groups, and [0018] ii) at least one
inorganic filler.
[0019] The combination used according to the invention makes it
possible to obtain a soft finish on the skin and cosmetic
properties which are stable over time, in particular throughout the
day. The product also glides over the skin, during application,
without a rubbing feeling and confers a soft touch on said
skin.
[0020] The composition according to the invention can be provided
in various forms, in particular in the form of powders (loose or
compact), of an anhydrous dispersion, of a water/oil, water/wax,
oil/water, multiple (such as a water/oil/water or oil/water/oil) or
wax/water emulsion or in the form of a gel. Preferably, the
composition according to the invention is provided in the form of
powders (loose or compact), of anhydrous dispersions or of
emulsions, preferably an inverse emulsion (i.e., water/oil
emulsion).
[0021] The composition according to the invention is intended in
particular for making up and/or caring for the skin.
Siloxane Resins
[0022] The siloxane resins which can be used according to the
invention can be obtained by a process comprising the reaction of:
[0023] A) an MQ resin comprising at least 80 mol % of
(R.sup.1.sub.3SiO.sub.1/2).sub.a and (SiO.sub.4/2).sub.d units,
[0024] R.sup.1 representing an alkyl group having from 1 to 8
carbon atoms, an aryl group, a carbinol group or an amino group,
[0025] a and d being greater than zero, [0026] the ratio a/d being
between 0.5 and 1.5; and of [0027] B) a propyl T resin comprising
at least 80 mol % of (R.sup.3SiO.sub.3/2).sub.c units, [0028]
R.sup.3 representing an alkyl group having from 1 to 8 carbon
atoms, an aryl group, a carbinol group or an amino group, [0029] c
being greater than zero, [0030] provided that at least 40 mol % of
the R.sup.3 groups are propyl groups, where the A/B ratio by weight
is between 95:5 and 15:85.
[0031] Preferably, the A/B ratio is less than or equal to 70:30.
Advantageously, the A/B ratio is equal to 30:70 or 50:50.
[0032] The resins which can be used according to the invention are
in particular those described in application WO 2005/075542.
[0033] The MQ-propyl T resin according to the invention comprises
units: [0034] (i) (R.sup.1.sub.3SiO.sub.1/2).sub.a [0035] (ii)
(R.sup.2.sub.2SiO.sub.2/2).sub.b [0036] (iii)
(R.sup.3SiO.sub.3/2).sub.c and [0037] (iv) (SiO.sub.4/2).sub.d
which are known from the prior art and which respectively
correspond to the M, D, T and Q units.
[0038] The amount of each unit present in the MQ-propyl T resin can
be expressed as a molar fraction (i.e. a, b, c or d) of the total
number of moles of all the M, D, T and Q units present in the
MQ-propyl T resin.
[0039] The value of a (molar fraction of M units) is between 0.05
and 0.5, or alternatively between 0.15 and 0.4.
[0040] The value of b (molar fraction of D units) is between 0 and
0.3, or alternatively between 0 and 0.1, or alternatively between 0
and 0.05. Thus, the MQ-propyl T resin according to the invention
can be devoid of D units or alternatively can comprise up to 0.3
molar fraction of D units.
[0041] Preferably, the MQ-propyl T resin according to the invention
is devoid of D units.
[0042] The value of c (molar fraction of T units) is greater than
0, or alternatively between 0.05 and 0.65, or alternatively between
0.4 and 0.65.
[0043] The value of d (molar fraction of Q units) is between 0.05
and 0.6, or alternatively between 0.2 and 0.6, or alternatively
between 0.2 and 0.55.
[0044] The MQ-propyl T resin according to the invention is
characterized in that at least 40 mol %, preferably at least 50 mol
%, preferably at least 90 mol % of R.sub.3 alkyl groups of the T
units are propyl groups.
[0045] The R.sup.1, R.sup.2 and R.sup.3 radicals of the units of
the MQ-propyl T resin independently represent an alkyl group having
from 1 to 8 carbon atoms, an aryl group, a carbinol group or an
amino group.
[0046] The alkyl groups can in particular be chosen from the
methyl, ethyl, propyl, butyl, pentyl, hexyl and octyl groups.
Preferably, the alkyl group is a methyl group or a propyl
group.
[0047] The aryl groups can be chosen from the phenyl, naphthyl,
benzyl, tolyl, xylyl, xenyl, methylphenyl, 2-phenylethyl,
2-phenyl-2-methylethyl, chlorophenyl, bromophenyl and fluorophenyl
groups, the aryl group preferably being a phenyl group.
[0048] In the present invention, "carbinol group" is understood to
mean any group comprising at least one hydroxyl radical bonded to a
carbon (COH). The carbinol groups can thus comprise more than one
COH radical, such as, for example:
##STR00001##
[0049] If the carbinol group is devoid of aryl groups, it comprises
at least 3 carbon atoms. If the carbinol group comprises at least
one aryl group, it comprises at least 6 carbon atoms.
[0050] Mention may be made, as examples of carbinol group devoid of
aryl groups comprising at least 3 carbon atoms, of the groups of
formula R.sup.4OH in which R.sup.4 represents a divalent
hydrocarbon radical comprising at least 3 carbon atoms or a
divalent hydrocarbonoxy radical comprising at least 3 carbon atoms.
Mention may be made, as examples of R.sup.4 group, of alkylene
radicals, such as --(CH.sub.2).sub.x--, the value of x being
between 3 and 10, --CH.sub.2CH(CH.sub.3)--,
--CH.sub.2CH(CH.sub.3)CH.sub.2--,
--CH.sub.2CH.sub.2CH(CH.sub.2CH.sub.3)CH.sub.2CH.sub.2CH.sub.2--
and --OCH(CH.sub.3)(CH.sub.2).sub.x--, the value of x being between
1 and 10.
[0051] Mention may be made, as examples of carbinol group
comprising aryl groups exhibiting at least 6 carbon atoms, of the
groups of formula R.sup.5OH in which R.sup.5 represents an arylene
radical such as --(CH.sub.2).sub.xC.sub.6H.sub.4--, x having a
value of between 0 and 10,
--CH.sub.2CH(CH.sub.3)(CH.sub.2).sub.xC.sub.6H.sub.4--, x having a
value of between 0 and 10,
--(CH.sub.2).sub.xC.sub.6H.sub.4(CH.sub.2).sub.x--, x having a
value of between 1 and 10. The carbinol groups comprising aryl
groups generally comprise from 6 to 14 atoms.
[0052] Amino group according to the invention is understood to mean
in particular groups of formula --R.sup.6NH.sub.2 or
--R.sup.6NHR.sup.7NH.sub.2, R.sup.6 representing a divalent
hydrocarbon radical having at least 2 carbon atoms and R.sup.7
representing a divalent hydrocarbon radical having at least 2
carbon atoms. The R.sup.6 group generally represents an alkylene
radical having from 2 to 20 carbon atoms. Mention may be made, as
examples of R.sup.6 group, of the ethylene, propylene,
--CH.sub.2CHCH.sub.3--, butylene, --CH.sub.2CH(CH.sub.3)CH.sub.2--,
pentamethylene, hexamethylene, 3-ethylhexamethylene, octamethylene
and decamethylene groups.
[0053] The R.sup.7 group generally represents an alkylene radical
having 2 to 20 carbon atoms. Mention may be made, as examples of
R.sup.7 group, of the ethylene, propylene, --CH.sub.2CHCH.sub.3--,
butylene, --CH.sub.2CH(CH.sub.3)CH.sub.2--, pentamethylene,
hexamethylene, 3-ethylhexamethylene, octamethylene and
decamethylene groups.
[0054] The amino groups are generally
--CH.sub.2CH.sub.2CH.sub.2NH.sub.2,
--CH.sub.2(CH.sub.3)CHCH.sub.2(H)NCH.sub.3,
--CH.sub.2CH.sub.2NHCH.sub.2CH.sub.2NH.sub.2,
--CH.sub.2CH.sub.2NH.sub.2, --CH.sub.2CH.sub.2NHCH.sub.3,
--CH.sub.2CH.sub.2CH.sub.2CH.sub.2NH.sub.2,
--(CH.sub.2CH.sub.2NH).sub.3H and
--CH.sub.2CH.sub.2NHCH.sub.2CH.sub.2NHC.sub.4H.sub.9.
[0055] Preferably, R.sup.1 represents a methyl group, R.sup.2
represents a methyl group or a phenyl group and R.sup.3 represents
a propyl group.
[0056] Preferably, the MQ-propyl T resin according to the invention
is devoid of D units, and R.sup.1 represents a methyl group, and
R.sup.3 represents a propyl group.
[0057] The D, T or Q siloxane units of the MQ-propyl T resin
according to the invention can comprise hydroxyl (--OH) groups
and/or alkoxy groups. Such siloxane units comprising hydroxyl
and/or alkoxy groups are commonly present in siloxane resins having
the general formula R.sub.nSiO.sub.(4-n)/2.
[0058] These hydroxyl groups typically result from the reaction of
a hydrolyzable group on the siloxane unit with water; the alkoxy
groups result from an incomplete hydrolysis when alkoxysilane
precursors are used or result from the exchange of alcohol with
hydrolyzable groups.
[0059] Preferably, the total amount by weight of --OH groups
present in the MQ-propyl T resin is approximately 3%, preferably
2%, preferably 1.5%. Preferably, the total amount by weight of
alkoxy groups present in the MQ-propyl T resin is less than or
equal to 20% by weight, preferably less than or equal to 10% by
weight.
[0060] Preferably, the siloxane resin present in said composition
comprises the units: [0061] (i) (R.sup.1.sub.3SiO.sub.1/2).sub.a
[0062] (iii) (R.sup.3SiO.sub.3/2).sub.c and [0063] (iv)
(SiO.sub.4/2).sub.d with [0064] R.sup.1 and R.sup.3 independently
representing an alkyl group having from 1 to 8 carbon atoms;
preferably, R.sup.1 is a methyl group and R.sup.3 is a propyl
group, [0065] a being between 0.05 and 0.5, [0066] c being greater
than zero, [0067] d being between 0.05 and 0.6,
[0067] a+c+d=1,
provided that more than 40 mol % of the R.sup.3 groups of the
siloxane resin are propyl groups.
[0068] There exist no restrictions relating to the molecular weight
of the MQ-propyl T siloxane resins but, generally, the
number-average molecular weight (M.sub.N) is between 3000 and 10
000 or between 5000 and 8000.
[0069] The MQ-propyl T resins which can be used according to the
invention can be prepared according to the processes known in the
state of the art for preparing siloxane resins of general formula
R.sub.nSiO.sub.(4-n)/2, where R is an alkyl group and n is less
than 1.8.
[0070] Alternatively, the MQ-propyl T resins can be prepared
according to the methods described below.
[0071] The MQ-propyl T resins according to the invention are
illustrated by the MQ-propyl T resins comprising the following
units: [0072] ((CH.sub.3).sub.3SiO.sub.1/2).sub.a [0073]
(R.sup.3SiO.sub.3/2).sub.c where
R.sup.3.dbd.CH.sub.3CH.sub.2CH.sub.2--, and [0074]
(SiO.sub.4/2).sub.d; [0075] or the following units: [0076]
((CH.sub.3).sub.3SiO.sub.1/2).sub.a [0077]
((CH.sub.3).sub.2SiO.sub.2/2).sub.b [0078]
(R.sup.3SiO.sub.3/2).sub.c where
R.sup.3.dbd.CH.sub.3CH.sub.2CH.sub.2--, and [0079]
(SiO.sub.4/2).sub.d; [0080] or the following units: [0081]
((CH.sub.3).sub.3SiO.sub.1/2).sub.a [0082]
((CH.sub.3).sub.2SiO.sub.2/2).sub.b'((CH.sub.3)(C.sub.6H.sub.5)SiO.sub.2/-
2).sub.b' [0083] (R.sup.3SiO.sub.3/2).sub.c where
R.sup.3.dbd.CH.sub.3CH.sub.2CH.sub.2--, and [0084]
(SiO.sub.4/2).sub.d; [0085] or the following units: [0086]
((CH.sub.3).sub.3SiO.sub.1/2).sub.a [0087]
((CH.sub.3).sub.2SiO.sub.2/2).sub.b [0088]
(R.sup.3SiO.sub.3/2).sub.c where
R.sup.3.dbd.CH.sub.3CH.sub.2CH.sub.2--,
(C.sub.6H.sub.5SiO.sub.3/2).sub.c and [0089] (SiO.sub.4/2).sub.d;
[0090] or the following units: [0091]
((CH.sub.3).sub.3SiO.sub.1/2).sub.a [0092]
((CH.sub.3).sub.2SiO.sub.2/2).sub.b'((CH.sub.3)(C.sub.6H.sub.5)SiO-
.sub.2/2).sub.b' [0093] (R.sup.3SiO.sub.3/2).sub.c where
R.sup.3.dbd.CH.sub.3CH.sub.2CH.sub.2--,
(C.sub.6H.sub.5SiO.sub.3/2).sub.c and [0094] (SiO.sub.4/2).sub.d;
where a has a total value in the resin of between 0.05 and 0.5, the
sum b+b' has a total value in the resin of between 0 and 0.3, c has
a total value in the resin of between 0.05 and 0.65 and d has a
total value in the resin of between 0.05 and 0.6.
