U.S. patent application number 13/132497 was filed with the patent office on 2012-04-26 for cosmetic composition for makeup and/or keratin material care, based on a mixture of resins mq and t-pr, and makeup method.
This patent application is currently assigned to L'OREAL. Invention is credited to Claudia Barba, Roberto Cavazzuti, Veronique Ferrari, Audrey Ricard.
Application Number | 20120100089 13/132497 |
Document ID | / |
Family ID | 40765715 |
Filed Date | 2012-04-26 |
United States Patent
Application |
20120100089 |
Kind Code |
A1 |
Barba; Claudia ; et
al. |
April 26, 2012 |
COSMETIC COMPOSITION FOR MAKEUP AND/OR KERATIN MATERIAL CARE, BASED
ON A MIXTURE OF RESINS MQ AND T-PR, AND MAKEUP METHOD
Abstract
The present invention relates to a composition that includes, in
a physiologically acceptable medium: A) a siloxane resin containing
at least 80 mol % of the following units: (i)
(R'.sub.3SiO.sub.1/2).sub.a and (ii) (SiO.sub.4/2).sub.b where R'
is, independently, an alkyl grouping having 1 to 8 carbon atoms, an
aryl grouping, a carbinol grouping, or an amino grouping with the
proviso that at least 95 mol % of the R' groups are alkyl groups; a
and b have values strictly greater than 0; and the ratio of a to b
is between 0.5 and 1.5; B) a propyl silsesquioxane resin containing
at least 80 mol % of (R''SiC>.sub.3/2) units where R'' is,
independently, an alkyl grouping having 1 to 8 carbon atoms, an
aryl grouping, a carbinol grouping, or an amino grouping with the
proviso that at least 80 mol % of the R'' groups are propyl groups,
the weight ratio between the resins a) and b) being between 1/99
and 99/1, but particularly between 85/15 and 15/85 the resins a)
and b) not being bonded to each other by covalent bonds, and the
number of M units in the final mixture being strictly less than the
number of (T+Q) units; and C) at least one film-forming polymer
selected from among the group including: an ethylene sequential
copolymer (also called an ethylene sequential polymer) containing
at least one first sequence having a vitreous transition
temperature (Tg) greater than or equal to 400.degree. C. and
derived, in whole or in part, from one or more first monomers, such
that the homopolymer prepared from said monomers at a vitreous
transition temperature less than or equal to 400.degree. C., and
from at least one second sequence having a vitreous transition
temperature less than or equal to 20.degree. C. and derived, in
whole or in part, from one or more second monomers, such that the
homopolymer prepared from said monomers has a vitreous transition
temperature less than or equal to 200.degree. C., said first
sequence and said second sequence being bonded together by an
intermediate statistical segment that contains at least one of said
first monomers that constitutes the first sequence and at least one
of said second monomers that constitutes the second sequence, and
said copolymer sequence having a polydispersity index I greater
than 2; and a vinyl polymer containing at least one pattern derived
from dendrimer carboxilane, a dispersion of radical, acrylic, or
vinyl homopolymer or copolymer particles being dispersed in said
liquid fatty phase.
Inventors: |
Barba; Claudia; (Paris,
FR) ; Cavazzuti; Roberto; (Paris, FR) ;
Ferrari; Veronique; (Maisons Alfort, FR) ; Ricard;
Audrey; (La Varenne, FR) |
Assignee: |
L'OREAL
Paris
FR
|
Family ID: |
40765715 |
Appl. No.: |
13/132497 |
Filed: |
December 2, 2009 |
PCT Filed: |
December 2, 2009 |
PCT NO: |
PCT/FR2009/052393 |
371 Date: |
December 16, 2011 |
Related U.S. Patent Documents
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Application
Number |
Filing Date |
Patent Number |
|
|
61120863 |
Dec 9, 2008 |
|
|
|
Current U.S.
Class: |
424/63 ; 424/64;
424/70.121 |
Current CPC
Class: |
A61K 8/891 20130101;
A61Q 1/12 20130101; A61K 2800/594 20130101; A61K 8/585 20130101;
A61K 8/06 20130101; A61Q 1/06 20130101; A61Q 1/10 20130101; A61Q
1/02 20130101; A61K 8/894 20130101; A61K 8/064 20130101 |
Class at
Publication: |
424/63 ; 424/64;
424/70.121 |
International
Class: |
A61K 8/58 20060101
A61K008/58; A61Q 1/04 20060101 A61Q001/04; A61Q 5/00 20060101
A61Q005/00; A61Q 1/02 20060101 A61Q001/02 |
Foreign Application Data
Date |
Code |
Application Number |
Dec 2, 2008 |
FR |
0858195 |
Claims
1. A composition comprising, in a physiologically acceptable
medium: a siloxane resin, a silsesquioxane resin, and at least one
film-forming polymer, wherein: the siloxane resin comprises at
least 80 mol % of: at least one M unit,
(R'.sub.3SiO.sub.1/2).sub.a; and at least one Q unit,
(SiO.sub.4/2).sub.b; R' independently represents an alkyl group
comprising 1 to 8 carbon atoms, an aryl group, a carbinol group or
an amino group; at least 95 mol % of the R' groups are alkyl
groups; a and b are greater than 0; a ratio of a/b is between 0.5
and 1.5; the silsesquioxane resin comprises at least 80 mol % of at
least one T unit, (R''SiO.sub.3/2); R'' independently represents an
alkyl group comprising 1 to 8 carbon atoms, an aryl group, a
carbinol group or an amino group; at least 80 mol % of the R''
groups are propyl groups; a weight ratio of the siloxane resin to
the silsesquioxane resin is between 1/99 and 99/1; the siloxane
resin and the silsesquioxane resin are not bonded to one another by
covalent bonds; the number of the at least one M unit is less than
the number of the at least one T unit plus the at least one Q unit;
and the at least one film-forming polymer is at least one polymeric
form selected from the group consisting of: (i) a sequenced
ethylene copolymer comprising: at least one first sequence with a
glass transition temperature (Tg) higher than or equal to
40.degree. C. and obtained completely or partly from at least one
first monomer, wherein a homopolymer prepared from the at least one
first monomer has a glass transition temperature higher than or
equal to 40.degree. C.; and at least one second sequence with a
glass transition temperature lower than or equal to 20.degree. C.
and obtained completely or partly from at least one second monomer,
wherein a homopolymer prepared from the at least one second monomer
has a glass transition temperature lower than or equal to
20.degree. C., wherein: the at least one first sequence and the at
least one second sequence are bonded together by a statistical
intermediate segment comprising at least one of the at least one
first monomer and at least one of the at least one second mononer;
and the sequenced ethylene copolymer has a polydispersity index I
greater than 2; (ii) a vinyl polymer comprising at least one moiety
derived from a carbosiloxane dendrimer; and (iii) a dispersion of
particles of an acrylic or vinyl radical homopolymer or copolymer
dispersed in a liquid fatty phase.
2. A composition comprising, in a physiologically acceptable
medium: a siloxane resin, a film-forming silsesquioxane resin, and
at least one film-forming polymer, wherein: the siloxane resin
comprises at least 80 mol % of: at least one M unit,
(R'.sub.3SiO.sub.1/2).sub.a; and at least one Q unit,
(SiO.sub.4/2).sub.b; R' independently represents an alkyl group
comprising 1 to 8 carbon atoms, an aryl group, a carbinol group or
an amino group; at least 95 mol % of the R' groups are alkyl
groups; a and b are greater than 0; a ratio of a/b is between 0.5
and 1.5; the film-forming silsesquioxane resin comprises at least
80 mol % of at least one T unit, (R''SiO.sub.3/2); R''
independently represents an alkyl group comprising 1 to 8 carbon
atoms, an aryl group, a carbinol group or an amino group; at least
40 mol % of the R'' groups are propyl groups; a weight ratio of the
siloxane resin to the film-forming silsesquioxane resin is between
1/99 and 99/1; the siloxane resin and the film-forming
selsesquioxane resin are not bonded to one another by covalent
bonds; the number of the at least one M unit is less than the
number of the at least one T unit plus the at least one Q unit; and
the at least one film-forming polymer is at least one polymeric
form selected from the group consisting of: (i) a sequenced
ethylene copolymer comprising: at least one first sequence with a
glass transition temperature (Tg) higher than or equal to
40.degree. C. and obtained completely or partly from at least one
first monomer, wherein a homopolymer prepared from the at least one
first monomer has a glass transition temperature higher than or
equal to 40.degree. C.; and at least one second sequence with a
glass transition temperature lower than or equal to 20.degree. C.
and obtained completely or partly from at least one second monomer,
wherein a homopolymer prepared from the at least one second monomer
has a glass transition temperature lower than or equal to
20.degree. C., wherein: the at least one first sequence and the at
least one second sequence are bonded together by a statistical
intermediate segment comprising at least one of the at least one
first monomer and at least one of the at least one second mononer;
and the sequenced ethylene copolymer has a polydispersity index I
greater than 2; (ii) a vinyl polymer comprising at least one moiety
derived from a carbosiloxane dendrimer; and (iii) a dispersion of
particles of an acrylic or vinyl radical homopolymer or copolymer
dispersed in a liquid fatty phase.
3. A composition comprising, in a physiologically acceptable
medium: a siloxane resin, a silsesquioxane resin, and at least one
film-forming polymer, wherein: the siloxane resin comprises at
least 80 mol % of: at least one M unit,
(R'.sub.3SiO.sub.1/2).sub.a; and at least one Q unit,
(SiO.sub.4/2).sub.b; R' independently represents an alkyl group
comprising 1 to 8 carbon atoms, an aryl group, a carbinol group or
an amino group; at least 95 mol % of the R' groups are alkyl
groups; a and b are greater than 0; a ratio of a/b is between 0.5
and 1.5; the silsesquioxane resin comprises at least 80 mol % of at
least one T unit, (R''SiO.sub.3/2); R'' independently represents an
alkyl group comprising 1 to 8 carbon atoms, an aryl group, a
carbinol group or an amino group; at least 40 mol % of the R''
groups are propyl groups; a weight ratio of the siloxane resin to
the silsesquioxane resin is between 1/99 and 99/1; the siloxane
resin and the silsequioxane resin are not bonded to one another by
covalent bonds; the number of the at least one M unit is less than
the number of the at least one T unit plus the at least one Q unit;
and the at least one film-forming polymer is at least one polymeric
form selected from the group consisting of: (i) a sequenced
ethylene copolymer comprising: at least one first sequence with a
glass transition temperature (Tg) higher than or equal to
40.degree. C. and obtained completely or partly from at least one
first monomer, wherein a homopolymer prepared from the at least one
first monomer has a glass transition temperature higher than or
equal to 40.degree. C.; and at least one second sequence with a
glass transition temperature lower than or equal to 20.degree. C.
and obtained completely or partly from at least one second monomer,
wherein a homopolymer prepared from the at least one second monomer
has a glass transition temperature lower than or equal to
20.degree. C., wherein: the at least one first sequence and the at
least one second sequence are bonded together by a statistical
intermediate segment comprising at least one of the at least one
first monomer and at least one of the at least one second mononer;
and the sequenced ethylene copolymer has a polydispersity index I
greater than 2; (ii) a vinyl polymer comprising at least one moiety
derived from a carbosiloxane dendrimer; and (iii) a dispersion of
particles of an acrylic or vinyl radical homopolymer or copolymer
dispersed in a liquid fatty phase.
4. (canceled)
5. (canceled)
6. (canceled)
7. The composition of claim 1, wherein the siloxane resin further
comprises at least one residual silanol group, --SiOH, in a
proportion between 2 and 10% by weight of the siloxane resin.
8. The composition of claim 1, wherein the silsesquioxane resin
further comprises at least one unit selected from the group
consisting of a residual silanol group, --SiOH, and an alkoxy
group, wherein: the residual silanol group, --SiOH, is present in
the composition in a proportion between 2 and 10% by weight of the
silsesquioxane resin; and the alkoxy group is present in the
composition in a proportion smaller than or equal to 20% by weight
of the silsesquioxane resin.
9. The composition of claim 1, wherein R' independently represents:
an alkyl group comprising 1 to 8 carbon atoms selected from at
least one group consisting of methyl, ethyl, propyl, butyl, pentyl,
hexyl and octyl; an aryl group selected from at least one group
consisting of phenyl, naphthyl, benzyl, tolyl, xylyl, xenyl,
methylphenyl, 2-phenylethyl, 2-phenyl-2-methylethyl, chlorophenyl,
bromophenyl and fluorophenyl; a carbinol group selected from at
least one group consisting of: (1) formula R.sup.1OH, wherein
R.sup.1 represents a bivalent hydrocarbon group comprising at least
3 carbon atoms or a bivalent hydrocarbonoxy group containing at
least 3 carbon atoms; and (2) formula R.sup.2OH, wherein R.sup.2
represents: (i) an arylene group
--(CH.sub.2).sub.xC.sub.6H.sub.4--, x having a value between 0 and
10; (ii) --CH.sub.2CH(CH.sub.3)(CH.sub.2).sub.xC.sub.6H.sub.4--, x
having a value between 0 and 10; and (iii)
--(CH.sub.2).sub.xC.sub.6H.sub.4(CH.sub.2).sub.x--, x having a
value between 1 and 10; and an amino group selected from at least
one group consisting of: (1) --R.sup.3NH.sub.2; and (2)
--R.sup.3NHR.sup.4NH.sub.2, wherein: R.sup.3 represents a bivalent
hydrocarbon comprising at least 2 carbon atoms; and R.sup.4
represents a bivalent hydrocarbon comprising at least 2 carbon
atoms.
10. The composition of claim 9, wherein the R.sup.1 group is at
least one moiety selected from the group consisting of: an alkylene
group --(CH.sub.2).sub.x--, x having a value 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--, x having a value between 1
and 10.
11. The composition of claim 9, wherein the R.sup.3 and R.sup.4
groups are at least one moiety selected from group consisting of
ethylene, propylene, --CH.sub.2CHCH.sub.3--, butylene,
--CH.sub.2CH(CH.sub.3)CH.sub.2--, pentamethylene, hexamethylene,
3-ethylhexamethylene, octamethylene and decamethylene.
12. The composition of claim 9, wherein the amino group is at least
one moiety selected from the group consisting of:
--CH.sub.2CH.sub.2CH.sub.2NH.sub.2;
--CH.sub.2(CH.sub.3)CHCH.sub.2(H)N(CH).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.
13. The composition of claim 1, wherein R' represents a methyl
group.
14. The composition of claim 1, wherein at least 90 mol % of the
R'' groups are propyl groups.
15. The composition of claim 1, wherein the sequenced ethylene
copolymer comprises an intermediate sequence comprising: at least
one constituent monomer of the at least one first sequence; and at
least one constituent monomer of the at least one second sequence,
wherein: the sequenced ethylene copolymer has a polydispersity
index greater than 2; the at least one second sequence is obtained
from acrylic acid and isobutyl acrylate; and the at least one first
sequence is obtained from isobornyl acrylate and isobornyl
methacrylate.
16. The composition of claim 1, wherein the at least one moiety
derived from a carbosiloxane dendrimer comprises at least one
dendritic carbosiloxane structure represented by formula (I):
##STR00127## wherein: Z is a divalent organic group; p is 0 or 1;
R.sup.1 is an aryl or alkyl group comprising 1 to 10 carbon atoms;
and X.sup.1 is a silylalkyl group represented by formula (II):
##STR00128## wherein: R.sup.1 is an aryl or alkyl group comprising
1 to 10 carbon atoms; R.sup.2 is an alkylene group comprising 1 to
10 carbon atoms; R.sup.3 is an alkyl group comprising 1 to 10
carbon atoms; and X.sup.i+1 is a at least one moiety selected from
the group consisting of: a hydrogen atom; an aryl group; an alkyl
group comprising up to 10 carbon atoms; and the silylalkyl group,
X.sup.i, wherein the exponent "i" is an integer from 1 to 10,
indicating the generation of the silylalkyl group beginning in each
dendritic carbosiloxane structure with a value of 1 for the group
X.sup.i in formula (I); and a.sup.i is an integer from 0 to 3.
17. The composition of claim 1, wherein the particles of the
acrylic or vinyl radical homopolymer or copolymer in the dispersion
of particles (iii) are: acrylic polymers or copolymers; insoluble
in the water-soluble alcohols.
18. The composition of claim 1, wherein the content of the at least
one film-forming polymer is 0.1 to 60% by weight as dry material of
the film-forming polymer.
19. The composition of claim 1, further comprising at least one
additional ingredient selected from the group consisting of a pasty
compound of non-animal origin, a fatty-phase thickening agent or a
gelling rheological agent, a wax, a hydrophilic gelling agent, a
filler, a film-forming polymer, an ionic surfactant, and a fiber,
wherein: the fatty-phase thickening agent or the gelling
rheological agent are not dimethicone crosspolymers; the wax is not
candelilla wax, ozokerite or silicone wax; and the ionic surfactant
is not lauryl ether sulfate.
20. A method for makeup and/or cosmetic care of at least one horny
tissue, comprising applying the composition of claim 1 on the at
least one horny tissues.
21. The composition of claim 3, wherein the siloxane resin and the
silsesquioxane resin are obtained by a process comprising: (1)
mixing a solution of the siloxane resin with a solution of the
silsesquioxane resin; then (2) heating a resulting mixture for at
least 1 hour between 90.degree. C. and 250.degree. C. without a
catalyst for chemical condensation of the two resins.
22. The composition of claim 21, wherein a partial or complete
distillation of at least one aromatic solvent is carried out during
or after the mixing (1) while replacing the aromatic solvent with a
cosmetically acceptable volatile solvent.
23. The composition of claim 3, wherein the siloxane resin and the
silsesquioxane resin are formulated by: (1) mixing a solution of
the siloxane resin with a solution of the silsesquioxane resin,
then (2) heating a resulting mixture in an extruder for at least 10
minutes between 90.degree. C. and 250.degree. C. without a catalyst
for chemical condensation of the two resins.
24. The composition of claim 23, wherein a partial or complete
distillation of at least one aromatic solvent is carried out during
or after the mixing (1), while discharging a mixture of resins
directly in the solid state.
25. The composition of claim 1, wherein the weight ratio of the
siloxane resin to the silsesquioxane resin is between 85/15 and
15/85.
26. The method of claim 20, the method applied to at least one
horny tissue of the lips.
Description
[0001] The invention relates to a cosmetic composition intended for
horny tissues, especially the lips and skin, the hair and nails.
The invention relates in particular to makeup compositions for the
said horny tissues, comprising at least one siloxane resin and at
least one film-forming polymer.
[0002] One of the objectives of the application is to provide
makeup compositions intended for horny tissues (skin, mucous
membranes, fiber, eyelashes and integument) permitting deposition
of a totally non-transfer film with good comfort and a good level
of gloss, particularly in the case of lipstick.
[0003] In the field of lipstick and of makeup in general, the
formulator is on the lookout for compositions that have good
staying power, so as to satisfy the expectations of the consumers.
These compositions must also be of non-transfer nature, while
offering good comfort properties.
[0004] The formulator is therefore on the lookout for raw materials
and/or systems that make it possible to obtain compositions
characterized by improved staying power and by a good level of
comfort when they are deposited. By comfort there will be
understood comfort upon application, or in other words a
composition that is deposited easily in terms of gliding and of
deposited amount, while the deposited film is not too thick and/or
not too tacky. By comfort there will also be understood comfort
after application, such that the user does not feel any tugging or
drying out in particular.
[0005] The person skilled in the art knows to use polymers to
obtain these properties of staying power in the course of the
day.
[0006] These polymers have very different chemical natures and are
conveyed either in a fatty phase or in an aqueous phase.
[0007] By way of examples there can be cited the silicone resins,
especially of MQ type, the polyacrylates, the latexes, etc.
[0008] Although these polymers effectively impart properties of
staying power, especially of non-transfer, they are most often
accompanied by discomfort either during application of the product
(difficult spreading, sticking, etc.) or in the course of the day
(tugging, mask effect, etc.).
[0009] It is therefore necessary to seek a technical solution that
makes it possible to obtain these properties of staying power while
preserving comfortable use.
[0010] This objective is achieved by virtue of the compositions
according to the invention.
[0011] The object of the present invention is effectively a
composition comprising, in a physiologically acceptable medium:
[0012] a) a siloxane resin comprising at least 80 mol % of the
units: [0013] (i) (R'.sub.3SiO.sub.12).sub.a (hereinafter "M"
units) and [0014] (ii) (SiO.sub.4/2).sub.b (hereinafter "Q" units)
[0015] wherein [0016] R' independently represents an alkyl group
having 1 to 8 carbon atoms, an aryl group, a carbinol group or an
amino group, [0017] with the proviso that at least 95 mol % of the
R' groups are alkyl groups, [0018] a and b have values strictly
greater than 0; [0019] and the a/b ratio ranges between 0.5 and
1.5, [0020] and [0021] b) a propyl silsesquioxane resin comprising
at least 80 mol % of (R''SiO.sub.3/2) units (hereinafter "T"
units), in which R'' independently represents an alkyl group having
1 to 8 carbon atoms, an aryl group, a carbinol group or an amino
group, with the proviso that at least 80 mol % of the R'' groups
are propyl groups, [0022] the weight ratio between resins a) and b)
being between 1/99 and 99/1, particularly between 85/15 and 15/85,
[0023] resins a) and b) not being bonded to one another by covalent
bonds, [0024] and the number of M units of the final mixture being
strictly smaller than the number of (T+Q) units, [0025] and [0026]
c) at least one film-forming polymer, preferably chosen from among
the group comprising: [0027] a sequenced ethylene copolymer (also
referred to as sequenced ethylene polymer), containing at least one
first sequence having a glass transition temperature (Tg) higher
than or equal to 40.degree. C. and being obtained completely or
partly from one or more first monomers, which are such that the
homopolymer prepared from these monomers has a glass transition
temperature higher than or equal to 40.degree. C., and at least one
second sequence having a glass transition temperature lower than or
equal to 20.degree. C. and being obtained completely or partly from
one or more second monomers, which are such that the homopolymer
prepared from these monomers has a glass transition temperature
lower than or equal to 20.degree. C., the said first sequence and
the said second sequence being bonded together by a statistical
intermediate segment comprising at least one of the said first
constituent monomers of the first sequence and at least one of the
said second constituent monomers of the second sequence, and the
said sequenced copolymer having a polydispersity index I greater
than 2, [0028] a vinyl polymer comprising at least one moiety
derived from carbosiloxane dendrimer, [0029] a dispersion of
particles of acrylic or vinyl radical homopolymer or copolymer
dispersed in the said liquid fatty phase.
[0030] The compositions according to the invention may also
comprise an additional ingredient, preferably chosen from among
pasty compounds of non-animal origin, fatty-phase thickening or
gelling rheological agents, waxes, hydrophilic gelling agents,
fillers, ionic surfactants, fibers and mixtures thereof.
[0031] Preferably, the compositions according to the invention may
comprise at least one additional ingredient, preferably chosen from
among pasty compounds of non-animal origin, fatty-phase thickening
or gelling rheological agents with the exception of dimethicone
cross-polymers, waxes with the exception of candelilla wax, of
ozokerite and of the silicone waxes, hydrophilic gelling agents,
fillers, ionic surfactants with the exception of lauryl ether
sulfate, fibers and mixtures thereof.
[0032] In particular, according to one embodiment, the waxes are
chosen from among beeswax, lanolin wax and Chinese insect wax; rice
wax, carnauba wax, ouricurry wax, esparto grass wax, cork fiber
wax, sugar cane wax, Japan wax and sumac wax; montan wax,
microcrystalline waxes, paraffins; polyethylene waxes, waxes
obtained by Fisher-Tropsch synthesis, waxes obtained by catalytic
hydrogenation of animal or vegetable oils having fatty, linear or
branched C8-C32 chains, fluoro waxes, wax obtained by hydrogenation
of olive oil esterified with stearyl alcohol, waxes obtained by
hydrogenation of castor oil esterified with cetyl alcohol, and
tacky waxes. Preferably, the ionic surfactants are chosen from
among cationic surfactants, amphoteric surfactants, carboxylates,
taurates and N-acyl N-methyltaurates, alkylsulfoacetates,
polypeptides, anionic derivatives of alkyl polyglycoside,
amine-derived salts of C16-C30 fatty acids, salts of
polyoxyethylenated fatty acids, phosphoric acids and their salts,
sulfosuccinates, alkyl sulfates, isethionates and
N-acylisethionates, acylglutamates, soy derivatives, citrates,
proline derivatives, lactylates, sarcosinates, sulfonates and
glycinates.
[0033] Preferably, the fatty-phase thickening or gelling
rheological agents are chosen from among crystalline polymers,
mineral lipophilic structuring agents, lipophilic polyamides,
lipophilic polyureas and polyurethanes, silicone polymers
comprising, as the case may be, at least one hydrocarbon moiety
composed of two groups capable of establishing hydrogen
interactions chosen from among ester, amide, sulfonamide,
carbamate, thiocarbamate, urea, urethane, thiourea, oxamido,
guanidino, biguanidino groups and combinations thereof, organo
gelling agents, block polymers, cholesteric liquid crystal agents,
dimethicone/vinyldimethicone copolymers and vinyldimethicone/alkyl
dimethicone copolymers, such as vinyldimethicone/lauryl dimethicone
copolymers.
[0034] Another object of the present invention is a composition
comprising, in a physiologically acceptable medium: [0035] a) a
siloxane resin comprising at least 80 mol % of the units: [0036]
(i) (R'.sub.3SiO.sub.1/2).sub.a (hereinafter "M" units) and [0037]
(ii) (SiO.sub.4/2).sub.b (hereinafter "Q" units) [0038] wherein
[0039] R' independently represents an alkyl group having 1 to 8
carbon atoms, an aryl group, a carbinol group or an amino group,
[0040] with the proviso that at least 95 mol % of the R' groups are
alkyl groups, [0041] a and b have values strictly greater than 0;
[0042] and the a/b ratio ranges between 0.5 and 1.5, [0043] and
[0044] b) a film-forming propyl silsesquioxane resin comprising at
least 80 mol % of (R''SiO.sub.3/2) units (hereinafter "T" units),
in which R'' independently represents an alkyl group having 1 to 8
carbon atoms, an aryl group, a carbinol group or an amino group,
with the proviso that at least 40 mol % of the R'' groups are
propyl groups, [0045] the weight ratio between resins a) and b)
being between 1/99 and 99/1, particularly between 85/15 and 15/85,
[0046] resins a) and b) not being bonded to one another by covalent
bonds, [0047] and the number of M units of the final mixture being
strictly smaller than the number of (T+Q) units, [0048] and [0049]
c) at least one film-forming polymer, preferably chosen from among
the group comprising: [0050] a sequenced ethylene copolymer (also
referred to as sequenced ethylene polymer), containing at least one
first sequence having a glass transition temperature (Tg) higher
than or equal to 40.degree. C. and being obtained completely or
partly from one or more first monomers, which are such that the
homopolymer prepared from these monomers has a glass transition
temperature higher than or equal to 40.degree. C., and at least one
second sequence having a glass transition temperature lower than or
equal to 20.degree. C. and being obtained completely or partly from
one or more second monomers, which are such that the homopolymer
prepared from these monomers has a glass transition temperature
lower than or equal to 20.degree. C., the said first sequence and
the said second sequence being bonded together by a statistical
intermediate segment comprising at least one of the said first
constituent monomers of the first sequence and at least one of the
said second constituent monomers of the second sequence, and the
said sequenced copolymer having a polydispersity index I greater
than 2, [0051] a vinyl polymer comprising at least one moiety
derived from carbosiloxane dendrimer, [0052] a dispersion of
particles of acrylic or vinyl radical homopolymer or copolymer
dispersed in the said liquid fatty phase.
[0053] Siloxane resin a), referred to as "MQ resin" hereinafter,
preferably comprises residual silanol groups (--SiOH). In this
case, the quantity of --OH groups preferably ranges between 2 and
10% by weight of the MQ resin, preferably between 2 and 5% by
weight of the MQ resin. Preferably, the R' groups of the MQ resin
are methyl groups.
[0054] Resin b), referred to as "propyl T resin" hereinafter,
preferably comprises residual silanol groups (--SiOH) and/or alkoxy
groups. In this case, the quantity of --OH groups preferably ranges
between 2 and 20% by weight of the propyl T resin, and/or the
quantity of alkoxy groups is smaller than or equal to 20% by weight
of the propyl T resin. Preferably, the quantity of --OH groups
ranges between 6 and 8% by weight of the propyl T resin, and/or the
quantity of alkoxy groups is smaller than or equal to 10% by weight
of the propyl T resin.
[0055] The propyl T resin according to the invention is such that
at least 40 mol % of the R'' groups are propyl groups; preferably
at least 50 mol %, and more preferentially at least 90 mol %.
[0056] By covalent bond there is understood a chemical bond between
at least 2 atoms (carbon, silicon, oxygen, etc.) in which each of
the bonded atoms commonly contributes an electron of one of its
outer layers in order to form an electron pair bonding the two
atoms.
[0057] The MQ resin according to the invention comprises at least
80 mol % of the units: [0058] (i) (R'.sub.3SiO.sub.1/2).sub.a
(hereinafter "M" units) and [0059] (ii) (SiO.sub.4/2).sub.b
(hereinafter "Q" units) [0060] wherein [0061] R' independently
represents an alkyl group having 1 to 8 carbon atoms, an aryl
group, a carbinol group or an amino group, [0062] with the proviso
that at least 95 mol % of the R' groups are alkyl groups, [0063] a
and b have values strictly greater than 0; [0064] and the a/b ratio
ranges between 0.5 and 1.5.
[0065] The R' radical of the MQ resin independently represents an
alkyl group having 1 to 8 carbon atoms, an aryl group, a carbinol
group or an amino group.
[0066] The alkyl groups may be chosen in particular from among the
methyl, ethyl, propyl, butyl, pentyl, hexyl and octyl groups.
Preferably the alkyl group is a methyl group.
[0067] The aryl groups may be chosen from among the phenyl,
naphthyl, benzyl, tolyl, xylyl, xenyl, methylphenyl, 2-phenylethyl,
2-phenyl-2-methylethyl, chlorophenyl, bromophenyl and fluorophenyl
groups, the aryl group preferentially being a phenyl group.
[0068] In the present invention, "carbinol group" is understood as
any group containing at least one hydroxyl radical bonded to a
carbon (COH). The carbinol groups may therefore contain more than
one COH radical, such as, for example
##STR00001##
[0069] If the carbinol group is free of aryl groups, it contains at
least 3 carbon atoms. If the carbinol group comprises at least one
aryl group, it contains at least 6 carbon atoms.