[0095] The siloxane resins which can be used according to the
invention can be obtained by a process comprising the reaction
between: [0096] A) an MQ resin comprising at least 80 mol % of
(R.sup.1.sub.3SiO.sub.1/2).sub.a and (SiO.sub.4/2).sub.d units,
[0097] R.sup.1 representing an alkyl group having from 1 to 8
carbon atoms, an aryl group, a carbinol group or an amino group,
[0098] a and d being greater than zero, [0099] the ratio aid being
between 0.5 and 1.5; and [0100] B) a propyl T resin comprising at
least 80 mol % of (R.sup.3SiO.sub.3/2).sub.c units, [0101] R.sup.3
representing an alkyl group having from 1 to 8 carbon atoms, an
aryl group, a carbinol group or an amino group, [0102] c being
greater than zero, [0103] provided that at least 40 mol % of the
R.sup.3 groups are propyl groups, where the A/B ratio by weight is
between 95:5 and 15:85.
[0104] The component A) is an MQ resin comprising at least 80 mol %
of (R.sup.1.sub.3SiO.sub.1/2).sub.a and (SiO.sub.4/2).sub.d units,
where R.sup.1 is as defined above, i.e. represents an alkyl group
having from 1 to 8 carbon atoms, an aryl group, a carbinol group or
an amino group, a and d are greater than zero and the ratio aid is
between 0.5 and 1.5.
[0105] The MQ resins which can be used as component A) and their
method of preparation are known from the prior art. For example,
U.S. Pat. No. 2,814,601, belonging to Currie and al., dated Nov.
26, 1957 describes a process for manufacturing MQ resins by
conversion of a water-soluble silicate into a silicic acid monomer
or a silicic acid oligomer by using an acid. Once the appropriate
polymerization has been carried out, trimethylchlorosilane ends are
introduced in order to obtain the MQ resin. Another process of
preparation of MQ resins is described in U.S. Pat. No. 2,857,356,
belonging to Goodwin, dated Oct. 21, 1958. Goodwin describes a
process for the manufacture of an MQ resin by cohydrolysis of a
mixture of an alkyl silicate and of a trialkylsilane
organopolysiloxane which can be hydrolyzed with water. The MQ
resins suitable as component A) in the present invention can
comprise D and T units, provided that at least 80 mol %, indeed
even 90 mol %, of the total siloxane units are M and Q units. The
MQ resins can also comprise hydroxyl groups. The MQ resins can thus
comprise hydroxyl groups in a total amount by weight of between 2
and 10%, preferably between 2 and 5%. The MQ resins can also
comprise additional ends, residual hydroxyl groups being for this
reacted with the M groups.
[0106] The component B) is a propyl T resin comprising at least 80
mol % of (R.sup.3SiO.sub.3/2).sub.c units, R.sup.3 being as defined
above, i.e. representing an alkyl group having from 1 to 8 carbon
atoms, an aryl group, a carbinol group or an amino group, c being
greater than 0, provided that at least 40 mol % of the R.sup.3
groups are propyl groups. Preferably, the propyl T resin according
to the invention is a silsesquioxane resin. Silsesquioxane resins
are well known in the state of the art and are generally obtained
by hydrolysis of an organosilane comprising three hydrolyzable
groups, such as halogen or alkoxy groups, present in the molecule.
The component B) can thus be obtained by hydrolysis of
propyltrimethoxysilane, propyltriethoxysilane or
propyltripropoxysilane or by cohydrolysis of the abovementioned
propylalkoxysilanes with various alkoxysilanes. Mention may be
made, as examples of these alkoxysilanes, of
methyltrimethoxysilane, methyltriethoxysilane,
methyltriisopropoxysilane, dimethyldimethoxysilane and
phenyltrimethoxysilane. Propyltrichlorosilane can also be
hydrolyzed, alone or in the presence of alcohol. In this case, the
cohydrolysis can be carried out by adding methyltrichlorosilane,
dimethyldichlorosilane, phenyltrichlorosilane or similar
chlorosilanes and methyltrimethoxysilane, methyltriethoxysilane,
methyltriisopropoxysilane or similar methylalkoxysilanes. Mention
may be made, as alcohols suitable for this purpose, of methanol,
ethanol, n-propyl alcohol, isopropyl alcohol, butanol,
methoxyethanol, ethoxyethanol or similar alcohols. Mention may be
made, as examples of solvents of hydrocarbon type which can be
used, of toluene, xylene or similar aromatic hydrocarbons; hexane,
heptane, isooctane or similar saturated and linear or partially
branched hydrocarbons; and cyclohexane or similar aliphatic
hydrocarbons.
[0107] The propyl T resins as component B) according to the
invention can comprise M, D and Q units, provided that at least 80
mol %, indeed even 90 mol % of the total siloxane units are T
units. The propyl T resins can also comprise hydroxyl groups.
Preferably, the propyl T resins comprise between 3 and 8% by weight
of hydroxyl groups.
[0108] A polyorganosiloxane can also be added to the process
according to the invention as component C).
[0109] The polyorganosiloxanes of use as component C) according to
the invention comprise R.sup.2.sub.2SiO.sub.2/2 or
R.sup.3SiO.sub.3/2 units. The polyorganosiloxane can be added in
order to introduce various D and T units into the MQ-propyl T
resins, in order to modify the properties of the resulting resins.
The structure or the formula of the polyorganosiloxane is not
limiting, provided that said polyorganosiloxane comprises a
measurable amount of R.sup.2.sub.2SiO.sub.2/2 or R.sup.3SiO.sub.3/2
units and that the total amount of polyorganosiloxane added to the
reaction between A) and B) does not result in more than 50 mol % of
D or T units in the reaction mixture.
[0110] The polyorganosiloxane can comprise combinations of M, D, T
and Q units, provided that at least the D or T units are present.
Thus, the polyorganosiloxane can be chosen from silicone fluids,
gums or resins known from the prior art and comprising D or T
units, or their mixtures. The D units typically comprise methyl or
phenyl groups or their mixtures as R.sup.2 groups. The T units
typically comprise methyl or phenyl groups or their mixtures as
R.sup.3 groups. The polyorganosiloxane can be a fluid linear
polydiorganosiloxane having a viscosity of between 10 and 1000 cS
(mm.sup.2/s). The fluid polydiorganosiloxane can be a
polydimethylsiloxane or a polymethylphenylsiloxane. The
polyorganosiloxane can also be an organosilsesquioxane resin. The
organosilsesquioxane resin is typically a methylsilsesquioxane
resin or a phenylsilsesquioxane resin.
[0111] The components A), B) and optionally C) can react by any
method known from the prior art for acting on M, D, T and Q units.
However, preferably, the components A), B) and optionally C) react
by a condensation reaction in the presence of a catalyst. The MQ
resin is typically present in an aromatic hydrocarbon or siloxane
solvent. Condensation reaction catalysts which can be used are in
particular metal hydroxides, such as potassium hydroxide or sodium
hydroxide; metal salts, such as silanolates, carboxylates and
carbonates; amines; titanates, such as tetrabutyl titanate; and
their mixtures. Typically, the reaction between the components A),
B) and optionally C) is carried out by heating the reaction mixture
to temperatures ranging from 50 to 140.degree. C., preferably
ranging from 100 to 140.degree. C. The reaction can take place in a
semicontinuous, continuous or batch process.
[0112] Preferably, said siloxane resin is obtained by a process
comprising the reaction between: [0113] A) an MQ resin comprising
at least 80 mol % of (R.sup.1.sub.2SiO.sub.1/2).sub.a and
(SiO.sub.4/2).sub.d units, [0114] R.sup.1 representing a methyl
group, [0115] a and d being greater than zero, [0116] the ratio a/d
being between 0.5 and 1.5; and [0117] B) a propyl T resin
comprising at least 80 mol % of (R.sup.3SiO.sub.3/2).sub.c units,
[0118] R.sup.3 representing a propyl group, [0119] c being greater
than zero, where the A/B ratio by weight is between 95:5 and 15:85;
preferably, the A/B ratio by weight is 30:70.
[0120] The A/B ratio by weight in the reaction is between 95:5 and
15:85, preferably between 95:5 and 20:80, preferably between 90:10
and 20:80.
[0121] Preferably, the A/B ratio by weight is equal to 85:15 or
50:50 or 30:70 or 95:5. Preferably, the A/B ratio by weight is
equal to 30:70.
[0122] The amount of component C) can vary but provided that it
results in a content of additional D or T units of less than 30 mol
%, with respect to the total molar amount of siloxane units of the
reaction mixture.
[0123] The composition according to the invention comprises an
amount of siloxane resin, by weight of active material (dry
matter), ranging from 0.5 to 60% by weight, with respect to the
total weight of the composition, preferably from 3 to 60% by weight
and better still from 4 to 60% by weight, with respect to the total
weight of said composition.
[0124] According to a specific form, the amount of siloxane resin,
by weight of active material (dry matter), will advantageously
range from 3 to 60% by weight and better still from 6 to 60% by
weight, with respect to the total weight of said composition. These
contents are in particular suitable for the compositions in
anhydrous form and especially for the compositions in the stick
form, such as lipsticks.
[0125] According to another specific form, the amount of siloxane
resin, by weight of active material (dry matter), will
advantageously range from 3 to 30% by weight and better still from
4 to 20% by weight, with respect to the total weight of said
composition. These contents are in particular suitable for
compositions in the form of emulsions and especially for
compositions in the form of W/O emulsions, such as liquid
foundations.
Filler
[0126] The composition according to the invention comprises one or
more fillers, in particular at least one inorganic filler.
[0127] The term "inorganic fillers" should be understood as meaning
colorless or white, lamellar or nonlamellar inorganic particles.
The inorganic particles can be of any shape, such as in particular
potatoid, lamellar, platelet, spherical or oblong. They can be of
any crystallographic form (for example sheet, cubic, hexagonal,
orthorhombic, and the like). Mention may in particular be made of
talc, mica, silica, kaolin, boron nitride, precipitated calcium
carbonate, magnesium carbonate, basic magnesium carbonate,
hydroxyapatite, hollow silica microspheres (Silica Beads.RTM. from
Maprecos), or glass or ceramic microcapsules, clay, quartz, natural
diamond powder or their mixture.
[0128] Mention may be made, as silica powder, of: [0129] the porous
silica microspheres sold under the name Silica Beads SB-700 by
Myoshi or "Sunsphere.RTM. H51" or "Sunsphere.RTM. H33" by Asahi
Glass; [0130] the amorphous silica microspheres coated with
polydimethylsiloxane sold under the name "SA Sunsphere.RTM. H 33"
or "SA Sunsphere.RTM. H53" by Asahi Glass.
[0131] Preferably, the inorganic filler is silica, talc or their
mixture.
[0132] Preference is given, among spherical fillers, to silicas,
such as hollow silica microspheres, in particular the SB700.RTM.
range from Miyoshi Kasei.
[0133] According to an alternative form of the invention, the
composition comprises at least one inorganic filler of potatoid
form (that is to say, a form with a surface exhibiting an irregular
outline which is reminiscent of the longitudinal cross section of a
potato), of lamellar form or their mixture.
[0134] The inorganic fillers can be present in the composition in a
content which can vary to a large extent according to the nature of
the inorganic fillers and also according to the product desired
and/or the effects desired; this amount is to be adjusted by a
person skilled in the art.
[0135] The inorganic filler(s) can be present in the composition in
a content ranging from 0.01 to 50% by weight, in particular from
0.01 to 30% by weight, with respect to the total weight of the
composition, preferably ranging from 0.01 to 20% by weight.
[0136] More specifically, the inorganic filler(s) can be present in
the composition in a content ranging from 1 to 50% by weight, with
respect to the total weight of the composition, and better still
from 2 to 35% by weight.
[0137] According to a preferred form, the composition according to
the invention additionally comprises at least one other filler.
Said at least one other filler can be inorganic or organic. It is
thus possible for a mixture of inorganic or organic fillers to be
involved.
[0138] According to one alternative, the composition according to
the invention can comprise an inorganic filler and another
inorganic filler, said inorganic fillers being as defined above,
and optionally at least one organic filler, as defined below.
[0139] According to another alternative, the composition according
to the invention can comprise an inorganic filler and an organic
filler.
[0140] The term "organic fillers" should be understood as meaning
colorless or white, and lamellar or nonlamellar organic particles.
Mention may in particular be made of powders formed of polyamide
(Nylon.RTM. or Orgasol.RTM. from Arkema), powders formed of acrylic
polymers, in particular powders formed of polymethyl methacrylate,
of poly(methyl methacrylate/ethylene glycol dimethacrylate), of
poly(allyl methacrylate/ethylene glycol dimethacrylate) or of
ethylene glycol dimethacrylate/lauryl methacrylate copolymer,
powders formed of cellulose, of poly-.beta.-alanine and of
polyethylene, powders formed of tetrafluoroethylene polymers
(Teflon.RTM.), lauroyl lysine, starch, hollow polymeric
microspheres, such as those of poly(vinylidene
chloride/acrylonitrile), such as Expancel.RTM. (Nobel Industrie),
or of acrylic acid copolymers (Polytrap.RTM. from Dow Corning),
silicone resin microbeads (Tospearls.RTM. from Toshiba, for
example), polyorganosiloxane elastomer particles, in particular
obtained by polymerization of organopolysiloxane having at least
two hydrogen atoms each bonded to a silicon atom and of an
organopolysiloxane comprising at least two groups possessing
ethylenic unsaturation (in particular two vinyl groups), in the
presence of a platinum catalyst, or else metal soaps derived from
organic carboxylic acids having from 8 to 22 carbon atoms,
preferably from 12 to 18 carbon atoms, for example zinc stearate,
magnesium stearate, lithium stearate, zinc laurate or magnesium
myristate.
[0141] Mention may be made, as powder formed of acrylic polymers,
of: [0142] the polymethyl methacrylate powders sold under the name
Covabead.RTM. LH85 by Wackherr; [0143] the poly(methyl
methacrylate/ethylene glycol dimethacrylate) powders sold under the
name Dow Corning 5640 Microsponge.RTM. Skin Oil Adsorber by Dow
Corning or Ganzpearl.RTM. GMP-0820 by Ganz Chemical; [0144] the
poly(allyl methacrylate/ethylene glycol dimethacrylate) powders
sold under the name Poly-Pore.RTM. L200 or Poly-Pore.RTM. E200 by
Amcol; [0145] the ethylene glycol dimethacrylate/lauryl
methacrylate copolymer powders sold under the name Polytrap.RTM.
6603 by Dow Corning.
[0146] Mention may be made, as silicone elastomer powder, of the
powders sold under the names "Trefil.RTM. Powder E-505C" and
"Trefil.RTM. Powder E-506C" by Dow Corning.
[0147] Preferably, the organic filler corresponds to polyamide
powders.
[0148] The amount of fillers can vary to a large extent according
to the nature of the filler and also according to the product
desired and/or the effects desired; this amount is to be adjusted
by a person skilled in the art.
[0149] The filler(s) can be present in the composition in a content
ranging from 0.01 to 50% by weight, in particular from 0.01 to 30%
by weight, with respect to the total weight of the composition,
preferably ranging from 0.01 to 20% by weight.
[0150] More specifically, the filler(s) can be present in the
composition in a content ranging from 1 to 50% by weight, with
respect to the total weight of the composition, and better still
from 2 to 35% by weight.
[0151] In the case where the composition according to the invention
comprises inorganic fillers and other fillers of organic type, they
will be in said composition in an inorganic fillers/organic fillers
ratio by weight preferably of greater than or equal to 1.
[0152] Another subject matter of the present invention is a
composition capable of being employed in a method according to the
invention comprising, in a physiologically acceptable medium, at
least one siloxane resin as defined above and at least one
inorganic filler as defined above, optionally additionally
comprising at least one organic filler as defined above.
[0153] The composition according to the invention can comprise one
or more other components and in particular oils, pasty compounds,
hard or soft waxes, rheological additives, coloring materials, in
particular pigments or pearlescent agents, which are or not
surface-treated with a hydrophobic agent, polymers, in particular
those comprising saccharide or carboxylate groups, or their
mixture.
Polymer:
[0154] The compositions according to the invention can additionally
comprise at least one polymer which may or may not be
film-forming.
[0155] In the present invention, the term "film-forming polymer" is
understood to mean a polymer capable of forming, by itself alone or
in the presence of an additional agent which is able to form a
film, a film which is macroscopically continuous and which adheres
to keratinous substances, and preferably a cohesive film, and
better still a film having a cohesion and mechanical properties
such that said film can be isolable and handleable in isolation,
for example when said film is produced by casting on a nonstick
surface, such as a Teflon- or silicone-treated surface.
[0156] The composition can comprise an aqueous phase and the
additional polymer can be present in this aqueous phase. In this
case, the additional polymer will preferably be a polymer in
dispersion or an amphiphilic or associative polymer.
[0157] The term "polymer in dispersion" is understood to mean
water-insoluble polymers present in the form of particles of
variable size. The polymer may or may not be crosslinked. The mean
particle size is typically between 25 and 500 nm, preferably
between 50 and 200 nm. The following polymers in aqueous dispersion
can be used: Ultrasol 2075 from Ganz Chemical, Daitosol 5000AD from
Daito Kasei, Avalure UR 450 from Noveon, DynamX from National
Starch, Syntran 5760 from Interpolymer, Acusol OP 301 from Rohm
& Haas or Neocryl A 1090 from Avecia.
[0158] 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
Avecia-Neoresins, Dow Latex 432.RTM. by Dow Chemical, Daitosol 5000
AD.RTM. or Daitosol 5000 SJ.RTM. by Daito Kasey Kogyo; Syntran
5760.RTM. by Interpolymer, Soltex OPT by Rohm & Haas, the
aqueous dispersions of acrylic or styrene/acrylic polymers sold
under the trade name Joncryl.RTM. by Johnson Polymer or also the
aqueous polyurethane dispersions sold under the names Neorez
R-981.RTM. and Neorez R-974.RTM. by Avecia-Neoresins, the names
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 Goodrich, Impranil 85.RTM. by
Bayer or Aquamere H-1511.RTM. by Hydromer; the sulfopolyesters sold
under the trade name Eastman AQ.RTM. by Eastman Chemical Products,
or vinylic dispersions, such as Mexomer PAM.RTM. from Chimex, and
their mixtures, are other examples of aqueous dispersions of
particles of film-forming polymers which are dispersible in
water.
[0159] The term "amphiphilic or associative polymers" is understood
to mean polymers comprising one or more hydrophilic parts which
render them partially soluble in water and one or more hydrophobic
parts via which the polymers form an association or interact. The
following associative polymers can be used: Nuvis FX1100 from
Elementis, Aculyn 22, Aculyn 44, Aculyn 46 from Rohm & Haas or
Viscophobe DB1000 from Amerchol. Diblock copolymers composed of a
hydrophilic block (polyacrylate, polyethylene glycol) and of a
hydrophobic block (polystyrene, polysiloxane) can also be used.
[0160] Polymers soluble in an aqueous phase comprising monodisperse
particles shall be avoided as they can bring about aggregation of
the monodisperse particles. The film-forming polymer can thus be
insoluble in such an aqueous phase.
[0161] The composition can comprise an oily phase and the
film-forming polymer can be present in this oily phase. The polymer
can then be in dispersion or in solution. Polymers of NAD
(nonaqueous dispersion) type or microgels (for example KSGs) can be
used, and also polymers of the silicone-modified polyamide type or
styrene-based copolymers (Kraton, Regalite).
[0162] Mention may be made, as examples of nonaqueous dispersions
of fat-dispersible film-forming polymer in the form of nonaqueous
dispersions of polymer particles in one or more silicone and/or
hydrocarbon oils, which particles can be stabilized at their
surface by at least one stabilizing agent, in particular a block,
grafted or random polymer, of acrylic dispersions in isododecane,
such as Mexomer PAP.RTM. from Chimex, or 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, such as described in particular in the document WO
04/055081.
[0163] Mention may be made, among film-forming polymers which can
be used in the composition of the present invention, of synthetic
polymers of radical type or of polycondensate type, polymers of
natural origin, and their blends.
[0164] The term "radical film-forming polymer" is understood to
mean a polymer obtained by polymerization of monomers possessing
unsaturation, in particular ethylenic unsaturation, each monomer
being capable of homopolymerizing.
[0165] The film-forming polymers of radical type can in particular
be vinyl polymers or copolymers, in particular acrylic
polymers.
[0166] The film-forming vinyl polymers can result from the
polymerization of monomers possessing ethylenic unsaturation having
at least one acid group and/or of the esters of these acidic
monomers and/or of the amides of these acidic monomers.
[0167] Use may be made, as monomer carrying an acid group, of
unsaturated .alpha.,.beta.-ethylenic carboxylic acids, such as
acrylic acid, methacrylic acid, crotonic acid, maleic acid or
itaconic acid. Use is preferably made of (meth)acrylic acid and
crotonic acid and more preferentially of (meth)acrylic acid.
[0168] The esters of acidic monomers are advantageously chosen from
esters of (meth)acrylic acid (also known as (meth)acrylates), in
particular alkyl (meth)acrylates, especially C.sub.1-C.sub.30 alkyl
(meth)acrylates, preferably C.sub.1-C.sub.20 alkyl (meth)acrylates,
aryl (meth)acrylates, in particular C.sub.6-C.sub.10 aryl
(meth)acrylates, or hydroxyalkyl (meth)acrylates, in particular
C.sub.2-C.sub.6 hydroxyalkyl (meth)acrylates.
[0169] Mention may be made, among alkyl (meth)acrylates, of methyl
methacrylate, ethyl methacrylate, butyl methacrylate, isobutyl
methacrylate, 2-ethylhexyl methacrylate, lauryl methacrylate or
cyclohexyl methacrylate.
[0170] Mention may be made, among hydroxyalkyl (meth)acrylates, of
hydroxyethyl acrylate, 2-hydroxypropyl acrylate, hydroxyethyl
methacrylate or 2-hydroxypropyl methacrylate.
[0171] Mention may be made, among aryl (meth)acrylates, of benzyl
acrylate and phenyl acrylate.
[0172] Esters of (meth)acrylic acid which are particularly
preferred are alkyl (meth)acrylates.
[0173] According to the present invention, the alkyl group of the
esters can be either fluorinated or perfluorinated, that is to say
that a portion or all of the hydrogen atoms of the alkyl group are
substituted by fluorine atoms.
[0174] Mention may be made, as amides of the acidic monomers, for
example, of (meth)acrylamides, in particular
N-alkyl(meth)acrylamides, especially N--(C.sub.2-C.sub.12
alkyl)(meth)acrylamides. Mention may be made, among
N-alkyl(meth)acrylamides, of N-ethylacrylamide,
N-(t-butyl)acrylamide, N-(t-octyl)acrylamide and
N-undecylacrylamide.
[0175] The film-forming vinyl polymers can also result from the
homopolymerization or from the copolymerization of monomers chosen
from vinyl esters and styrene monomers. In particular, these
monomers can be polymerized with acidic monomers and/or their
esters and/or their amides, such as those mentioned above.
[0176] Mention may be made, as examples of vinyl esters, of vinyl
acetate, vinyl neodecanoate, vinyl pivalate, vinyl benzoate and
vinyl t-butylbenzoate.
[0177] Mention may be made, as styrene monomers, of styrene and
.alpha.-methylstyrene.
[0178] Mention may be made, among film-forming polycondensates, of
polyurethanes, polyesters, polyesteramides, polyamides, epoxy ester
resins or polyureas.
[0179] The polyurethanes can be chosen from anionic, cationic,
nonionic or amphoteric polyurethanes, polyurethane-acrylics,
polyurethane-polyvinylpyrrolidones, polyester-polyurethanes,
polyether-polyurethanes, polyureas, polyurea-polyurethanes, and
their blends.
[0180] The polyesters can be obtained in a known way by
polycondensation of dicarboxylic acids with polyols, in particular
diols.
[0181] The dicarboxylic acid can be aliphatic, alicyclic or
aromatic. Mention may be made, as examples of such acids, of:
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-naphthalenedicarboxylic acid or 2,6-naphthalenedicarboxylic
acid. These dicarboxylic acid monomers can be used alone or as a
combination of at least two dicarboxylic acid monomers. The choice
is preferably made, among these monomers, of phthalic acid,
isophthalic acid or terephthalic acid.
[0182] The diol can be chosen from aliphatic, alicyclic or aromatic
diols. Use is preferably made of a diol chosen from: ethylene
glycol, diethylene glycol, triethylene glycol, 1,3-propanediol,
cyclohexanedimethanol or 4-butanediol. Use may be made, as other
polyols, of glycerol, pentaerythritol, sorbitol or
trimethylolpropane.
[0183] Polyesteramides can be obtained analogously to the
polyesters by polycondensation of diacids with diamines or amino
alcohols. Use may be made, as diamines, of ethylenediamine,
hexamethylenediamine, meta-phenylenediamine or
para-phenylenediamine. Use may be made, as amino alcohol, of
monoethanolamine.
[0184] The polyester can additionally comprise at least one monomer
carrying at least one --SO.sub.3M group, 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. Use may in
particular be made of a bifunctional aromatic monomer comprising
such an --SO.sub.3M group.
[0185] The aromatic ring system of the bifunctional aromatic
monomer additionally carrying an --SO.sub.3M group as described
above can be chosen, for example, from the benzene, naphthalene,
anthracene, biphenyl, oxydiphenyl, sulfonyldiphenyl or
methylenediphenyl ring systems. Mention may be made, as example of
bifunctional aromatic monomer additionally carrying an --SO.sub.3M
group, of: sulfoisophthalic acid, sulfoterephthalic acid,
sulfophthalic acid or 4-sulfonaphthalene-2,7-dicarboxylic acid.
[0186] By way of example, the film-forming polymer can be a polymer
dissolved in a liquid fatty phase comprising oils or organic
solvents (the film-forming polymer is then described as a
fat-soluble polymer). Preferably, the liquid fatty phase comprises
a volatile oil, optionally as a mixture with a nonvolatile oil.
[0187] Mention may be made, as examples of fat-soluble polymer, of
copolymers of vinyl ester (the vinyl group being directly connected
to the oxygen atom of the ester group and the vinyl ester having a
saturated, linear or branched, hydrocarbon radical of 1 to 19
carbon atoms bonded to the carbonyl of the ester group) and of at
least one other monomer which can be a vinyl ester (other than the
vinyl ester already present), an .alpha.-olefin (having from 8 to
28 carbon atoms), an alkyl vinyl ether (the alkyl group of which
comprises from 2 to 18 carbon atoms) or an allyl or methallyl ester
(having a saturated, linear or branched, hydrocarbon radical of 1
to 19 carbon atoms bonded to the carbonyl of the ester group).
[0188] These copolymers can be crosslinked using crosslinking
agents which can be either of the vinyl type or of the allyl or
methallyl type, such as tetraallyloxyethane, divinylbenzene,
divinyl octanedioate, divinyl dodecanedioate and divinyl
octadecanedioate.