[0070] As examples of carbinol groups free of aryl groups and
containing at least 3 carbon atoms there can be cited the groups of
formula R.sup.1OH, in which R.sup.1 represents a bivalent
hydrocarbon radical containing at least 3 carbon atoms or a
bivalent hydrocarbonoxy radical containing at least 3 carbon atoms.
As examples of the R.sup.1 group there can be cited alkylene
radicals such as --(CH.sub.2).sub.x--, the value of x ranging
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 ranging
between 1 and 10.
[0071] As examples of carbinol groups containing aryl groups having
at least 6 carbon atoms there can be cited the groups of formula
R.sup.2OH, in which R.sup.2 represents an arylene radical such as
--(CH.sub.2).sub.xC.sub.6H.sub.4--, x having a value between 0 and
10, --CH.sub.2CH(CH.sub.3)(CH.sub.2).sub.xC.sub.6H.sub.4--, x
having a value between 0 and 10,
--(CH.sub.2).sub.xC.sub.6H.sub.4(CH.sub.2).sub.x--, x having a
value between 1 and 10. The carbinol groups containing aryl groups
generally contain 6 to 14 atoms.
[0072] By amino group according to the invention, there is
understood in particular groups of formula --R'NH.sub.2 or
--R.sup.3NHR.sup.4NH.sub.2, R.sup.3 representing a bivalent
hydrocarbon radical having at least 2 carbon atoms and R.sup.4
representing a bivalent hydrocarbon radical having at least 2
carbon atoms. The R.sup.3 group generally represents an alkylene
radical having 2 to 20 carbon atoms. As examples of R.sup.3 groups
there can be cited 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. The R.sup.4 group generally represents an
alkylene radical having 2 to 20 carbon atoms. As examples of
R.sup.4 groups there can be cited 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.
[0073] The amino groups are generally
--CH.sub.2CH.sub.2CH.sub.2NH.sub.2 and
--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.
[0074] MQ resins suitable for use as component a), as well as their
manufacturing methods, are known in the prior art. U.S. Pat. No.
2,814,601 of Currie et al., dated 26 Nov. 1957, incorporated into
the present document by reference, describes a method for
manufacturing MQ resins by transformation of a water-soluble
silicate into a silicic acid monomer or a silicic acid oligomer by
using an acid. Once adequate polymerization has been achieved,
trimethylchlorosilane terminal groups are introduced to obtain the
MQ resin. Another method for preparation of MQ resins is described
in U.S. Pat. No. 2,857,356 of Goodwin, dated 21 Oct. 1958,
incorporated into the present document by reference. Goodwin
describes a method for manufacturing an MQ resin by cohydrolysis of
a mixture of an alkyl silicate and of an organopolysiloxane
trialkylsilane capable of being hydrolyzed by water.
[0075] The MQ resins suitable as component a) in the present
invention may contain D and T units, with the proviso that at least
80 mol %, even 90 mol % of the total siloxane units are M and Q
units. The MQ resins may also contain residual hydroxy groups as
mentioned hereinabove. The MQ resins may also contain additional
terminal groups, in which case the residual hydroxy groups are made
to react with appropriate M groups.
[0076] Propyl T resin b) according to the invention comprises at
least 80 mol % of (R''SiO.sub.3/2) units, in which R''
independently represents an alkyl group having 1 to 8 carbon atoms,
an aryl group, a carbinol group or an amino group, with the proviso
that at least 40 mol % of the R'' groups are propyl groups.
[0077] Preferably, the propyl T resin according to the invention is
such that at least 50 mol % of the R'' groups are propyl groups,
preferably at least 90 mol %.
[0078] Preferably, propyl T resin b) is film-forming. By
"film-forming resin" there is understood a resin capable of
forming, on its own or in the presence of an auxiliary filmifying
agent, a macroscopically continuous film that adheres to horny
tissues, and preferably a cohesive film, and even better a film
whose cohesion and mechanical properties are such that the said
film may be isolated and manipulated in isolation, for example when
the said film is formed by casting on a non-sticking surface, such
as a Teflon-coated or silicone-coated surface.
[0079] The definition of the R'' radical is the same as that of the
R' radical. The aforementioned definitions applicable to R' are
therefore applicable to R''.
[0080] Propyl T resin b) according to the invention is a
silsesquioxane resin. Silsesquioxane resins are well known in the
prior art and are generally obtained by hydrolysis of an
organosilane containing three hydrolyzable groups, such as halogen
or alkoxy groups, present in the molecule. Propyl T resin b) may
therefore be obtained by hydrolysis of propyltrimethoxysilane,
propyltriethoxysilane, propyltripropoxysilane, or by cohydrolysis
of the aforementioned propylalkoxysilanes with diverse
alkoxysilanes. As examples of these alkoxysilanes there can be
cited methyltrimethoxysilane, methyltriethoxysilane,
methyltriisopropoxysilane, dimethyldimethoxysilane and
phenyltrimethoxysilane. Propyltrichlorosilane may also be
hydrolyzed alone or in the presence of alcohol. In this case, the
cohydrolysis may be achieved by adding methyltrichlorosilane,
dimethyldichlorosilane, phenyltrichlorosilane or similar
chlorosilanes and methyltrimethoxysilane, methyltriethoxysilane,
methyltriisopropoxysilane or similar methylalkoxysilanes. As
alcohols suitable for this purpose there may be cited methanol,
ethanol, n-propyl alcohol, isopropyl alcohol, butanol,
methoxyethanol, ethoxyethanol or similar alcohols. As examples of
solvents of hydrocarbon type that may be used simultaneously there
may be cited toluene, xylene or similar aromatic hydrocarbons,
hexane, heptane, isooctane or similar linear or partly branched
saturated hydrocarbons; as well as cyclohexane or similar aliphatic
hydrocarbons.
[0081] Propyl T resins b) according to the invention may contain M,
D and Q units, with the proviso that at least 80 mol %, even 90 mol
% of the total siloxane units are T units. The propyl T resins may
also contain residual hydroxy and/or alkoxy groups, as mentioned in
the foregoing.
[0082] The composition according to the invention also comprises a
physiologically acceptable medium. By physiologically acceptable
medium there is understood a medium compatible with the skin, the
mucous membranes and the integument.
[0083] This medium may comprise at least one volatile silicone or
organic solvent, this solvent preferably being compatible with
resins a/ and b/ and compatible with a cosmetic use.
[0084] As volatile silicone solvent there may be cited the cyclic
polysiloxanes, the linear polysiloxanes and mixtures thereof.
[0085] As volatile linear polysiloxanes there may be cited
hexamethyldisiloxane, octamethyltrisiloxane,
decamethyltetrasiloxane, tetradecamethylhexasiloxane and
hexadecamethylheptasiloxane.
[0086] As volatile cyclic polysiloxanes there may be cited
hexamethylcyclotrisiloxane, octamethylcyclotetrasiloxane,
decamethylcyclopentasiloxane and dodecamethylcyclohexasiloxane.
[0087] The organic solvent may also be an alcohol such as ethanol,
isopropanol, butanol, n-propanol; a ketone such as acetone, methyl
ethyl ketone or methyl isobutyl ketone; an aliphatic hydrocarbon
such as heptane, hexane, octane or isododecane; a glycol ether such
as propylene glycol methyl ether, dipropylene glycol methyl ether,
propylene glycol n-butyl ether, propylene glycol n-propyl ether,
ethylene glycol n-butyl ether.
[0088] The mixture of resins at and b/ may be obtained from each of
the resins in solution in a solvent.
[0089] In general, at the end of synthesis of the MQ resin
according to the invention, this resin is obtained directly in
solution in xylene.
[0090] Similarly, at the end of synthesis of propyl T resin b)
according to the invention, this resin is obtained directly in
solution in toluene.
[0091] Each of these resins in solution is mixed with the other
according to the following protocol: [0092] 1) Mixing the two resin
solutions under agitation, then heating, especially in a reactor or
in an autoclave (in order to be able to operate under pressure if
necessary, or on the other hand by establishing a partial vacuum),
even in an extruder, which may or may not be equipped with a
solvent "devolatilization" system, under the following specific
conditions: [0093] heating is carried out homogeneously: the
heating temperature must be higher than 90.degree. C. and lower
than or equal to 250.degree. C., and preferably between 90.degree.
C. and 190.degree. C. [0094] Either heating is carried out at a
single temperature, between 90.degree. C. and 250.degree. C.,
[0095] Or heating may be carried out at successive temperature
levels: [0096] first between 90.degree. C. and T1.degree. C.,
[0097] T1.degree. C. being a temperature value intermediate between
90.degree. C. and [0098] T2.degree. C., which is the final
temperature, [0099] for a duration between 10 minutes and 2 hours,
then [0100] between T1.degree. C. and T2.degree. C., for a duration
between 10 minutes and 4 hours, [0101] the temperature T2.degree.
C. corresponding to the maximum temperature chosen for the
reaction. [0102] This value of T2.degree. C. is variable depending
on the chosen mode of operation and on the chosen reactor type:
traditional reactor or autoclave or extruder, but T2.degree. C.
remains lower than or equal to 250.degree. C. It is also possible
to interpose intermediate temperature levels between T1.degree. C.
and T2.degree. C.; [0103] the duration of heating is at least one
hour in the reactor or in the autoclave and at least 10 minutes in
the extruder, preferably between 1 h and 5 h in the reactor or in
the autoclave, and preferably between 10 minutes and 2 hours in the
extruder; [0104] with the proviso that these heat treatments are
carried out without the presence of a catalyst for chemical
condensation between the two MQ and propyl T resins. Such a
catalyst is in particular a mineral base, especially NaOH, KOH or
ammonia. [0105] 2) Optionally, partial or complete distillation of
the aromatic solvents is carried out after or even during step 1)
of the heat treatment of the two resins at the indicated
temperature level, while replacing them by a cosmetically
acceptable volatile solvent. Such a volatile solvent may be in
particular a volatile or non-volatile silicone, preferably
decamethylcyclopentasiloxane, or a volatile or non-volatile organic
solvent, preferably isododecane. [0106] 3) Also optionally, after
mixing of the two initial solutions of each resin in a volatile
solvent, the mixture of the solutions is processed in a
single-screw or twin-screw kneader of the "devolatilization"
extruder type, in a temperature interval between 90.degree. and
250.degree. C., making it possible to volatilize the volatile
solvents by establishing a partial vacuum, while operating
continuously, and then to pass the molten, solvent-free mixture
into a die. The molten mixture is then cooled at the outlet of the
die and chopped into solid granules or into powder form. In this
case the mixture is directly in solid form and will be redissolved
in the chosen solvents when it is time for formulation.
[0107] Furthermore, another object of the present invention is a
composition such as described hereinabove comprising, in a
physiologically acceptable medium:
[0108] 1) the mixture between a siloxane resin a) and a propyl
silsesquioxane resin b), the mixture being such as described
hereinabove, and
[0109] 2) at least one film-forming polymer, preferably chosen from
among the group comprising: [0110] a sequenced ethylene copolymer
(also referred to as sequenced ethylene polymer), containing at
least one first sequence having a glass transition temperature (Tg)
higher than or equal to 40.degree. C. and being obtained completely
or partly from one or more first monomers, which are such that the
homopolymer prepared from these monomers has a glass transition
temperature higher than or equal to 40.degree. C., and at least one
second sequence having a glass transition temperature lower than or
equal to 20.degree. C. and being obtained completely or partly from
one or more second monomers, which are such that the homopolymer
prepared from these monomers has a glass transition temperature
lower than or equal to 20.degree. C., the said first sequence and
the said second sequence being bonded together by a statistical
intermediate segment comprising at least one of the said first
constituent monomers of the first sequence and at least one of the
said second constituent monomers of the second sequence, and the
said sequenced copolymer having a polydispersity index I greater
than 2, [0111] a vinyl polymer comprising at least one moiety
derived from carbosiloxane dendrimer, [0112] a dispersion of
particles of acrylic or vinyl radical homopolymer or copolymer
dispersed in the said liquid fatty phase.
[0113] the siloxane resin a) and the propyl silsesquioxane resin b)
being formulated in the composition via a mixture capable of being
obtained according to the following method: [0114] Mixing,
preferably under agitation, of a solution of siloxane resin with a
solution of propyl silsesquioxane resin, the solvent present in
each of the solutions preferably being volatile, then [0115]
Heating, especially in a reactor or in an autoclave or in an
extruder, under the following specific conditions: [0116] heating
is carried out homogeneously at a temperature higher than
90.degree. C. and lower than or equal to 250.degree. C., and
preferably between 90.degree. C. and 190.degree. C.; heating may be
carried out at a single temperature, or in temperature levels, as
indicated hereinabove; [0117] the duration of heating is at least
one hour in the reactor or in the autoclave and at least 10 minutes
in the extruder, preferably between 1 h and 5 h in the reactor or
in the autoclave, and preferably between 10 minutes and 2 hours in
the extruder; [0118] with the proviso that these heat treatments
are carried out without the presence of a catalyst for chemical
condensation between the two MQ and propyl T resins. Such a
catalyst is in particular a mineral base, especially NaOH, KOH or
ammonia.
[0119] This method may comprise, after or even during the mixing
step, an additional step of partial or complete distillation of the
aromatic solvents, while replacing them with a cosmetically
acceptable solvent.
[0120] In the case that an extruder is used, this method may
comprise, after or even during the mixing step, an additional step
of partial or complete distillation of the aromatic solvents, while
discharging the mixture directly in the solid state.
[0121] The final heat-treatment step, or even the heat treatment
itself may be achieved in a kneader provided for agitation of very
viscous media such as: [0122] a kneader of "Z-arm" type ("Zigma
blender"), especially a Brabender kneader, [0123] a screw kneader
of extruder type, particularly a single-screw or a twin-screw
extruder (with or without a stage for "devolatilization" of
starting volatile solvents) or in a kneader that permits
devolatilization by establishing a thin film on the walls.
[0124] Resin mixtures 1) suitable for use according to the
invention are especially those described in Application WO
2005/075567, the contents of which are incorporated here by
reference, particularly those described in Tables 1 and 3 of the
said Application. It is also possible to use resin mixtures 1)
described in Application WO2007/145765, particularly those
described in Examples 12 to 14 of that Application, wherein the
weight ratios between resins a) and b) are respectively 50/50,
60/40 and 71/29 (70/30).
[0125] According to a particular mode, there is used resin mixture
1) described in Example 22 of the said Application WO2005/075567,
wherein the weight ratio between resin a) and b) is 85/15.
[0126] According to a particular mode, there is used resin mixture
1) described in Example 13 of the said Application WO2007/145765,
wherein the weight ratio between resin a) and b) is 60/40.
[0127] Preferably, the siloxane resin is present in the composition
in a total content of dry resin material ranging from 1% to 80% by
weight relative to the total weight of the composition, preferably
ranging from 5% to 70% by weight, and better ranging from 6% to 60%
by weight.
[0128] The compositions according to the invention may assume
diverse forms, especially the form of powder, anhydrous dispersion,
water-in-oil or water-in wax emulsion, oil-in-water emulsion,
multiple emulsions or wax-in-water emulsion, or gel.
[0129] Preferably, the composition according to the invention
comprises less than 3%, or better less than 1% of water by weight
relative to the total weight of the composition. Even more
preferably, the composition is completely anhydrous. By anhydrous
there is understood in particular that preferably water is not
deliberately added to the composition but may be present in the
trace state in the different compounds used in the composition.
[0130] The compositions according to the invention may also
comprise an additional ingredient, preferably chosen from among
pasty compounds of non-animal origin, fatty-phase thickening or
gelling rheological agents, waxes, hydrophilic gelling agents,
fillers, ionic surfactants, fibers and mixtures thereof.
Film-Forming Polymers
[0131] The composition according to the invention comprises at
least one film-forming polymer. The compositions according to the
invention may therefore comprise at least one film-forming polymer
and mixture 1) described hereinabove.
[0132] In the present invention, there is understood by
"film-forming polymer" a polymer capable of forming, on its own or
in the presence of an auxiliary filmifying agent, a macroscopically
continuous film that adheres to horny tissues, and preferably a
cohesive film, and even better a film whose cohesion and mechanical
properties are such that the said film may be isolated and
manipulated in isolation, for example when the said film is formed
by casting on a non-sticking surface, such as a Teflon-coated or
silicone-coated surface.
[0133] The film-forming polymer or polymers used, in association
with the mixtures of MQ and propyl T resins, may be conveyed in the
oil phase (fat-soluble or fat-dispersible polymers) or conveyed in
an aqueous phase (water soluble polymers or latex).
[0134] Preferably, the composition according to the invention
comprises at least one polymer chosen from among the group
comprising: [0135] a sequenced ethylene copolymer (also referred to
as sequenced ethylene polymer), containing at least one first
sequence having a glass transition temperature (Tg) higher than or
equal to 40.degree. C. and being obtained completely or partly from
one or more first monomers, which are such that the homopolymer
prepared from these monomers has a glass transition temperature
higher than or equal to 40.degree. C., and at least one second
sequence having a glass transition temperature lower than or equal
to 20.degree. C. and being obtained completely or partly from one
or more second monomers, which are such that the homopolymer
prepared from these monomers has a glass transition temperature
lower than or equal to 20.degree. C., the said first sequence and
the said second sequence being bonded together by a statistical
intermediate segment comprising at least one of the said first
constituent monomers of the first sequence and at least one of the
said second constituent monomers of the second sequence, and the
said sequenced copolymer having a polydispersity index I greater
than 2, [0136] a vinyl polymer comprising at least one moiety
derived from carbosiloxane dendrimer, [0137] a dispersion of
particles of acrylic or vinyl radical homopolymer or copolymer
dispersed in the said liquid fatty phase.
Sequenced Ethylene Polymer:
[0138] According to an exemplary embodiment of the invention, the
film-forming polymer is a film-forming sequenced ethylene polymer,
which preferably comprises at least one first sequence and at least
one second sequence having different glass transition temperatures
(Tg), the said first and second sequences being bonded together by
an intermediate sequence comprising at least one constituent
monomer of the first sequence and at least one constituent monomer
of the second sequence.
[0139] Advantageously, the first and second sequences of the
sequenced polymer are incompatible with one another.
[0140] Such polymers are described, for example, in the documents
of EP 1411069 or WO04/028488. The Application EP 1411069 describes
the possibility of preparing sequenced polymers from acrylate
monomer or methacrylate monomer.
[0141] In particular, according to one embodiment, the composition
according to the present invention contains at least one sequenced
ethylene copolymer (also referred to as sequenced ethylene
polymer), containing at least one first sequence having a glass
transition temperature (Tg) higher than or equal to 40.degree. C.
and being obtained completely or partly from one or more first
monomers, which are such that the homopolymer prepared from these
monomers has a glass transition temperature higher than or equal to
40.degree. C., and at least one second sequence having a glass
transition temperature lower than or equal to 20.degree. C. and
being obtained completely or partly from one or more second
monomers, which are such that the homopolymer prepared from these
monomers has a glass transition temperature lower than or equal to
20.degree. C., the said first sequence and the said second sequence
being bonded together by a statistical intermediate segment
comprising at least one of the said first constituent monomers of
the first sequence and at least one of the said second constituent
monomers of the second sequence, and the said sequenced copolymer
having a polydispersity index I greater than 2.
[0142] The sequenced polymer used according to the invention
therefore comprises at least one first sequence and at least one
second sequence.
[0143] By "at least" one sequence there is understood one or more
sequences.
[0144] By "sequenced" polymer there is understood a polymer
comprising at least two distinct sequences, preferably at least
three distinct sequences.
[0145] By "ethylene" polymer there is understood a polymer obtained
by polymerization of monomers containing an ethylenic
unsaturation.
[0146] The sequenced ethylene polymer used according to the
invention is prepared exclusively from monofunctional monomers.
[0147] That means that the sequenced ethylene polymer used
according to the present invention does not contain multifunctional
monomers, which make it possible to break the linearity of a
polymer in order to obtain a branched or even cross-linked polymer,
according to the proportion of the multifunctional polymer. Neither
does the polymer used according to the invention contain
macromonomers (by "macromonomer" there is understood a
monofunctional monomer having a pendant group of polymeric nature,
and preferably having a molecular weight greater than 500 g/mol, or
else a polymer containing, at one of its ends, a polymerizable
terminal group (or an ethylenically unsaturated group)), which are
used in preparation of a graft polymer.
[0148] It is emphasized that the terms "first" and "second"
hereinabove and hereinafter in no way affect the order of the said
sequences (or blocks) in the polymer structure.
[0149] Advantageously, the first sequence and the second sequence
of the polymer used in the invention may be incompatible with one
another.
[0150] By "sequences incompatible with one another" it is
understood that the mixture formed by a polymer corresponding to
the first sequence and by a polymer corresponding to the second
sequence is not miscible in the polymerization solvent,
constituting the majority by weight, of the sequenced polymer, at
room temperature (20.degree. C.) and atmospheric pressure (10.sup.5
Pa), for a content of the mixture of the said polymers greater than
or equal to 5% by weight relative to the total weight of the
mixture of the said polymers and of the said polymerization
solvent, its being understood that:
i) the said polymers are present in the mixture in a content such
that the respective weight ratio ranges from 10/90 to 90/10, and
that ii) each of the polymers corresponding to the first and second
sequences has a (weight or number) average molecular weight equal
to that of the sequenced polymer.+-.15%.
[0151] In the case of a mixture of polymerization solvents, and
assuming two or more solvents present in identical proportions by
weight, the said polymer mixture is not miscible in at least one of
those.
[0152] Of course, in the case of polymerization carried out in a
single solvent, this is the majority solvent.
[0153] The sequenced polymer according to the invention comprises
at least one first sequence and at least one second sequence,
bonded together by an intermediate segment comprising at least one
constituent monomer of the first sequence and at least one
constituent monomer of the second sequence. The intermediate
segment (also referred to as intermediate sequence) has a glass
transition temperature Tg between the glass transition temperatures
of the first and second sequences.
[0154] The intermediate segment is a sequence comprising at least
one constituent monomer of the first sequence and at least one
constituent monomer of the second sequence is capable of making
these sequences "compatible".
[0155] Advantageously, the intermediate segment comprising at least
one constituent monomer of the first sequence and at least one
constituent monomer of the second sequence of the polymer is a
statistical polymer.
[0156] Preferably, the intermediate sequence is obtained
substantially from constituent monomers of the first sequence and
of the second sequence.
[0157] By "substantially" there is understood at least 85%,
preferably at least 90%, better at least 95% and even better
100%.
[0158] The sequenced polymer according to the invention is
advantageously a film-forming sequenced ethylene polymer.
[0159] By "ethylene" polymer there is understood a polymer obtained
by polymerization of monomers containing an ethylenic
unsaturation.
[0160] By "film-forming polymer" there is understood a polymer
capable of forming, on its own or in the presence of an auxiliary
filmifying agent, a continuous deposit on a substrate, especially
on horny tissues.
[0161] Preferentially, the polymer according to the invention does
not comprise silicon atoms in its skeleton. By "skeleton" there is
understood the main chain of the polymer, as opposed to pendant
side chains.
[0162] Preferably, the polymer according to the invention is not
water-soluble, meaning that the polymer is not soluble in water or
in a mixture of water and lower linear or branched monohydric
alcohols having 2 to 5 carbon atoms, such as ethanol, isopropanol
or n-propanol, without modification of pH, at an active material
content of at least 1% by weight, at room temperature (20.degree.
C.).
[0163] Preferably, the polymer according to the invention is not an
elastomer.
[0164] By "non-elastomeric polymer" there is understood a polymer
which, when it is subjected to a stress tending to stretch it (for
example by 30% relative to its initial length), does not return to
a length substantially identical to its initial length when the
stress ceases.
[0165] More specifically, by "non-elastomeric polymer" there is
denoted a polymer having an instantaneous recovery R.sub.i<50%
and a delayed recovery R.sub.2h<70% after having undergone an
elongation of 30%. Preferably, R.sub.i is <30% and R.sub.2h is
<50%.
[0166] More precisely, the non-elastomeric character of the polymer
is determined according to the following protocol:
[0167] A polymer film is prepared by casting a polymer solution in
a Teflon-coated die then drying it for 7 days in a controlled
environment at 23.+-.5.degree. C. and 50.+-.10% relative
humidity.
[0168] In this way there is obtained a film of approximately 100
.mu.m thickness, from which there are cut rectangular specimens
(for example, with a punch) having a width of 15 mm and a length of
80 mm.
[0169] This specimen is subjected to tensile load by means of an
apparatus sold under the name Zwick, under the same temperature and
humidity conditions as for drying.
[0170] The specimens are drawn at a speed of 50 mm/min, and the
distance between the jaws is 50 mm, corresponding to the initial
length (l.sub.0) of the specimen.
[0171] The instantaneous recovery Ri is determined as follows:
[0172] the specimen is drawn by 30% (.epsilon..sub.max), or in
other words by approximately 0.3 times its initial length (l.sub.a)
[0173] the stress is relaxed by imposing a return speed equal to
the tension speed, or in other words 50 mm/min, and the residual
elongation of the specimen is measured in percent, after return to
zero load stress (.epsilon..sub.i).
[0174] The instantaneous recovery in % (R.sub.i) is given by the
following formula:
R.sub.i=(.epsilon..sub.max-.epsilon..sub.i)/.epsilon..sub.max).times.100
[0175] To determine the delayed recovery, the percentage residual
elongation of the specimen after 2 hours (.epsilon..sub.2h) is
measured 2 hours after return to zero load stress.
[0176] The delayed recovery (R.sub.2h) in % is given by the
following formula:
R.sub.2h=(.epsilon..sub.max-.epsilon..sub.2h)/.epsilon..sub.max).times.1-
00
[0177] Purely by way of indication, a polymer according to an
embodiment of the invention preferably has an instantaneous
recovery R.sub.i of 10% and a delayed recovery R.sub.2h of 30%.
[0178] The polydispersity index of the polymer of the invention is
greater than 2.
[0179] Advantageously, the sequenced polymer used in the
compositions according to the invention has a polydispersity index
I greater than 2, for example ranging from 2 to 9, preferably
greater than or equal to 2.5, for example ranging from 2.5 to 8,
and better greater than or equal to 2.8, and especially ranging
from 2.8 to 6.
[0180] The polydispersity index I of the polymer is equal to the
ratio of weight-average molecular weight Mw to number-average
molecular weight Mn.
[0181] The weight-average and number-average molecular weights (Mw
and Mn respectively) are determined by gel permeation liquid
chromatography (THF solvent, calibration curve established with
linear polystyrene standards, refractometer detector).
[0182] The weight-average molecular weight (Mw) of the polymer
according to the invention is preferably smaller than or equal to
300,000; for example, it ranges from 35,000 to 200,000, and better
from 45,000 to 150,000 g/mol.
[0183] The number-average molecular weight (Mn) of the polymer
according to the invention is preferably smaller than or equal to
70,000; for example, it ranges from 10,000 to 60,000, and better
from 12,000 to 50,000 g/mol.
[0184] Preferably, the polydispersity index of the polymer
according to the invention is greater than 2, for example ranging
from 2 to 9, preferably greater than or equal to 2.5, for example
ranging from 2.5 to 8, and better greater than or equal to 2.8 and
especially ranging from 2.8 to 6.
First Sequence Having a Tg Higher than or Equal to 40.degree.
C.
[0185] The sequence having a Tg higher than or equal to 40.degree.
C. has, for example, a Tg ranging from 40 to 150.degree. C.,
preferably higher than or equal to 50.degree. C., for example
ranging from 50 to 120.degree. C., and better higher than or equal
to 60.degree. C., for example ranging from 60 to 120.degree. C.
[0186] The indicated glass transition temperatures of the first and
second sequences may be theoretical Tg values determined from the
theoretical Tg values of the constituent monomers of each of the
sequences, as can be found in a reference manual such as Polymer
Handbook, 3.sup.rd ed., 1989, John Wiley, according to the
following relationship, which is known as Fox's law:
1 / Tg = i ( .PI. i / Tg i ) , ##EQU00001##
where .omega.l is the weight fraction of monomer i in the sequence
under consideration and Tg.sub.i is the glass transition
temperature of the homopolymer of monomer i.
[0187] Unless otherwise indicated, the Tg values indicated for the
first and second sequences in the present Application are
theoretical Tg values.
[0188] The difference between the glass transition temperatures of
the first and second sequences is generally larger than 10.degree.
C., preferably larger than 20.degree. C., and better larger than
30.degree. C. [0189] In the present invention, the expression
"between . . . and . . . " is understood to denote an interval of
values that excludes the indicated bounds, and "from . . . to . . .
" and "ranging from . . . to . . . " an interval of values that
includes the bounds.
[0190] The sequence having a Tg higher than or equal to 40.degree.
C. may be a homopolymer or a copolymer.
[0191] The sequence having a Tg higher than or equal to 40.degree.
C. may be obtained completely or partly from one or more monomers,
which are such that the homopolymer prepared from these monomers
has a glass transition temperature higher than or equal to
40.degree. C. This sequence may also be referred to as "rigid
sequence".
[0192] In the case in which this sequence is a homopolymer, it is
obtained from monomers, which are such that the homopolymers
prepared from these monomers have glass transition temperatures
higher than or equal to 40.degree. C. This first sequence may be a
homopolymer composed of a single type of monomer (for which the Tg
of the corresponding homopolymer is higher than or equal to
40.degree. C.).
[0193] In the case in which the first sequence is a copolymer, it
may be obtained completely or partly from one or more monomers,
whose nature and concentration are chosen such that the Tg of the
resulting copolymer is higher than or equal to 40.degree. C. As an
example, the copolymer may comprise: [0194] monomers that are such
that the homopolymers prepared from these monomers have Tg values
higher than or equal to 40.degree. C., for example a Tg ranging
from 40 to 150.degree. C., preferably higher than or equal to
50.degree. C., for example ranging from 50 to 120.degree. C., and
better higher than or equal to 60.degree. C., for example ranging
from 60 to 120.degree. C., and [0195] monomers that are such that
the homopolymers prepared from these monomers have Tg values lower
than 40.degree. C., chosen from among the monomers having a Tg
between 20 and 40.degree. C. and/or the monomers having a Tg lower
than or equal to 20.degree. C., for example a Tg ranging from -100
to 20.degree. C., preferably lower that 15.degree. C., especially
ranging from -80 to 15.degree. C., and better lower than 10.degree.
C., for example ranging from -50 to 0.degree. C., such as described
hereinafter.