[0189] Mention may be made, as examples of these copolymers, of 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% of
divinylbenzene, vinyl dimethylpropionate/vinyl laurate, crosslinked
with 0.2% of divinylbenzene, vinyl acetate/octadecyl vinyl ether,
crosslinked with 0.2% of tetraallyloxyethane, vinyl acetate/allyl
stearate, crosslinked with 0.2% of divinylbenzene, vinyl
acetate/1-octadecene, crosslinked with 0.2% of divinylbenzene, and
allyl propionate/allyl stearate, crosslinked with 0.2% of
divinylbenzene.
[0190] Mention may be made, as example of fat-soluble film-forming
polymers, of copolymers of a vinyl ester and of at least one other
monomer which can be a vinyl ester, in particular vinyl
neodecanoate, vinyl benzoate and vinyl t-butylbenzoate, an
.alpha.-olefin, an alkyl vinyl ether or an allyl or methallyl
ester.
[0191] Mention may also be made, as fat-soluble film-forming
polymers, of fat-soluble copolymers and in particular those
resulting from the copolymerization of vinyl esters having from 9
to 22 carbon atoms or of alkyl acrylates or methacrylates, the
alkyl radicals having from 10 to 20 carbon atoms.
[0192] Such fat-soluble copolymers can be chosen from copolymers of
poly(vinyl stearate), of poly(vinyl stearate) crosslinked using
divinylbenzene, diallyl ether or diallyl phthalate, copolymers of
poly(stearyl (meth)acrylate), of poly(vinyl laurate), of
poly(lauryl (meth)acrylate), it being possible for these
poly(meth)acrylates to be crosslinked using ethylene glycol
dimethacrylate or tetraethylene glycol dimethacrylate.
[0193] The fat-soluble copolymers defined above are known and are
described in particular in application FR-A-2 232 303; they can
have a weight-average molecular weight ranging from 2000 to 500 000
and preferably from 4000 to 200 000.
[0194] Mention may also be made, as fat-soluble film-forming
polymers which can be used in the invention, of polyalkylenes and
in particular copolymers of C.sub.2-C.sub.20 alkenes, such as
polybutene, alkylcelluloses with a saturated or unsaturated and
linear or branched C.sub.1 to C.sub.8 alkyl radical, such as
ethylcellulose and propylcellulose, copolymers of vinylpyrrolidone
(VP) and in particular copolymers of vinylpyrrolidone and of
C.sub.2 to C.sub.40 alkene and better still C.sub.3 to C.sub.20
alkene. Mention may be made, as examples of VP copolymer which can
be used in the invention, of the VP/vinyl acetate, VP/ethyl
methacrylate, butylated polyvinylpyrrolidone (PVP), VP/ethyl
methacrylate/methacrylic acid, VP/eicosene, VP/hexadecene,
VP/triacontene, VP/styrene or VP/acrylic acid/lauryl methacrylate
copolymer.
[0195] Mention may also be made of silicone resins, generally
soluble or swellable in silicone oils, which are crosslinked
polyorganosiloxane polymers. The nomenclature of silicone resins is
known under the name of "MDTQ", the resin being described according
to the various siloxane monomer units which it comprises, each of
the letters "MDTQ" characterizing one type of unit.
[0196] Mention may be made, as examples of commercially available
polymethylsilsesquioxane resins, of those which are sold by Wacker
under the reference Resin MK, such as Belsil PMS MK, or by
Shin-Etsu under the reference KR-220L.
[0197] Mention may be made, as examples of commercially available
polypropylsilsesquioxane resins, of those which are sold under the
reference DC670 by Dow Corning.
[0198] Mention may be made, as siloxysilicate resins, of
trimethylsiloxysilicate (TMS) resins, such as those sold under the
reference SR1000 by General Electric or under the reference TMS 803
by Wacker. Mention may also be made of trimethylsiloxysilicate
resins sold in a solvent, such as cyclomethicone, sold under the
names KF-7312J by Shin-Etsu or "DC 749" or "DC 593" by Dow
Corning.
[0199] Mention may also be made of copolymers of silicone resins,
such as those mentioned above with polydimethylsiloxanes, for
example the pressure-sensitive adhesive copolymers sold by Dow
Corning under the reference BIO-PSA and described in the document
U.S. Pat. No. 5,162,410 or the silicone copolymers resulting from
the reaction of a silicone resin, such as those described above,
and of a diorganosiloxane, such as are described in the document WO
2004/073626.
[0200] By way of example, the film-forming polymer can be a
film-forming linear ethylenic block polymer which preferably
comprises at least one first block and at least one second block
having different glass transition temperatures (Tg), said first and
second blocks being connected to one another via an intermediate
block comprising at least one constituent monomer of the first
block and at least one constituent monomer of the second block.
[0201] Advantageously, the first and second blocks of the block
polymer are incompatible with one another.
[0202] Such polymers are described, for example, in the documents
EP 1 411 069 and WO 04/028488.
[0203] The film-forming polymer can be chosen from polymers and/or
block or random copolymers comprising in particular polyurethanes,
polyacrylics, silicones, fluoropolymers, butyl rubbers, ethylene
copolymers, natural gums and polyvinyl alcohols and their blends.
The monomers of the block or random copolymers comprising at least
one combination of monomers, the polymer of which results in a
glass transition temperature below ambient temperature (25.degree.
C.), can be chosen in particular from butadiene, ethylene,
propylene, acrylic, methacrylic, isoprene, isobutene, a silicone
and their mixtures.
[0204] The film-forming polymer can also be present in the
composition in the form of particles in dispersion in an aqueous
phase or in a nonaqueous solvent phase, generally known under the
name of latex or pseudolatex. The techniques for the preparation of
these dispersions are well known to a person skilled in the
art.
[0205] The composition according to the invention can comprise a
plasticizing agent which promotes the formation of a film with the
film-forming polymer. Such a plasticizing agent can be chosen from
all the compounds known to a person skilled in the art as being
capable of performing the desired role.
[0206] Mention may be made, as other examples of a film-forming
system which can be used in the compositions according to the
invention, of the systems in which the film is formed in situ
during the application of the composition or of a mixture of
compositions comprising two silicone compounds which react when
they are brought into contact with one another. Such systems are
described in particular in application WO 2007/071706, the content
of which is incorporated here by way of reference. Systems of this
type are also described in applications US 2007/142575 or US
2007/142599, the contents of which are also incorporated here by
way of reference.
Other Polymers:
[0207] The compositions according to the invention can comprise an
elastomer, in particular a polyglycerolated silicone elastomer. Use
is made, by way of example, of a crosslinked organopolysiloxane
elastomer which can be obtained by a crosslinking addition reaction
of a diorganopolysiloxane comprising at least one hydrogen bonded
to the silicon and of polyglycerolated compounds having groups
possessing ethylenic unsaturation, in particular in the presence of
a platinum catalyst.
[0208] Use may be made, as polyglycerolated silicone elastomers, of
those sold under the names "KSG-710", "KSG-810", "KSG-820",
"KSG-830" and "KSG-840" by Shin-Etsu.
[0209] The compositions according to the invention can in addition
comprise an additional emulsifying silicone elastomer.
[0210] Use is made, by way of examples, of polyoxyalkylenated
elastomers, such as described in particular 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 contents of which are incorporated by
way of reference.
[0211] Use may be made, as polyoxyalkylenated silicone elastomer,
of 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 Shin-Etsu and "DC9010" and
"DC9011" by Dow Corning.
[0212] These specific elastomers, when they are in combination with
the resins according to the invention, can make it possible to
improve the transfer-free and comfort (suppleness) properties of
the compositions comprising them.
[0213] The compositions according to the invention can additionally
comprise a nonemulsifying elastomer.
[0214] Nonemulsifying elastomers are described in particular in
applications JP-A-61-194009, EP-A-242 219, EP-A-285 886 and
EP-A-765 656, the contents of which are incorporated by way of
reference.
[0215] Use may be made, as spherical nonemulsifying elastomers, of
those sold under the names "DC9040", "DC9041", "DC9509", "DC9505"
and "DC 9506" by Dow Corning.
[0216] The spherical nonemulsifying silicone elastomer can also be
provided in the form of a crosslinked organopolysiloxane elastomer
powder coated with silicone resin, in particular with
silsesquioxane resin, as described, for example, in U.S. Pat. No.
5,538,793, the content of which is incorporated by way of
reference. Such elastomers are sold under the names "KSP-100",
"KSP-101", "KSP-102", "KSP-103", "KSP-104" and "KSP-105" by
Shin-Etsu.
[0217] Other crosslinked organopolysiloxane elastomers in the form
of spherical powders can be powders formed of hybrid silicone
functionalized by fluoroalkyl groups, sold in particular under the
name "KSP-200" by Shin-Etsu; or powders formed of hybrid silicone
functionalized by phenyl groups, sold in particular under the name
"KSP-300" by Shin-Etsu.
[0218] Use may also be made, in the compositions according to the
invention, of silicone elastomers with an MQ group, such as those
sold by Wacker under the names Belsil RG100, Belsil RPG33 and,
preferably, Belsil RG80. These specific elastomers, when they are
in combination with the resins according to the invention, can make
it possible to improve the transfer-free properties of the
compositions comprising them.
Structuring Agents:
[0219] The composition according to the invention can comprise at
least one structuring agent.
[0220] The term "structuring agent" is understood to mean a
compound capable of increasing the viscosity of the composition.
The structuring agent makes it possible in particular to obtain a
composition which can exhibit a texture ranging from fluid textures
to solid textures.
[0221] The structuring agent can be present in the composition in a
content ranging from 0.05% to 40% by weight, with respect to the
total weight of the composition, preferably ranging from 0.1% to
30% by weight and preferentially ranging from 0.1% to 25% by
weight.
[0222] The structuring agent can be chosen in particular from
thickeners (thickeners for an oily medium; thickeners for an
aqueous medium), organic gelling agents, waxes, pasty compounds or
gums.
[0223] The thickening agent for an aqueous medium can be chosen
from: [0224] hydrophilic clays, [0225] hydrophilic pyrogenic
silica, [0226] water-soluble cellulose thickeners, [0227] guar,
xanthan, locust bean, scleroglucan, gellan, rhamsan, karaya or
carrageenan gums, [0228] alginates, maltodextrins, starch and its
derivatives, or hyaluronic acid and its salts, [0229] the
poly(glyceryl (meth)acrylate) polymers sold under the names of
"Hispagel" or "Lubragel" by Hispano Quimica or Guardian, [0230]
polyvinylpyrrolidone, [0231] polyvinyl alcohol, [0232] crosslinked
polymers and copolymers of acrylamide, such as those sold under the
names of "PAS 5161" or "Bozepol C" by Hoechst, of "Sepigel 305" by
SEPPIC by Allied Colloids, [0233] the crosslinked
methacryloyloxyethyltrimethylammonium chloride homopolymers sold
under the name of "Salcare SC95" by Allied Colloids, or [0234]
associative polymers and in particular associative
polyurethanes.
[0235] Such thickening agents are described in particular in
application EP-A-1 400 234, the content of which is incorporated by
way of reference.
[0236] The thickening agent for an oily medium can be chosen from:
[0237] silicone carboxylates, [0238] silicone saccharides, [0239]
organophilic clays, [0240] hydrophobic pyrogenic silicas, [0241]
alkylated guar gums (with C.sub.1-C.sub.6 alkyl group), such as
those described in EP-A-708 114; [0242] hydrophobic celluloses,
[0243] gelling polymers for an oil, such as triblock or star
polymers resulting from the polymerization or copolymerization of
at least one monomer comprising an ethylene group, such as the
polymers sold under the name Kraton; [0244] polymers with a
weight-average molecular weight of less than 100 000, comprising a)
a polymer backbone having hydrocarbon repeat units which are
provided with at least one heteroatom and optionally b) at least
one optionally functionalized pendant fatty chain and/or at least
one optionally functionalized end fatty chain, having from 6 to 120
carbon atoms, which are bonded to these hydrocarbon units, such as
described in applications WO-A-02/056847 and WO-A-02/47619, the
contents of which are incorporated by way of reference; especially,
polyamide resins (in particular comprising alkyl groups having 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 way of
reference; [0245] silicone-modified polyamide resins, such as
described in application EP-A-1 266 647 and in the French patent
application filed under No. 02/16039, the content of which is
incorporated by way of reference.
[0246] Such thickening agents are described in particular in
application EP-A-1 400 234, the content of which is incorporated by
way of reference.
[0247] The organic gelling agents can be chosen from those
described in application WO-A-03/105788, the content of which is
incorporated by way of reference.
[0248] Mention may in particular be made, by way of examples, of:
[0249] bisurea derivatives of general formula (II):
[0249] ##STR00002## [0250] in which: [0251] A is a group of
formula:
[0251] ##STR00003## [0252] with R' being a linear or branched
C.sub.1 to C.sub.4 alkyl radical and the * symbolizing the points
of attachment of the group A to each of the two nitrogen atoms of
the remainder of the compound of general formula (I), and [0253] R
is a saturated or unsaturated noncyclic monobranched C.sub.6 to
C.sub.15 alkyl radical, the hydrocarbon chain of which is
optionally interrupted by 1 to 3 heteroatoms chosen from O, S and
N, or [0254] one of their salts or isomers described in particular
in patent application FR-A-2 892 303, [0255] silicone-modified
bisurea derivatives of general formula (III) or one of their salts
and/or isomers:
[0255] ##STR00004## [0256] in which: [0257] A is a group of formula
(IV):
[0257] ##STR00005## [0258] with R.sub.1 being a linear or branched
C.sub.1 to C.sub.4 alkyl radical and the * symbolizing the points
of attachment of the group A to each of the two nitrogen atoms of
the remainder of the compound of general formula (I), and [0259] R
and R', which are identical or different, are chosen from: [0260]
i) radicals of formula (V):
[0260] ##STR00006## [0261] in which: [0262] L is a simple bond or a
saturated or unsaturated, linear, branched and/or cyclic, divalent
carbon, in particular hydrocarbon (alkylene), radical which
comprises from 1 to 18 carbon atoms and which can comprise from 1
to 4 heteroatoms chosen from N, O and S; [0263] R.sub.a is: [0264]
a) a saturated or unsaturated, linear, branched and/or cyclic,
carbon, in particular hydrocarbon (alkyl), radical which comprises
from 1 to 18 carbon atoms and which can comprise from 1 to 8
heteroatoms chosen from N, O, Si and S; or else [0265] b) a
silicone radical of formula:
[0265] ##STR00007## [0266] with n being between 0 and 100, in
particular between 1 and 80, indeed even from 2 to 20; [0267] and
R2 to R6 being, independently of one another, linear or branched
carbon, in particular hydrocarbon (alkyl), radicals which have from
1 to 12, in particular from 1 to 6, carbon atoms and which can
comprise from 1 to 4 heteroatoms, in particular O; [0268] R.sub.b
and R.sub.c are chosen, independently of one another, from: [0269]
a) saturated or unsaturated, linear, branched and/or cyclic,
carbon, in particular hydrocarbon (alkyl), radicals which comprise
from 1 to 18 carbon atoms and which can comprise from 1 to 4
heteroatoms chosen from N, O, Si and S; [0270] b) radicals of
formula:
[0270] ##STR00008## [0271] with n being between 0 and 100, in
particular between 1 and 80, indeed even from 2 to 20; [0272] and
R'.sub.2 to R'.sub.6 being, independently of one another, linear or
branched carbon, in particular hydrocarbon (alkyl), radicals which
have from 1 to 12, in particular from 1 to 6, carbon atoms and
which can comprise from 1 to 4 heteroatoms, in particular O, [0273]
and [0274] ii) saturated or unsaturated, linear, branched and/or
cyclic, C.sub.1 to C.sub.30 alkyl radicals optionally comprising
from 1 to 3 heteroatoms chosen from O, S, F and N; it being
understood that at least one of the R and/or R' radicals is of
formula (III), such as those described in patent application FR-A-2
900 819, [0275] the bisurea derivatives described in patent
application FR-A-2 8994 476.
[0276] The structuring agents can be composed of waxes. The term
"wax" is understood to mean, within the meaning of the present
invention, a lipophilic compound which is solid at ambient
temperature (25.degree. C.), which exhibits a reversible
solid/liquid change in state and which has a melting point of
greater than or equal to 30.degree. C. which can range up to
120.degree. C.
[0277] On bringing the wax to the liquid state (melting), it is
possible to render it miscible with the oils which may be present
and to form a microscopically homogeneous mixture but, on bringing
the temperature of the mixture back to ambient temperature,
recrystallization of the wax in the oils of the mixture is
obtained. The melting point of the wax can be measured using a
differential scanning calorimeter (DSC), for example the
calorimeter sold under the name DSC 30 by Mettler.
[0278] The wax can also exhibit a hardness ranging from 0.05 MPa to
15 MPa and preferably ranging from 6 MPa to 15 MPa. The hardness is
determined by the measurement of the compressive force measured at
20.degree. C. using the texture analyzer sold under the name
TA-TX21 by Rheo, equipped with a stainless steel cylinder with a
diameter of 2 mm which is displaced at the measuring rate of 0.1
mm/s and which penetrates the wax to a penetration depth of 0.3
mm.
[0279] The waxes can be hydrocarbon, fluorinated and/or silicone
waxes and can be of vegetable, mineral, animal and/or synthetic
origin. In particular, the waxes exhibit a melting point of greater
than 30.degree. C. and better still of greater than 45.degree.
C.
[0280] Mention is preferably made, as wax which can be used in the
composition of the invention, of beeswax, carnauba wax, candelilla
wax, paraffin wax, microcrystalline waxes, rice bran wax, olive
waxes (photowax olive 14L48, photowax olive 18L57), ceresin or
ozokerite; synthetic waxes, such as polyethylene waxes or
Fischer-Tropsch waxes, or silicone waxes, such as alkyl or alkoxy
dimethicones having from 16 to 45 carbon atoms.
[0281] By way of indication, the composition can comprise from 0.1
to 50% by weight of waxes, with respect to the total weight of the
composition, and better still from 1 to 30% by weight.
[0282] The gums are generally high molecular weight
polydimethylsiloxanes (PDMSs) or cellulose gums or
polysaccharides.
Surfactants
[0283] The composition according to the invention can comprise at
least one surfactant.
[0284] The surfactant can be lipophilic and/or hydrophilic, and
used alone or as a blend.
[0285] The surfactant can be chosen from nonionic, anionic,
cationic or amphoteric surfactants.
[0286] The nonionic surfactant can be chosen from: [0287] a
C.sub.8-C.sub.22 alkyl dimethicone copolyol, that is to say an
oxypropylenated and/or oxyethylenated
polymethyl[(C.sub.8-C.sub.22)alkyl](dimethyl)(methyl)siloxane.
[0288] The C.sub.8-C.sub.22 alkyl dimethicone copolyol is
advantageously a compound of following formula (VI):
##STR00009##
in which: [0289] 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, [0290] m ranging from 1 to 40, [0291] n
ranging from 10 to 200, [0292] o ranging from 1 to 100, [0293] p
ranging from 7 to 21, [0294] q ranging from 0 to 4, and,
preferably: [0295] R.dbd.H [0296] m=1 to 10, [0297] n=10 to 100,
[0298] o=1 to 30, [0299] p=15 [0300] q=3.
[0301] Mention may be made, as C.sub.8-C.sub.22 alkyl dimethicone
copolyol, of cetyl dimethicone copolyol, such as the product sold
under the name Abil EM-90 by Goldschmidt. [0302] a dimethicone
copolyol, that is to say an oxypropylenated and/or oxyethylenated
polydimethyl(methyl)siloxane. It does not comprise a long-chain
alkyl group of more than 8 carbon atoms, in particular a
C.sub.8-C.sub.22 alkyl group.
[0303] Use may be made, as dimethicone copolyol, of those
corresponding to the following formula (VII):
##STR00010##
in which: R.sub.1, R.sub.2 and R.sub.3 represent, independently of
one another, a C.sub.1-C.sub.6 alkyl radical or a
--(CH.sub.2).sub.x--(OCH.sub.2CH.sub.2).sub.y--(OCH.sub.2CH.sub.2CH.sub.2-
).sub.z--OR.sub.4 radical, at least one R.sub.1, R.sub.2 or R.sub.3
radical not being an alkyl radical; R.sub.4 being a hydrogen, a
C.sub.1-C.sub.3 alkyl radical or a C.sub.2-C.sub.4 acyl radical; A
is an integer ranging from 0 to 200; B is an integer ranging from 0
to 50; provided that A and B are not simultaneously equal to zero;
x is an integer ranging from 1 to 6; y is an integer ranging from 1
to 30; z is an integer ranging from 0 to 5.
[0304] According to a preferred embodiment of the invention, in the
compound of formula (VII), 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.
[0305] Mention may be made, as example of compounds of formula
(VII), of the compounds of formula (VIII):
##STR00011##
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.
[0306] Mention may also be made, as example of silicone compounds
of formula (VII), of the compounds of formula (IX):
HO--(CH2CH2O)y-(CH2)3-[(CH3)2SiO]A'-[(CH3)2Si]--(CH2)3-(OCH2CH2)y-OH
in which A' and y are integers ranging from 10 to 20.
[0307] Use may be made, as dimethicone copolyol, of those sold
under the names DC 5329, DC 7439-146, DC2-5695 and Q4-3667 by Dow
Corning and KF-6013, KF-6015, KF-6016 and KF-6017 by Shin-Etsu.
[0308] The compounds DC 5329, DC 7439-146 and DC.sub.2-5695 are
compounds of formula (VIII) where, respectively, A is 22, B is 2
and y is 12, A is 103, B is 10 and y is 12, and A is 27, B is 3 and
y is 12.
[0309] Mention may also be made, as nonionic surfactant, of polyol
fatty acid esters, such as sorbitol mono-, di-, tri- or
sesqui-oleates or -stearates, glycerol mono-, di-, tri- or
sesqui-oleates or -stearates, or glycerol or polyethylene glycol
laurates; polyethylene glycol fatty acid esters (polyethylene
glycol monostearate or monolaurate); polyoxyethylenated sorbitol
fatty acid esters (stearate, oleate); or polyoxyethylenated alkyl
(lauryl, cetyl, stearyl, octyl)ethers.
[0310] Mention may be made, as anionic surfactant, of carboxylates
(sodium 2-(2-hydroxyalkyloxy)acetate), amino acid derivatives
(N-acylglutamates, N-acylglycinates, acylsarcosinates), alkyl
sulfates, alkyl ether sulfates and their oxyethylenated
derivatives, sulfonates, isethionates and N-acylisethionates,
taurates and N-acyl-N-methyltaurates, sulfosuccinates, alkyl
sulfoacetates, phosphates and alkyl phosphates, polypeptides, alkyl
polyglycoside anionic derivatives (acyl-D-galactoside uronate),
soaps of fatty acids, and their mixtures.
[0311] Use may be made, as amphoteric and zwitterionic surfactant,
of betaines, N-alkyl amido betaines and their derivatives, glycine
derivatives, sultaines, alkyl polyaminocarboxylates, alkyl
amphoacetates, and their mixtures.
[0312] Such surfactants are described in particular in application
WO-A-02/056854, the content of which is incorporated by way of
reference.
[0313] The surfactant can be present in the composition according
to the invention in a content ranging from 0.1% to 10% by weight,
with respect to the total weight of the composition, preferably
ranging from 0.5% to 8% by weight and preferentially ranging from
0.5% to 7% by weight.
Coloring Materials:
[0314] The composition according to the invention can additionally
comprise at least one coloring material.
[0315] The coloring material can be chosen from pulverulent
coloring materials (in particular pigments and pearlescent agents)
or water-soluble or fat-soluble coloring materials.
[0316] In particular, the pigments can be white or colored and
inorganic and/or organic. Mention may be made, among inorganic
pigments, of titanium dioxide, zirconium or cerium oxides, and also
zinc, iron (black, yellow or red) or chromium oxides, manganese
violet, ultramarine blue, chromium hydrate and ferric blue, or
metal powders, such as aluminum powder or copper powder.
[0317] Mention may be made, among organic pigments, of carbon
black, pigments of D & C type, and lakes, based on cochineal
carmine, of barium, strontium, calcium or aluminum.
[0318] Mention may also be made of effect pigments, such as
particles comprising an organic or inorganic and natural or
synthetic substrate, for example glass, acrylic resins, polyester,
polyurethane, polyethylene terephthalate, ceramics or aluminas,
said substrate being covered or not being covered with metal
substances, such as aluminum, gold, silver, platinum, copper or
bronze, or with metal oxides, such as titanium dioxide, iron oxide
or chromium oxide, and their mixtures.
[0319] The pearlescent pigments can be chosen from white
pearlescent pigments, such as mica covered with titanium oxide or
with bismuth oxychloride, colored pearlescent pigments, such as
titanium oxide-coated mica covered with iron oxides, titanium
oxide-coated mica covered with in particular ferric blue or
chromium oxide, or titanium oxide-coated mica covered with an
organic pigment of the abovementioned type, and pearlescent
pigments based on bismuth oxychloride. Use may also be made of
interferential pigments, in particular liquid crystal or multilayer
pigments.
[0320] The water-soluble dyes are, for example, beetroot juice or
methylene blue.
[0321] The synthetic or natural fat-soluble 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 or curcumin.
[0322] The solid particles, such as pulverulent coloring materials
(pigments and pearlescent agents), can be completely or partially
surface-treated with a compound of silicone nature, a compound of
fluorinated nature, a compound of fluorinated/silicone nature, a
fatty acid or amino acid or one of their mixtures.
[0323] According to one embodiment, the compositions, in particular
the compositions for making up or caring for the skin and in
particular foundations, can comprise at least one solid particle
(more specifically pigments and/or pearlescent agents) completely
or partially surface-treated with a compound of fluorinated nature,
in particular in order to improve the persistence of the color and
mattness.
[0324] The hydrophobic treatment agent can be chosen from
silicones, such as methicones, dimethicones, perfluoroalkylsilanes,
perfluoroalkylsilazanes, triethoxycapryloylsilane or
triethoxysilylethyl polydimethylsiloxyethyl hexyl dimethicone;
fatty acids such as stearic acid; metal soaps, such as aluminum
dimyristate or the aluminum salt of hydrogenated tallow glutamate;
perfluoroalkyl phosphates, polyhexafluoropropylene oxides,
polyorganosiloxanes comprising perfluoroalkyl perfluoropolyether
groups or silicone-grafted acrylic polymers (described in
particular in application JP-A-05-339125, the content of which is
incorporated by way of reference); amino acids; N-acylated amino
acids or their salts; lecithin, isopropyl triisostearoyltitanate,
isostearyl sebacate, and their mixtures.
[0325] The N-acylated amino acids can comprise an acyl group having
from 8 to 22 carbon atoms, such as, for example, a 2-ethylhexanoyl,
caproyl, lauroyl, myristoyl, palmitoyl, stearoyl or cocoyl group.
The salts of these compounds can be aluminum, magnesium, calcium,
zirconium, zinc, sodium or potassium salts. The amino acid can be,
for example, lysine, glutamic acid or alanine.