[0196] The first monomers, whose homopolymers have a glass
transition temperature higher than or equal to 40.degree. C., are
preferably chosen from among the following monomers, also referred
to as main monomers: [0197] the methacrylates of formula
CH.sub.2.dbd.C(CH.sub.3)--COOR.sub.1, in which R.sub.1 represents a
linear or branched unsubstituted alkyl group containing 1 to 4
carbon atoms, such as a methyl, ethyl, propyl or isobutyl group, or
R.sub.1 represents a C.sub.4 to C.sub.12 cycloalkyl group,
preferably a C.sub.8 to C.sub.12 cycloalkyl group, such as
isobornyl methacrylate, [0198] the acrylates of formula
CH.sub.2.dbd.CH--COOR.sub.1, in which R.sub.1 represents a C.sub.4
to C.sub.12 cycloalkyl group, such as an isobornyl group or a
tert-butyl group, [0199] the (meth)acrylamides of formula:
##STR00002##
[0199] where R.sub.7 or R.sub.8, which may be identical or
different, each represent a hydrogen atom or a linear or branched
C.sub.1 to C.sub.12 alkyl group, such as an n-butyl, t-butyl,
isopropyl, isohexyl, isooctyl or isononyl group; or R.sub.7
represents H and R.sub.8 represents a 1,1-dimethyl-3-oxobutyl
group, and R' denotes H or methyl. As an example of monomers there
may be cited N-butyl acrylamide, N-t-butyl acrylamide, N-isopropyl
acrylamide, N,N-dimethyl acrylamide and N,N-dibutyl acrylamide,
[0200] and mixtures thereof.
[0201] The first sequence is advantageously obtained from at least
one acrylate monomer of formula CH.sub.2.dbd.CH--COOR.sub.2 and
from at least one methacrylate monomer of formula
CH.sub.2.dbd.C(CH.sub.3)--COOR.sub.2, in which R.sub.2 represents a
C.sub.4 to C.sub.12 cycloalkyl group, preferably a C.sub.8 to
C.sub.12 cycloalkyl group, such as isobornyl. The monomers and
their proportions are preferably chosen such that the glass
transition temperature of the first sequence is higher than or
equal to 40.degree. C.
[0202] According to one embodiment, the first sequence is obtained
from:
i) at least one acrylate monomer of formula
CH.sub.2.dbd.CH--COOR.sub.2, in which R.sub.2 represents a C.sub.4
to C.sub.12 cycloalkyl group, preferably a C.sub.8 to C.sub.12
cycloalkyl group, such as isobornyl, ii) and at least one
methacrylate group of formula
CH.sub.2.dbd.C(CH.sub.3)--COOR'.sub.2, in which R'.sub.2 represents
a C.sub.4 to C.sub.12 cycloalkyl group, preferably a C.sub.8 to
C.sub.12 cycloalkyl group, such as isobornyl.
[0203] According to one embodiment, the first sequence is obtained
from at least one acrylate monomer of formula
CH.sub.2.dbd.CH--COOR.sub.2, in which R.sub.2 represents a C.sub.8
to C.sub.12 cycloalkyl group, such as isobornyl, and from at least
one methacrylate monomer of formula
CH.sub.2.dbd.C(CH.sub.3)--COOR'.sub.2, in which R'.sub.2 represents
a C.sub.8 to C.sub.12 cycloalkyl group, such as isobornyl.
[0204] Preferably, R.sub.2 and R'.sub.2 independently or
simultaneously represent an isobornyl group.
[0205] Preferably, the sequenced polymer comprises 50 to 80% by
weight of isobornyl methacrylate/acrylate, 10 to 30% by weight of
isobutyl acrylate and 2 to 10% by weight of acrylic acid.
[0206] The first sequence may be obtained exclusively from the said
acrylate monomer and from the said methacrylate monomer.
[0207] The acrylate monomer and the methacrylate monomer are
preferably in weight propositions between 30:70 and 70:30,
preferably between 40:60 and 60:40, especially on the order of
50:50.
[0208] The proportion of the first sequence will advantageously
range from 20 to 90% by weight of the polymer, better from 30 to
80% and even better from 60 to 80%.
[0209] According to one embodiment, the first sequence is obtained
by polymerization of isobornyl methacrylate and isobornyl
acrylate.
Second Sequence Having a Glass Transition Temperature Lower than
20.degree. C.
[0210] The second sequence advantageously has a glass transition
temperature Tg lower than or equal to 20.degree. C., for example
has a Tg ranging from -100 to 20.degree. C., preferably lower than
or equal to 15.degree. C., for example ranging from -80 to
15.degree. C., and better lower than or equal to 10.degree. C., for
example ranging from -100.degree. C. to 10.degree. C., especially
ranging from -30.degree. C. to 10.degree. C.
[0211] The second sequence is obtained completely or partly from
one or more second monomers, which are such that the homopolymer
prepared from these monomers has a glass transition temperature
lower than or equal to 20.degree. C.
[0212] This sequence may also be referred to as "flexible
sequence".
[0213] The monomer having a Tg lower than or equal to 20.degree. C.
(referred to as second monomer) is preferably chosen from among the
following monomers: [0214] the acrylates of formula
CH.sub.2.dbd.CHCOOR.sub.3, R.sub.3 representing a linear or
branched unsubstituted C.sub.1 to C.sub.12 alkyl group, with the
exception of the tert-butyl group, in which one or more hetero
atoms chosen from among O, N, S are present, possibly intercalated,
[0215] the methacrylates of formula
CH.sub.2.dbd.C(CH.sub.3)--COOR.sub.4, R.sub.4 representing a linear
or branched unsubstituted C.sub.6 to C.sub.12 alkyl group, in which
one or more hetero atoms chosen from among O, N, S are present,
possibly intercalated; [0216] the vinyl esters of formula
R.sub.5--CO--O--CH.dbd.CH.sub.2 where R.sub.5 represents a linear
or branched C.sub.4 to C.sub.12 alkyl group; [0217] the ethers of
vinyl alcohol and C.sub.4 to C.sub.12 alcohol, [0218] the
N--(C.sub.4 to C.sub.12)-alkyl acrylamides, such as N-octyl
acrylamide, [0219] and mixtures thereof.
[0220] The preferred monomers having a Tg lower than or equal to
20.degree. C. are isobutyl acrylate, ethyl-2-hexyl acrylate or
mixtures thereof in all proportions.
[0221] Each of the first and second sequences may contain, in
minority proportion, at least one constituent monomer of the other
sequence.
[0222] Thus the first sequence may contain at least one constituent
monomer of the second sequence and vice versa.
[0223] Each of the first and/or second sequences may comprise, in
addition to the monomers indicated hereinabove, one or more other
monomers, referred to as additional monomers, different from the
main monomers cited in the foregoing.
[0224] The nature and quantity of this or those additional monomer
or monomers are chosen such that the sequence in which they are
present has the desired glass transition temperature. As an
example, this additional monomer is chosen from among:
[0225] the monomers having ethylene unsaturations and comprising at
least one tertiary amine function, such as 2-vinylpyridine,
4-vinylpyridine, dimethylaminoethyl methacrylate, diethylaminoethyl
methacrylate, dimethylaminopropyl methacrylamide and the salts
thereof, [0226] the methacrylates of formula
CH.sub.2.dbd.C(CH.sub.3)--COOR.sub.6 in which R.sub.6 represents a
linear or branched alkyl group containing 1 to 4 carbon atoms, such
as a methyl, ethyl, propyl or isobutyl group, the said alkyl group
being substituted by one or more substituents chosen from among the
hydroxyl groups (such as 2-hydroxypropyl methacrylate,
2-hydroxyethyl methacrylate) and the halogen atoms (Cl, Br, I, F),
such as trifluoroethyl methacrylate, [0227] the methacrylates of
formula CH.sub.2.dbd.C(CH.sub.3)--COOR.sub.9, R.sub.9 representing
a linear or branched C.sub.6 to C.sub.12 alkyl group, in which one
or more hetero atoms chosen from among O, N, S are present,
possibly intercalated, the said alkyl group being substituted by
one or more substituents chosen from among the hydroxyl groups and
the halogen atoms (Cl, Br, I, F); [0228] the acrylates of formula
CH.sub.2.dbd.CHCOOR.sub.10, R.sub.10 representing a linear or
branched C.sub.6 to C.sub.12 alkyl group substituted by one or more
substituents chosen from among the hydroxyl groups and the halogen
atoms (Cl, Br, I, F), such as 2-hydroxypropyl acrylate and
2-hydroxyethyl acrylate, or R.sub.10 represents a (C.sub.1 to
C.sub.12)-alkyl-O-POE (polyoxyethylene) with 5 to 10 repetitions of
the oxyethylene moiety, for example methoxy-POE, or R.sub.8
represents a polyoxyethylene group comprising 5 to 10 ethylene
oxide moieties.
[0229] In particular, the first sequence may comprise, by way of
additional monomer: [0230] (meth)acrylic acid, preferably acrylic
acid, [0231] tert-butyl acrylate [0232] the methacrylates of
formula CH.sub.2.dbd.C(CH.sub.3)--COOR.sub.1 in which R.sub.1
represents a linear or branched unsubstituted alkyl group
containing 1 to 4 carbon atoms, such as a methyl, ethyl, propyl or
isobutyl group, [0233] the (meth)acrylamides of formula:
##STR00003##
[0233] where R.sub.7 or R.sub.8, which may be identical or
different, each represent a hydrogen atom or a linear or branched
C.sub.1 to C.sub.12 alkyl group, such as an n-butyl, t-butyl,
isopropyl, isohexyl, isooctyl or isononyl group; or R.sub.7
represents H and R.sub.8 represents a 1,1-dimethyl-3-oxobutyl
group, and R' denotes H or methyl. As an example of monomers there
may be cited N-butyl acrylamide, N-t-butyl acrylamide, N-isopropyl
acrylamide, N,N-dimethyl acrylamide and N,N-dibutyl acrylamide,
[0234] and mixtures thereof.
[0235] The additional monomer may represent 0.5 to 30% by weight of
the polymer. According to one embodiment, the polymer of the
invention does not contain additional monomer.
[0236] Preferably, the polymer of the invention comprises at least
isobornyl acrylate and isobornyl methacrylate monomers in the first
sequence and isobutyl acrylate and acrylic acid monomers in the
second sequence.
[0237] Preferably, the polymer comprises at least isobornyl
acrylate and isobornyl methacrylate monomers in equivalent
proportions by weight in the first sequence and isobutyl acrylate
and acrylic acid monomers in the second sequence.
[0238] Preferably, the polymer comprises at least isobornyl
acrylate and isobornyl methacrylate monomers in equivalent
proportions by weight in the first sequence and isobutyl acrylate
and acrylic acid monomers in the second sequence, the first
sequence representing 70% by weight of the polymer.
[0239] Preferably, the polymer comprises at least isobornyl
acrylate and isobornyl methacrylate monomers in equivalent
proportions by weight in the first sequence and isobutyl acrylate
and acrylic acid monomers in the second sequence. Preferably, the
sequence of Tg higher than 40.degree. C. representing 70% by weight
of the polymer, and the acrylic acid representing 5% by weight of
the polymer.
[0240] According to one embodiment, the first sequence does not
contain additional monomer. According to a preferred embodiment,
the second sequence comprises acrylic acid by way of additional
monomer. In particular, the second sequence is advantageously
obtained from an acrylic acid monomer and at least one other
monomer having a Tg lower than or equal to 20.degree. C.
[0241] According to a preferred embodiment, the sequenced ethylene
polymer is a copolymer comprising at least one acrylate monomer of
formula CH.sub.2.dbd.CH--COOR.sub.2, in which R.sub.2 represents a
C.sub.8 to C.sub.12 cycloalkyl group, and/or at least one
methacrylate monomer of formula
CH.sub.2.dbd.C(CH.sub.3)--COOR'.sub.2, in which R'.sub.2 represents
a C.sub.8 to C.sub.12 cycloalkyl group, at least one second
acrylate monomer of formula CH.sub.2.dbd.CHCOOR.sub.3, in which
R.sub.3 represents a linear or branched unsubstituted C.sub.1 to
C.sub.12 alkyl group, with the exception of the tert-butyl group,
and at least one acrylic acid monomer.
[0242] Preferably, the copolymer used in the compositions according
to the invention is obtained from at least one isobornyl
methacrylate monomer, at least one isobornyl acrylate monomer, at
least one isobutyl acrylate monomer and at least one acrylic acid
monomer.
[0243] Advantageously, the copolymer used in the invention
comprises 50 to 80% by weight of isobornyl methacrylate/acrylate
mixture, 10 to 30% by weight of isobutyl acrylate and 2 to 10% by
weight of acrylic acid.
[0244] The sequenced copolymer may advantageously comprise more
than 2% by weight of acrylic acid monomers, and especially from 2
to 15% by weight, for example from 3 to 15% by weight, in
particular from 4 to 15% by weight, even from 4 to 10% by weight of
acrylic acid monomers relative to the total weight of the said
copolymer.
[0245] The constituent monomers of the second sequence and the
proportions thereof are chosen such that the glass transition
temperature of the second sequence is lower than or equal to
20.degree. C.
Intermediate Segment
[0246] The intermediate segment (also referred to as intermediate
sequence) bonds the first sequence and the second sequence of the
polymer used according to the present invention. The intermediate
segment results from the polymerization:
i) of the first monomer or monomers, and possibly of the additional
monomer or monomers, remaining available after their polymerization
to a degree of conversion of 90% at most, to form the first
sequence, ii) and of the second monomer or monomers, and possibly
of the additional monomer or monomers, added to the reaction
mixture.
[0247] The formation of the second sequence is initiated when the
first monomers no longer react or are no longer being incorporated
into the polymer chain, either because they have all been consumed
or because their reactivity does not permit them to be further
consumed.
[0248] Thus the intermediate segment comprises the available first
monomers resulting from a degree of conversion of these first
monomers smaller than or equal to 90%, during introduction of the
second monomer or monomers during synthesis of the polymer.
[0249] The intermediate segment of the sequenced polymer is a
statistical polymer (which may also be referred to as a statistical
sequence). This means that it comprises a statistical distribution
of the first monomer or monomers and of the second monomer or
monomers as well as of any additional monomer or monomers that may
be present.
[0250] Thus the intermediate segment is a statistical sequence,
just as the first sequence and the second sequence if they are not
homopolymers (or in other words if they are both formed from at
least two different monomers).
Method for Preparation of the Copolymer:
[0251] The sequenced ethylene copolymer according to the invention
is prepared by free radical polymerization, according to well known
techniques for this type of polymerization.
[0252] The free radical polymerization is carried out in the
presence of an initiator, whose nature is adapted, in known manner,
according to the desired polymerization temperature and the
polymerization solvent. In particular, the initiator may be chosen
among the peroxide function initiators, the oxidation-reduction
couples, or other radical polymerization initiators known to those
skilled in the art.
[0253] In particular, by way of peroxide function initiator, the
following examples may be cited: [0254] a. the peroxy esters, such
as tert-butyl peroxyacetate, tert-butyl perbenzoate, tert-butyl
peroxy-2-ethylhexanoate (Trigonox 21S of Akzo Nobel),
2,5-bis(2-ethylhexanoylperoxy)-2,5-dimethylhexane (Trigonox 141 of
Akzo Nobel); [0255] b. the peroxydicarbonates, such as diisopropyl
peroxydicarbonate; [0256] c. the peroxyketones, such as methyl
ethyl ketone peroxide; [0257] d. hydroperoxides, such as hydrogen
peroxide (H.sub.2O.sub.2), tert-butyl hydroperoxide; [0258] e. the
diacyl peroxides, such as acetyl peroxide, benzoyl peroxide; [0259]
f. the dialkyl peroxides, such as di-tert-butyl peroxide; [0260] g.
the inorganic peroxides, such as potassium peroxodisulfate
(K.sub.2S.sub.2O.sub.8);
[0261] By way of initiator in the form of oxidation-reduction
couple, there may be cited the couple potassium
thiosulfate+potassium peroxodisulfate, for example.
[0262] According to a preferred embodiment, the initiator is chosen
from among the organic peroxides comprising 8 to 30 carbon atoms.
Preferably, the initiator used is
2,5-bis(2-ethylhexanoylperoxy)-2,5-dimethylhexane, sold under the
name Trigonox.RTM. 141 by the Akzo Nobel Company.
[0263] The sequenced copolymer used according to the invention is
prepared by free radical polymerization and not by controlled or
living polymerization. In particular, the polymerization of the
sequenced ethylene copolymer is carried out in the absence of
control agents, and in particular in the absence of control agent
traditionally used in living or controlled polymerization
processes, such as the nitroxides, the alkoxyamines, the dithio
esters, the dithiocarbamates, the dithiocarbonates or xanthates,
the trithiocarbonates, the copper-based catalysts, for example.
[0264] As indicated in the foregoing, the intermediate segment is a
statistical sequence, just as the first sequence and the second
sequence if they are not homopolymers (or in other words if they
are both formed from at least two different monomers).
[0265] The sequenced copolymer may be prepared by free radical
polymerization, and in particular by a method consisting of mixing,
in the same reactor, a polymerization solvent, an initiator, at
least one monomer with glass transition higher than or equal to
40.degree. C., at least one monomer of glass transition lower than
or equal to 20.degree. C., according to the following sequence:
[0266] part of the polymerization solvent and if necessary part of
the initiator and monomers of the first charge are poured into the
reactor, and the mixture is heated to a reaction temperature
between 60 and 120.degree. C., [0267] the said at least one first
monomer of Tg higher than or equal to 40.degree. C. and if
necessary part of the initiator are then poured into a first
charge, which is allowed to react for a duration T corresponding to
a degree of conversion of the said monomers of 90% at most, [0268]
more polymerization initiator, the said at least one second monomer
of glass transition lower than or equal to 20.degree. C. are then
poured into the reactor in a second charge, which is allowed to
react for a duration T', at the end of which the degree of
conversion of the said monomers reaches a plateau, [0269] the
reaction mixture is returned to room temperature.
[0270] Preferably, the copolymer may be prepared by free radical
polymerization, in particular by a method consisting of mixing, in
the same reactor, a polymerization solvent, an initiator, an
acrylic acid monomer, at least one monomer of glass transition
lower than or equal to 20.degree. C., at least one acrylate monomer
of formula CH.sub.2.dbd.CH--COOR.sub.2, in which R.sub.2 represents
a C.sub.4 to C.sub.12 cycloalkyl group, and at least one
methacrylate monomer of formula
CH.sub.2.dbd.C(CH.sub.3)--COOR'.sub.2, in which R'.sub.2 represents
a C.sub.4 to C.sub.12 cycloalkyl group, according to the following
step sequence: [0271] part of the polymerization solvent and if
necessary part of the initiator and monomers of the first charge
are poured into the reactor, and the mixture is heated to a
reaction temperature between 60 and 120.degree. C., [0272] the said
at least acrylate monomer of formula CH.sub.2.dbd.CH--COOR.sub.2
and the said at least methacrylate monomer of formula
CH.sub.2.dbd.C(CH.sub.3)--COOR'.sub.2, in the capacity of monomers
of Tg higher than or equal to 40.degree. C., and if necessary part
of the initiator are then poured into a first charge, which is
allowed to react for a duration T corresponding to a degree of
conversion of the said monomers of 90% at most, [0273] more
polymerization initiator, the acrylic acid monomer and the said at
least monomer of glass transition lower than or equal to 20.degree.
C. are then poured into the reactor in a second charge, which is
allowed to react for a duration T', at the end of which the degree
of conversion of the said monomers reaches a plateau, [0274] the
reaction mixture is returned to room temperature.
[0275] By polymerization solvent there is understood a solvent or a
mixture of solvents. In particular, by way of usable polymerization
solvent, there may be cited: [0276] the ketones that are liquid at
room temperature, such as methyl ethyl ketone, methyl isobutyl
ketone, diisobutyl ketone, isophorone, cyclohexanone, acetone;
[0277] the propylene glycol ethers that are liquid at room
temperature, such as propylene glycol monomethyl ether, propylene
glycol monomethyl ether acetate, mono-n-butyl ether of dipropylene
glycol; [0278] the short-chain esters (having 3 to 8 carbon atoms
in total), such as ethyl acetate, methyl acetate, propyl acetate,
n-butyl acetate, isopentyl acetate; [0279] the ethers that are
liquid at room temperature, such as diethyl ether, dimethyl ether
or dichlorodiethyl ether; [0280] the alkanes that are liquid at
room temperature, such as decane, heptane, dodecane, isododecane,
cyclohexane, isohexadecane; [0281] the aromatic cyclic compounds
that are liquid at room temperature, such as toluene and xylene;
the aldehydes that are liquid at room temperature, such as
benzaldehyde, acetaldehyde and mixtures thereof.
[0282] Traditionally, the polymerization solvent is a volatile oil
with flash point below 80.degree. C. The flash point is measured in
particular according to ISO Standard 3679.
[0283] The polymerization solvent may be chosen in particular from
among ethyl acetate, butyl acetate, the alcohols such as
isopropanol, ethanol, the aliphatic alkanes such as isododecane and
mixtures thereof. Preferably, the polymerization solvent is a
mixture of butyl acetate and isopropanol or isododecane.
[0284] According to another embodiment, the copolymer may be
prepared by free radical polymerization according to a method
consisting of mixing, in the same reactor, a polymerization
solvent, an initiator, at least one monomer with glass transition
lower than or equal to 20.degree. C., and at least one monomer of
Tg higher than or equal to 40.degree. C., according to the
following step sequence: [0285] part of the polymerization solvent
and if necessary part of the initiator and monomers of the first
charge are poured into the reactor, and the mixture is heated to a
reaction temperature between 60 and 120.degree. C., [0286] the said
at least one monomer of glass transition lower than or equal to
20.degree. C. and if necessary part of the initiator are then
poured into a first charge, which is allowed to react for a
duration T corresponding to a degree of conversion of the said
monomers of 90% at most, [0287] more polymerization initiator, the
said at least one monomer of Tg higher than or equal to 40.degree.
C. are then poured into the reactor in a second charge, which is
allowed to react for a duration T', at the end of which the degree
of conversion of the said monomers reaches a plateau, [0288] the
reaction mixture is returned to room temperature.
[0289] According to a preferred embodiment, the copolymer may be
prepared by free radical polymerization according to a preparation
method consisting of mixing, in the same reactor, a polymerization
solvent, an initiator, an acrylic acid monomer, at least one
monomer of glass transition lower than or equal to 20.degree. C.,
at least one monomer of Tg higher than or equal to 40.degree. C.,
and, in particular, in the capacity of monomers of Tg higher than
or equal to 40.degree. C., at least one acrylate monomer of formula
CH.sub.2.dbd.CH--COOR.sub.2, in which R.sub.2 represents a C.sub.4
to C.sub.12 cycloalkyl group, and at least one methacrylate monomer
of formula CH.sub.2.dbd.C(CH.sub.3)--COOR'.sub.2, in which R'.sub.2
represents a C.sub.4 to C.sub.12 cycloalkyl group, according to the
following step sequence: [0290] part of the polymerization solvent
and if necessary part of the initiator and monomers of the first
charge are poured into the reactor, and the mixture is heated to a
reaction temperature between 60 and 120.degree. C., [0291] the
acrylic acid monomer and the said at least monomer of glass
transition lower than or equal to 20.degree. C. and if necessary
part of the initiator are then poured into a first charge, which is
allowed to react for a duration T corresponding to a degree of
conversion of the said monomers of 90% at most, [0292] more
polymerization initiator, the said at least one acrylate monomer of
formula CH.sub.2.dbd.CH--COOR.sub.2 and the said at least one
methacrylate monomer of formula
CH.sub.2.dbd.C(CH.sub.3)--COOR'.sub.2, in the capacity of monomer
of Tg higher than or equal to 40.degree. C., are then poured into
the reactor in a second charge, which is allowed to react for a
duration T', at the end of which the degree of conversion of the
said monomers reaches a plateau, [0293] the reaction mixture is
returned to room temperature.
[0294] The polymerization temperature is preferably on the order of
90.degree. C.
[0295] The duration of reaction after the second charge is
preferably between 3 and 6 hours.
[0296] Sequenced copolymers such as those described in the
foregoing are described in particular in Patent Applications EP A
1411069 and EP A 1882709.
[0297] The film-forming polymer may be chosen from among the block
or static polymers and/or copolymers composed in particular of
polyurethanes, polyacrylics, silicones, fluoro polymers, butyl
rubbers, ethylene copolymers, natural rubbers and polyvinyl
alcohols and mixtures thereof. The monomers of the block or static
copolymers comprising at least one association of monomers whose
polymer results in a glass transition temperature lower than room
temperature (25.degree. C.) may be chosen in particular from among
butadiene, ethylene, propylene, acrylic, methacrylic, isoprene,
isobutene, a silicone and mixtures thereof.
Vinyl Polymer Grafted with a Carbosiloxane Dendrimer
[0298] According to a second embodiment, the composition according
to the invention may comprise, by way of film-forming polymer, a
film-forming polymer chosen from among the vinyl polymers
comprising at least one moiety derived from carbosiloxane
dendrimer.
[0299] The vinyl polymer may have in particular a skeleton and at
least one side chain, which comprises a carbosiloxane dendrimer
structure. Within the context of the present invention, the term
"carbosiloxane dendrimer structure" represents a molecular
structure possessing branched groups having high molecular weights,
the said structure having high regularity in the radial direction
starting from the bond to the skeleton. Such carbosiloxane
dendrimer structures are described in the form of a highly branched
siloxane-silylalkylene copolymer in Kokai 9-171 154, a Japanese
Patent Application laid open to public inspection.
[0300] The vinyl polymer contains moieties derived from
carbosiloxane dendrimers that can be represented by the following
general formula:
##STR00004##
in which R.sup.1 represents an aryl group or an alkyl group
possessing 1 to 10 carbon atoms, and X.sup.1 represents a
silylalkyl group which, when i=1, is represented by the
formula:
##STR00005##
in which R.sup.1 is the same as defined hereinabove, R.sup.2
represents an alkylene group possessing 2 to 10 carbon atoms,
R.sup.3 represents an alkyl group possessing 1 to 10 carbon atoms,
X.sup.i+1 represents a hydrogen atom, an alkyl group possessing 1
to 10 carbon atoms, an aryl group or the silylalkyl group defined
hereinabove with i=i+1; i is an integral number from 1 to 10,
representing the generation of the said silylalkyl group, and
a.sup.i is an integral number from 0 to 3; Y represents a
radical-polymerizable organic group chosen from the group
constituted by an organic group that contains a methacrylic group
or an acrylic group and that is represented by the formulas:
##STR00006##
in which R.sup.4 represents a hydrogen atom or an alkyl group,
R.sup.5 represents an alkylene group possessing 1 to 10 carbon
atoms, such as a methylene group, an ethylene group, a propylene
group or a butylene group, the methylene group and the propylene
group being preferred; and an organic group that contains a styryl
group and is represented by the formula:
##STR00007##
in which R.sup.6 represents a hydrogen atom or an alkyl group,
R.sup.7 represents an alkyl group possessing 1 to 10 carbon atoms,
such as a methyl group, an ethyl group, a propyl group or a butyl
group, the methyl group being preferred; R.sup.8 represents an
alkylene group possessing 1 to 10 carbon atoms, such as a methylene
group, an ethylene group, a propylene group, a butylene group, the
ethylene group being preferred; b in an integral number from 0 to 4
and c is equal to 0 or 1, such that if c is equal to 0,
--(R.sup.8).sub.c-- represents a bond. R.sup.1 represents an aryl
group or an alkyl group possessing 1 to 10 carbon atoms, where the
alkyl group is preferably represented by a methyl group, an ethyl
group, a propyl group, butyl group, a pentyl group, an isopropyl
group, an isobutyl group, a cyclopentyl group, a cyclohexyl group,
and where the aryl group is preferably represented by a phenyl
group and a naphthyl group, in which the methyl and phenyl groups
are particularly preferred, and the methyl group is preferred above
all.
[0301] The vinyl polymer that contains a carbosiloxane dendrimer
structure may be the product of polymerization of
[0302] (A) 0 to 99.9 parts by weight of a monomer of vinyl type;
and
[0303] (B) 100 to 0.1 parts by weight of a carbosiloxane dendrimer
that contains a group that can be polymerized by means of radicals,
represented by the general formula:
##STR00008##
in which Y represents a radical-polymerizable organic group,
R.sup.1 represents an aryl group or an alkyl group possessing 1 to
10 carbon atoms, and X.sup.1 represents a silylalkyl group which,
when i=1, is represented by the formula:
##STR00009##
in which R.sup.1 is the same as defined hereinabove, R.sup.2
represents an alkylene group possessing 2 to 10 carbon atoms,
R.sup.3 represents an alkyl group possessing 1 to 10 carbon atoms,
X.sup.1+1 represents a hydrogen atom, an alkyl group possessing 1
to 10 carbon atoms, an aryl group or the silylalkyl group defined
hereinabove with i=i+1; i is an integral number from 1 to 10,
representing the generation of the said silylalkyl group, and
a.sup.1 is an integral number from 0 to 3; where the said
radical-polymerizable organic group contained in component (B) is
chosen from the group constituted by an organic group that contains
a methacrylic group or an acrylic group and that is represented by
the formulas:
##STR00010##
in which R.sup.4 represents a hydrogen atom or an alkyl group,
R.sup.5 represents an alkylene group possessing 1 to 10 carbon
atoms; and an organic group that contains a styryl group and is
represented by the formula:
##STR00011##
in which R.sup.6 represents a hydrogen atom or an alkyl group,
R.sup.7 represents an alkyl group possessing 1 to 10 carbon atoms,
R.sup.8 represents an alkylene group possessing 1 to 10 carbon
atoms, b is an integral number from 0 to 4 and c is equal to 0 or
1. In the case that c is equal to 0, --(R.sup.8).sub.c-- represents
a bond.
[0304] The monomer of vinyl type that is component (A) in the vinyl
polymer is a monomer of vinyl type that contains a
radical-polymerizable vinyl group. There is no particular
limitation as regards the type of such a monomer. What follows are
examples of this monomer of vinyl type: methyl methacrylate, ethyl
methacrylate, n-propyl methacrylate, isopropyl methacrylate, or a
lower analogous alkyl methacrylate; glycidyl methacrylate; n-butyl
methacrylate, isobutyl methacrylate, tert-butyl methacrylate,
n-hexyl methacrylate, methacrylic acid, cyclohexyl methacrylate,
2-ethylhexyl methacrylate, octyl methacrylate, lauryl methacrylate,
stearyl methacrylate or a higher analogous methacrylate; vinyl
acetate, vinyl propionate, or a vinyl ester of lower analogous
fatty acid; vinyl caproate, vinyl 2-ethylhexanoate, vinyl laurate,
vinyl stearate, or an ester of higher analogous fatty acid;
styrene, vinyltoluene, benzyl methacrylate, phenoxyethyl
methacrylate, vinylpyrrolidone, or analogous aromatic vinyl
monomers; methacrylamide, N-methylol methacrylamide,
N-methoxymethyl methacrylamide, isobutoxymethoxy methacrylamide,
N,N-dimethyl methacrylamide, or analogous monomers of vinyl type
that contain amide groups; hydroxyethyl methacrylate, hydroxypropyl
alcohol methacrylate, or analogous monomers of vinyl type that
contain hydroxyl groups; methacrylic acid, itaconic acid, crotonic
acid, fumaric acid, maleic acid, or analogous monomers of vinyl
type that contain a carboxylic acid group; tetrahydrofurfuryl
methacrylate, butoxyethyl methacrylate, ethoxydiethylene glycol
methacrylate, polyethylene glycol methacrylate, polypropylene
glycol monomethacrylate, hydroxybutyl vinyl ether, cetyl vinyl
ether, 2-ethylhexyl vinyl ether, or an analogous monomer of vinyl
type with ether bonds; methacryloxypropyltrimethoxysilane,
polydimethylsiloxane having a methacrylic group on one of its
molecular ends, polydimethylsiloxane having a styryl group on one
of its molecular ends, or an analogous silicone compound possessing
unsaturated groups; butadiene; vinyl chloride; vinylidine chloride;
methacrylonitrite; dibutyl fumarate; anhydrous maleic acid;
anhydrous succinic acid; methacryt glycidyl ether; an organic salt
of an amine, an ammonium salt, and an alkali metal salt of
methacrylic acid, of itaconic acid, of crotonic acid, of maleic
acid or of fumaric acid; a radical-polymerizable unsaturated
monomer possessing a sulfonic acid group, such as a styrenesulfonic
acid group; a quaternary ammonium salt derived from methacrylic
acid, such as 2-hydroxy-3-methacryloxypropyltrimethylammonium
chloride; and an ester of methacrylic acid of an alcohol possessing
a tertiary amine group, such as an ester of methacrylic acid and
diethylamine.
[0305] Multifunctional monomers of vinyl type may also be used.
What follows represents examples of such compounds:
trimethylolpropane trimethacrylate, pentaerythritol
trimethacrylate, ethylene glycol dimethacrylate, tetraethylene
glycol dimethacrylate, polyethylene glycol dimethacrylate,
1,4-butanediol dimethacrylate, 1,6-hexanediol dimethacrylate,
neopentyl glycol dimethacrylate, trimethylolpropane trioxyethyl
methacrylate, tris-(2-hydroxyethyl)isocyanurate dimethacrylate,
tris-(2-hydroxyethyl)isocyanurate trimethacrylate,
polydimethylsiloxane capped with styryl groups possessing
divinylbenzene groups at both ends, or analogous silicone compounds
possessing unsaturated groups.
[0306] The carbosiloxane dendrimer, which is component (B), is
represented by the following formula:
##STR00012##
[0307] What follows are preferred examples of the
radical-polymerizable organic group Y: an acryloxymethyl group, a
3-acryloxypropyl group, a methacryloxymethyl group, a
3-methacryloxypropyl group, a 4-vinylphenyl group, a 3-vinylphenyl
group, a 4-(2-propenyl)phenyl group, a 3-(2-propenyl)phenyl group,
a 2-(4-vinylphenyl)ethyl group, a 2-(3-vinylphenyl)ethyl group, a
vinyl group, an allyl group, a methallyl group and a 5-hexenyl
group.
[0308] R.sup.1 represents an alkyl group or an aryl group
possessing 1 to 10 carbon atoms, where the alkyl group may be a
methyl group, an ethyl group, a propyl group, a butyl group, a
pentyl group, an isopropyl group, an isobutyl group, a cyclopentyl
group or a cyclohexyl group; and the aryl group may be a phenyl
group or a naphthyl group. The methyl and phenyl groups are
particularly preferred, the methyl group being preferred above all.
X.sup.1 represents a silylalkyl group which, when i=1, is
represented by the formula:
##STR00013##
in which R.sup.2 represents an alkylene group possessing 2 to 10
carbon atoms, such as an ethylene group, a propylene group, a
butylene group, a hexylene group or an analogous linear alkylene
group; a methylmethylene group, a methylethylene group, a
1-methylpentylene group, a 1,4-dimethylbutylene group or an
analogous branched alkylene group. The ethylene, methylethylene,
hexylene, 1-methylpentylene and 1,4-dimethylbutylene groups are
preferred above all. R.sup.3 represents an alkyl group possessing 1
to 10 carbon atoms, such as the methyl, ethyl, propyl, butyl and
isopropyl groups. R.sup.1 is the same as defined hereinabove.
X.sup.i+1 represents a hydrogen atom, an alkyl group possessing 1
to 10 carbon atoms, an aryl group or the silylalkyl group with
i=i+1; a.sup.i is an integral number from 0 to 3 and i is an
integral number from 1 to 10, indicating the generation number,
which represents the number of repetitions of the silylalkyl
group.
[0309] For example, when the generation number is equal to one, the
carbosiloxane dendrimer may be represented by the first general
formula shown below, in which Y, R.sup.1, R.sup.2 and R.sup.3 are
the same as defined hereinabove, R.sup.12 represents a hydrogen
atom or is identical to R.sup.1; a.sup.1 is identical to a.sup.i.
Preferably, the mean total number of OR.sup.3 groups in a molecule
is in the range from 0 to 7. When the generation number is equal to
2, the carbosiloxane dendrimer may be represented by the second
general formula shown below, in which Y, R.sup.1, R.sup.2, R.sup.3
and R.sup.12 are the same as defined hereinabove; a.sup.1 and
a.sup.2 represent the a.sup.i of the indicated generation.
Preferably, the mean total number of OR.sup.3 groups in a molecule
is in the range from 0 to 25. In the case that the generation
number is equal to 3, the carbosiloxane dendrimer may be
represented by the third general formula shown below, in which Y,
R.sup.1, R.sup.2, R.sup.3 and R.sup.12 are the same as defined
hereinabove; a.sup.1, a.sup.2 and a.sup.3 represent the a.sup.i of
the indicated generation. Preferably, the mean total number of
OR.sup.3 groups in a molecule is in the range from 0 to 79.
##STR00014##
[0310] A carbosiloxane dendrimer containing a radical-polymerizable
organic group may be represented by the following mean structural
formulas:
##STR00015## ##STR00016##
[0311] The carbosiloxane dendrimer may be manufactured according to
the method for manufacturing a branched siloxane silalkylene
described in Japanese Patent Hei 9-171154. For example, it may be
produced by subjecting to a hydrosilylation reaction an
organosilicon compound that contains a hydrogen atom bonded to a
silicon atom, represented by the following general formula:
##STR00017##
and an organosilicon compound that contains an alkenyl group. In
the above formula, the organosilicon compound may be represented by
3-methacryloxypropyltris(dimethylsiloxy)silane,
3-acryloxypropyltris-(dimethylsiloxy)silane and
4-vinylphenyltris-(dimethylsiloxy)silane. The organosilicon
compound that contains an alkenyl group may be represented by
vinyltris-(trimethylsiloxy)silane,
vinyltris-(dimethylphenylsiloxy)silane, and
5-hexenyltris-(trimethylsiloxy)silane. The hydrosilylation reaction
is carried out in the presence of a chloroplatinic acid, of a
complex of vinylsiloxane and platinum or of an analogous catalyst
of a transition metal.
[0312] In the vinyl polymer that contains a dendrimer structure,
the polymerization ratio between components (A) and (B), in terms
of weight ratio between (A) and (B), may be in a range of 0/100 to
99.9/0.1, and preferably in a range of 1/99 to 99/1. A ratio of
0/100 between components (A) and (B) means that the compound
becomes a homopolymer of component (B).
[0313] The vinyl polymer contains a carbosiloxane dendrimer
structure and this polymer may be obtained by copolymerization of
components (A) and (B) or by polymerization of component (B) alone.
The polymerization may be a radical polymerization or an ionic
polymerization, but radical polymerization is preferred. The
polymerization may be carried out by causing a reaction between
components (A) and (B) in a solution during a period of 3 to 20
hours in the presence of a radical initiator at a temperature of
50.degree. C. to 150.degree. C. An appropriate solvent for this
purpose is hexane, octane, decane, cyclohexane or an analogous
aliphatic hydrocarbon; benzene, toluene, xylene or an analogous
aromatic hydrocarbon; diethyl ether, dibutyl ether,
tetrahydrofuran, dioxane or analogous ethers; acetone, methyl ethyl
ketone, methyl isobutyl ketone, diisobutyl ketone or analogous
ketones; methyl acetate, ethyl acetate, butyl acetate, isobutyl
acetate or analogous esters; methanol, ethanol, isopropanol,
butanol or analogous alcohols; octamethylcyclotetrasiloxane,
decamethylcyclopentasiloxane, hexamethyldisiloxane,
octamethyltrisiloxane or an analogous organosiloxane oligomer. A
radical initiator may be any compound known in the art for
traditional radical polymerization reactions. Specific examples of
such radical initiators are 2,2'-azobis(isobutyronitrile),
2,2'-azobis(2-methylbutyronitrile),
2,2'-azobis(2,4-dimethylvaleronitrile) or analogous compounds of
azobis type; benzoyl peroxide, lauroyl peroxide, tert-butyl
peroxybenzoate, tert-butyl peroxy-2-ethylhexanoate or an analogous
organic peroxide. These radical initiators may be used alone or in
a combination of two or more. The radical initiators may be used in
a quantity of 0.1 to 5 parts by weight per 100 parts by weight of
components (A) and (B). A chain transfer agent may be added. The
chain transfer agent may be 2-mercaptoethanol, butyl mercaptan,
n-dodecyl mercaptan, 3-mercaptopropyltrimethoxysilane, a
polydimethylsiloxane possessing a mercaptopropyl group or an
analogous compound of mercapto type; methylene chloride,
chloroform, carbon tetrachloride, butyl bromide,
3-chloropropyltrimethoxysilane or an analogous halogen compound. In
the manufacture of the polymer of vinyl type, the residual vinyl
monomer that has not reacted may be eliminated after the
polymerization under conditions of heating under vacuum.
[0314] To facilitate the preparation of the mixture of raw material
for cosmetic products, the number-average molecular weight of the
vinyl polymer containing a carbosiloxane dendrimer may be chosen in
a range between 3,000 and 2,000,000, preferably between 5,000 and
800,000. It may be a liquid, a gum, a paste, a solid, a powder or
any other form. The preferred forms are solutions constituted by
dilution of a dispersion or of a powder in solvents.
[0315] The vinyl polymer may be a dispersion, in a liquid such as a
silicone oil, an organic oil, an alcohol or water, of a polymer of
vinyl type having a carbosiloxane dendrimer structure in its side
molecular chain.
[0316] In this embodiment, the vinyl polymer having a carbosiloxane
dendrimer structure in its side molecular chain is the same as that
described hereinabove. The liquid may be a silicone oil, an organic
oil, an alcohol or water. The silicone oil may be a
dimethylpolysiloxane having the two molecular ends capped by
trimethylsiloxy groups, a copolymer of methylphenylsiloxane and
dimethylsiloxane having both molecular ends capped with
trimethylsiloxy groups, a copolymer of
methyl-3,3,3-trifluoropropylsiloxane and dimethylsiloxane having
both molecular ends capped with trimethylsiloxy groups, or
analogous non-reactive linear silicone oils, as well as
hexamethylcyclotrisiloxane, octamethylcyclotetrasiloxane,
decamethylcyclopentasiloxane, dodecamethylcyclohexasiloxane or an
analogous cyclic compound. In addition to non-reactive silicone
oils, there may be used modified polysiloxanes possessing
functional groups such as silanol groups, amino groups and
polyether groups at the ends or in the interior of the side
molecular chains.
[0317] The organic oils may be paraffin oil, isoparaffin, hexyl
laurate, isopropyl myristate, myristyl myristate, cetyl myristate,
2-octyldodecylmyristate; isopropyl palmitate, 2-ethylhexyl
palmitate, butyl stearate, decyl oleate, 2-octyldodecyl oleate,
myristyl lactate, cetyl lactate, lanolin acetate, stearic alcohol,
cetostearic alcohol, oleic alcohol, avocado oil, almond oil, olive
oil, cocoa oil, jojoba oil, gum oil, sunflower seed oil, soy oil,
camellia oil, squalane, castor oil, mink oil, cottonseed oil,
coconut oil, egg yolk oil, beef suet, lard, polypropylene glycol
monooleate, neopentyl glycol 2-ethylhexanoate or an analogous
glycol ester oil; triglyceryl isostearate, the triglyceride of a
fatty acid of coconut oil or an ester oil of an analogous
polyhydric alcohol; polyoxyethylene lauryl ether, polyoxypropylene
cetyl ether or an analogous polyoxyalkylene ether.
[0318] The alcohol may be any type whatsoever that is appropriate
for use in conjunction with a raw material for cosmetic products.
For example, it may be methanol, ethanol, butanol, isopropanol or
analogous lower alcohols. A solution or a dispersion of alcohol
should have a viscosity in the range of 10 to 10.sup.9 mPa at
25.degree. C. To improve the sensory properties of use in a
cosmetic product, the viscosity should be in the range of 100 to
5.times.10.sup.8 mPas.
[0319] The solutions and the dispersions may be easily prepared by
mixing the vinyl polymer having a carbosiloxane dendrimer structure
with a silicone oil, an organic oil, an alcohol or water. The
liquids may be present in the step of polymerization of the polymer
of vinyl type having a carbosiloxane dendrimer structure. In this
case, the residual vinyl monomer that has not reacted should be
completely eliminated by heat treatment of the solution or of the
dispersion under atmospheric or reduced pressure. In the case of a
dispersion, the dispersity of the polymer of vinyl type may be
improved by adding a surfactant. Such an agent may be
hexylbenzenesulfonic acid, octylbenzenesulfonic acid,
decylbenzenesulfonic acid, dodecylbenzenesulfonic acid,
cetylbenzenesulfonic acid, myristylbenzenesulfonic acid, or anionic
surfactants of sodium salts of these acids; octyltrimethylammonium
hydroxide, dodecyltrimethylammonium hydroxide,
hexadecyltrimethylammonium hydroxide, octyldimethylbenzylammonium
hydroxide, decyldimethylbenzylammonium hydroxide,
dioctadecyldimethylammonium hydroxide, beef suet trimethylammonium
hydroxide, coconut oil trimethylammonium hydroxide or an analogous
cationic surfactant; a polyoxyalkylene alkyl ether, a
polyoxyalkylene alkylphenol, a polyoxyalkylene alkyl ester,
polyoxyalkylene sorbitol ester, polyethylene glycol, polypropylene
glycol, an ethylene oxide adduct of diethylene glycol
trimethylnonanol, and nonionic surfactants of polyester type, as
well as mixtures. In addition, the solvents and the dispersions may
be combined with iron oxide appropriate for use with cosmetic
products, or an analogous pigment, as well as zinc oxide, titanium
dioxide, silicon oxide, mica, talc or analogous inorganic oxides in
the form of powder. In the dispersion, a mean diameter of the
particles of polymer of vinyl type may be in a range between 0.001
and 100 microns, preferably between 0.01 and 50 microns. In fact,
outside the recommended range, a cosmetic product mixed in the
emulsion will not have a sufficiently good sensation on the skin or
to the touch, and will not have sufficient spreading properties or
a pleasant sensation.
[0320] The vinyl polymer contained in the dispersion or solution
may have a concentration in a range between 0.1 and 95% by weight,
preferably between 5 and 85% by weight. However, to facilitate the
manipulation and preparation of the mixture, the range should
preferably be between 10 and 75% by weight.
[0321] The vinyl polymer may be one of the polymers described in
the examples of Patent Application EP0963751 or, for example, the
product TIB-4-200 sold by Dow Corning.
[0322] According to one embodiment, the vinyl polymer additionally
comprises at least one fluoro organic group.
[0323] Particularly preferred are structures in which the
polymerized vinyl moieties constitute the skeleton, and
carbosiloxane dendritic structures as well as fluoro organic groups
are fixed to the side chains.
[0324] The fluoro organic groups may be obtained by substituting,
with fluorine atoms, all or part of the hydrogen atoms of methyl,
ethyl, propyl, isopropyl, butyl, isobutyl, tert-butyl, pentyl,
neopentyl, hexyl, cyclohexyl, heptyl, octyl, nonyl, decyl, undecyl,
dodecyl, tridecyl, tetradecyl, hexadecyl, octadecyl and other alkyl
groups having 1 to 20 carbon atoms, as well as of alkyloxyalkylene
groups having 6 to 22 carbon atoms.
[0325] The groups represented by the formula:
--(CH.sub.2).sub.x--(CF.sub.2).sub.y--R.sup.13 are suggested by way
of example of fluoroalkyl groups, obtained by substituting fluorine
atoms for hydrogen atoms of alkyl groups. In the formula, the index
"x" is 0, 1, 2 or 3 and "y" is an integer from 1 to 20. R.sup.13 is
an atom or a group chosen from among a hydrogen atom, a fluorine
atom, --CH(CF.sub.3).sub.2-- or CF(CF.sub.3).sub.2. Such
fluorine-substituted alkyl groups are exemplified by linear or
branched polyfluoroalkyl or perfluoroalkyl groups represented by
the formulas presented below.
[0326] --CF.sub.3, --C.sub.2F.sub.5, -nC.sub.3F.sub.7,
--CF(CF.sub.3).sub.2, -nC.sub.4F.sub.9, CF.sub.2CF(CF.sub.3).sub.2,
-nC.sub.6F.sub.13, -nC.sub.8F.sub.17, --CH.sub.2CF.sub.3,
--CH(CF.sub.3).sub.2,
CH.sub.2CH(CF.sub.3).sub.2--CH.sub.2(CF.sub.2).sub.2F,
--CH.sub.2(CF.sub.2).sub.3F, --CH.sub.2(CF.sub.2).sub.4F,
--CH.sub.2(CF.sub.2).sub.6F, --CH.sub.2(CF.sub.2).sub.8F,
--CH.sub.2CH.sub.2CF.sub.3, --CH.sub.2CH.sub.2(CF.sub.2).sub.2F,
--CH.sub.2CH.sub.2(CF.sub.2).sub.3F,
--CH.sub.2CH.sub.2(CF.sub.2).sub.4F,
--CH.sub.2CH.sub.2(CF.sub.2).sub.6F,
--CH.sub.2CH.sub.2(CF.sub.2).sub.8F,
--CH.sub.2CH.sub.2(CF.sub.2).sub.10F,
--CH.sub.2CH.sub.2(CF.sub.2).sub.12F,
--CH.sub.2CH.sub.2(CF.sub.2).sub.14F,
--CH.sub.2CH.sub.2(CF.sub.2).sub.16F,
--CH.sub.2CH.sub.2CH.sub.2CF.sub.3,
--CH.sub.2CH.sub.2CH.sub.2(CF.sub.2).sub.2F,
--CH.sub.2CH.sub.2CH.sub.2(CF.sub.2).sub.2H--CH.sub.2(CF.sub.2).sub.4H
and --CH.sub.2CH.sub.2(CF.sub.2).sub.3H. The groups represented
by
--CH.sub.2CH.sub.2--(CF.sub.2).sub.m--CFR.sup.14-[OCF.sub.2CF(CF.sub.3)].-
sub.n--OC.sub.3F.sub.7 are suggested as
fluoroalkyloxyfluoroalkylene groups obtained by substituting
fluorine atoms for hydrogen atoms of alkyloxyalkylene groups. In
the formula, the index "m" is 0 or 1, "n" is 0, 1, 2, 3, 4 or 5,
and R.sup.14 is a fluorine atom or CF.sub.3. Such
fluoroalkyloxyfluoroalkylene groups are exemplified by the
perfluoroalkyloxyfluoroalkylene groups represented by the formulas
presented below.
--CH.sub.2CH.sub.2CF(CF.sub.3)--[OCF.sub.2CF(CF.sub.3)].sub.n--OC.sub.3F.-
sub.7,
--CH.sub.2CH.sub.2CF.sub.2CF.sub.2--[OCF.sub.2CF(CF.sub.3)].sub.n---
OC.sub.3F.sub.7.
[0327] The number-average molecular weight of the vinyl polymer
used in the present invention may be between 3,000 and 2,000,000,
and more preferably between 5,000 and 800,000.
[0328] This type of fluoro vinyl polymer may be obtained by
addition [0329] of a vinyl monomer (B) that does not have a fluoro
organic group in the molecule [0330] to a vinyl monomer containing
fluoro organic groups in molecule (A), and [0331] a carbosiloxane
dendrimer (C) containing radical-polymerizable organic groups
represented by the following general formula (III):
##STR00018##
[0331] in which Y is a radical-polymerizable organic group and
R.sup.1 and X.sup.i are as hereinabove, and by subjecting them to
copolymerization.
[0332] The vinyl monomers (A) containing fluoro organic groups in
the molecule are preferably monomers represented by the general
formula:--(CH.sub.2).dbd.CR.sup.15COOR.sup.f. In the formula,
R.sup.15 is a hydrogen atom or a methyl group, R.sup.f is a fluoro
organic group exemplified by the fluoroalkyl and
fluoroalkyloxyfluoroalkylene groups described above. The compounds
represented by the formulas presented below are suggested by way of
specific examples of component (A). In the formulas presented
below, "z" is an integer from 1 to 4. [0333]
CH.sub.2.dbd.CCH.sub.3COO--CF.sub.3.
CH.sub.2.dbd.CCH.sub.3COO--C.sub.2F.sub.5.
CH.sub.2.dbd.CCH.sub.3COO-nC.sub.3F.sub.7. [0334]
CH.sub.2.dbd.CCH.sub.3COO--CF(CF.sub.3).sub.2.
CH.sub.2.dbd.CCH.sub.3COO-nC.sub.4F.sub.9. [0335]
CH.sub.2.dbd.CCH.sub.3COO--CF.sub.2CF(CF.sub.3).sub.2.
CH.sub.2.dbd.CCH.sub.3COO-nC.sub.5F.sub.11. [0336]
CH.sub.2.dbd.CCH.sub.3COO-nC.sub.6F.sub.13.
CH.sub.2.dbd.CCH.sub.3COO-nC.sub.8F.sub.17.
CH.sub.2.dbd.CCH.sub.3COO--CH.sub.2CF.sub.3. [0337]
CH.sub.2.dbd.CCH.sub.3COO--CH(CF.sub.3).sub.2.
CH.sub.2.dbd.CCH.sub.3COO--CH.sub.2CH(CF.sub.3).sub.2. [0338]
CH.sub.2.dbd.CCH.sub.3COO--CH.sub.2(CF.sub.2)F. [0339]
CH.sub.2.dbd.CCH.sub.3COO--CH.sub.2(CF.sub.2).sub.3F.
CH.sub.2.dbd.CCH.sub.3COO--CH.sub.2(CF.sub.2).sub.4F. [0340]
CH.sub.2.dbd.CH.sub.3COO--CH.sub.2(CF.sub.2).sub.6F.
CH.sub.2.dbd.CCH.sub.3COO--CH.sub.2(CF.sub.2).sub.8F. [0341]
CH.sub.2.dbd.CH.sub.3COO--CH.sub.2CH.sub.2CF.sub.3.
CH.sub.2.dbd.CCH.sub.3COO--CH.sub.2CH.sub.2(CF.sub.2).sub.2F.
[0342]
CH.sub.2.dbd.CCH.sub.3COO--CH.sub.2CH.sub.2(CF.sub.2).sub.3F.
CH.sub.2.dbd.CCH.sub.3COO--CH.sub.2CH.sub.2(CF.sub.2).sub.4F.
[0343]
CH.sub.2.dbd.CCH.sub.3COO--CH.sub.2CH.sub.2(CF.sub.2).sub.6F.
CH.sub.2.dbd.CCH.sub.3COO--CH.sub.2CH.sub.2(CF.sub.2).sub.8F.
[0344]
CH.sub.2.dbd.CCH.sub.3COO--CH.sub.2CH.sub.2(CF.sub.2).sub.10F.
CH.sub.2.dbd.CCH.sub.3COO--CH.sub.2CH.sub.2(CF.sub.2).sub.12F.
[0345]
CH.sub.2.dbd.CCH.sub.3COO--CH.sub.2CH.sub.2(CF.sub.2).sub.14F.
CH.sub.2CCH.sub.3COO--CH.sub.2CH.sub.2(CF.sub.2).sub.16F. [0346]
CH.sub.2.dbd.CCH.sub.3COO--CH.sub.2CH.sub.2CH.sub.2CF.sub.3.
CH.sub.2.dbd.CCH.sub.3COO--CH.sub.2CH.sub.2CH.sub.2(CF.sub.2).sub.2F.
[0347]
CH.sub.2.dbd.CCH.sub.3COO--CH.sub.2CH.sub.2CH.sub.2(CF.sub.2)H.
CH.sub.2.dbd.CCH.sub.3COO--CH.sub.2(CF.sub.2).sub.4H. [0348]
CH.sub.2.dbd.CCH.sub.3COO--CH.sub.2CH.sub.2(CF.sub.2).sub.3H.
[0349]
CH.sub.2.dbd.CCH.sub.3COO--CH.sub.2CH.sub.2CF(CF.sub.3)--[OCF.sub.2CF(CF.-
sub.3)].sub.Z--OC.sub.3F.sub.7. [0350]
CH.sub.2.dbd.CCH.sub.3COO--CH.sub.2CH.sub.2CF.sub.2CF.sub.2--[OCF.sub.2CF-
(CF.sub.3)].sub.Z--OC.sub.3F.sub.7. [0351]
CH.sub.2.dbd.CHCOO--CF.sub.3. CH.sub.2.dbd.CHCOO--C.sub.2F.sub.5.
CH.sub.2.dbd.CHCOO-nC.sub.3F.sub.7.
CH.sub.2.dbd.CHCOO--CF(CF.sub.3).sub.2. [0352]
CH.sub.2--CHCOO-nC.sub.4F.sub.9.
CH.sub.2.dbd.CHCOO--CF.sub.2CF(CF.sub.3).sub.2.
CH.sub.2.dbd.CHCOO-nC.sub.5F.sub.11. [0353]
CH.sub.2.dbd.CHCOO-nC.sub.6F.sub.13.
CH.sub.2.dbd.CHCOO-nC.sub.8F.sub.17.
CH.sub.2.dbd.CHCOO--CH.sub.2CF.sub.3. [0354]
CH.sub.2.dbd.CHCOO--CH(CF.sub.3).sub.2.
CH.sub.2--CHCOO--CH.sub.2CH(CF.sub.3).sub.2.
CH.sub.2.dbd.CHCOO--CH.sub.2(CF.sub.2).sub.2F. [0355]
CH.sub.2.dbd.CHCOO--CH.sub.2(CF.sub.2).sub.8F.
CH.sub.2--CHCOO--CH.sub.2(CF.sub.2).sub.4F.
CH.sub.2.dbd.CHCOO--CH.sub.2(CF.sub.2).sub.6F. [0356]
CH.sub.2.dbd.CHCOO--CH.sub.2(CF.sub.2).sub.8F.
CH.sub.2.dbd.CHCOO--CH.sub.2CH.sub.2CF.sub.3. [0357]
CH.sub.2.dbd.CHCOO--CH.sub.2CH.sub.2(CF.sub.2).sub.2F. [0358]
CH.sub.2.dbd.CHCOO--CH.sub.2CH.sub.2(CF.sub.2).sub.3F.
CH.sub.2.dbd.CHCOO--CH.sub.2CH.sub.2(CF.sub.2).sub.4F. [0359]
CH.sub.2.dbd.CHCOO--CH.sub.2CH.sub.2(CF.sub.2).sub.6F.
CH.sub.2.dbd.CHCOO--CH.sub.2CH.sub.2(CF.sub.2).sub.8F. [0360]
CH.sub.2.dbd.CHCOO--CH.sub.2CH.sub.2(CF.sub.2).sub.10F.
CH.sub.2.dbd.CHCOO--CH.sub.2CH.sub.2(CF.sub.2).sub.12F. [0361]
CH.sub.2.dbd.CHCOO--CH.sub.2CH.sub.2(CF.sub.2).sub.14F.
CH.sub.2.dbd.CHCOO--CH.sub.2CH.sub.2(CF.sub.2).sub.16F. [0362]
CH.sub.2.dbd.CHCOO--CH.sub.2CH.sub.2CH.sub.2CF.sub.3.
CH.sub.2.dbd.CHCOO--CH.sub.2CH.sub.2CH.sub.2(CF.sub.2).sub.2F.
[0363] CH.sub.2.dbd.CHCOO--CH.sub.2CH.sub.2CH.sub.2(CF).sub.2H.
CH.sub.2.dbd.CHCOO--CH.sub.2(CF.sub.2).sub.4H. [0364]
CH.sub.2.dbd.CHCOO--CH.sub.2CH.sub.2(CF.sub.2).sub.3H. [0365]
CH.sub.2.dbd.CHCOO--CH.sub.2CH.sub.2CF(CF.sub.3)--[OCF.sub.2CF(CF.sub.3)]-
.sub.Z--OC.sub.3F.sub.7. [0366]
CH.sub.2.dbd.CHCOO--CH.sub.2CH.sub.2CF.sub.2CF.sub.2--[CF.sub.2CF(CF.sub.-
3)].sub.Z--OC.sub.3F.sub.7.
[0367] Among those, the vinyl polymers represented by the formulas
presented below are preferable. [0368]
CH.sub.2.dbd.CHCOO--CH.sub.2CH.sub.2(CF.sub.2).sub.6F.
CH.sub.2.dbd.CHCOO--CH.sub.2CH.sub.2(CF.sub.2).sub.8F. [0369]
CH.sub.2.dbd.CCH.sub.3COO--CH.sub.2CH.sub.2(CF.sub.2).sub.6F.
CH.sub.2.dbd.CCH.sub.3COO--CH.sub.2CH.sub.2(CF.sub.2).sub.8F.
[0370] CH.sub.2.dbd.CHCOO--CH.sub.2CF.sub.3.
CH.sub.2.dbd.CCH.sub.3COO--CH.sub.2CF.sub.3
[0371] The vinyl polymers represented by the formulas presented
below are particularly preferable. [0372]
CH.sub.2.dbd.CHCOO--CH.sub.2CF.sub.3.