[0326] The fluorinated surface-active agents can be chosen from
perfluoroalkyl phosphates, perfluoropolyethers,
polytetrafluoroethylenes (PTFEs) and perfluoroalkanes.
[0327] The perfluoropolyethers are described in particular in
patent application EP-A-486 135 and are sold under the Fomblin
trade names by Montefluos.
[0328] Perfluoroalkyl phosphates are described in particular in
application JP H05-86984. The diethanolamine perfluoroalkyl
phosphates sold by Asahi Glass under the reference AsahiGuard AG530
can be used.
[0329] Mention may be made, among linear perfluoroalkanes, of
perfluorocycloalkanes, perfluoro(alkylcycloalkanes),
perfluoropolycycloalkanes, aromatic perfluorinated hydrocarbons
(perfluoroarenes) and organoperfluorinated hydrocarbon compounds
comprising at least one heteroatom.
[0330] Mention may be made, among perfluoroalkanes, of the series
of the linear alkanes, such as perfluorooctane, perfluorononane or
perfluorodecane.
[0331] Mention may be made, among perfluorocycloalkanes and
perfluoro(alkylcycloalkanes), of perfluorodecalin, sold under the
name of "Flutec PP5 GMP" by Rhodia, perfluoro(methyldecalin) or
perfluoro(C.sub.3-C.sub.5 alkylcyclohexanes), such as
perfluoro(butylcyclohexane).
[0332] Mention may be made, among perfluoropolycycloalkanes, of
bicyclo[3.3.1]nonane derivatives, such as
perfluorotrimethylbicyclo[3.3.1]nonane, adamantane derivatives,
such as perfluorodimethyladamantane, and perfluorinated derivatives
of hydrogenated phenanthrene, such as
tetracosafluorotetradecahydrophenanthrene.
[0333] Mention may be made, among perfluoroarenes, of
perfluorinated derivatives of naphthalene, such as
perfluoronaphthalene and perfluoro-1-methylnaphthalene.
[0334] Mention may be made, as example of commercial references for
pigments treated with a fluorinated compound, of: [0335] Yellow
iron oxide/perfluoroalkyl phosphate, sold under the reference PF 5
Yellow 601 by Daito Kasei, [0336] Red iron oxide/perfluoroalkyl
phosphate, sold under the reference PF 5 Red R 516L by Daito Kasei,
[0337] Black iron oxide/perfluoroalkyl phosphate, sold under the
reference PF 5 Black BL 100 by Daito Kasei, [0338] Titanium
dioxide/perfluoroalkyl phosphate, sold under the reference PF 5
TiO2 CR 50 by Daito Kasei, [0339] Yellow iron
oxide/perfluoropolymethyl isopropyl ether, sold under the reference
Iron Oxide [0340] Yellow BF-25-3 by Toshiki, [0341] DC Red
7/perfluoropolymethyl isopropyl ether, sold under the reference
D&C Red 7 FHC by Cardre Inc., [0342] DC Red 6/PTFE, sold under
the reference T 9506 by Warner-Jenkinson.
[0343] The coloring materials, in particular the pigments, can be
present in the composition in a content ranging from 0.1% to 30% by
weight, with respect to the total weight of the composition,
preferably ranging from 0.5% to 20% by weight and preferentially
ranging from 1% to 10% by weight.
Fibers:
[0344] The composition can additionally comprise fibers.
[0345] The term "fiber" should be understood as meaning an object
with a length L and a diameter D such that L is greater than D, D
being the diameter of the circle in which the cross section of the
fiber is framed. In particular, the L/D ratio (or aspect ratio) is
chosen within the range from 3.5 to 2500, preferably from 5 to 500
and better still from 5 to 150.
[0346] The fibers which can be used in the composition of the
invention can be fibers of synthetic or natural and inorganic or
organic origin. They can be short or long, individual or organized,
for example braided, and hollow or solid. They can have any shape
and can in particular be circular or polygonal (square, hexagonal
or octagonal) in cross section, according to the specific
application envisaged. In particular, their ends are blunted and/or
polished to prevent injury.
[0347] In particular, the fibers have a length ranging from 1 .mu.m
to 10 mm, preferably from 0.1 mm to 5 mm and better still from 0.3
mm to 3 mm. Their cross section can be included within a circle
with a diameter ranging from 2 nm to 500 .mu.m, preferably ranging
from 100 nm to 100 .mu.m and better still from 1 .mu.m to 50 .mu.m.
The weight or count of the fibers is often given in denier or
decitex and represents the weight in grams per 9 km of yarn.
Preferably, the fibers according to the invention have a count
chosen within the range from 0.01 to 10 denier, preferably from 0.1
to 2 denier and better still from 0.3 to 0.7 denier.
[0348] Such fibers are described in particular in the French patent
application filed under No. 0 450 074 and applications FR-A-2 844
710 and EP-A-1 201 221, the contents of which are incorporated by
way of reference.
[0349] The fibers can be present in the composition in a content
ranging from 0.1% to 30% by weight, with respect to the total
weight of the composition, preferably ranging from 0.1% to 20% by
weight and preferentially ranging from 0.1% to 10% by weight.
[0350] The term "physiologically acceptable medium" is intended to
denote a medium suitable in particular for the application of a
composition of the invention to the skin or its superficial body
growths.
[0351] The physiologically acceptable medium is generally suited to
the nature of the support on which the composition has to be
applied and to the appearance under which the composition has to be
packaged.
[0352] The composition according to the invention can be provided
in various forms, in particular in the form of powders (loose or
compact), of an anhydrous composition, of a dispersion, of an
emulsion, such as in particular a water/oil, water/wax, oil/water,
multiple or wax/water emulsion, or else in the form of a gel.
[0353] A composition of the invention is preferably an emulsion, in
particular a direct or inverse emulsion, or an anhydrous
composition.
[0354] A dispersion can be produced in an aqueous phase or in an
oily phase.
[0355] An emulsion can have an oily or aqueous continuous phase.
Such an emulsion can, for example, be an inverse (W/O) or direct
(0/W) emulsion, or a multiple (W/O/W or O/W/O) emulsion.
[0356] In the case of the emulsions, the inverse (W/O) emulsions
are preferred.
[0357] An anhydrous composition is a composition comprising less
than 2% by weight of water, indeed even less than 0.5% of water,
and is in particular devoid of water. If appropriate, amounts of
water which are as low can in particular be introduced by
ingredients of the composition which may comprise residual amounts
thereof.
[0358] The composition according to the invention can be provided
in the form of a fluid, for example a pasty or liquid fluid. It can
also be provided in the form of a loose or compact powder, of a
soft paste or of a cream. For example, it can be an oil-in-water,
water-in-oil or multiple emulsion, a solid emulsion, in particular
of water-in-oil type, a solid or soft gel which is in particular
anhydrous, in the loose or compact powder form and even in a
two-phase form.
[0359] The composition under consideration according to the
invention is generally provided in the form of a composition for
making up and/or caring for keratinous substances, for example of a
foundation, in particular to be applied to the face or the neck, of
a concealer, of a complexion corrector, of a tinted cream, of a
face powder or of a makeup composition for the body.
Aqueous Phase
[0360] The composition according to the invention can comprise at
least one aqueous phase.
[0361] The aqueous phase comprises water. A water suitable for the
invention can be a floral water, such as cornflower water, and/or a
mineral water, such as water from Vittel, water from Lucas or water
from La Roche Posay, and/or a thermal water.
[0362] The aqueous phase can also comprise water-miscible (at
ambient temperature -25.degree. C.) organic solvents, such as, for
example, monoalcohols having from 2 to 6 carbon atoms, such as
ethanol or isopropanol; polyols having in particular from 2 to 20
carbon atoms, preferably having from 2 to 10 carbon atoms, and
preferentially having from 2 to 6 carbon atoms, such as glycerol,
propylene glycol, butylene glycol, pentylene glycol, hexylene
glycol, dipropylene glycol or diethylene glycol; glycol ethers
(having in particular from 3 to 16 carbon atoms), such as mono-,
di- or tripropylene glycol (C.sub.1-C.sub.4)alkyl ethers or mono-,
di- or triethylene glycol (C.sub.1-C.sub.4)alkyl ethers, and their
mixtures.
[0363] The aqueous phase can additionally comprise stabilizing
agents, for example sodium chloride, magnesium dichloride and
magnesium sulfate.
[0364] The aqueous phase can also comprise any water-soluble or
water-dispersible compound compatible with an aqueous phase, such
as gelling agents, film-forming polymers, thickeners, surfactants
and their mixtures.
[0365] In particular, a composition of the invention can comprise
an aqueous phase in a content varying from 1% to 80% by weight, in
particular from 5% to 50% by weight and more particularly from 10%
to 45% by weight, with respect to the total weight of the
composition.
[0366] According to another embodiment, a composition of the
invention can be anhydrous.
[0367] An anhydrous composition can comprise less than 5% by weight
of water, with respect to the total weight of the composition, and
in particular less than 3% by weight of water, especially less than
2% by weight of water and more particularly less than 1% by weight
of water, with respect to the total weight of the composition.
[0368] More particularly, an anhydrous composition can be devoid of
water.
Fatty Phase
[0369] A cosmetic composition in accordance with the present
invention can comprise at least one liquid and/or solid fatty
phase.
[0370] In particular, a composition of the invention can comprise
at least one liquid fatty phase, in particular at least one oil, as
mentioned below.
[0371] The term "oil" is understood to mean any fatty substance in
the liquid form at ambient temperature (20-25.degree. C.) and at
atmospheric pressure.
[0372] A composition of the invention can comprise a liquid fatty
phase in a content varying from 1 to 90% by weight, in particular
from 5 to 80% by weight, in particular from 10 to 70% by weight and
more particularly from 20 to 50% by weight, with respect to the
total weight of the composition.
[0373] The oily phase suitable for the preparation of the cosmetic
compositions according to the invention can comprise oils which may
or may not be hydrocarbon, silicone or fluorinated oils, or their
mixtures.
[0374] The oils can be volatile or nonvolatile.
[0375] They can be of animal, vegetable, mineral or synthetic
origin.
[0376] Within the meaning of the present invention, the term
"volatile oil" is understood to mean an oil (or nonaqueous medium)
capable of evaporating on contact with the skin in less than one
hour at ambient temperature and at atmospheric pressure. The
volatile oil is a volatile cosmetic oil which is liquid at ambient
temperature and which has in particular a nonzero vapor pressure at
ambient temperature and at atmospheric pressure, especially which
has a vapor 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).
[0377] Within the meaning of the present invention, the term
"nonvolatile oil" is understood to mean an oil having a vapor
pressure of less than 0.13 Pa.
[0378] Within the meaning of the present invention, the term
"silicone oil" is understood to mean an oil comprising at least one
silicon atom and in particular at least one Si--O group.
[0379] The term "fluorinated oil" is understood to mean an oil
comprising at least one fluorine atom. The term "hydrocarbon oil"
is understood to mean an oil comprising mainly hydrogen and carbon
atoms.
[0380] The oils can optionally comprise oxygen, nitrogen, sulfur
and/or phosphorus atoms, for example in the form of hydroxyl or
acid radicals.
Volatile Oils
[0381] The volatile oils can be chosen from hydrocarbon oils having
from 8 to 16 carbon atoms and in particular branched
C.sub.3-C.sub.16 alkanes (also known as isoparaffins), such as
isododecane (also known as 2,2,4,4,6-pentamethylheptane),
isodecane, isohexadecane and, for example, the oils sold under the
Isopars.RTM. or Permethyl.RTM. trade names.
[0382] Use may also be made, as volatile oils, of volatile
silicones, such as, for example, volatile linear or cyclic silicone
oils, in particular those having a viscosity .ltoreq.8 centistokes
(cSt) (8.times.10.sup.-6 m.sup.2/s), and having in particular from
2 to 10 silicon atoms and especially from 2 to 7 silicon atoms,
these silicones optionally comprising alkyl or alkoxy groups having
from 1 to 10 carbon atoms. Mention may in particular be made, as
volatile silicone oil which can be used in the invention, of
dimethicones with viscosities of 5 and 6 cSt,
octamethylcyclotetrasiloxane, decamethylcyclopentasiloxane,
dodecamethylcyclohexasiloxane, heptamethylhexyltrisiloxane,
heptamethyloctyltrisiloxane, hexamethyldisiloxane,
octamethyltrisiloxane, decamethyltetrasiloxane,
dodecamethylpentasiloxane, and their mixtures.
[0383] Use may also be made of volatile fluorinated oils, such as
nonafluoromethoxybutane or perfluoromethylcyclopentane, and their
mixtures.
[0384] According to one embodiment, a composition of the invention
can comprise from 1% to 80% by weight, indeed even from 5% to 70%
by weight, indeed even from 10% to 60% by weight and in particular
from 15% to 50% by weight of volatile oil, with respect to the
total weight of the composition.
Nonvolatile Oils
[0385] The nonvolatile oils can be chosen in particular from
nonvolatile fluorinated hydrocarbon oils and/or nonvolatile
silicone oils.