CH.sub.2.dbd.CCH.sub.3COO--CH.sub.2CF.sub.3.
[0373] The vinyl monomers (B) that do not contain fluoro organic
groups in the molecule may be any molecules whatsoever having
radical-polymerizable vinyl groups, which molecules are exemplified
for example by methyl acrylate, methyl methacrylate, ethyl
acrylate, ethyl methacrylate, n-propyl acrylate, n-propyl
methacrylate, isopropyl acrylate, isopropyl methacrylate, and other
lower alkyl acrylates or methacrylates; glycidyl acrylate, glycidyl
methacrylate; n-butyl acrylate, n-butyl methacrylate, isobutyl
acrylate, isobutyl methacrylate, tert-butyl acrylate, tert-butyl
methacrylate, n-hexyl acrylate, n-hexyl methacrylate, cyclohexyl
acrylate, cyclohexyl methacrylate, 2-ethylhexyl acrylate,
2-ethylhexyl methacrylate, octyl acrylate, octyl methacrylate,
lauryl acrylate, lauryl methacrylate, stearyl acrylate, stearyl
methacrylate, and other higher acrylates and methacrylates; vinyl
acetate, vinyl propionate and other vinyl esters of lower fatty
acids; vinyl butyrate, vinyl caproate, vinyl 2-ethylhexanoate,
vinyl laurate, vinyl stearate, and other esters of higher fatty
acids; styrene, vinyltoluene, benzyl acrylate, benzyl methacrylate,
phenoxyethyl acrylate, phenoxyethyl methacrylate, vinylpyrrolidone
and other aromatic vinyl monomers; dimethylaminoethyl acrylate,
dimethylaminoethyl methacrylate, diethylaminoethyl acrylate,
diethylaminoethyl methacrylate, and other vinyl esters with amino
groups, acrylamide, methacrylamide, N-methylol acrylamide,
N-methylol methacrylamide, N-methoxymethyl acrylamide,
N-methoxymethyl methacrylamide, isobutoxymethoxy acrylamide,
isobutoxymethoxy methacrylamide, N,N-dimethyl acrylamide,
N,N-dimethyl methacrylamide, and other monomers of vinyl type that
contain amide groups; hydroxyethyl acrylate, hydroxyethyl
methacrylate, hydroxypropyl alcohol of acrylic acid, hydroxypropyl
alcohol of methacrylic acid, and other vinyl monomers that contain
hydroxy groups; acrylic acid, methacrylic acid, itaconic acid,
crotonic acid, fumaric acid, maleic acid, and other vinyl monomers
that contain a carboxylic acid group; tetrahydrofurfuryl acrylate,
tetrahydrofurfuryl methacrylate, butoxyethyl acrylate, butoxyethyl
methacrylate, ethoxydiethylene glycol acrylate, ethoxydiethylene
glycol methacrylate, polyethylene glycol acrylate, polyethylene
glycol methacrylate, polypropylene glycol monoacrylate,
polypropylene glycol monomethacrylate, hydroxybutyl vinyl ether,
cetyl vinyl ether, 2-ethylhexyl vinyl ether, and other vinyl
monomers with ether bonds; acryloxypropyltrimethoxysilane,
methacryloxypropyltrimethoxysilane, polydimethylsiloxanes having
acryl or methacryl groups on one of the ends, polydimethylsiloxanes
containing alkenaryl groups on one of the ends, and other silicone
compounds containing unsaturated groups; butadiene; vinyl chloride;
vinylidine chloride; acrylonitrile, methacrylonitrile; dibutyl
fumarate; maleic anhydride; dodecylsuccinic anhydride; acryl
glycidyl ether, methacryl glycidyl ether, 3,4-epoxycyclohexylmethyl
acrylate, 3,4-epoxycyclohexylmethyl methacrylate, alkali metal
salts, ammonium salts and the organic amine salts of acrylic acid,
methacrylic acid, itaconic acid, crotonic acid, fumaric acid,
maleic acid and other radical-polymerizable unsaturated carboxylic
acids, radical-polymerizable unsaturated monomers containing
sulfonic acid groups, such as styrenesulfonic acid as well as their
alkali metal salts, their ammonium salts and their organic amine
salts; quaternary ammonium salts derived from acrylic acid or
methacrylic acid, such as
2-hydroxy-3-methacryloxypropyltrimethylammonium chloride; esters of
methacrylic acid of an alcohol possessing a tertiary ammonium
group, such as the diethylamine ester of methacrylic acid and their
quaternary ammonium salts.
[0374] In addition, it is also possible to use, by way of vinyl
monomers (B), the polyfunctional vinyl monomers that are
exemplified for example by trimethylolpropane triacrylate,
trimethylolpropane trimethacrylate, pentaerythritol triacrylate,
pentaerythritol trimethacrylate, ethylene glycol diacrylate,
ethylene glycol dimethacrylate, tetraethylene glycol diacrylate,
tetraethylene glycol dimethacrylate, polyethylene glycol
diacrylate, polyethylene glycol dimethacrylate, 1,4-butanediol
diacrylate, 1,4-butanediol dimethacrylate, 1,6-hexanediol
diacrylate, 1,6-hexanediol dimethacrylate, neopentyl glycol
diacrylate, neopentyl glycol dimethacrylate, trimethylolpropane
trioxyethyl acrylate, trimethylolpropane trioxyethyl methacrylate,
tris-(2-hydroxyethyl)isocyanurate diacrylate,
tris-(2-hydroxyethyl)isocyanurate dimethacrylate,
tris-(2-hydroxyethyl)isocyanurate triacrylate,
tris-(2-hydroxyethyl)isocyanurate trimethacrylate,
polydimethylsiloxane in which both ends of the molecular chain are
blocked by alkenaryl groups, and other silicone compounds with
unsaturated groups.
[0375] As regards the aforementioned ratio in which component (A)
and component (B) are copolymerized, the weight ratio of compound
(A) to compound (B) must be in the range from 0.1:99.9 to 100:0,
and preferably in the range of 1:99 to 100:0.
[0376] Carbosiloxane dendrimer (C) is represented by general
formula (III) indicated hereinabove. In formula (III), Y is a
radical-polymerizable organic group, whose type is not subject to
any special limitations whatsoever, provided it is an organic group
capable of undergoing a radical addition reaction. Organic groups
containing acryl and methacryl, organic groups containing
alkenaryl, or alkenyl groups with 2 to 10 carbon atoms represented
by the general formulas presented below are suggested by way of
specific examples.
##STR00019##
[0377] In the formulas, R.sup.4 and R.sup.6 are hydrogen atoms or
methyl groups, R.sup.5 and R.sup.8 are alkylene groups with 1 to 10
carbon atoms, and R.sup.7 is an alkyl group with 1 to 10 carbon
atoms. The index "b" is an integer from 0 to 4, and "c" is 0 or 1.
Acryloxymethyl, 3-acryloxypropyl, methacryloxymethyl,
3-methacryloxypropyl, 4-vinylphenyl, 3-vinylphenyl,
4-(2-propenyl)phenyl, 3-(2-propenyl)phenyl, 2-(4-vinylphenyl)ethyl,
2-(3-vinylphenyl)enyl, vinyl, allyl, methallyl and 5-hexenyl are
suggested by way of examples of such radical-polymerizable organic
groups. The exponent "i" in formula (II), which is an integer from
1 to 10, is the number of generations of the said silylalkyl group,
or in other words the number of times that the silylalkyl group is
repeated. Thus the carboxyloxane dendrimer of this component with a
generation number of 1 is represented by the general formula:
##STR00020##
(in which Y, R.sup.1, R.sup.2 and R.sup.3 are such as hereinabove
and R.sup.12 is a hydrogen atom or such as R.sup.1 described
hereinabove. The index "a.sup.1" is an integer from 0 to 3, the
mean total of "a.sup.1" per molecule being from 0 to 7). The
carbosiloxane dendrimers of this component with a generation number
of 2 are represented by the general formula:
##STR00021##
(in which Y, R.sup.1, R.sup.2, R.sup.3 and R.sup.12 are such as
hereinabove and the indices "a.sup.1" and "a.sup.2" are integers
from 0 to 3, the mean total of "a.sup.1" and of "a.sup.2" per
molecule being from 0 to 25).
[0378] The carbosiloxane dendrimers of this component with a
generation number of 3 are represented by the general formula:
##STR00022##
(in which Y, R.sup.1, R.sup.2, R.sup.3 and R.sup.12 are such as
hereinabove and the indices "a.sup.1", "a.sup.2" and "a.sup.3" are
integers from 0 to 3, the mean total of "a.sup.1" of "a.sup.2" and
of "a.sup.3" per molecule being from 0 to 79).
[0379] Component (C) is exemplified by carbosiloxane dendrimers
represented by the formulas of mean composition represented
below.
##STR00023## ##STR00024##
[0380] The carbosiloxane dendrimers of component (C) may be
prepared by using the method of preparation of branched
siloxane/silalkylene copolymers described in the document
EP1055674. For example, they may be prepared by subjecting organic
silicone compounds containing alkenyl groups and silicone compounds
comprising hydrogen atoms bonded to the silicon, represented by the
general formula:
##STR00025##
(in which R.sup.1 and Y are such as hereinabove) to a
hydrosilylation reaction. For example,
3-methacyloxypropyltris(dimethylsiloxy)silane,
3-acryloxypropyltris(dimethylsiloxy)silane and
4-vinylphenyltris(dimethylsiloxy)silane are used by way of silicon
compounds represented by the above formula.
Vinyltris(dimethylsiloxy)silane,
vinyltris(dimethylphenylsiloxy)silane and
5-hexenyltris(trimethylsiloxy)silane are used as organic silicon
compounds containing alkenyl groups. In addition, it is preferable
to carry out the hydrosilylation reaction in the presence of a
transition metal catalyst such as chloroplatinic acid and the
complex of platinum/vinylsiloxane.
[0381] The copolymerization ratio of component (C), in terms of its
weight ratio relative to the total of compound (A) and of compound
(B), must be in the range of 0.1:99.9 to 99.9:0.1, and preferably
in the range of 1:99 to 99:1, and even more preferably in the range
of 5:95 to 95:5.
[0382] Amino groups may be introduced into the side chains of the
vinyl polymer by using, included in component (B), vinyl monomers
containing amino groups, such as dimethylaminoethyl acrylate,
dimethylaminoethyl methacrylate, diethylaminoethyl acrylate and
diethylaminoethyl methacrylate, then carrying out a modification
with potassium monochloroacetate, ammonium monochloroacetate, the
aminomethylpropanol salt of monochloroacetic acid, the
triethanolamine salt of monobromoacetic acid, sodium
monochloropropionate, and other alkali metal salts of halo fatty
acids; otherwise it is possible to introduce carboxylic acid groups
into the side chains of the vinyl polymer by using, included in
component (B), vinyl monomers containing carboxylic acids, such as
acrylic acid, methacrylic acid, itaconic acid, crotonic acid,
fumaric acid and maleic acid and similar compounds, then
neutralizing the product with triethylamine, diethylamine,
triethanolamine and other amines.
[0383] The fluoro vinyl polymer may be one of the polymers
described in the examples of Patent Application WO03/045337 or, for
example, the product TIB-4-100 sold by Dow Corning.
Polymer in Dispersion
[0384] According to a third embodiment of the invention, the
film-forming polymer present in the composition according to the
invention is a dispersion of particles of acryl or vinyl radical
homopolymer or copolymer dispersed in the liquid fatty phase of the
composition.
[0385] According to the invention, the polymer in the form of
particles dispersed in the volatile liquid fatty phase is a solid
insoluble in the liquid fatty phase of the composition even at its
softening temperature, in contrast to a wax that itself is of
polymeric origin which itself is soluble in the liquid organic
phase (or fatty phase) at its melting temperature.
[0386] The composition according to the invention advantageously
comprises at least one stable dispersion of generally spherical
particles or one or more polymers in a volatile liquid fatty phase.
In particular, these dispersions may have the form of polymer
nanoparticles in stable dispersion in the said liquid organic
phase. The nanoparticles preferably have a mean size between 5 and
800 nm, and better between 50 and 500 nm. Nevertheless, it is
possible to obtain polymer particle sizes as large as 1 .mu.m.
[0387] Preferably, the polymer particles in dispersion are
insoluble in the water-soluble alcohols, such as ethanol, for
example.
[0388] The polymers in dispersion that can be used in the first
composition of the invention preferably have a molecular weight on
the order to 2,000 to 10,000,000 g/mol, and a Tg of -100.degree. C.
to 300.degree. C. and better of -50.degree. C. to 100.degree. C.,
preferably of -10.degree. C. to 50.degree. C.
[0389] It is possible to use filmifiable polymers, preferably
having a low Tg, lower than or equal to skin temperature and
especially lower than or equal to 40.degree. C.
[0390] Preferably, the polymer used is filmifiable, or in other
words capable of forming, on its own or in association with a
plasticizing agent, an isolable film. Nevertheless, it is possible
to use a non-filmifiable polymer.
[0391] By "non-filmifiable polymer" there is understood a polymer
that is not capable, on its own, of forming an isolable film. This
polymer makes it possible, in association with a non-volatile
compound of the oil type, to form a continuous and homogeneous
deposit on the skin and/or the lips.
[0392] Among the filmifiable polymers there may be cited the
acrylic or vinyl radical homopolymers or copolymers, preferably
having a Tg lower than or equal to 40.degree. C. and in particular
ranging from -10.degree. to 30.degree. C., used alone or in a
mixture.
[0393] Among the non-filmifiable polymers, there may be cited vinyl
or acrylic radical homopolymers or copolymers, possibly
cross-linked, preferably having a Tg higher than o 40.degree. C.
and in particular ranging from -40.degree. C. to 150.degree. C.,
used alone or in a mixture.
[0394] By radical polymer there will be understood a polymer
obtained by polymerization of monomers having in particular
ethylenic unsaturation, each monomer being capable of
homopolymerization (as opposed to the polycondensates). The radical
polymers may be in particular vinyl polymers or copolymers,
especially acrylic polymers.
[0395] The acrylic polymers may result from the polymerization of
ethylenically unsaturated monomers having at least one acid group
and/or of esters of these acid monomers and/or of amides of these
acids.
[0396] As monomer carrying an acid group there may be used
.alpha.,.beta.-ethylenic unsaturated carboxylic acids, such as
acrylic acid, methacrylic acid, crotonic acid, maleic acid,
itaconic acid. Preferably there will be used (meth)acrylic acid and
crotonic acid, and more preferentially (meth)acrylic acid.
[0397] The esters of acid monomers are advantageously chosen from
among the esters of (meth)acrylic acids (also referred to as
(meth)acrylates), such as the alkyl (meth)acrylates, in particular
with C.sub.1-C.sub.20 alkyl, preferably C.sub.1-C.sub.8, the aryl
(meth)acrylates, in particular with C.sub.6-C.sub.10 aryl, the
hydroxyalkyl (meth)acrylates, in particular with C.sub.2-C.sub.6
hydroxyalkyl. As alkyl (meth)acrylates there may be cited methyl,
ethyl, butyl, isobutyl, 2-ethylhexyl and lauryl (meth)acrylate. As
hydroxyalkyl (meth)acrylates there may be cited hydroxyethyl
(meth)acrylate, 2-hydroxypropyl (meth)acrylate. As aryl
(meth)acrylates there may be cited benzyl or phenyl acrylate.
[0398] The particularly preferred (meth)acrylic acid esters are the
alkyl (meth)acrylates.
[0399] As radical polymer there are preferably used the copolymers
of (meth)acrylic acid and alkyl (meth)acrylate, especially with
C.sub.1-C.sub.4 alkyl. More preferentially, there may be used the
methyl acrylates, copolymerized if necessary with acrylic acid.
[0400] As amides of acid monomers there may be cited the
(meth)acrylamides and especially the N-alkyl (meth)acrylamides, in
particular with C.sub.2-C.sub.12 alkyl, such as N-ethyl acrylamide,
N-t-butyl acrylamide, N-octyl acrylamide; the N-dialkyl
(C.sub.1-C.sub.4) (meth)acrylamides.
[0401] The acrylic polymers may also result from the polymerization
of ethylenically unsaturated monomers having at least one amine
group, in free or else partly or completely neutralized form, or
else even partly or completely quaternized. Such monomers may be,
for example, dimethylaminoethyl (meth)acrylate, dimethylaminoethyl
methacrylamide, vinylamine, vinylpyridine, diallyldimethylammonium
chloride.
[0402] The vinyl polymers may also result from the
homopolymerization or copolymerization of at least one monomer
chosen from among the vinyl esters and the styrene monomers. In
particular, these monomers may be polymerized with acid monomers
and/or their esters and/or their amides, such as those mentioned in
the foregoing. As examples of vinyl esters there may be cited vinyl
acetate, vinyl propionate, vinyl neodecanoate, vinyl pivalate,
vinyl benzoate and vinyl t-butylbenzoate. As styrene monomers there
may be cited styrene and alpha-methylstyrene.
[0403] The list of monomers given is not limitative, and it is
possible to use any monomer known to those skilled in the art and
falling within the categories of acrylic and vinyl monomers
(including the monomers modified by a silicone chain).
[0404] As other usable vinyl monomers there may also be cited:
[0405] N-vinylpyrrolidone, vinyl caprolactam, the vinyl
N--(C.sub.1-C.sub.6)alkyl pyrroles, the vinyloxazoles, the
vinylthiazoles, the vinylpyrimidines, the vinylimidazoles. [0406]
the olefins such as ethylene, propylene, butylene, isoprene,
butadiene.
[0407] The vinyl polymer may be cross-linked by means of one or
more difunctional monomers, especially comprising at least two
ethylenic unsaturations, such as ethylene glycol dimethacrylate of
diallyl phthalate.
[0408] The polymer or polymers in dispersion in the organic liquid
phase may represent, as dry material, 5 to 40% by weight of the
composition, preferably 5 to 35% and better 8 to 30%.
[0409] Preferably the choice is to use a dispersion of particles of
filmifiable polymer, the particles being dispersed in a volatile
oil.
[0410] According to one embodiment, the composition contains a
stabilizer solid at room temperature. The polymer particles are
preferably stabilized at the surface by virtue of a stabilizer,
which may be a sequenced polymer, a graft polymer and/or a
statistical polymer, alone or in a mixture. Stabilization may be
effected by any known means, and in particular by direct addition
of the sequenced polymer, graft polymer and/or statistical polymer
during polymerization.
[0411] The stabilizer is preferably also present in the mixture
before polymerization of the polymer. Nevertheless, it is also
possible to add it continuously, especially when the monomers are
also added continuously.
[0412] There may be used 2-30% by weight of stabilizer relative to
the initial mixture of monomers, and preferably 5-20% by
weight.
[0413] Among the graft polymers there may be cited the silicone
polymers grafted with a hydrocarbon chain; the hydrocarbon polymers
grafted with a silicone chain.
[0414] Thus there may be used grafted or sequenced block copolymers
comprising at least one block of polyorganosiloxane type and at
least one block of a radical polymer, such as the graft copolymers
of acrylic/silicone type, which may be employed in particular when
the non-aqueous medium is a silicone.
[0415] There may also be used grafted or sequenced block copolymers
comprising at least one block of polyorganosiloxane type and at
least one polyether. The polyorganopolysiloxane block may be in
particular a polydimethylsiloxane or else even a poly
(C.sub.2-C.sub.18) alkyl methylsiloxane; the polyether block may be
a poly (C.sub.2-C.sub.18) alkylene, particularly polyoxyethylene
and/or polyoxypropylene. In particular, there may be used copolyol
dimethicones or copolyol (C.sub.2-C.sub.18) alkyl dimethicones,
such as those sold under the name "Dow Corning 3225C" by the Dow
Corning Company, the lauryl dimethicones, such as those sold under
the name "Dow Corning Q2-5200" by the Dow Corning Company.
[0416] As grafted or sequenced block copolymers there may also be
cited those comprising at least one block resulting from the
polymerization of at least one ethylenic monomer having one or more
ethylenic bonds, which may be conjugated, such as ethylene or the
dienes such as butadiene and isoprene, and at least one block of a
vinyl and better styrene polymer. When the ethylenic monomer
contains several ethylenic bonds, which may be conjugated, the
residual ethylenic unsaturations after polymerization are generally
hydrogenated. Thus, in known manner, the polymerization of isoprene
leads, after hydrogenation, to the formation of ethylene-propylene
block, and the polymerization of butadiene leads, after
hydrogenation, to the formation of ethylene-butylene block. Among
these polymers there may be cited the sequenced copolymers,
especially of "diblock" or "triblock" type of the
polystyrene/polyisoprene (SI), polystyrene/polybutadiene (SB) type,
such as those sold under the name of `LUVITOL HSB` by BASF, of the
polystyrene/copoly(ethylene-propylene) (SEP) type, such as those
sold under the name of `Kraton` by Shell Chemical Co or even of the
polystyrene/copoly(ethylene-butylene) (SEB) type. In particular,
there may be used Kraton G1650 (SEBS), Kraton G1651 (SEBS), Kraton
G1652 (SEBS), Kraton G1657X (SEBS), Kraton G1701X (SEP), Kraton
G1702X (SEP), Kraton G1726X (SEB), Kraton D-1101 (SBS), Kraton
D-1102 (SBS), Kraton D-1107 (SIS). The polymers are generally
referred to as hydrogenated or non-hydrogenated diene
copolymers.
[0417] There may also be used Gelled Permethyl 99A-750, 99A-753-59
and 99A-753-58 (mixture of triblock and star polymer), Versagel
5960 of Penreco (triblock+star polymer); OS129880, OS129881 and
OS84383 of Lubrizol (styrene/methacrylate copolymer).
[0418] As grafted or sequenced block copolymers comprising at least
one block resulting from the polymerization of at least one
ethylenic monomer having one or more ethylenic bonds and at least
one block of an acrylic polymer there may be cited the poly(methyl
methacrylate)/polyisobutylene bisequenced or trisequenced
copolymers or the graft copolymers with poly(methyl methacrylate)
skeleton and polyisobutylene grafts.
[0419] As grafted or sequenced block copolymers comprising at least
one block resulting from the polymerization of at least one
ethylenic monomer having one or more ethylenic bonds and at least
one block of a polyether such as a C.sub.2-C.sub.18 polyalkylene
(especially containing polyethylene and/or polyoxypropylene) there
may be cited the polyoxyethylene/polybutadiene or
polyoxyethylene/polyisobutylene bisequenced or trisequenced
copolymers.
[0420] Thus there may be employed copolymers based on alkyl
acrylates or methacrylates obtained from C.sub.1-C.sub.4 alcohols
and on alkyl acrylates or methacrylates obtained from
C.sub.8-C.sub.30 alcohols. In particular, there may be cited the
copolymer of stearyl methacrylate/methyl methacrylate.
[0421] When the liquid synthesis solvent comprises at least one
silicone oil, the stabilizing agent is preferably chosen from among
the group consisting of the grafted or sequenced block copolymers
comprising at least one block of polyorganosiloxane type and at
least one block of a radical polymer or of a polyether or of a
polyester, such as the polyoxypropylene and/or oxyethylene
blocks.
[0422] When the liquid fatty phase does not comprise silicone oil,
the stabilizing agent is preferably chosen from among the group
consisting of: [0423] (a) the grafted or sequenced block copolymers
comprising at least one block of polyorganosiloxane type and at
least one block of a radical polymer or of a polyether or of a
polyester, [0424] (b) copolymers based on alkyl acrylates or
methacrylates obtained from C.sub.1-C.sub.4 alcohols and on alkyl
acrylates or methacrylates obtained from C.sub.8-C.sub.30 alcohols,
[0425] (c) the grafted or sequenced block copolymers comprising at
least one block resulting from the polymerization of at least one
ethylenic monomer with conjugated ethylenic bonds and at least one
block of a vinyl or acrylic polymer or of a polyether or polyester
or mixtures thereof.
[0426] Preferably diblock polymers are used as stabilizing
agent.
[0427] When the polymer has a glass transition temperature too high
for the desired application, there may be associated therewith a
plasticizer so as to lower this temperature of the mixture used.
The plasticizer may be chosen from among the plasticizers usually
used in the field of application and especially from among the
compounds capable of being polymer solvents. There may also be used
coalescence agents in order to help the polymer to form a
continuous and homogeneous deposit.
[0428] The coalescence agents or plasticizers that can be used in
the invention are especially those cited in the document FR A
2782917.
[0429] The composition may contain a polymer plasticizer, so as to
lower the Tg of the polymer film and to improve the adherence of
the polymer film on its substrate, in particular the horny tissues.
The plasticizing compound lowers especially the glass transition
temperature of the polymer by at least 2, 3 or 4.degree. C.,
preferably by 5.degree. C. to 20.degree. C. In a preferred
embodiment, the plasticizing compound lowers especially the glass
transition temperature of the polymer by at least 2, 3 or 4.degree.
C., preferably by 5.degree. C. to 20.degree. C., when the
plasticizing compound represents at most 10% by weight of the
polymer.
[0430] According to one embodiment, the compound may be chosen from
among the esters with at least one carboxylic acid group comprising
1 to 7 carbon atoms and one polyol comprising at least 4 hydroxyl
groups.
[0431] The polyol according to the invention may be an ose or a
polyol derived from an ose, such as erythritol, xylitol or
sorbitol. The polyol may be a mono or polysaccharide comprising one
to 10 oses, preferably from one to 4, even more preferably one or
two oses. The polyol may be chosen from among erythritol, xylitol,
sorbitol, glucose and sucrose.
[0432] The polyol according to the invention is preferably a
disaccharide. Among the disaccharides, there may be cited sucrose
(alpha-D-glucopyranosyl-(1-2)-beta-D-fructofuranose), lactose
(beta-D-galactopyranosyl-(1-4)-beta-D-glucopyranose) and maltose
(alpha-D-glucopyranosyl-(1-4)-beta-D-glucopyranose).
[0433] The plasticizer may be composed of a polyol substituted by
at least two different monocarboxylic acids or by at least three
different monocarboxylic acids. The acid is preferably a
monocarboxylic acid chosen in particular from among the acids
comprising 1 to 7 carbon atoms, preferably 1 to 5 carbon atoms, for
example acetic, n-propanoic, isopropanoic, n-butanoic, isobutanoic,
tert-butanoic, n-pentanoic and benzoic acids.
[0434] According to a preferred embodiment, the ester is sucrose
di-acetate-hexa-(2-methylpropanoate).
Solvent for Synthesis of Polymer Particles
[0435] The polymer dispersion may be manufactured as described in
the document of EP A 749747.
[0436] A mixture comprising the initial monomers as well as a
radical initiator is prepared. This mixture is dissolved in a
solvent referred to hereinafter in the present description as
"synthesis solvent". When the fatty acid is a non-volatile oil, the
polymerization may be carried out in an apolar organic solvent
(synthesis solvent) then the non-volatile oil (which must be
miscible with the said synthesis solvent) may be added and the
synthesis solvent selectively distilled.
[0437] The synthesis solvent is chosen such that the initial
monomers and the radical initiator are soluble therein and the
obtained polymer particles are insoluble therein, in order that
they precipitate during their formation. In particular, the
synthesis solvent may be chosen from among the alkanes such as
heptane, isododecane or cyclohexane.
[0438] When the chosen fatty phase is a volatile oil, the
polymerization may be carried out directly in the said oil, which
therefore also has the function of synthesis solvent. The monomers
must also be soluble therein, and also the radical initiator and
the polymer obtained must be soluble therein.
[0439] Before polymerization, the monomers are preferably present
in the synthesis solvent in a concentration of 5-20% by weight of
the reaction mixture. The totality of the monomers may be present
in the solvent before the start of the reaction, or part of the
monomers may be added at a rate commensurate with the evolution of
the polymerization reaction.
[0440] The radical initiator may be in particular
azo-bis-isobutyronitrile or tert-butylperoxy-2-ethyl hexanoate.
[0441] The volatile phase of the composition may be constituted by
or may comprise the solvent for synthesis of the dispersed polymer
particles.
[0442] As examples of non-aqueous dispersions of fat-dispersible
film-forming polymer in the form of non-aqueous dispersions of
polymer particles in one or more silicone and/or hydrocarbon oils
and capable of being stabilized at their surface by at least one
stabilizing agent, especially a sequenced, grafted or statistical
polymer, there may be cited the acrylic dispersions in isododecane,
such as Mexomere PAP.RTM. of the CHIMEX Co., the dispersions of
particles of a graft ethylene, preferably acrylic polymer in a
liquid fatty phase, the ethylene polymer being advantageously
dispersed in the absence of additional surface stabilizer of the
particles such as described in particular in the document WO
04/055081.
Reactive Silicones
[0443] According to another embodiment, the composition according
to the invention may comprise, by way of film-forming polymer,
two-component systems such as the compounds X and Y defined
hereinafter, capable of polymerizing in situ, at atmospheric
pressure and room temperature, and of forming films advantageously
biocompatible, non-sticking, slightly opalescent and even peelable.
Such systems are especially described in part in Patents WO
01/96450 and GB 2407496 of Dow Corning.
[0444] According to a particular embodiment, the compounds X and
the compounds Y are silicones.
[0445] The compounds X and Y may or may not be amines.
[0446] According to another embodiment, at least one of the
compounds X and Y is a polymer whose main chain is formed
predominantly by organosiloxane units.
[0447] Among the silicone compounds cited hereinafter, some may
exhibit both film-forming and adhesive properties, depending, for
example, on their proportion of silicone or depending on whether
they are used in a mixture with a particular additive.
Consequently, it is possible to modulate the film-forming
properties or the adhesive properties of such compounds depending
on the envisioned use, and this is the case in particular for the
reactive elastomeric silicones referred to as "room temperature
vulcanization".
[0448] The compounds X and Y may react together at a temperature
varying between room temperature and 180.degree. C. Advantageously,
the compounds X and Y are capable of reacting together at room
temperature (20.+-.5.degree. C.) and atmospheric pressure, or
advantageously in the presence of a catalyst, via a hydrosilylation
reaction or a condensation reaction, or a cross-linking reaction in
the presence of a peroxide.
[0449] According to a particular embodiment, the compounds X and Y
react by hydrosilylation in the presence of a catalyst.
[0450] Advantageously, the compounds X and Y are chosen from among
the silicone compounds capable of reacting by hydrosilylation in
the presence of a catalyst; in particular, the compound X is chosen
from among the polyorganosiloxanes comprising units of formula (I)
described below and the compound Y is chosen from among the
organosiloxanes comprising alkylhydrogenosiloxanes of formula (III)
described below.