[0386] Mention may in particular be made, as nonvolatile
hydrocarbon oil, of: [0387] hydrocarbon oils of animal origin, such
as perhydrosqualene, [0388] hydrocarbon oils of vegetable origin,
such as phytosteryl esters, such as phytosteryl oleate, phytosteryl
isostearate and phytosteryl/octyldodecyl lauroyl glutamate
(Ajinomoto, Eldew PS203), triglycerides composed of esters of fatty
acids and of glycerol, in particular, the fatty acids of which can
have chain lengths varying from C.sub.4 to C.sub.36 and in
particular from C.sub.18 to C.sub.36, it being possible for these
oils to be linear or branched and saturated or unsaturated; these
oils can in particular be heptanoic or octanoic triglycerides, shea
oil, alfalfa oil, poppy oil, Hokkaido squash oil, millet oil,
barley oil, quinoa oil, rye oil, candlenut oil, passionflower oil,
shea butter, aloe oil, sweet almond oil, peach kernel oil, peanut
oil, argan oil, avocado oil, baobab oil, borage oil, broccoli oil,
calendula oil, camelina oil, canola oil, carrot oil, safflower oil,
hemp oil, rapeseed oil, cottonseed oil, coconut oil, cucumber seed
oil, wheat germ oil, jojoba oil, lily oil, macadamia oil, maize
oil, meadowfoam oil, Saint John's wort oil, monoi oil, hazelnut
oil, apricot kernel oil, walnut oil, olive oil, evening primrose
oil, palm oil, blackcurrant seed oil, kiwi seed oil, grape seed
oil, pistachio oil, pumpkinseed oil, musk rose oil, sesame oil,
soybean oil, sunflower oil, castor oil and watermelon oil, and
their mixtures, or triglycerides of caprylic/capric acids, such as
those sold by Stearineries Dubois or those sold under the names
Miglyol 810.RTM., 812.RTM. and 818.RTM. by Dynamit Nobel, [0389]
linear or branched hydrocarbons of mineral or synthetic origin,
such as liquid paraffins and their derivatives, liquid petrolatum,
polydecenes, polybutenes, hydrogenated polyisobutene, such as
Parleam, or squalane, [0390] synthetic ethers having from 10 to 40
carbon atoms, [0391] synthetic esters, such as oils of formula
R.sub.1COOR.sub.2, in which R.sub.1 represents a residue of a
linear or branched fatty acid comprising from 1 to 40 carbon atoms
and R.sub.2 represents a hydrocarbon chain, in particular a
branched hydrocarbon chain, comprising from 1 to 40 carbon atoms,
provided that R.sub.1+R.sub.2 is .gtoreq.10. The esters can be
chosen in particular from fatty acid and alcohol esters, such as,
for example, cetostearyl octanoate, isopropyl alcohol esters, such
as isopropyl myristate or isopropyl palmitate, ethyl palmitate,
2-ethylhexyl palmitate, isopropyl stearate or isostearate,
isostearyl isostearate, octyl stearate, hydroxylated esters, such
as isostearyl lactate or octyl hydroxystearate, diisopropyl
adipate, heptanoates, in particular isostearyl heptanoate,
octanoates, decanoates or ricinoleates of alcohols or polyalcohols,
such as propylene glycol dioctanoate, cetyl octanoate, tridecyl
octanoate, 2-ethylhexyl palmitate and 4-diheptanoate, alkyl
benzoate, polyethylene glycol diheptanoate, propylene glycol
di(2-ethylhexanoate) and their mixtures, benzoates of
C.sub.12-C.sub.15 alcohols, hexyl laurate, esters of neopentanoic
acid, such as isodecyl neopentanoate, isotridecyl neopentanoate,
isostearyl neopentanoate or octyldodecyl neopentanoate, esters of
isononanoic acid, such as isononyl isononanoate, isotridecyl
isononanoate or octyl isononanoate, or hydroxylated esters, such as
isostearyl lactate or diisostearyl malate, [0392] esters of polyols
and esters of pentaerythritol, such as dipentaerythritol
tetrahydroxystearate/tetraisostearate, [0393] esters of dimer diols
and of dimer diacids, such as Lusplan DD-DA5.RTM. and Lusplan
DD-DA7.RTM., which are sold by Nippon Fine Chemical and are
described in application US 2004-175338, [0394] copolymers of dimer
diol and of dimer diacid and their esters, such as dimer dilinoleyl
diol/dimer dilinoleic copolymers and their esters, such as, for
example, Plandool-G, [0395] copolymers of polyols and of dimer
diacids, and their esters, such as Hailuscent ISDA, or the
dilinoleic acid/butanediol copolymer, [0396] fatty alcohols
comprising a branched and/or unsaturated carbon chain having from
12 to 26 carbon atoms which are liquid at ambient temperature, such
as 2-octyldodecanol, isostearyl alcohol, oleyl alcohol,
2-hexyldecanol, 2-butyloctanol and 2-undecylpentadecanol, [0397]
higher C.sub.12-C.sub.22 fatty acids, such as oleic acid, linoleic
acid, linolenic acid and their mixtures, and [0398] dialkyl
carbonates, it being possible for the 2 alkyl chains to be
identical or different, such as dicaprylyl carbonate, sold under
the name Cetiol CC.RTM. by Cognis, [0399] oils of high molar mass
having in particular a molar mass ranging from approximately 400 to
approximately 10 000 g/mol, in particular from approximately 650 to
approximately 10 000 g/mol, in particular from approximately 750 to
approximately 7500 g/mol and more particularly varying from
approximately 1000 to approximately 5000 g/mol. Mention may in
particular be made, as oil of high molar mass which can be used in
the present invention, of the oils chosen from: [0400] lipophilic
polymers, [0401] esters of linear fatty acids having a total carbon
number ranging from 35 to 70, [0402] hydroxylated esters, [0403]
aromatic esters, [0404] esters of fatty alcohols or of fatty acids
which are branched and comprise from 24 to 28 carbon atoms, [0405]
silicone oils, [0406] oils of vegetable origin, [0407] and their
mixtures, fluorinated oils which are optionally partially
hydrocarbon-modified and/or silicone-modified, such as
fluorosilicone oils, fluorinated polyethers or fluorosilicones,
such as described in the document EP-A-847 752; silicone oils, such
as polydimethylsiloxanes (PDMS), which are nonvolatile and linear
or cyclic; polydimethylsiloxanes comprising pendant alkyl, alkoxy
or phenyl groups or alkyl, alkoxy or phenyl groups at the end of
the silicone chain, which groups have from 2 to 24 carbon atoms; or
phenylated silicones, such as phenyl trimethicones, phenyl
dimethicones, phenyl(trimethylsiloxy)diphenylsiloxanes, diphenyl
dimethicones, diphenyl(methyldiphenyl)trisiloxanes or
(2-phenylethyl)trimethylsiloxysilicates, and their mixtures.
[0408] According to a specific embodiment, the fatty phase of the
composition according to the invention can comprise only volatile
compounds.
[0409] A composition according to the invention can comprise at
least one pasty compound.
[0410] The presence of a pasty compound can make it possible to
advantageously confer improved comfort during the deposition of a
composition of the invention on keratinous fibers.
[0411] Such a compound can advantageously be chosen from lanolin
and its derivatives; polymeric or nonpolymeric silicone compounds;
polymeric or nonpolymeric fluorinated compounds; vinyl polymers, in
particular olefin homopolymers; olefin copolymers; homopolymers and
copolymers of hydrogenated dienes; linear or branched oligomers
which are homo- or copolymers of alkyl (meth)acrylates preferably
having a C.sub.8-C.sub.30 alkyl group; oligomers which are homo-
and copolymers of vinyl esters having C.sub.8-C.sub.30 alkyl
groups; oligomers which are homo- and copolymers of vinyl ethers
having C.sub.8-C.sub.30 alkyl groups; fat-soluble polyethers
resulting from the polyetherification between one or more
C.sub.2-C.sub.100, in particular C.sub.2-C.sub.50 diols; fatty
alcohol or acid esters; and their mixtures.
[0412] Mention may in particular be made among esters, of: [0413]
esters of an oligomeric glycerol, in particular diglycerol esters,
such as polyglyceryl-2 triisostearate, condensates of adipic acid
and of glycerol, for which a portion of the hydroxyl groups of the
glycerols have reacted with a mixture of fatty acids, such as
stearic acid, capric acid, isostearic acid and 12-hydroxystearic
acid, like in particular those sold under the Softisan 649 brand by
Sasol, or such as bisdiglyceryl polyacyladipate-2; arachidyl
propionate, sold under the Waxenol 801 brand by Alzo; phytosterol
esters; triglycerides of fatty acids and their derivatives, such as
hydrogenated cocoglycerides; noncrosslinked polyesters resulting
from the 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; ester aliphatic esters resulting
from the esterification of an aliphatic hydroxycarboxylic acid
ester by an aliphatic carboxylic acid; polyesters resulting from
the esterification, by a polycarboxylic acid, of an aliphatic
hydroxycarboxylic acid ester, said ester comprising at least two
hydroxyl groups, such as the products Risocast DA-H.RTM. and
Risocast DA-L.RTM.; and their mixtures.
[0414] The pasty compound or compounds can be present in a
composition of the invention in a content ranging from 0.1 to 30%
by weight of agents, more preferably from 0.5 to 20% by weight,
with respect to the total weight of the composition.
[0415] The composition according to the invention can also comprise
ingredients commonly used in cosmetics, such as vitamins,
thickeners, trace elements, softeners, sequestering agents,
fragrances, basifying or acidifying agents, preservatives,
sunscreens, surfactants, antioxidants, agents for combating hair
loss, antidandruff agents, propellants, or their mixtures.
[0416] Of course, a person skilled in the art will take care to
choose this or these optional additional compounds and/or their
amounts so that the advantageous properties of the corresponding
composition according to the invention are not, or not
substantially, detrimentally affected by the envisioned
addition.
[0417] A composition according to the invention can in particular
be provided in the form of a composition for making up and/or
caring for the skin, in particular a foundation.
[0418] According to another aspect, the invention also relates to a
cosmetic combination comprising: [0419] i) a container delimiting
at least one compartment, said container being closed by a closing
element; and [0420] ii) a composition positioned inside said
compartment, the composition being in accordance with the
invention.
[0421] The container can have any appropriate form. It can in
particular be in the form of a bottle, a tube, a pot, a box, a tin,
a bag or a case.
[0422] The closing element can be in the form of a removable
stopper, of a lid, of a seal, of a tear-off strip or of a capsule,
in particular of the type comprising a body fixed to the container
and a cap articulated over the body. It can also be in the form of
an element providing the selective closure of the container, in
particular a pump, a valve or a flap.
[0423] The container can be used in combination with an applicator,
in particular in the form of a brush comprising an arrangement of
hairs held by a twisted wire. Such a twisted brush is described in
particular in U.S. Pat. No. 4,887,622. It can also be in the form
of a comb comprising a plurality of application elements, obtained
in particular from molding. Such combs are described, for example,
in patent FR 2 796 529. The applicator can be in the form of a fine
brush, such as described, for example, in patent FR 2 722 380. The
applicator can be in the form of a pad of foam or elastomer, of a
felt-tipped pen or of a spatula. The applicator can be free (powder
puff or sponge) or integrally attached to a rod carried by the
closing element, such as described, for example, in U.S. Pat. No.
5,492,426. The applicator can be integrally attached to the
container, such as described, for example, in patent FR 2 761
959.
[0424] The product may be contained directly in the container or
indirectly. By way of example, the product can be positioned on an
impregnated support, particularly in the form of a wipe or of a
wad, and can be positioned (singly or severally) in a tin or in a
bag. Such a support incorporating the product is described, for
example, in application WO 01/03538.
[0425] The closing element can be coupled to the container by
screwing. Alternatively, the coupling between the closing element
and the container is carried out other than by screwing, in
particular via a bayonet mechanism, by snapping, clamping, welding
or adhesive bonding, or by magnetic attraction. The term "snapping"
is understood to mean in particular any system involving the
crossing of a row or strip of material by elastic deformation of a
portion, in particular of the closing element, and then by
elastically returning said portion to the unstressed position after
the row or strip has been crossed.
[0426] The container can be at least partially made of
thermoplastic material. Mention may be made, as examples of
thermoplastic materials, of polypropylene or polyethylene.
[0427] Alternatively, the container is made of non-thermoplastic
material, in particular of glass or of metal (or alloy).
[0428] The container can have rigid walls or deformable walls, in
particular in the form of a tube or of a tube bottle.
[0429] The container can comprise means intended to bring about or
facilitate the distribution of the composition. By way of example,
the container can have deformable walls, so as to bring about the
departure of the composition in response to excess pressurization
inside the container, which excess pressurization is brought about
by the elastic (or non-elastic) crushing of the walls of the
container. Alternatively, in particular when the product is in the
form of a stick, the latter can be driven by a piston mechanism.
Still in the case of a stick, in particular of a makeup product
(foundation, and the like), the container can comprise a mechanism,
in particular a rack-and-pinion mechanism or a mechanism with a
screw rod or a mechanism with a helical groove, capable of moving a
stick in the direction of said opening. 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.
[0430] The container can be composed of a case with a bottom
delimiting at least one receptacle comprising the composition and a
lid, in particular articulated over the bottom, capable of at least
partially covering said bottom. Such a case is described, for
example, in application WO 03/018423 or in patent FR 2 791 042.
[0431] The container can be equipped with a drainer positioned in
the vicinity of the opening of the container. Such a drainer makes
it possible to wipe the applicator and optionally the rod to which
it may be integrally attached. Such a drainer is described, for
example, in patent FR 2 792 618.
[0432] The composition can be at atmospheric pressure inside the
container (at ambient temperature) or pressurized, in particular
using a propellent gas (aerosol). In the latter case, the container
is equipped with a valve (of the type of those used for
aerosols).
[0433] The contents of all the patents or patent applications
mentioned above are incorporated by reference in the present patent
application.
[0434] The composition of the invention can be provided in the form
of a product for caring for or preferably making up, in particular
in colored form, the skin, more specifically the face, such as a
foundation, a face powder, an eyeshadow, a concealer, a blush, or a
loose or compact powder, or alternatively a product for making up
the body, such as a semi-permanent tattooing product.