[0451] According to a particular embodiment, the compound X is a
polydimethylsiloxane containing terminal vinyl groups, and the
compound Y is a polymethylhydrogenosiloxane.
[0452] The compound X is therefore advantageously chosen from among
the polyorganosiloxanes comprising siloxane units of formula:
R m R ' SiO ( 3 - m ) 2 ( I ) ##EQU00002## [0453] in which: [0454]
R represents a linear or cyclic monovalent hydrocarbon group
comprising 1 to 30 carbon atoms, preferably 1 to 20 and better 1 to
10 carbon atoms, such as, for example, a short-chain alkyl radical
comprising, for example, 1 to 10 carbon atoms, in particular a
methyl radical or else a phenyl group, preferably a methyl radical,
[0455] m is equal to 1 or 2 and [0456] R' represents: [0457] an
unsaturated aliphatic hydrocarbon group comprising 2 to 10,
preferably 3 to 5 carbon atoms, such as, for example, a vinyl group
or a --R''--CH.dbd.CHR''' group, in which R'' is a divalent
aliphatic hydrocarbon chain, comprising 1 to 8 carbon atoms, bonded
to the silicon atom, and R''' is a hydrogen atom or an alkyl
radical comprising 1 to 4 carbon atoms, preferably a hydrogen atom;
as the R' group there may be cited the vinyl and allyl groups and
mixtures thereof; or [0458] an unsaturated cyclic hydrocarbon group
comprising 5 to 8 carbon atoms, such as, for example, a
cyclohexenyl group.
[0459] Preferably, R' is an unsaturated aliphatic hydrocarbon
group, preferably a vinyl group.
[0460] According to one embodiment, R represents an alkyl radical
comprising 1 to 10 carbon atoms or else a phenyl group, and
preferably a methyl radical, and R' is a vinyl group.
[0461] The compound Y may be advantageously chosen from among the
polyorganosiloxanes comprising at least one alkylhydrogenosiloxane
unit of the following formula:
R p HSiO ( 3 - p ) 2 ( III ) ##EQU00003## [0462] in which: [0463] R
represents a linear or cyclic monovalent hydrocarbon group
comprising 1 to 30 carbon atoms such as, for example an alkyl
radical having 1 to 30 carbon atoms, preferably 1 to 20 and better
1 to 10 carbon atoms, in particular a methyl radical, or else a
phenyl group, and p is equal to 1 or 2. Preferably, R is a
hydrocarbon group, preferably methyl.
[0464] According to one embodiment, the compositions comprising the
component X and/or Y may also comprise an additional reactive
compound such as: [0465] the organic or mineral particles
comprising at least 2 unsaturated aliphatic groups at their
surface; for example there may be cited the silicas surface-treated
for example by silicone compounds containing vinyl groups, such as,
for example, silica treated with
cyclotetramethyltetravinylsiloxane, [0466] silazane compounds such
as hexamethyldisilazane.
[0467] The hydrosilylation reaction is carried out in the presence
of a catalyst, which may be present with one or the other of the
compounds X or Y or may be present in isolated manner. For example,
this catalyst may be present in the composition in an encapsulated
form, if the two components X and Y, whose interaction it must
bring about, are present in this same composition in a
non-encapsulated form or, conversely, it may be present in the
composition in a non-encapsulated form if at least one of the
compounds X and Y is present in the composition in an encapsulated
form. The catalyst is preferably based on platinum or tin.
[0468] The catalyst may be present in a content ranging from
0.0001% to 20% by weight relative to the total weight of the
composition comprising it.
[0469] The compounds X and/or Y may be associated with
polymerization inhibitors or retarders, and more particularly with
catalyst inhibitors. Without imposing any limitation, there may be
cited the cyclic polymethylvinylsiloxanes, and in particular
tetravinyl tetramethyl cyclotetrasiloxane, the acetylenic alcohols,
preferably volatile, such as methylisobutynol.
[0470] The presence of ionic salts, such as sodium acetate, may
have an influence on the rate of polymerization of the
compounds.
[0471] By way of example of a combination of compounds X and Y
reacting by hydrosilylation in the presence of a catalyst, there
may be cited the following references proposed by the Dow Corning
Company: DC 7-9800 Soft Skin Adhesive Parts A & B, as well as
the combination of the following mixtures A and B prepared by Dow
Corning:
TABLE-US-00001 MIXTURE A: Ingredient (INCI name) CAS No. Contents
(%) Function Dimethylsiloxane, 68083-19-2 55-95 Polymer
dimethylvinylsiloxy terminals Silica silylate 68909-20-6 10-40
Filler 1,3-Diethenyl-1,1,3,3- 68478-92-2 Trace Catalyst
tetramethyldisiloxane complexes Tetramethyldivinyldisiloxane
2627-95-4 0.1-1 Polymer
TABLE-US-00002 MIXTURE B: Ingredient (INCI name) CAS No. Contents
(%) Function Dimethylsiloxane, 68083-19-2 55-95 Polymer
dimethylvinylsiloxy terminals Silica silylate 68909-20-6 10-40
Filler Dimethyl, methylhydrogen siloxane, 68037-59-2 1-10 Polymer
trimethylsiloxy terminals
[0472] The compound X may represent from 0.1% to 95% by weight
relative to the total weight of the composition containing it,
preferably from 1% to 90%, and better from 5% to 80%.
[0473] The compound Y may represent from 0.1% to 95% by weight
relative to the total weight of the composition containing it,
preferably from 1% to 90%, and better from 5% to 80%.
[0474] The composition according to the invention may comprise a
plasticizing agent favoring the formation of a film with the
film-forming polymer. Such a plasticizing agent may be chosen from
among all the compounds known to those skilled in the art as being
capable of fulfilling the sought function.
Other Film-Forming Polymers:
Polymer in Dispersion or in Solution in an Oil Phase:
[0475] According to another embodiment, the composition according
to the invention may also comprise, by way of film-forming
polymers, a film-forming polymer in dispersion or in solution
different from those cited in the foregoing. It must be verified
that none of these are doubles of those cited in the foregoing
[0476] Among the film-forming polymers that can be used in the
composition of the present invention, there may be cited the
synthetic polymers of radical type or polycondensate type, the
polymers of natural origin, and mixtures thereof.
[0477] By radical film-forming polymer there is understood a
polymer obtained by polymerization of monomers having unsaturation,
especially ethylenic, each monomer being capable of
homopolymerization (unlike the polycondensates).
[0478] The film-forming polymers of radical type may be in
particular vinyl polymers or copolymers, especially acrylic
polymers.
[0479] The vinyl film-forming polymers may result from the
polymerization of ethylenically unsaturated monomers having at
least one acid group and/or esters of these acid monomers and/or
amides of these acid monomers.
[0480] As monomer carrying acid groups there may be used
.alpha.,.beta.-ethylenically unsaturated carboxylic acids, such as
acrylic acid, methacrylic acid, crotonic acid, maleic acid,
itaconic acid. Preferably there are used (meth)acrylic acid and
crotonic acid, and more preferably (meth)acrylic acid.
[0481] The esters of acid monomers are advantageously chosen from
among the esters of (meth)acrylic acid (also referred to as the
(meth)acrylates), especially alkyl (meth)acrylates, in particular
C1-C30 alkyl, preferably C1-C20, aryl (meth)acrylates, in
particular C6-C10 aryl, hydroxyalkyl (meth)acrylates), in
particular C2-C6 hydroxyalkyl.
[0482] Among the alkyl (meth)acrylates there may be cited methyl
methacrylate, ethyl methacrylate, butyl methacrylate, isobutyl
methacrylate, 2-ethylhexyl methacrylate, lauryl methacrylate,
cyclohexyl methacrylate.
[0483] Among the hydroxyalkyl (meth)acrylates there may be cited
hydroxyethyl acrylate, 2-hydroxypropyl acrylate, hydroxyethyl
methacrylate, 2-hydroxypropyl methacrylate.
[0484] Among the aryl (meth)acrylates there may be cited benzyl
acrylate and phenyl acrylate.
[0485] The particularly preferred esters of (meth)acrylic acid are
the alkyl (meth)acrylates.
[0486] According to the present invention, the alkyl group of the
esters may be either fluorinated or pefluorinated, meaning that
part or all of the hydrogen atoms of the alkyl group have been
substituted by fluorine atoms.
[0487] As amides of acid monomers there may be cited, for example,
the (meth)acrylamides, and especially the N-alkyl
(meth)acrylamides, in particular C2-C12 alkyl. Among the N-alkyl
(meth)acrylamides there may be cited N-ethyl acrylamide, N-t-butyl
acrylamide, N-t-octyl acrylamide and N-undecyl acrylamide.
[0488] The vinyl film-forming polymers may also result from the
homopolymerization or the copolymerization of monomers chosen from
among the vinyl esters and the styrene monomers. In particular,
these monomers may be polymerized with acid monomers and/or their
esters and/or their amides, such as those mentioned in the
foregoing.
[0489] As examples of vinyl esters there may be cited vinyl
acetate, vinyl neodecanoate, vinyl pivalate, vinyl benzoate and
vinyl t-butylbenzoate.
[0490] As styrene monomers, there may be cited styrene and
alpha-methylstyrene.
[0491] Among the film-forming polycondensates there may be cited
the polyurethanes, the polyesters, the amide polyesters, the
polyamides and the epoxy ester resins, the polyureas.
[0492] The polyurethanes may be chosen among the anionic, cationic,
non-ionic or amphoteric polyurethanes, the polyurethane acrylics,
the polyurethane polyvinylpyrrolidones, the polyester
polyurethanes, the polyether polyurethanes, the polyureas, the
polyurea polyurethanes and mixtures thereof.
[0493] The polyesters may be obtained in known manner by
polycondensation of dicarboxylic acids with polyols, especially
diols.
[0494] The dicarboxylic acid may be aliphatic, alicyclic or
aromatic. As examples of such acids there may be cited: 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-norbornane dicarboxylic
acid, diglycolic acid, thiodipropionic acid,
2,5-naphthalenedicarboxylic acid, 2,6-naphthalenedicarboxylic acid.
These dicarboxylic acid monomers may be used alone or in
combination of at least two dicarboxylic acid monomers. Among these
monomers, phthalic acid, isophthalic acid and terephthalic acid
preferentially are chosen.
[0495] The diol may be chosen from among the aliphatic, alicyclic,
aromatic diols. Preferably there is used a dial chosen from among:
ethylene glycol, diethylene glycol, triethylene glycol,
1,3-propanediol, cyclohexane dimethanol, 4-butanediol. As other
polyols there may be used glycerol, pentaerythritol, sorbitol,
trimethylol propane.
[0496] The amide polyesters may be obtained in a manner analogous
to that for the polyesters, by polycondensation of diacids with
diamines or amino alcohols. As diamine there may be used
ethylenediamine, hexamethylenediamine, meta- or
para-phenylenediamine. As amino alcohol there may be used
monoethanolamine.
[0497] According to an example of composition according to the
invention, the film-forming polymer may be a polymer solubilized in
a liquid fatty phase comprising organic oils or solvents (it is
then said that the film-forming polymer is a fat-soluble polymer).
Preferably the liquid fatty phase comprises a volatile oil, if
necessary in a mixture with a non-volatile oil.
[0498] By way of example of fat-soluble polymer there may be cited
the copolymers of vinyl ester (the vinyl group being bonded
directly to the oxygen atom of the ester group and the vinyl ester
having a linear or branched, saturated hydrocarbon radical with 1
to 19 carbon atoms, bonded to the carbonyl of the ester group) and
of at least one other monomer, which may be a vinyl ester
(different from the already present vinyl ester), an .alpha.-olefin
(having 8 to 28 carbon atoms), an alkyl vinyl ether (whose alkyl
group contains 2 to 18 carbon atoms), or an allyl or methallyl
ester (having a linear or branched, saturated hydrocarbon radical
with 1 to 19 carbon atoms, bonded to the carbonyl of the ester
group).
[0499] These copolymers may be cross-linked by means of
cross-linking agents, which may be either of the vinyl type or of
the allyl or methallyl type, such as tetrallyloxyethane,
divinylbenzene, divinyl octanedioate, divinyl dodecanedioate and
divinyl octadecanedioate.
[0500] As examples of these copolymers there may be cited 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/octadecene-1, vinyl acetate/dodecene-1, vinyl
stearate/ethyl vinyl ether, vinyl propionate/cetyl vinyl ether,
vinyl stearate/allyl acetate, vinyl 2,2-dimethyl octanoate/vinyl
laurate, allyl 2,2-dimethyl pentanoate/vinyl laurate, vinyl
dimethyl propionate/vinyl stearate, allyl dimethyl propionate/vinyl
stearate, vinyl propionate/vinyl stearate, cross-linked with 0.2%
divinylbenzene, vinyl dimethyl propionate/vinyl laurate
cross-linked with 0.2% divinylbenzene, vinyl acetate/octadecyl
vinyl ether, cross-linked with 0.2% tetraallyloxyethane, vinyl
acetate/allyl stearate, cross-linked with 0.2% divinylbenzene,
vinyl acetate/1-octadecene, cross-linked with 0.2% divinylbenzene;
and allyl propionate/allyl stearate cross-linked with 0.2%
divinylbenzene.
[0501] As supplementary examples of fat-soluble film-forming
polymers there may be cited the copolymers of vinyl ester and at
least one other monomer, which may be a vinyl ester, especially
vinyl neodecanoate, vinyl benzoate and vinyl t-butylbenzoate, an
.alpha.-olefin, an alkyl vinyl ether, or an allyl or a methallyl
ester.
[0502] As fat-soluble film-forming polymers there may also be cited
fat-soluble copolymers, and in particular those resulting from
copolymerization of vinyl esters having 9 to 22 carbon atoms or
acrylates or alkyl methacrylates, the alkyl radicals having 10 to
20 carbon atoms.
[0503] Such fat-soluble copolymers may be chosen from among the
copolymers of: vinyl polystearate, vinyl polystearate cross-linked
by means of divinylbenzene, diallyl ether, or diallyl phthalate,
the copolymers of stearyl poly(meth)acrylate, vinyl polylaurate,
lauryl poly(meth)acrylate, these poly(meth)acrylates being capable
of being cross-linked by means of ethylene glycol dimethacrylate or
tetraethylene glycol.
[0504] The fat-soluble polymers defined in the foregoing are known
and are described especially in the Application FR A 2232303; they
may have a weight-average molecular weight ranging from 2,000 to
500,000, and preferably from 4,000 to 200,000.
[0505] As fat-soluble film-forming polymers that can be used in the
invention there may also be cited polyalkylenes and especially
C2-C20 alkene copolymers such as polybutene, the alkyl celluloses
with a C1 to C8 saturated or unsaturated, linear or branched alkyl
radical such as ethyl cellulose and propyl cellulose, the
copolymers of vinylpyrrolidone (VP) and especially the copolymers
of vinylpyrrolidone and C.sub.2 to C.sub.40 alkene, and better C3
to C20. By way of examples of VP copolymers that can be used in the
invention there may be cited the copolymer of VP/vinyl acetate,
VP/ethyl methacrylate, butylated polyvinylpyrrolidone (PVP);
VP/ethyl methacrylate/methacrylic acid, VP/eicosene, VP/hexadecene,
VP/triacontene, VP/styrene, VP/acrylic acid/lauryl
methacrylate.
[0506] There may also be cited the silicone resins, generally
soluble or swellable in silicone oils, that are cross-linked
polyorganosiloxane polymers.
[0507] By way of examples of commercially available
polymethylsilsesquioxane resins there may be cited those sold by
the Wacker Company under the reference Resin MK, such as Belsil PMS
MK, or by the SHIN-ETSU Company under the references KR-220L.
[0508] By way of examples of commercially available
polypropylsilsesquioxane resins there may be cited those sold under
the reference DC670 by the Dow Corning Company.
[0509] As siloxysilicate resins there may be cited the
trimethylsiloxysilicate resins (TMS), such as those sold under the
reference SR1000 by the General Electric Company or under the
reference TMS 803 by the Wacker Company. There may also be cited
the trimethylsiloxysilicate resins sold in a solvent such as
cyclomethicone, sold under the trade name KF-7312J by the Shin-Etsu
Company, or "DC 749", "DC 593" by the Dow Corning Company.
[0510] There may also be cited copolymers of silicone resins such
as those cited hereinabove with polydimethylsiloxanes, such as the
pressure-sensitive adhesive copolymers sold by the Dow Corning
Company under the reference BIO-PSA and described in the document
U.S. Pat. No. 5,162,410, or else the silicone copolymers obtained
by the reaction of a silicone resin, such as those described
hereinabove, and a diorganosiloxane such as those described in the
document WO 2004/073626.
[0511] There may also be cited the acrylic/silicone graft
copolymers having a vinyl, methacrylic or acrylic polymeric
skeleton and organosiloxane or polyorganoxilane pendant grafts.
Such polymers are described in particular in U.S. Pat. Nos.
4,693,935, 4,981,903 and 4,981,902.
[0512] Preferably, these polymers comprise monomers A, C and
optionally B, for which: [0513] A is at least one vinyl,
methacrylate or acrylate monomer that can undergo free radical
polymerization; [0514] B, when present, is at least one rigidifying
monomer that can be copolymerized with A; [0515] C is a monomer of
the following formula:
[0515] X(Y).sub.nSi(R).sub.3-mZ.sub.m
Where
[0516] X is a vinyl group that can be copolymerized with monomers A
and B; [0517] Y is a divalent linker; [0518] n is 0 or 1; [0519] m
is an integer between 1 and 3; [0520] R is a hydrogen atom, an
alkyl radical having 1 to 10 carbon atoms, a substituted or
unsubstituted phenyl radical, an alkoxy radical having 1 to 10
carbon atoms; [0521] Z is a monovalent polymeric siloxane
group.
[0522] Examples of monomers A are lower to intermediate esters of
methacrylic acid and C1-12 alcohols with linear or branched chain,
of styrene, vinyl esters, vinyl chloride, vinylidine chloride or
acryloyl monomers.
[0523] Examples of monomers B are polar acrylic or methacrylic
monomers having at least one hydroxy, amino, ester or ionic group
(such as the quaternary ammoniums, the carboxylate salt or the
acids such as the carboxylic acids, the acrylic acids, sulfonic
acid or salts thereof).
[0524] Monomer C is defined above.
[0525] As examples of acrylic/silicone graft copolymers there may
be cited those sold by 3M under the reference 3M Silicones "Plus"
VS70 Dry Polymer.RTM., with the INCI name: Polysilicone-6, or else
KP-561.RTM. sold by SHIN-ETSU with the INCI name: Acrylates/Stearyl
Acrylate/Dimethicone Methacrylate Copolymer, KP-56210 sold by
SHIN-ETSU with the INCI name: Acrylates/Behenyl
Acrylate/Dimethicone Acrylate Copolymer.
Polymer in Aqueous Dispersion (Latex) or Water-Soluble Polymer
[0526] The composition may contain an aqueous phase, and the
film-forming polymer may be present in this aqueous phase. In this
case it will preferably be a polymer in aqueous dispersion or a
water-soluble polymer.
[0527] Among the film-forming polymers that can be used in the
composition of the present invention there may be cited the
synthetic polymers of radical type or of polycondensate type, the
polymers of natural origin and mixtures thereof.
[0528] As examples of water-soluble film-forming polymers there may
be cited: [0529] the proteins, such as the proteins of vegetable
origin, such as the proteins of wheat, of soy; the proteins of
animal origin, such as the keratins, for example the hydrolyzates
of keratin and the sulfonic keratins; [0530] the polymers of
cellulose, such as hydroxyethyl cellulose, hydroxypropyl cellulose,
methyl cellulose, ethylhydroxyethyl cellulose, carboxymethyl
cellulose, as well as the quaternized derivatives of cellulose;
[0531] the acrylic polymers or copolymers, such as the
polyacrylates or the polymethacrylates; [0532] the vinyl polymers,
such as the polyvinylpyrrolidones, the copolymers of methyl vinyl
ether and malic anhydride, the copolymer of vinyl acetate and
crotonic acid, the copolymers of vinylpyrrolidone and vinyl
acetate; the copolymers of vinylpyrrolidone and caprolactam;
polyvinyl alcohol; [0533] the polymers of anionic, cationic,
amphoteric or non-ionic chitin or chitosan, [0534] the gums arabic,
guar gum, the xanthan derivatives, karaya gum; [0535] the alginates
and the carragenanes; [0536] the glycoaminoglycanes, hyaluronic
acid and its derivatives; [0537] shellac resin, sandarac gum, the
dammars, the elemis, the copals; [0538] deoxyribonucleic acid;
[0539] the mucopolysaccharides, such as the chondroitin sulfates,
[0540] and mixtures thereof.
[0541] The film-forming polymer may also be present in the
composition in the form of particles in dispersion in an aqueous
phase, known generally under the name of latex or pseudolatex. The
techniques for preparation of these dispersions are well known to
those skilled in the art.
[0542] As aqueous dispersion of film-forming polymer there may be
used the acrylic dispersions sold under the trade names: Neocryl
XK-90.RTM., Neocryl A-10708, Neocryl A-10908, Neocryl BT-62.RTM.,
Neocryl A-1079.RTM., and Neocryl A-523.RTM. by the AVECIA-NEORESINS
Company; Dow Latex 432.RTM. by the DOW CHEMICAL Company; Daitosol
5000 AD.RTM. or Daitosol 5000 SJ.RTM. by the DAITO KASEY KOGYO
Company; Syntran 5760.RTM. by the Interpolymer Allianz Company,
Opt.RTM. by the Rohm and Haas Company, the aqueous dispersions of
acrylic or styrene/acrylic polymers sold under the trade name
JONCRYL.RTM. by the JOHNSON POLYMER Company or else the aqueous
dispersions of polyurethane sold under the trade names Neorez
R-981.RTM. and Neorez R-974.RTM. by the AVECIA-NEORESINS Company,
Avalure UR-405.RTM., Avalure UR-410.RTM., Avalure UR-425.RTM.,
Avalure UR-450.RTM., Sancure 875.RTM., Avalure UR-445.RTM. and
Sancure 2060.RTM. by the NOVEON Company, Impranil 85.RTM. by the
BAYER Company, Aquamere H-1511.RTM. by the HYDROMER Company, the
sulfopolyesters sold under the brand Eastman AQ.RTM. by the EASTMAN
CHEMICAL PRODUCTS Company, the vinyl dispersions such as Mexomere
PAM.RTM. of the CHIMEX Company, the aqueous dispersions of
polyvinyl acetate such as "Vinybran.RTM." of the Nisshin Chemical
Company or those sold by the UNION CARBIDE Company, the aqueous
dispersions of vinylpyrrolidone, dimethylaminopropyl methacrylamide
and lauryldimethylpropylmethylacrylamidoammonium chloride
terpolymer such as Styleze W of ISP, the aqueous dispersions of
polyurethane/polyacrylic hybrid polymers such as those sold under
the references "Hybridur.RTM." by the AIR PRODUCTS Company or
"Duromer.RTM." of NATIONAL STARCH, the dispersions of core/shell
type: for example, those sold by the ATOFINA Company under the
reference Kynar (core:fluoro-shell:acrylic) or else those described
in the document U.S. Pat. No. 5,188,899
(core:silica-shell:silicone) and mixtures thereof.
[0543] According to a particular embodiment, the composition
according to the invention comprises, by way of hydrophilic
film-forming polymers, at least the association of a cationic
polymer and an anionic polymer.
[0544] The cationic polymer may be chosen from among the ether
derivatives of quaternary cellulose, the copolymers of cellulose
with a water-soluble monomer of quaternary ammonium, the
cyclopolymers, the cationic polysaccharides, the
silicone-containing cationic polymers, the quaternized or
non-quaternized copolymers of vinylpyrrolidone and
dialkylaminoalkyl acrylate or methacrylate, the quaternary polymers
of vinylpyrrolidone and vinylimidazole, the polyamidoamines and
mixtures thereof.
[0545] Preferably, the cationic polymer is a
hydroxy(C.sub.1-C.sub.4)alkyl cellulose containing quaternary
ammonium groups.
[0546] The anionic polymer is advantageously chosen from among:
A) the acrylic or methacrylic acid homopolymers or copolymers or
their salts, the copolymers of acrylic acid and acrylamide and
their salts, the sodium salts of polyhydroxycarboxylic acids such
as the copolymers of acrylic acid and acrylamide sold in the form
of their sodium salt under the trade names RETEN.RTM. by the
HERCULES Company, the sodium polymethacrylate sold under the trade
name DARVAN No. 7.RTM. by the VANDERBILT Company, the sodium salts
of polyhydroxycarboxylic acids sold under the trade name HYDAGEN
F.RTM. by the HENKEL Company. B) the copolymers of acrylic or
methacrylic acids with a monoethylene monomer such as ethylene,
styrene, the vinyl esters, the esters of acrylic or methacrylic
acid, possibly grafted onto a polyalkylene glycol such as
polyethylene glycol; the copolymers of this type containing, in
their chain, an acrylamide moiety, which may be N-alkylated and/or
hydroxyalkylated, the copolymers of acrylic acid and C1-C4 alkyl
methacrylate and the terpolymers of vinylpyrrolidone, acrylic acid
and C1-C20 alkyl methacrylate; C) the copolymers derived from
crotonic acid, such as those containing, in their chain, vinyl
acetate or propionate moieties and possibly other monomers such as
allyl or methallyl esters, vinyl ether or vinyl ester of a linear
or branched, saturated carboxylic acid having a long-chain
hydrocarbon, such as those containing at least 5 carbon atoms,
these polymers possibly being able to be grafted; D) the polymers
derived from maleic, fumaric, itaconic acids or anhydrides with
vinyl esters, vinyl ethers, vinyl halides, phenylvinyl derivatives,
acrylic acid and its esters; the copolymers of maleic, citraconic,
itaconic anhydrides and an allyl or methallyl ester, possibly
containing an acrylamide, methacrylamide group, an .alpha.-olefin,
acrylic or methacrylic esters, acrylic or methacrylic acids or
vinylpyrrolidone in their chain, the anhydride functions being
monoesterified or monoamidified; E) the polyacrylamides containing
carboxylate groups, F) deoxyribonucleic acid; G) the copolymers of
at least one carboxylic diacid, of at least one diol and of at
least one bifunctional aromatic monomer carrying a --SO3M group
with M representing a hydrogen atom, an ammonium ion NH4+ or a
metal ion; [0547] and mixtures thereof.
[0548] The most particularly preferred anionic polymers are chosen
from among the non-cross-linked anionic polymers such as the methyl
vinyl ether/monoesterified maleic anhydride copolymers sold under
the trade name GANTREZ ES 425 by the ISP Company, the acrylic
acid/ethyl acrylate/N-tert-butyl acrylamide terpolymers sold under
the trade name ULTRAHOLD STRONG by the BASF Company, the copolymers
of methacrylic acid and methyl methacrylate sold under the trade
name EUDRAGIT L by the ROHM PHARMA Company, the vinyl acetate/vinyl
tert-butyl benzoate/crotonic acid terpolymers and the crotonic
acid/vinyl acetate/vinyl neododecanoate terpolymers sold under the
trade name Resin 28-29-30 by the NATIONAL STARCH Company, the
copolymers of methacrylic acid and ethyl acrylate sold under the
trade name LUVIMER MAEX or MAE by the BASF Company, the
vinylpyrrolidone/acrylic acid/lauryl methacrylate terpolymers sold
under the trade name ACRYLIDONE LM by the ISP Company and the
homopolymers of acrylic or methacrylic acid sold, for example,
under the trade name VERSICOL E 5 or the sodium polymethacrylate
sold under the trade name DARVAN 7 by the VANDERBILT Company, and
mixtures thereof.
[0549] Preferably, the anionic polymer is a sodium
polymethacrylate.
Pastes of Non-Animal Origin
[0550] The compositions according to the invention may comprise at
least one paste of non-animal origin.
[0551] The compositions according to the invention may therefore
comprise at least one paste of non-animal origin and the mixture 1)
described hereinabove.
[0552] By "pasty compound" within the meaning of the present
invention there is understood a lipophilic fatty compound capable
of reversible change of state from solid to liquid and containing,
at the temperature of 23.degree. C., a liquid fraction and a solid
fraction.
[0553] At the temperature of 23.degree. C., a pasty compound is in
the form of a liquid fraction and a solid fraction. In other words,
the starting melting temperature of the pasty compound is lower
than 23.degree. C. The liquid fraction of the pasty compound,
measured at 23.degree. C., represents 20 to 97% by weight of the
pasty compound. More preferentially, at 23.degree. C., this liquid
fraction represents 25 to 85% and better 30 to 60% by weight of the
pasty compound.
[0554] The liquid fraction by weight of the pasty compound at
23.degree. C. is equal to the ratio of the enthalpy of melting
consumed at 23.degree. C. to the enthalpy of melting of the pasty
compound.
[0555] The enthalpy of melting consumed at 23.degree. C. is the
quantity of energy absorbed by the sample for transition from the
solid state to the state in which it exists at 23.degree. C.,
consisting of a liquid fraction and a solid fraction.
[0556] The enthalpy of melting of the pasty compound is the
enthalpy consumed by the compound in changing from the solid state
to the liquid state. The pasty compound is said to be in the solid
state when the entirety of its mass is in solid form. The pasty
compound is said to be in the liquid state when the entirety of its
mass is in liquid form.
[0557] The enthalpy of melting of the pasty compound is equal to
the area under the curve of the thermogram obtained by means of a
differential scanning calorimeter (D. S. C.), such as the
calorimeter sold under the trade name MDSC 2920 by the TA
Instrument Company, with a temperature rise of 5 or 10.degree. C.
per minute, according to ISO standard 11357-3:1999. The enthalpy of
melting of the pasty compound is the quantity of energy necessary
to make the compound change from the solid state to the liquid
state. It is expressed in J/g.
[0558] The liquid fraction of the pasty compound, measured at
32.degree. C., preferably represents 40 to 100% by weight of the
pasty compound, even better 50 to 100% by weight of the pasty
compound. When the liquid fraction of the pasty compound measured
at 32.degree. C. is equal to 100%, the temperature of the end of
the melting range of the pasty compound is lower than or equal to
32.degree. C. The liquid fraction of the pasty compound, measured
at 32.degree. C., is equal to the ratio of the enthalpy of melting
consumed at 32.degree. C. to the enthalpy of melting of the pasty
compound. The enthalpy of melting consumed at 32.degree. C. is
calculated in the same way as the enthalpy of melting consumed at
23.degree. C.
[0559] By "non-animal origin" there is understood a pasty compound
chosen from among the pasty compounds of synthetic and vegetable
origin (produced or derived from plants).