[0435] The composition according to the invention can be
manufactured by known processes used generally in the cosmetics
field.
[0436] The present invention also relates to a method, more
specifically a cosmetic method, for caring for or in particular
making up the skin and/or superficial body growths (in particular
hair or nails) comprising the application of a composition
according to the invention described above to the skin and/or its
superficial body growths.
[0437] The aim of the following examples is to illustrate, without
any limitation, the subject matter of the present invention. In the
patent application, the contents, unless expressly indicated
otherwise, are expressed by weight with respect to the total weight
of the composition.
EXAMPLES
Example 1
Preparation of the MQT.sup.Pr Resin
[0438] The following resins are used:
[0439] Resin MQ=an MQ resin of formula M.sub.0.43Q.sub.0.57 and
with M.sub.n=3230 dissolved in xylene at 70.8% by weight of solids.
The MQ resin was manufactured according to the techniques described
by Daudt in patent U.S. Pat. No. 2,676,182.
[0440] Propyl T resin=a propyl silsesquioxane resin at 74.8% by
weight in toluene. The propyl silsesquioxane resin was obtained by
hydrolysis of propyltrichlorosilane.
[0441] An MQ resin, a propyl T resin, xylene and 1M KOH in water,
in the proportions shown in table 1, are introduced into a
three-necked flask equipped with a stirrer, with a temperature
probe and Dean and Stark apparatus equipped with a condenser at the
top. Xylene is preintroduced into the Dean and Stark apparatus in
order to ensure that a level of solids at 50% is maintained in the
reactor. The mixture in the reactor is maintained at a reflux
temperature (between 100 and 140.degree. C.) for at least 3 hours.
Any water which is formed in the reaction mixture is continuously
removed, if appropriate, and trapped in the form of an azeotrope in
the Dean and Stark apparatus. After refluxing for 3 hours, the
water is removed from the apparatus and heating is continued for an
additional 30 minutes. After cooling the mixture, an excess of
acetic acid is added in order to neutralize the KOH in the mixture.
The mixture is subsequently filtered, in order to remove the salts
formed, by passing it through a filter under pressure. A solvent
exchange is carried out 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
spectroscopy and GPC and the results are summarized in table 2
below.
TABLE-US-00001 TABLE 1 % by % by Ratio by weight % by weight of %
by % by weight of of MQ/T.sup.Pr resins weight of propyl T weight
of weight of acetic Example # added MQ resin resin xylene 1M 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 Structure of the resin according to the % by
Example # NMR characterization weight of OH Mn Mw Mw/Mn MQ resin
M.sup.0.43Q.sup.0.57 3230 1516 4.7 Propyl T 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
Examples 2-5
W/O Emulsion
[0442] According to a specific form of the invention, use is made
of example 1-c described in example 1 above.
TABLE-US-00003 Example 3 Example 4 % by % by weight weight Example
2 (according (according Example 5 % by weight to the to the % by
weight (comparative) invention) invention) (comparative) A1
Bis-PEG/PPG-14/14 Dimethicone & Cyclopentasiloxane 1.8 1.8 1.8
1.8 (Abil EM97 from Goldschmidt) Isostearyl Diglyceryl Succinate
(Inwitor 780K from Sasol) 0.6 0.6 0.6 0.6 PEG-10 Dimethicone 0.5
0.5 0.5 0.5 Isododecane 13.32 13.32 13.32 13.32 Disteardimonium
Hectorite & Propylene Carbonate 5 5 5 5 (bentone gel ISD V from
Elementis) Dicaprylyl carbonate (Cetiol CC from Cognis) 6 6 6 6
MQ/Propyl T resin 30:70, as prepared according to example 11.38
11.38 11.38 11.38 1-c described above, in isododecane A2 Decamethyl
cyclopentasiloxane 3.5 3.5 3.5 3.5 CI 77492 & Disodium Stearoyl
Glutamate & Aluminum 1.43 1.43 1.43 1.43 Hydroxide (1) CI 77491
& Disodium Stearoyl Glutamate & Aluminum 0.46 0.46 0.46
0.46 Hydroxide (2) CI 77499 & Disodium Stearoyl Glutamate &
Aluminum 0.22 0.22 0.22 0.22 Hydroxide (3) CI 77891 & Disodium
Stearoyl Glutamate & Aluminum 7.89 7.89 7.89 7.89 Hydroxide (4)
A3 Talc -- 4 2 -- Nylon-12 8 4 4 4 Silica (and) Methicone (SB700
from Miyoshi Kasei) -- -- 2 -- Diphenyl Dimethicone/Vinyl Diphenyl
-- -- -- 4 Dimethicone/Silsesquioxane Crosspolymer (KSP300 from
Shin Etsu) B1 Demineralized water q.s. for q.s. for q.s. for q.s.
for Magnesium sulfate 0.7 0.7 0.7 0.7 Preservatives 0.3 0.3 0.3 0.3
TOTAL 100% 100% 100% 100% (1) 96.5% CI 77492 & 3.0% Disodium
Stearoyl Glutamate & 0.5% Aluminum Hydroxide, sold under the
name NAI-C33-9001-10 by Miyoshi Kasei (2) 96.5% CI 77491 & 3.0%
Disodium Stearoyl Glutamate & 0.5% Aluminum Hydroxide, sold
under the name NAI-C33-8001-10 by Miyoshi Kasei (3) 96.5% CI 77499
& 3.0% Disodium Stearoyl Glutamate & 0.5% Aluminum
Hydroxide, sold under the name NAI-C33-7001-10 by Miyoshi Kasei (4)
97% CI 77891 & 2.5% Disodium Stearoyl Glutamate & 0.5%
Aluminum Hydroxide, sold under the name NAI-TAO-77891 by Miyoshi
Kasei
[0443] Examples 3 and 4 correspond to compositions according to the
invention.
[0444] Examples 2 and 5 are comparative examples.
Procedure
[0445] The constituents of phase A2 are weighed out. The mixture is
passed through a triple roll mill. The constituents of phase A1 are
subsequently weighed out into the main beaker and the latter is
placed in a water bath (75-80.degree. C.). When the mixture is
homogeneous, it is cooled to ambient temperature.
[0446] A2 is incorporated in phase A1 with stirring with a Moritz
stirrer at 1500 revolutions/min. The constituents of phase A3 are
then successively added while retaining the same stirring.
[0447] The constituents of phase B are weighed out. Phase B is
brought to boiling, until the constituents have completely
dissolved. Phase B is cooled to 50.degree. C.
[0448] Phase B is subsequently trickled into phase A1+A2+A3 while
stirring with a Moritz stirrer at 3200 rev/min.
Protocol for Instrumental Measurements of the Immediate Mattness
and the Persistence of the Mattness
[0449] The mattness and the persistence of the mattness can be
measured using the protocol described below.
[0450] The mattness of a region of the skin, for example the face,
is measured using a polarimetric camera, which is a black and white
polarimetric imaging system, with which images are acquired in
parallel (P) and crossed (C) polarized light.
[0451] By analyzing the image resulting from the subtraction of the
two images (P-C), the shine is quantified by measuring the mean
level of gray of the 5% of shiniest pixels corresponding to the
regions of shine.
[0452] More specifically, the measurements are carried out on a
panel of individuals who are kept in an air-conditioned (22.degree.
C.+/-2.degree. C.) waiting room for 15 min before the beginning of
the test. They remove their makeup and an image of one of their
cheeks is acquired with the polarimetric camera. This image makes
it possible to measure the shine at T0 before applying makeup.
Approximately 100 mg of each cosmetic composition as prepared above
are then weighed out into a watch glass and are applied with the
bare fingers to the half of the face on which the T0 measurement
was carried out.
[0453] After a drying time of 15 min, an image of the made-up cheek
is acquired with the polarimetric camera. This image makes it
possible to measure the shine immediately after applying makeup
(Timm). The models then return to the air-conditioned room for 3
h.
[0454] Finally, an image of the made-up cheek after waiting for 3 h
is acquired with the polarimetric camera. This image makes it
possible to measure the shine after wearing makeup for 3 h (T3
h).
[0455] The results are expressed by calculating the difference
(Timm-T0), which measures the effect of the makeup. A negative
value means that the makeup reduces the shine of the skin and that
it is thus mattifying.
[0456] The difference (T3 h-Timm) measuring the persistence of this
effect is subsequently calculated. The value obtained should be as
low as possible, which means that the mattness of the makeup does
not change over time.
[0457] For the measurements carried out, it is considered that:
+ slight effect or low persistence ++ moderate effect or moderate
persistence +++ significant effect or good persistence ++++ very
significant effect or very good persistence
Protocol for Instrumental Measurements of the Immediate Color and
the Persistence of the Color
[0458] Use is made of the same protocol as above for the mattness
but, instead of measuring the shine, a colorimetric measurement of
the skin, before and after applying makeup, is carried out by
measuring the a*,b* and L* indices, namely the red and yellow
indices and the brightness.
[0459] For each woman, an image of the cheeks is taken at T0
(before applying makeup), at Timm (15 minutes after applying
makeup) and at T3 h (3 h after applying makeup), using a
chromasphere, with a definition of 410.times.410 pixels.
[0460] Each image obtained with the camera is made use of in color.
The color is quantified by the red and yellow indices, the
brightness and the color difference (respectively a*,b*, L* and
deltaE).
[0461] The deltaE, dE or .DELTA.E is defined as a measurement of
difference between two colors. The formula established in 1976 is
shown below:
.DELTA.E*= {square root over
(((L.sub.1-L.sub.2).sup.2+(a.sub.1-a.sub.2).sup.2+(b.sub.1-b.sub.2).sup.2-
)}{square root over
(((L.sub.1-L.sub.2).sup.2+(a.sub.1-a.sub.2).sup.2+(b.sub.1-b.sub.2).sup.2-
)}{square root over
(((L.sub.1-L.sub.2).sup.2+(a.sub.1-a.sub.2).sup.2+(b.sub.1-b.sub.2).sup.2-
)}, where:
L.sub.1, a.sub.1 and b.sub.1 are the coordinates in the
colorimetric space of the first color to be compared and L.sub.2,
a.sub.2 and b.sub.2 those of the second.
Results
[0462] In terms of persistence of the cosmetic properties, examples
2, 3, 4 and 5 exhibit good persistence of the cosmetic properties
(mattness and color):
(T3 h-Timm) grading +++
[0463] On the other hand, disparities are observed in terms of
comfort on application and of makeup result.
[0464] Specifically, a sensory evaluation of said compositions was
carried out on a panel of individuals who use foundation. After
free application of each composition to the face, each individual
evaluates the perception of said composition at the time of
application and in terms of makeup result. For examples 3 and 4
according to the invention, application is easy without a
"crunching" effect on the skin. The product glides perfectly under
the fingers, which makes application pleasant. The makeup finish is
soft to the touch and nontacky.
[0465] Conversely, when formulations 2 and 5, which are comparative
examples, are applied, rubbing over the skin is felt, which makes
application uncomfortable and bothersome. The makeup finish is much
less soft to the touch.
[0466] These results show that the fillers of inorganic nature,
such as talc and silica, make it possible, in combination with the
siloxane resins according to the invention, to confer good
persistence on the cosmetic properties (mattness and color) while
giving the composition good properties of comfort on application
(soft and nontacky touch), in comparison with organic fillers, such
as organic fillers of polyamide (nylon-12) type or siloxane
elastomer powders (KSP300) type. The latter can be used as
additional fillers but necessarily in combination with at least one
inorganic filler in an amount which is predominant or at least
equal to the sum of the organic fillers according to the
invention.
Example 6
Compact Powder
TABLE-US-00004 [0467] % by weight A1 Titanium dioxide CI 77891 2
Yellow iron oxide CI 77492 0.92 Red iron oxide CI 77491 0.64 Black
iron oxide CI 77499 0.1 Mica 10 A2 Magnesium stearate 2.51 Mica 20
Nylon 12 powder 20 Talc 34 B1 MQ/Propyl T resin 30:70, as prepared
according to 8 example 1-c described above, in isododecane
Polydimethylsiloxane (Viscosity: 10 cSt) (Fluid DC 200 1.23 10 cSt
from Dow Corning) Caprylic/capric triglyceride (Myritol 318 .RTM.
from Cognis) 4 B2 Preservatives 0.6 TOTAL 100%
Procedure
[0468] The constituents of phase A1 are weighed out.
[0469] The constituents of phase A2 are weighed out. Phases A1 and
A2 are added to a mixer of Lodige type over 10 minutes.
[0470] The constituents of phase B1 are successively added and then
homogenized in the Lodige mixer for 10 minutes.
[0471] Finally, phase B2 is added and homogenization is carried out
with the mixer for 3 minutes. The composition is sieved using a 250
.mu.m sieve.
[0472] Finally, the composition is passed through a mill of Alpine
type.
Example No. 7
Foundation Powder
TABLE-US-00005 [0473] Example No. 6 A Pigments 10 Talc 64.7 Nylon
powder 10 Preservative 0.3 B Parleam oil 8 Resin as described in 10
WO 2005/075542* *MQ/Propyl T resin 30:70, as prepared according to
example 1-c described above, in isododecane
Procedure
[0474] The starting materials of phase A are weighed out and
homogenization is carried out with a mixer for 10 minutes.
[0475] The starting materials of phase B are weighed out, which
phase is added to phase A.
[0476] The mixture is homogenized with the mixer for 3 minutes.
[0477] The mixture A+B is passed through an Alpine mill.
* * * * *