[0560] The pasty compound preferably has a hardness at 20.degree.
C. ranging from 0.001 to 0.5 MPa, preferably from 0.002 to 0.4
MPa.
[0561] The hardness is measured according to the method of
penetration of an indenter into a sample of the compound, and in
particular by means of a texture analyzer (for example the TA-TX2i
of Rheo), equipped with a stainless steel cylinder with a diameter
of 2 mm. The hardness measurement is carried out at 20.degree. C.
at the center of 5 specimens. The cylinder is introduced into each
specimen, the penetration depth being 0.3 mm. The value recorded as
the hardness is that of the maximum peak.
[0562] The pasty compound of non-animal origin is chosen from among
the synthetic compounds and the compounds of vegetable origin. A
pasty compound of non-animal origin may be obtained by synthesis
from starting products of vegetable origin.
[0563] The pasty compound is advantageously chosen from among:
[0564] the polymeric or non-polymeric silicone compounds, such as
the polydimethylsiloxanes of high molecular weights, the
polydimethylsiloxanes with side and/or terminal chains of alkyl or
alkoxy type having 8 to 24 carbon atoms, especially the stearyl
dimethicones, [0565] the polymeric or non-polymeric fluoro
compounds, [0566] the vinyl polymers, especially [0567] the olefin
homopolymers, [0568] the olefin copolymers, [0569] the homopolymers
and copolymers of hydrogenated dienes, [0570] the linear or
branched homopolymeric or copolymeric oligomers of alkyl
(meth)acrylates, preferably having C.sub.8-C.sub.30 alkyl groups,
[0571] the homopolymeric and copolymeric oligomers of vinyl esters
having C.sub.8-C.sub.30 alkyl groups, [0572] the homopolymeric and
copolymeric oligomers of vinyl ethers having C.sub.8-C.sub.30 alkyl
groups, [0573] the fat-soluble polyethers resulting from the
polyetherification between one or more C.sub.2-C.sub.100 diols,
preferably C.sub.2-C.sub.50, [0574] the esters and the polyesters,
[0575] and mixtures thereof.
[0576] The pasty compound may be a polymer, especially of
hydrocarbon type.
[0577] A preferred pasty silicone and fluoro compound is
polymethyl-trifluoropropyl-methylalkyl-dimethylsiloxane,
manufactured under the trade name X22-1088 by SHIN-ETSU.
[0578] When the pasty compound is a silicone and/or fluoro polymer,
the composition advantageously comprises a compatibilizing agent,
such as the short-chain esters, such as isodecyl neopentanoate.
[0579] Among the fat-soluble polyethers there may be cited in
particular the copolymers of ethylene oxide and/or propylene oxide
with C.sub.6-C.sub.30 alkylene oxides. Preferably, the weight ratio
of the ethylene oxide and/or of the propylene oxide to the alkylene
oxides in the copolymer is 5:95 to 70:30. In this family, there
will be cited in particular the block copolymers comprising
C.sub.6-C.sub.30 alkylene oxide blocks having a molecular weight
ranging from 1,000 to 10,000, for example, a
polyoxyethylene/polydodecylene glycol block copolymer such as the
ethers of dodecanediol (22 mol) and of polyethylene glycol (45
oxyethylene moieties or OE) sold under the brand ELFACOS ST9 by
Akzo Nobel.
[0580] Among the esters, there are especially preferred: [0581] the
esters of a glycerol oligomer, especially the esters of diglycerol,
in particular the condensates of adipic acid and glycerol for which
part of the hydroxyl groups of the glycerols have reacted with a
mixture of fatty acids such as stearic acid, capric acid, stearic
acid, isostearic acid and 12-hydroxystearic acid, such as those
sold in particular under the brand Softisan 649 by the Sasol
Company; [0582] the esters of phytosterol; [0583] the esters of
pentaerythritol; [0584] the esters formed from: [0585] at least one
C.sub.16-40 alcohol, at least one of the alcohols being a Guerbet
alcohol and [0586] a diacid dimer formed from at least one C18-40
unsaturated fatty acid, such as the ester of fatty acid dimer of
tall oil comprising 36 carbon atoms and of a mixture i) of Guerbet
alcohols comprising 32 carbon atoms and ii) behenyl alcohol; the
ester of linoleic acid dimer and of a mixture of two Guerbet
alcohols, 2-tetradecyloctadecanol (32 carbon atoms) and
2-hexadecyleicosanol (36 carbon atoms); [0587] the non-cross-linked
polyesters resulting from the polycondensation between a
dicarboxylic acid or a C.sub.4-C.sub.50 linear or branched
polycarboxylic acid and a C.sub.2-C.sub.50 diol or polyol; [0588]
the polyesters that result from the esterification between a
polycarboxylic acid and an ester of aliphatic hydroxylated
carboxylic acid such as Risocast DA-L and Risocast DA-H sold by the
Japanese company KOKYU ALCOHOL KOGYO, which are esters resulting
from the esterification reaction of hydrogenated castor oil with
dilinoleic acid or isostearic acid; and [0589] the aliphatic esters
of ester resulting from esterification between an ester of
aliphatic hydroxylated carboxylic acid and an aliphatic carboxylic
acid, for example that sold under the trade name Salacos HCIS (V)-L
by the Nishing Oil Company.
[0590] A Guerbet alcohol is the reaction product of the Guerbet
reaction, well known to those skilled in the art. It is a reaction
in which a primary aliphatic alcohol is transformed into its
alkylated dimer alcohol with loss of one equivalent of water.
[0591] The aliphatic carboxylic acids described above generally
comprise 4 to 30 and preferably 8 to 30 carbon atoms. They are
preferably chosen from among hexanoic acid, heptanoic acid,
octanoic acid, 2-ethylhexanoic acid, nonanoic acid, decanoic acid,
undecanoic acid, dodecanoic acid, tridecanoic acid, tetradecanoic
acid, pentadecanoic acid, hexadecanoic acid, hexyldecanoic acid,
heptadecanoic acid, octadecanoic acid, isostearic acid,
nonadecanoic acid, eicosanoic acid, isoarachidic acid,
octyldodecanoic acid, heneicosanoic acid, docosanoic acid and
mixtures thereof.
[0592] The aliphatic carboxylic acids are preferably branched.
[0593] The esters of hydroxylated aliphatic carboxylic acid are
advantageously obtained from a hydroxylated aliphatic carboxylic
acid containing 2 to 40 carbon atoms, preferably 10 to 34 carbon
atoms and better 12 to 28 carbon atoms, and 1 to 20 hydroxyl
groups, preferably 1 to 10 hydroxyl groups and better 1 to 6
hydroxyl groups. The esters of hydroxylated aliphatic carboxylic
acid are chosen especially from among:
a) the partial or total esters of saturated linear monohydroxylated
aliphatic monocarboxylic acids; b) the partial or total esters of
unsaturated monohydroxylated aliphatic monocarboxylic acids; c) the
partial or total esters of saturated monohydroxylated aliphatic
carboxylic polyacids; d) the partial or total esters of saturated
polyhydroxylated aliphatic carboxylic polyacids; e) the partial or
total esters of C.sub.2 to C.sub.16 aliphatic polyols that have
been reacted with a mono or polyhydroxylated aliphatic mono or
polycarboxylic acid; f) and mixtures thereof.
[0594] The aliphatic esters of ester are advantageously chosen from
among: [0595] the ester resulting from the esterification reaction
of hydrogenated castor oil with isostearic acid in proportions of 1
to 1 (1/1), which is referred to as hydrogenated castor oil
monoisostearate, [0596] the ester resulting from the esterification
reaction of hydrogenated castor oil with isostearic acid in
proportions of 1 to 2 (1/2), which is referred to as hydrogenated
castor oil diisostearate, [0597] the ester resulting from the
esterification reaction of hydrogenated castor oil with isostearic
acid in proportions of 1 to 3 (1/3), which is referred to as
hydrogenated castor oil triisostearate, and mixtures thereof.
[0598] Preferably, the pasty compound is chosen from among the
compounds of vegetable origin.
[0599] Among those there may be cited in particular isomerized
jojoba oil, such as the trans isomerized partly hydrogenated jojoba
oil manufactured or sold by the Desert Whale Company under the
commercial reference Iso-Jojoba-50.RTM., orange wax such as, for
example, that sold under the reference Orange Peel Wax by the
Koster Keunen Company, shea butter, partly hydrogenated olive oil
such as, for example, the compound sold under the reference
Beurrolive by the Soliance Company, cocoa butter, mango oil such
as, for example, Lipex 302 of the Aarhuskarlshamm Company.
[0600] The pasty compound or compounds are preferably present in a
quantity greater than or equal to 1% by weight relative to the
total weight of the composition, for example 1 to 15% by weight,
better in a quantity greater than or equal to 2% by weight, ranging
for example from 2 to 10% by weight, and even more preferentially
from 3 to 8% by weight relative to the total weight of the
composition.
Fatty-Phase Thickening or Gelling Rheological Agent
[0601] The composition according to the invention may comprise a
fatty-phase thickening or gelling rheological agent.
[0602] The compositions according to the invention may therefore
comprise at least one fatty-phase thickening or gelling rheological
agent and the mixture of MQ and propyl T resins described
hereinabove.
[0603] By "fatty-phase thickening or gelling rheological agent"
there is understood a compound capable of increasing the viscosity
of the fatty phase of the composition. The fatty-phase thickening
or gelling rheological agent makes it possible in particular to
obtain a composition that may have a texture ranging from fluid to
solid textures.
[0604] The fatty-phase thickening or gelling rheological agent may
be chosen from among: [0605] the crystalline polymers, preferably
chosen from among the semi-crystalline polymers, the esters of
dextrin and fatty acid, the hydrophobic modified polysaccharides,
the crystalline olefin copolymers and the crystalline
polycondensates; [0606] the mineral lipophilic structuring agents,
such as the lipophilic clays and the hydrophobic silicas, such as
hydrophobic treated pyrogenic silica, [0607] the lipophilic
polymers of polyamide type, [0608] the lipophilic polyureas and
polyurethanes, [0609] the silicone polymers containing, as the case
may be, at least one hydrocarbon moiety containing two groups
capable of establishing hydrogen interactions chosen from among the
ester, amide, sulfonamide, carbamate, thiocarbamate, urea,
urethane, thiourea, oxamido, guanidino, biguanidino groups and
combinations thereof, preferably amide groups, [0610] the organo
gelling agents; [0611] the block polymers; [0612] the cholesteric
liquid crystal agents; [0613] the silicone elastomers; [0614] and
mixtures thereof.
[0615] Preferably the fatty-phase rheological agent is chosen from
among the semi-crystalline polymers, the block polymers, the
lipophilic polymers of polyamide type and the silicone polymers
comprising at least one hydrocarbon moiety containing two groups
capable of establishing hydrogen interactions chosen from among the
amide groups, the mineral lipophilic structuring agents, in
particular the lipophilic clays and the hydrophobic silicas, and
the silicone elastomers.
[0616] It is pointed out that, according to the invention, in the
case of associations of a fatty-phase rheological agent with an
oil, there is understood by "oil" a fatty substance that is liquid
at room temperature.
[0617] It is also pointed out that, by "volatile compound", for
example "volatile oil", there is understood, within the meaning of
the invention, any compound (or non-aqueous medium) capable of
evaporating on contact with the skin or the horny fiber in less
than one hour, at room temperature and atmospheric pressure. The
volatile compound is a volatile cosmetic compound, liquid at room
temperature, having in particular a non-zero vapor pressure at room
temperature and atmospheric pressure, especially having a vapor
pressure ranging from 0.13 Pa to 40,000 Pa (10.sup.-3 to 300 mm
Hg), in particular ranging from 1.3 Pa to 13,000 Pa (0.01 to 100 mm
Hg), and more particularly ranging from 1.3 Pa to 1,300 Pa (0.01 to
10 mm Hg).
[0618] In contrast, by "non-volatile compound", for example
"non-volatile oil", there is understood a compound that remains on
the skin or horny fiber at room temperature and atmospheric
pressure for at least several hours, and having in particular a
vapor pressure lower than 10.sup.4 mm Hg (0.13 Pa).
[0619] The oil may be chosen from among the volatile and
non-volatile hydrocarbon and/or silicone and/or fluoro oils and
their mixtures. These oils may be of animal, vegetable, mineral or
synthetic origin. By "hydrocarbon oil" there is understood an oil
containing mainly carbon and hydrogen atoms and possibly one or
more functions chosen from among the hydroxyl, ester, ether,
carboxylic functions. By way of example of oil that can be used in
the invention, there may be cited: [0620] the hydrocarbon oils of
animal origin, such as perhydrosqualene; [0621] the vegetable
hydrocarbon oils, such as the liquid triglycerides of fatty acids
with 4 to 24 carbon atoms, such as the triglycerides of heptanoic
or octanoic acids or else sunflower seed, corn, soy, gourd, grape
seed, sesame, hazelnut, apricot, macadamia, castor, avocado oils,
the triglycerides of caprylic/capric acids such as those sold by
the Stearineries Dubois Company or those sold under the trade names
Miglyol 810, 812 and 818 by the Dynamit Nobel Company, jojoba oil,
shea butter; [0622] the linear or branched hydrocarbons of mineral
or synthetic origin, such as the paraffin oils and their
derivatives, vaseline, the polydecenes, the polybutenes,
hydrogenated polyisobutene such as Parleam; [0623] the synthetic
esters and ethers especially of fatty acids, such as the oils of
formula R.sub.1COOR.sub.2, in which R.sub.1 represents the residue
of a higher fatty acid containing 1 to 40 carbon atoms and R.sub.2
represents a hydrocarbon chain containing 1 to 40 carbon atoms,
with R.sub.1+R.sub.2.gtoreq.10, such as, for example, Purcellin
oil, isononyl isononanoate, isopropyl myristate, ethyl 2-hexyl
palmitate, octyl 2-dodecyl stearate, octyl 2-dodecyl erucate,
isostearyl isostearate, tridecyl trimellitate; the hydroxylated
esters such as isostearyl lactate, octyl hydroxy stearate, octyl
dodecyl hydroxy stearate, diisostearyl malate, triisocetyl citrate,
heptanoates, octanoates, decanoates of fatty alcohols; polyol
esters, such as propylene glycol dioctanoate, neopentyl glycol
diheptanoate, diethylene glycol diisononanoate; and the
pentaerythritol esters, such as pentaerythrityl tetraisostearate;
[0624] fatty alcohols having 12 to 26 carbon atoms, such as
octyldodecanol, 2-butyloctanol, 2-hexyldecanol,
2-undecylpentadecanol, oleic alcohol; [0625] the fluoro, possibly
partly hydrocarbon and/or silicone oils; [0626] the silicone oils,
such as the linear or cyclic volatile or non-volatile
polydimethylsiloxanes (PDMS); the polydimethylsiloxanes containing
alkyl, alkoxy or phenyl groups pendant from or at the end of the
silicone chain, groups having 2 to 24 carbon atoms; the phenyl
silicones, such as the phenyl trimethicones, the phenyl
dimethicones, the phenyl trimethylsiloxy diphenyl siloxanes, the
diphenyl dimethicones, the diphenyl methyldiphenyl trisiloxanes,
the 2-phenyl ethyl trimethyl-siloxy silicates; [0627] mixtures
thereof.
[0628] Preferably, the oil has a molecular weight greater than or
equal to 250 g/mol, especially between 250 and 10,000 g/mol,
preferably greater than or equal to 300 g/mol, especially between
300 and 8,000 g/mol and better, greater than or equal to 400 g/mol,
especially between 400 and 5,000 g/mol.
[0629] In general, in the fatty phase, the ratio of the oil or oils
to the particular compound or compounds is from 10/90 to 90/10,
preferably from 20/80 to 80/20 and more preferably from 30/70 to
70/30.
[0630] This oil may be chosen from among: [0631] the polybutylenes,
such as INDOPOL H-100 (of molecular weight or MW=965 g/mol),
INDOPOL H-300 (MW=1340 g/mol), INDOPOL H-1500 (MW=2160 g/mol) sold
or manufactured by the AMOCO Company; [0632] the hydrogenated
polyisobutylenes, such as PANALANE H-300 E sold or manufactured by
the AMOCO Company (M=1340 g/mol), VISEAL 20000 sold or manufactured
by the SYNTEAL Company (MW=6,000 g/mol), REWOPAL PIB 1000 sold or
manufactured by the WITCO Company (MW=1,000 g/mol); [0633] the
polydecenes and the hydrogenated polydecenes, such as: PURESYN 10
(MW=723 g/mol), PURESYN 150 (MW=9,200 g/mol) sold or manufactured
by the MOBIL CHEMICALS Company, [0634] the esters such as [0635]
the esters of linear fatty acids having a total carbon number
ranging from 30 to 70, such as pentaerythrityl tetrapelargonate
(MW=697.05 g/mol), [0636] the hydroxylated esters, such as
diisostearyl malate (MW=639 g/mol), [0637] the aromatic esters such
as tridecyl trimellitate (MW=757.19 g/mol), [0638] the esters of
fatty alcohol or of C24-C28 branched fatty acids, such as those
described in Application EP A 0955039, and especially triisocetyl
citrate (MW=865 g/mol), pentaerythrityl tetraisononanoate
(MW=697.05 g/mol), glyceryl triisostearate (MW=891.51 g/mol),
glyceryl tridecyl-2 tetradecanoate (MW=1143.98 g/mol),
pentaerythrityl tetraisostearate (MW=1202.02 g/mol), polyglyceryl-2
tetraisostearate (MW=1232.04 g/mol) or else pentaerythrityl
tetradecyl-2 tetradecanoate (MW=1538.66 g/mol), [0639] the oils of
vegetable origin, such as sesame oil (820.6 g/mol), [0640] and
mixtures thereof.
Crystalline Polymers
a) Semi-Crystalline Polymers
[0641] It is pointed out that, according to the invention, in the
case of the aforementioned associations, there is understood by
"semi-crystalline polymer" polymers containing a crystallizable
part, crystallizable pendant and/or terminal chain or
crystallizable sequence in the skeleton and/or at the ends, and an
amorphous part in the skeleton and having a first-order reversible
phase-change temperature, particularly of melting (solid-liquid
transition). When the crystallizable part is in the form of a
crystallizable sequence of the polymer skeleton, the amorphous part
of the polymer is in the form of an amorphous sequence; in this
case the semi-crystalline polymer is a sequenced copolymer, for
example of the diblock, triblock or multiblock type, containing at
least one crystalline sequence and at least one amorphous sequence.
By "sequence" there is generally understood at least 5 identical
repeating moieties. The crystallizable sequence or sequences are
then of chemical nature different from that of the amorphous
sequence or sequences.
[0642] The semi-crystalline polymer according to the invention has
a melting temperature higher than or equal to 30.degree. C.
(especially ranging from 30.degree. C. to 80.degree. C.),
preferably ranging from 30.degree. C. to 60.degree. C. This melting
temperature is a first-order state-change temperature.
[0643] This melting temperature may be measured by any known method
and in particular by means of a differential scanning calorimeter
(D.S.C.).
[0644] Advantageously, the semi-crystalline polymer or polymers to
which the invention applies have a number-average molecular weight
greater than or equal to 1,000.
[0645] Advantageously, the semi-crystalline polymer or polymers of
the composition of the invention have a number-average molecular
weight Mn ranging from 2,000 to 800,000, preferably from 3,000 to
500,000, better from 4,000 to 150,000, especially lower than
100,000 and better from 4,000 to 99,000. Preferably, they have a
number-average molecular weight greater than 5,600, ranging for
example from 5,700 to 99,000.
[0646] By "crystallizable chain or sequence" within the meaning of
the invention there is understood a chain or sequence that, if it
were alone, would change reversibly from the amorphous state to the
crystalline state depending on whether it was above or below the
melting temperature. A chain within the meaning of the invention is
a group of atoms in pendant or side position relative to the
polymer skeleton. A sequence is a group of atoms belonging to the
skeleton, this group constituting one of the repetitive moieties of
the polymer. Advantageously, the "crystallizable pendant chain" may
be a chain containing at least 6 carbon atoms.
[0647] Preferably, the crystallizable sequence or sequences or
chains of semi-crystalline polymers represent at least 30% of the
total weight of each polymer and better at least 40%. The
semi-crystalline polymers of the invention with crystallizable
sequences are sequenced or multisequenced polymers. They may be
obtained by polymerization of monomers with reactive double (or
ethylenic) bonds or by polycondensation. When the polymers of the
invention are polymers with crystallizable side chains, the latter
are advantageously in random or statistical form.
[0648] Preferably, the semi-crystalline polymers of the invention
are of synthetic origin. In addition, they do not contain any
polysaccharide skeleton. In general, the crystallizable moieties
(chains or sequences) of semi-crystalline polymers according to the
invention are derived from monomers with a crystallizable sequence
or sequences or chain or chains used for the manufacture of
semi-crystalline polymers.
[0649] According to the invention, the semi-crystalline polymer may
be chosen from among the sequenced copolymers containing at least
one crystallizable sequence and at least one amorphous sequence,
the homopolymers and the copolymers carrying at least one
crystallizable side chain per repetitive moiety, and mixtures
thereof.
[0650] The semi-crystalline polymers that can be used in the
invention are in particular: [0651] the sequenced copolymers of
polyolefins with controlled crystallization, especially those whose
monomers are described in EP A 0951897, [0652] the polycondensates,
and especially of aliphatic or aromatic polyester or
aliphatic/aromatic copolyester type. [0653] the homopolyers or
copolymers carrying at least one crystallizable side chain and the
homopolymers or copolymers carrying at least one crystallizable
sequence in the skeleton, such as those described in the document
U.S. Pat. No. 5,156,911, [0654] the homopolyers or copolymers
carrying at least one crystallizable side chain, in particular with
a fluoro group or groups, such as described in the document WO A
01/19333, [0655] and mixtures thereof.
[0656] In the two latter cases, the crystallizable side chain or
chains or sequence or sequences are hydrophobic.
[0657] A) Semi-Crystalline Polymers with Crystallizable Side
Chains:
[0658] There may be cited in particular those defined in the
documents U.S. Pat. No. 5,156,911 and WO A 01/19333. These are
homopolymers or copolymers containing 50 to 100% by weight of
moieties resulting from the polymerization of one or more monomers
carrying crystallizable hydrophobic side chains. [0659] These
homopolymers or copolymers are of any nature, provided they exhibit
the conditions indicated in the foregoing.
[0660] They may result: [0661] from the polymerization, especially
radical, of one or more monomers with double or ethylenic bonds
that are reactive with respect to polymerization, or in other words
with vinyl, (meth)acrylic or allyl groups. [0662] from the
polycondensation of one or more monomers carrying co-reactive
groups (carboxylic or sulfonic acid, alcohol, amine or isocyanate),
such as, for example, the polyesters, the polyurethanes, the
polyethers, the polyureas, the polyamides.
[0663] In general, these polymers are chosen in particular from
among the homopolymers and copolymers resulting from the
polymerization of at least one monomer with crystallizable chain or
chains that may be represented by the formula X:
##STR00026##
[0664] with M representing an atom of the polymer skeleton, S
representing a spacer, C representing a crystallizable group.
[0665] The crystallizable "S--C" chains may be aliphatic or
aromatic, possibly fluorinated or perfluorinated. "S" represents in
particular a linear or branched or cyclic (CH.sub.2).sub.n group or
(CH.sub.2CH.sub.2O).sub.n or (CH.sub.2O), where n is an integer
ranging from 0 to 22. Preferably, "S" is a linear group.
Preferably, "S" and "C" are different.
[0666] When the crystallizable "S--C" chains are aliphatic
hydrocarbon chains, they contain alkyl hydrocarbon chains with at
least 11 carbon atoms and at most 40 carbon atoms and better at
most 24 carbon atoms. In particular, they are aliphatic chains or
alkyl chains possessing at least 12 carbon atoms and preferably
they are C.sub.14-C.sub.24 alkyl chains. When they are fluorinated
or perfluorinated alkyl chains, they contain at least 6 fluorinated
carbon atoms and especially at least 11 carbon atoms, of which at
least 6 carbon atoms are fluorinated.
[0667] As examples of semi-crystalline polymers or copolymers with
a crystallizable chain or chains there may be cited those resulting
from the polymerization of one or more of the following monomers:
the saturated alkyl (meth)acrylates with the C.sub.14-C.sub.24
alkyl group, the perfluoroalkyl (meth)acrylates with a
C.sub.11-C.sub.15 perfluoroalkyl group, the N-alkyl
(meth)acrylamides with the C.sub.14 to C.sub.24 alkyl group with or
without fluorine atoms, the vinyl esters with alkyl or perfluoro
(alkyl) chains with the C.sub.14 to C.sub.24 alkyl group (with at
least 6 fluorine atoms for a perfluoro alkyl chain), the vinyl
ethers with alkyl or perfluoro (alkyl) chains with the C.sub.14 to
C.sub.24 alkyl group and at least 6 fluorine atoms for a
perfluoroalkyl chain, the C.sub.14 to C.sub.24 alpha-olefins, such
as, for example, octadecene, the para-alkylstyrenes with an alkyl
group containing 12 to 24 carbon atoms, mixtures thereof.
[0668] When the polymers result from a polycondensation, the
hydrocarbon and/or fluoro crystallizable chains such as defined
hereinabove are carried by a monomer, which may be a diacid, a
diol, a diamine, a diisocyanate.
[0669] When the polymers comprising objects of the invention are
copolymers, they additionally contain 0 to 50% of groups Y or Z
resulting from the copolymerization:
[0670] .alpha.) of Y, which is a polar or non-polar monomer or a
mixture of both: [0671] When Y is a polar monomer, it is either a
monomer carrying polyoxyalkylene groups (especially oxyethylene
and/or oxypropylene), a hydroxyalkyl (meth)acrylate such as
hydroxyethyl acrylate, (meth)acrylamide, an N-alkyl
(meth)acrylamide, an N,N-dialkyl (meth)acrylamide such as, for
example, N,N-diisopropyl acrylamide or N-vinylpyrrolidone (NVP),
N-vinyl caprolactam, a monomer carrying at least one carboxylic
acid group such as (meth)acrylic, crotonic, itaconic, maleic,
fumaric acids, or carrying a carboxylic acid anhydride group such
as maleic anhydride, and mixtures thereof. [0672] When Y is a
non-polar monomer, it may be an ester of the linear, branched or
cyclic alkyl (meth)acrylate type, a vinyl ester, an alkyl vinyl
ether, an alpha-olefin, styrene or styrene substituted by a C.sub.1
to C.sub.10 alkyl group, such as .alpha.-methylstyrene, a
macromonomer of the polyorganosiloxane type with vinyl
unsaturation.
[0673] By "alkyl" there is understood within the meaning within the
meaning of the invention a saturated group, especially with C.sub.8
to C.sub.24 unless otherwise expressly mentioned, and better with
C.sub.14 to C.sub.24.
[0674] .beta.) of Z, which is a polar monomer or a mixture of polar
monomers. In this case, Z has the same definition as "polar Y"
defined above.
[0675] Preferably, the semi-crystalline polymers with
crystallizable side chain are homopolymers of alkyl (meth)acrylate
or alkyl (meth)acrylamide with an alkyl group such as defined
above, and especially with C.sub.14 to C.sub.24, copolymers of
these monomers with a hydrophilic monomer, preferably of different
nature from that of (meth)acrylic acid, such as N-vinylpyrrolidone
or hydroxyethyl (meth)acrylate and mixtures thereof.
[0676] B) The polymers carrying at least one crystallizable
sequence in the skeleton:
[0677] These polymers are especially sequenced copolymers composed
of at least 2 sequences of different chemical nature, one of which
is crystallizable. [0678] There may be used the sequenced polymers
defined in U.S. Pat. No. 5,156,911; [0679] The sequenced copolymers
of olefin or cycloolefin with a crystallizable chain, such as those
obtained from the sequenced polymerization of: [0680] cyclobutene,
cyclohexene, cyclooctene, norbornene (or in other words
bicyclo(2,2,1)heptene-2), 5-methylnorbornene, 5-ethylnorbornene,
5,6-dimethylnorbornene, 5,5,6-trimethylnorbornene,
5-ethylidene-norbornene, 5-phenylnorbornene, 5-benzylnorbornene,
5-vinylnorbornene,
1,4,5,8-dimethano-1,2,3,4,4a,5,8a-octahydronaphthalene,
dicyclopentadiene or mixtures thereof, [0681] with ethylene,
propylene, 1-butene, 3-methyl-1-butene, 1-hexene,
4-methyl-1-pentene, 1-octene, 1-decene, 1-eicosene or mixtures
thereof. [0682] and in particular the block
copoly(ethylene/norbornene)s and the block
(ethylene/propylene/ethylidene-norbornene) terpolymers. There may
also be used those resulting from the sequenced copolymerization of
at least two C.sub.2-C.sub.16 .alpha.-olefins and better
C.sub.2-C.sub.12 and even better C.sub.4-C.sub.12, such as those
cited in the foregoing, and in particular the sequenced bipolymers
of ethylene and 1-octene. [0683] The copolymers may be copolymers
having at least one crystallizable sequence, the rest of the
copolymer being amorphous (at room temperature). These copolymers
may additionally have two crystallizable sequences of different
chemical nature. The preferred copolymers are those that possess,
at room temperature, sequentially distributed, both a
crystallizable sequence and an amorphous sequence that are both
hydrophobic and lipophilic; for example, there may be cited the
polymers possessing crystallizable sequences and one of the
following amorphous sequences: [0684] Naturally crystallizable
sequence: a) polyester such as the poly(alkylene terephthalate), b)
polyolefin such as the polyethylenes or polypropylenes. [0685]
Amorphous and lipophilic sequence such as the amorphous polyolefins
or copoly(olefin)s, such as poly(isobutylene), hydrogenated
polybutadiene, hydrogenated poly(isoprene).
[0686] As examples of such copolymers with separate crystallizable
sequence and amorphous sequence there may be cited:
[0687] .alpha.) the sequenced
poly(.epsilon.-caprolactone)-b-poly(butadiene) copolymers, used
preferably in hydrogenated form, such as those described in the
article "Melting behavior of
poly(e-caprolactone)-block-polybutadiene copolymers" of S. Nojima,
Macromolecules, 32, 3727-3734 (1999).
[0688] .beta.) the sequenced or multisequenced hydrogenated
sequenced poly(butylene terephthalate)-b-poly(isoprene) sequenced
copolymers cited in the article "Study of morphological and
mechanical properties of PP/PBT" of B. Boutevin et al., Polymer
Bulletin, 34, 117-123 (1995).
[0689] .gamma.) the sequenced
poly(ethylene)-b-copoly(ethylene/propylene) copolymers cited in the
articles "Morphology of semi-crystalline block copolymers of
ethylene-(ethylene-alt-propylene)" of P. Rangarajan et al.,
Macromolecules, 26, 4640-4645 (1993) and "Polymer aggregates with
crystalline cores: the system
poly(ethylene)-poly(ethylene-propylene)" of P. Richter et al.,
Macromolecules, 30, 1053-1068 (1997).
[0690] .delta.) the sequenced poly(ethylene)-b-poly(ethylethylene)
copolymers cited in the general article "Crystallization in block
copolymers" of I. W. Hamley, Advances in Polymer Science, vol. 148,
113-137 (1999).
[0691] The semi-crystalline polymers of the composition of the
invention may or may not be partly cross-linked, since the degree
of cross-linking does not impair their dissolution or dispersion in
the liquid fatty phase by heating above their melting point. They
may then be chemically cross-linked, by reaction with a
multifunctional monomer during polymerization. They may also be
physically cross-linked, which may then be due either to the
establishment of bonds of hydrogen or dipole type between groups
carried by the polymer, such as, for example, the dipole
interactions between carboxylate ionomers, these interactions being
of small quantity and carried by the polymer skeleton; or to phase
separation between the crystallizable sequences and the amorphous
sequences carried by the polymer.
[0692] Preferably, the semi-crystalline polymers of the composition
according to the invention are non-cross-linked.
[0693] According to a particular embodiment of the invention, the
polymer is chosen from among the copolymers resulting from the
polymerization of at least one monomer with crystallizable chain
chosen from among the saturated C.sub.14 to C.sub.24 alkyl
(meth)acrylates, the C.sub.11 to C.sub.15 perfluoroalkyl
(meth)acrylates, the N--(C.sub.14 to C.sub.24)alkyl
(meth)acrylamides with or without fluorine atoms, the vinyl esters
with C.sub.14 to C.sub.24 alkyl or perfluoroalkyl chains, the vinyl
ethers with C.sub.14 to C.sub.24 alkyl or perfluoroalkyl chains,
the C.sub.14 to C.sub.24 alpha-olefins, the para-alkylstyrenes with
an alkyl group containing 12 to 24 carbon atoms, with at least one
ester or amide of C.sub.1 to C.sub.10 monocarboxylic acid, possibly
fluorinated, which may be represented by the following formula:
##STR00027##
[0694] in which R.sub.1 is H or CH.sub.3, R represents a
C.sub.1-C.sub.10 alkyl group, which may be fluorinated, and X
represents O, NH or NR.sub.2, where R.sub.2 represents a
C.sub.1-C.sub.10 alkyl group, which may be fluorinated.
[0695] According to a more particular embodiment of the invention,
the polymer is obtained from a monomer with crystallizable chain
chosen from among the saturated C.sub.14 to C.sub.22 alkyl
(meth)acrylates.
[0696] By way of particular example of structuring semi-crystalline
polymer that can be used in the composition according to the
invention there may be cited the products Intelimer.RTM. of the
Landec Company described in the brochure "Intelimer.RTM. polymers",
Landec IP22 (Rev. 4-97). These polymers are in solid form at room
temperature (25.degree. C.). They carry crystallizable side chains
and have the foregoing formula X.
[0697] The semi-crystalline polymers may be especially:
[0698] those described in Examples 3, 4, 5, 7, 9, 13 of U.S. Pat.
No. 5,156,911, with --COHO group, resulting from the
copolymerization of acrylic acid and C.sub.5 to C.sub.16 alkyl
(meth)acrylate and more particularly from the copolymerization:
[0699] of acrylic acid, hexadecyl acrylate and isodecyl acrylate in
a weight ratio of 1/16/3, [0700] of acrylic acid and pentadecyl
acrylate in a weight ratio of 1/19, [0701] of acrylic acid,
hexadecyl acrylate, ethyl acrylate in a weight ratio of
2.5/76.5/20, [0702] of acrylic acid, hexadecyl acrylate and methyl
acrylate in a weight ratio of 5/85/10, [0703] of acrylic acid and
octadecyl methacrylate in a weight ratio of 2.5/97.5, [0704] of
hexadecyl acrylate, monomethyl ether of polyethylene glycol
methacrylate with 8 ethylene glycol moieties, and acrylic acid in a
weight ratio of 8.5/1/0.5.
[0705] There may also be used the polymer of structure "O" of
National Starch, such as that described in the document U.S. Pat.
No. 5,736,125 of melting point 44.degree. C. as well as the
semi-crystalline polymers with crystallizable pendant chains
containing fluoro groups such as described in Examples 1, 4, 6, 7
and 8 of the document of WO A 01/19333.
[0706] There may also be used the semi-crystalline polymers
obtained by copolymerization of stearyl acetate and acrylic acid or
NVP such as described in the documents U.S. Pat. No. 5,519,063 or
EP A 550745, with melting temperatures of 40.degree. C. and
38.degree. C. respectively.
[0707] There may also be used the semi-crystalline polymers
obtained by copolymerization of behenyl acrylate and acrylic acid
or NVP, such as described in the documents U.S. Pat. No. 5,519,063
and EP A 550745, with melting temperatures of 60.degree. C. and
58.degree. C. respectively.
[0708] Preferably, the semi-crystalline polymers do not contain any
carboxylic group.
Waxy Polymer Obtained by Metallocene Catalysis:
[0709] Finally, the semi-crystalline polymers according to the
invention may also be chosen from among the waxy polymers obtained
by metallocene catalysis, such as those described in US Application
2007/0031361.
[0710] These polymers are homopolymers or copolymers of ethylene
and/or propylene prepared by metallocene catalysis, or in other
words by polymerization at low pressure and in the presence of a
metallocene catalyst.
[0711] The weight-average molecular weight (Mw) of the waxes
obtained by metallocene catalysis described in that document is
smaller than or equal to 25,000 g/mol; for example, it ranges from
2,000 to 22,000 g/mol and better from 4,000 to 20,000 g/mol.
[0712] The number-average molecular weight (Mn) of the waxes
obtained by metallocene catalysis described in that document is
preferably smaller than or equal to 15,000 g/mol; for example, it
ranges from 1,000 to 12,000 g/mol and better from 2,000 to 10,000
g/mol.
[0713] The polydispersity index I of the polymer is equal to the
ratio of the weight-average molecular weight Mw to the
number-average molecular weight Mn. Preferably, the polydispersity
index of the waxy polymers is between 1.5 and 10, preferably
between 1.5 and 5, preferably between 1.5 and 3 and even better
between 2 and 2.5.
[0714] The waxy homopolymers and copolymers may be obtained in
known manner from ethylene and/or propylene monomers, for example
by metallocene catalysis according to the method described in the
document EP 571882.
[0715] The homopolymers and copolymers of ethylene and/or propylene
prepared by metallocene catalysis may or may not be modified
"polarly" (polar modified waxes, or in other words waxes modified
so that they exhibit the properties of a polar wax). The
polar-modified waxy homopolymers and copolymers may be prepared in
known manner from the non-modified waxy homopolymers and copolymers
such as those described in the foregoing by oxidation with
oxygen-containing gases, such as air, or by grafting with polar
monomers such as maleic acid or acrylic acid or else with
derivatives of these acids. These two routes making it possible to
achieve polar modification of the polyolefins obtained by
metallocene catalysis are described respectively in the documents
EP 890583 and U.S. Pat. No. 5,998,547 for example, the content of
these two documents being incorporated by way of reference.
[0716] According to the present invention, the polar modified
homopolymers and copolymers of ethylene and/or propylene prepared
by metallocene catalysis and particularly preferred are polymers
modified so that they exhibit hydrophilic properties. By way of
example, there may be cited homopolymers or copolymers of ethylene
and/or propylene modified by the presence of hydrophilic groups,
such as maleic anhydride, acrylate, methacrylate,
polyvinylpyrrolidone (PVP), etc.
[0717] The waxy homopolymers or copolymers of ethylene and/or
propylene modified by the presence of hydrophilic groups such as
maleic anhydride or acrylate are particularly preferred.
[0718] By way of example there may be cited: [0719] the
polypropylene waxes modified by maleic anhydride (PPMA) sold by the
Clariant Company or the polypropylene-ethylene-maleic anhydride
copolymers, such as those sold by the Clariant Company under the
name of LicoCare, such as LicoCare PP207 LP3349, LicoCare CM401
LP3345, LicoCare CA301 LP 3346 and LicoCare CA302 LP 3347, or else
[0720] the non-modified polyethylene waxes sold by the Clariant
Company, such as the product LicoCare PE 102 LP3329.
[0721] Within the scope of a composition for the lips, there will
be preferred a polar-modified waxy polymer having a low degree of
crystallinity, preferably of less than 40%.
[0722] The use of these waxy polymers makes it possible in
particular to limit the loss of gloss of lipstick compositions.
[0723] b) Esters of Dextrin and Fatty Acid:
[0724] The esters of dextrin and fatty acids may be chosen
especially from among the mono or poly esters of dextrin and at
least one fatty acid, and the compounds represented by formula
(C):
##STR00028##
in which: [0725] n is an integer ranging from 3 to 200, especially
ranging from 20 to 150, and in particular ranging from 25 to 50,
[0726] the radicals R.sub.1, R.sub.2 and R.sub.3, identical or
different, are chosen from among hydrogen or an acyl group
(R--CO--), in which the R radical is a saturated or unsaturated,
linear or branched hydrocarbon group possessing 7 to 29, in
particular 7 to 21, especially 11 to 19, more particularly 13 to
17, even 15 carbon atoms, with the proviso that at least one of the
said radicals R.sub.1, R.sub.2 or R.sub.3 is different from
hydrogen.
[0727] In particular, R.sub.1, R.sub.2 and R.sub.3 may represent
hydrogen or an acyl group (R--CO--), in which R is a hydrocarbon
radical such as defined in the foregoing, with the proviso that at
least two of the said radicals R.sub.1, R.sub.2 or R.sub.3 are
different from hydrogen.
[0728] All radicals R.sub.1, R.sub.2 and R.sub.3 may represent an
identical or different acyl group (R--CO), and especially
identical.
[0729] In particular, n advantageously varies from 25 to 50, and
especially it is equal to 38 in general formula (C) of the ester
according to the invention.
[0730] Especially when the radicals R.sub.1, R.sub.2 and/or
R.sub.3, identical or different, represent an acyl group (R--CO),
they may be chosen from among the caprylic, capric, lauric,
myristic, palmitic, stearic, arachic, behenic, isobutyric,
isovaleric, ethyl-2-butyric, ethylmethylacetic, isoheptanoic,
ethyl-2-hexanoic, isononanoic, isodecanoic, isotridecanolc,
isomyristic, isopalmitic, isostearic, isoarachic, isohexanoic,
decenoic, dodecenoic, tetradecenoic, myristoleic, hexadecenoic,
palmitoleic, oleic, elaidic, asclepinic, gondoleic, eicosenoic,
sorbic, linoleic, linolenic, punicic, stearidonic, arachidonic,
stearolic radicals and mixtures thereof.
[0731] Preferably, there are used by way of ester of dextrin and
fatty acid or acids at least one dextrin palmitate, This may be
used alone or in a mixture with other esters.
[0732] Advantageously, the ester of dextrin and fatty acid has a
degree of substitution smaller than or equal to 2.5 on the basis of
one glucose unit, especially varying from 1.5 to 2.5, preferably
from 2 to 2.5. The weight-average molecular weight of the dextrin
ester may be in particular 10,000 to 150,000, especially 12,000 to
100,000 and even 15,000 to 80,000.
[0733] Dextrin esters, in particular dextrin palmitates, are
commercially available under the trade name RHEOPEARL TL or
RHEOPEARL KL of the Chiba Flour Company.
[0734] c) Hydrophobic Modified Polysaccharides
[0735] The polysaccharide used in the present invention is
preferably chosen from among the fructans.
[0736] The fructans or fructosans are oligosaccharides or
polysaccharides comprising a chain of anhydrofructose units,
possibly associated with one more different saccharidic residues of
fructose. The fructans may be linear or branched. The fructans may
be products obtained directly from a vegetable or microbial source
or else products whose chain length has been modified (increased or
decreased) by fractionation, synthesis or hydrolysis, especially
enzymatically. The fructans generally have a degree of
polymerization of 2 to approximately 1000 and preferably of 2 to
approximately 60.
[0737] Three groups of fructans are distinguished. The first group
corresponds to products whose fructose units are for the most part
bonded by .beta.-2-1 bonds. These are substantially linear fructans
such as the inulins. The second group also corresponds to linear
fructoses, but the fructose units are substantially bonded by
.beta.-3-2-6 bonds. These products are levans. The third group
corresponds to mixed fructans, or in other words having
.beta.-2-6-1 and .beta.-2-1 chains. These are substantially
branched fructans such as the graminans.
[0738] The fructans used in the compositions according to the
invention are inulins. Inulin may be obtained, for example, from
chicory, dahlia or Jerusalem artichoke. Preferably, the inulin used
in the composition according to the invention is obtained, for
example, from chicory.
[0739] The polysaccharides, in particular the inulins, used in the
composition according to the invention are hydrophobically
modified. In particular, they are obtained by grafting hydrophobic
chains onto the hydrophilic skeleton of the fructan.
[0740] The hydrophobic chains capable of being grafted onto the
main chain of the fructan may be especially saturated or
unsaturated, linear or branched hydrocarbon chains having 1 to 50
carbon atoms, such as the alkyl, arylalkyl, alkylaryl, alkoylene
groups; divalent cycloaliphatic groups or organopolysiloxane
chains. These hydrocarbon or organopolysiloxane chains may comprise
in particular one or more ester, amide, urethane, carbamate,
thiocarbamate, urea, thiourea and/or sulfonamide functions such as
especially methylenedicyclohexyl and isophorone; or divalent
aromatic groups such as phenylene.
[0741] In particular, the polysaccharide, especially inulin, has a
degree of polymerization of 2 to approximately 1,000 and preferably
of 2 to approximately 60, and a degree of substitution smaller than
2 on the basis of one fructose unit.
[0742] According to a preferred embodiment, the hydrophobic chains
have at least one alkyl carbamate group of formula R--NH--CO--, in
which R is an alkyl group having 1 to 22 carbon atoms.
[0743] According to a more preferred embodiment, the hydrophobic
chains are lauryl carbamate groups.
[0744] In particular, by way of non-limitative illustration of
hydrophobically modified inulins that may be used in the
compositions according to the invention, there may be cited
stearoyl inulin such as those sold under the trade names Lifidrem
INST by the Engelhard Company and Rheopearl INS by the Chiba
Company; palmitoyl inulin; undecylenoyl inulin, such as those sold
under the trade names Lifidrem INUK and Lifidrem INUM by the
Engelhard Company; and inulin lauryl carbamate, such as that sold
under the name INUTEC SP1 by the ORAFTI Company.
[0745] In particular, the hydrophobically modified polysaccharide
is an inulin grafted with lauryl carbamate, especially resulting
from the reaction of lauryl isocyanate with an inulin, in
particular resulting from chicory. By way of examples of these
compounds there may be cited in particular the product sold under
the name INUTEC SP1 by the ORAFTI Company.
[0746] d) Copolymers of Crystalline Olefins:
[0747] The copolymer of crystalline olefins used in the
compositions of the present application may be any olefin
copolymer, or in other words a copolymer containing only olefinic
moieties, having a controlled and moderate crystalline character,
or in other words a degree of crystallinity at most equal to 50%,
preferably between 5 and 40%, and better between 10 and 35%.
[0748] These copolymers are generally elastomers or plastomers and
may be synthesized by any known method, in particular by radical
reaction, by Ziegler-Natta catalysis or by metallocene catalysis,
preferably by metallocene catalysis.
[0749] A first class of crystalline olefin copolymers that can be
used in the compositions according to the invention are copolymers
of .alpha.-olefin, in particular of C.sub.2-C.sub.16 and better
C.sub.2-C.sub.12 .alpha.-olefin. Preferably, these copolymers are
bipolymers or terpolymers and most particularly bipolymers.
[0750] Among the bipolymers recommended for the compositions of the
invention there may be cited the bipolymers of ethylene and
C.sub.4-C.sub.16, preferably C.sub.4-C.sub.12 .alpha.-olefin and
the bipolymers of propylene and C.sub.4-C.sub.16, preferably
C.sub.4-C.sub.12 .alpha.-olefin. Even more preferably, the
.alpha.-olefin is chosen from among butene-1, pentene-1, hexene-1,
octene-1, nonene-1, decene-1, undecene-1,
dodecene-1,3,5,5-trimethylhexene-1,3-methylpentene-1 and
4-methylpentene-1.
[0751] Among these monomers, butene-1 and octene-1 are particularly
preferred.
[0752] The proportion of .alpha.-olefin in the bipolymer is
generally between 2 and 40 mol %, preferably 3 to 30 mol %, and
better 4 to 20 mol %.
[0753] The recommended ethylene-octene bipolymers are the
plastomers having an octene content between 5.2 and 6.2 mol %, a
degree of crystallinity between 28% and 38% and the elastomers
having an octene content between 8 and 14 mol % and a degree of
crystallinity between 10 and 28%.
[0754] These bipolymers are synthesized by metallocene
catalysis.
[0755] Such bipolymers are sold by the DOW CHEMICAL Company under
the trade names AFFINITY (plastomers) and ENGAGE (elastomers).
[0756] Ethylene-butene bipolymers are sold by the EXXON Company
under the commercial name EXACT RESINS.
[0757] Among the terpolymers there may be cited the terpolymers of
ethylene, propylene and C.sub.4-C.sub.16 preferably
C.sub.4-C.sub.12-olefin.
[0758] In these terpolymers, the contents of
C.sub.4-C.sub.16-olefin are as indicated in the foregoing, and the
preferred .alpha.-olefins are butene, hexene and octene.
[0759] A second class of olefin copolymers suitable for the
compositions according to the invention are copolymers of ethylene
or propylene and a cycloolefin, in particular the bipolymers.
[0760] In general, the cycloolefin content of the copolymers is
smaller than 20 mol %.
[0761] Among the usable cycloolefins, there may be cited
cyclobutene, cyclohexene, cyclooctadiene, norbornene,
dimethano-octahydronaphthalene (DMON), ethylidene norbornene, vinyl
norbornene and 4-vinylcyclohexene.
[0762] The recommended copolymers of this class are the copolymers
of ethylene and norbornene. The norbornene content of these
copolymers is generally smaller than 18 mol % in order to exhibit
the required crystalline character, and these copolymers are
synthesized by metallocene catalysis.
[0763] Appropriate ethylene/norbornene copolymers are sold by the
MITSUI PETROCHEMICAL or MITSUI-SEKKA Company under the trade name
APEL and by the HOECHST-CELANESE Company under the trade name
TOPAS.
[0764] Other recommended ethylene/cycloolefin copolymers are the
ethylene/cyclobutene and ethylene/cyclohexene bipolymers with low
cycloolefin content, generally lower than 20 mol %.
[0765] A third class of appropriate olefin copolymers is
constituted by the olefin copolymers of controlled tacticity, or in
other words copolymers containing moieties of different
tacticity.
[0766] Among these copolymers of controlled tacticity there may be
cited the isotactic propylene/atactic propylene and syndiotactic
propylene/atactic propylene copolymers.
[0767] The isotactic or syndiotactic moieties or sequences confer
the crystalline character on the copolymer, while the amorphous
atactic moieties or sequences prevent excessive crystallinity of
the copolymer and regulate the degree of crystallinity as well as
the morphology and size of the crystallites.
[0768] The content of isotactic or syndiotactic moieties, the
moieties conferring the crystalline character on the copolymer, is
therefore determined so as to obtain the desired percentage
crystallinity (.ltoreq.50%) in the copolymer.
[0769] The content of tactic moieties is generally between 10 and
80 mol %. Nevertheless, the content of atactic moieties is
preferably smaller than 30 mol %.
[0770] These copolymers are synthesized by metallocene
catalysis.
[0771] A fourth class of olefin copolymers suitable for the present
invention is constituted by the copolymers of monoolefin and diene,
for example the ethylene/butadiene, propylene/butadiene,
ethylene/isoprene and propylene/isoprene bipolymers and the
ethylene/propylene/diene terpolymers, also obtained by metallocene
synthesis.
[0772] The proportion of diene moieties in the controlled
crystallization copolymer is generally between 3 and 20 mol %.
[0773] To improve the regulation of the crystallinity of the
polymer, there may be added if necessary to the composition
according to the invention additives that impair crystallization
and favor formation of small crystals. These additives, although
used in small proportion, constitute numerous and small nucleation
"sites" distributed uniformly in the mass. These additives are
typically crystals of an organic or mineral substance.
[0774] In the case of an organic additive that must crystallize,
this must have a melting point higher than the melting zone of the
copolymer and preferably must form small crystals.
[0775] At a temperature above its melting point, this substance is
preferably soluble in the mixture of liquid fatty phase and molten
polymer. Thus, during cooling, the initially dissolved additive
recrystallizes in the form of numerous small crystals, thoroughly
distributed in the mixture, then the polymer recrystallizes by
forming small crystalline domains due to the presence of the
additive crystals. This technique for recrystallization of polymers
is traditional.
[0776] The degree of crystallization, the size and the morphology
of the olefin copolymers according to the invention may also be
adjusted by mixing a first olefin copolymer according to the
invention with a second crystalline polymer or copolymer, partly
compatible with the first olefin copolymer. The second polymer or
copolymer may be an olefin copolymer according to the invention,
but with a degree of crystallinity different from that of the first
copolymer, including a higher degree of crystallinity than the
degree of crystallinity of the olefin copolymers according to the
invention.
[0777] The second crystallizable polymer may also be a polymer of
different nature, for example a copolyethylene/vinyl acetate
obtained by radical copolymerization or even a crystallizable
polyethylene such as those commonly used in the cosmetic field.
[0778] For more details as to this method for adjusting the degree
of crystallinity, reference is made to the articles entitled
"Elastomeric blends of homogeneous ethylene-octene copolymers
(Elastomeric mixtures of homogeneous ethylene-octene copolymers)"
S. Bensason et al., Polymer, Volume 38, No. 15, 1997, pages
3913-19, and "Blends of homogeneous ethylene-octene copolymers
(Mixtures of homogeneous ethylene-octene copolymers)" S. Bensason
et al., Polymer, Volume 38, No. 14, 1997, pages 3513-20.
[0779] d) Crystalline Polycondensates:
[0780] The usable polycondensate may be capable of being obtained
by reaction: [0781] of 10 to 30% by weight, relative to the total
weight of the polycondensate, of at least one polyol comprising 3
to 6 hydroxyl groups; [0782] of 30 to 80% by weight, relative to
the total weight of the polycondensate, of at least one linear,
branched and/or cyclic, saturated or unsaturated non-aromatic
monocarboxylic acid comprising 6 to 32 carbon atoms; [0783] of 0.1
to 10% by weight, relative to the total weight of the
polycondensate, of at least one aromatic monocarboxylic acid
comprising 7 to 11 carbon atoms, possibly substituted in addition
by 1 to 3 linear, branched and/or cyclic, saturated or unsaturated
alkyl radicals comprising 1 to 32 carbon atoms; [0784] of 5 to 40%
by weight, relative to the total weight of the polycondensate, of
at least one linear, branched and/or cyclic, saturated or
unsaturated, even aromatic polycarboxylic acid comprising at least
2 carboxylic groups COOH, especially 2 to 4 COOH groups; and/or a
cyclic anhydride of such a polycarboxylic acid.
[0785] Preferably, the polycondensate is capable of being obtained
by reaction: [0786] of 10% by weight of at least one aromatic
monocarboxylic acid comprising 7 to 11 carbon atoms, possibly
additionally substituted by 1 to 3 linear, branched and/or cyclic,
saturated or unsaturated alkyl radicals comprising 1 to 32 carbon
atoms; and [0787] of 15 to 30% by weight, relative to the total
weight of the polycondensate, of at least one polyol comprising 3
to 6 hydroxyl groups; and [0788] of 30 to 40% by weight, relative
to the total weight of the polycondensate, of at least one linear,
branched and/or cyclic, saturated or unsaturated non-aromatic
monocarboxylic acid comprising 6 to 32 carbon atoms; [0789] of 10
to 25% by weight, relative to the total weight of the
polycondensate, of at least one linear, branched and/or cyclic,
saturated or unsaturated, even aromatic polycarboxylic acid
comprising at least 2 carboxylic groups COOH, especially 2 to 4
COOH groups; and/or a cyclic anhydride of such a polycarboxylic
acid; these conditions being cumulative, then the ratio between the
number of moles of aromatic monocarboxylic acid and the number of
moles of non-aromatic monocarboxylic acid is between 0.08 and
0.70.
[0790] The polycondensate may also be capable of being obtained by
reaction: [0791] of 10 to 30% by weight, relative to the total
weight of the polycondensate, of at least one polyol comprising 3
to 6 hydroxyl groups; [0792] of 45 to 80% by weight, relative to
the total weight of the polycondensate, of at least one linear,
branched and/or cyclic, saturated non-aromatic monocarboxylic acid
comprising 6 to 32 carbon atoms; [0793] of 0.1 to 10% by weight,
relative to the total weight of the polycondensate, of at least one
aromatic monocarboxylic acid comprising 7 to 11 carbon atoms,
possibly substituted in addition by 1 to 3 linear, branched and/or
cyclic, saturated or unsaturated alkyl radicals comprising 1 to 32
carbon atoms; [0794] of 5 to 40% by weight, relative to the total
weight of the polycondensate, of at least one linear, branched
and/or cyclic, saturated or unsaturated, even aromatic
polycarboxylic acid comprising at least 2 carboxylic groups COOH,
especially 2 to 4 COOH groups; and/or a cyclic anhydride of such a
polycarboxylic acid.
[0795] One of the constituents necessary for the preparation of
polycondensates according to the invention is a compound comprising
3 to 6 hydroxyl groups (polyol), especially 3 to 4 hydroxyl groups.
Quite obviously, a mixture of such polyols may be used. The said
polyol may be in particular a carbon compound, especially a
saturated or unsaturated, linear, branched and/or cyclic
hydrocarbon compound comprising 3 to 18 carbon atoms, especially 3
to 12, even 4 to 10 carbon atoms, and 3 to 6 hydroxy (OH) groups,
and being able to comprise additionally one or more oxygen atoms
intercalated in the chain (ether function). The said polyol is
preferably a linear or branched, saturated hydrocarbon compound
comprising 3 to 18 carbon atoms, especially 3 to 12, even 4 to 10
carbon atoms, and 3 to 6 hydroxy (OH) groups. It may be chosen from
among the following compounds, alone or in a mixture: [0796] the
triols, such as 1,2,4-butanetriol, 1,2,6-hexanetriol,
trimethylolethane, trimethylolpropane, glycerol; [0797] the
tetraols, such as pentaerythritol (tetramethylolmethane),
erythritol, diglycerol or ditrimethylolpropane; [0798] the pentols
such as xylitol, [0799] the hexyls such as sorbitol and mannitol;
or else dipentaerythritol or triglycerol.
[0800] Preferably, the polyol is chosen from among glycerol,
pentaerythritol, diglycerol, sorbitol and mixtures thereof; and
pentaerythritol is even better. The polyol or the polyol mixture
preferably represents 10 to 30% by weight, especially 12 to 25% by
weight, and better 14 to 22% by weight of the total weight of the
final polycondensate.
[0801] Another constituent necessary for the preparation of the
polycondensates according to the invention is a linear, branched
and/or cyclic, saturated or unsaturated non-aromatic monocarboxylic
acid comprising 6 to 32 carbon atoms, especially 8 to 28 carbon
atoms and still better 10 to 24, even 12 to 20 carbon atoms. Quite
obviously a mixture of such non-aromatic monocarboxylic acids may
be used. By non-aromatic monocarboxylic acid there is understood a
compound of formula RCOOH, in which R is a linear, branched and/or
cyclic, saturated or unsaturated hydrocarbon radical comprising 5
to 31 carbon atoms, especially 7 to 27 carbon atoms, and still
better 9 to 23 carbon atoms, even 11 to 19 carbon atoms.
Preferably, the R radical is saturated. Still better, the said R
radical is linear or branched, and preferentially with C5-C31, even
C11-C21.
[0802] In one particular embodiment of the invention, the
non-aromatic monocarboxylic acid has a melting point higher than or
equal to 25.degree. C., especially higher than or equal to
28.degree. C., even to 30.degree. C.; in fact it has been observed
that, when such an acid is employed, in particular in large
quantity, it is possible on the one hand to obtain good gloss and
staying power of the said gloss and, on the other hand, to reduce
the quantity of waxes usually present in the envisioned
composition.
[0803] Among the non-aromatic monocarboxylic acids capable of being
employed there may be cited, alone or in mixtures: [0804] the
saturated monocarboxylic acids such as caproic acid, caprylic acid,
isoheptanoic acid, 4-ethylpentanoic acid, ethyl-2-hexanoic acid,
4,5-dimethylhexanoic acid, 2-heptylheptanoic acid,
3,5,5-trimethylhexanoic acid, octanoic acid, isooctanoic acid,
nonanoic acid, decanoic acid, isononanoic acid, lauric acid,
tridecanoic acid, myristic acid, palmitic acid, stearic acid,
isostearic acid, arachidic acid, behenic acid, cerotic acid
(hexacosanoic acid); cyclopentanecarboxylic acid,
cyclopentaneacetic acid, 3-cyclopentylpropionic acid,
cyclohexanecarboxylic acid, cyclohexylacetic acid,
4-cyclohexylbutyric acid; [0805] the unsaturated but non-aromatic
monocarboxylic acids, such as caproleic acid, obtusilic acid,
undecylenic acid, dodecylenic acid, linderic acid, myristoleic
acid, physeteric acid, tsuzuic acid, palmitoleic acid, oleic acid,
petroselinic acid, vaccenic acid, elaidic acid, gondoic acid,
gadoleic acid, erucic acid, cetoleic acid, nervonic acid, linoleic
acid, linolenic acid, arachidonic acid.
[0806] Among the non-aromatic monocarboxylic acids having a melting
temperature higher than or equal to 25.degree. C. there may be
cited, alone or in mixtures: [0807] among the saturated
monocarboxylic acids: decanoic (capric) acid, lauric acid,
tridecanoic acid, myristic acid, palmitic acid, stearic acid,
arachidic acid, behenic acid, cerotic (hexacosanoic) acid; [0808]
among the unsaturated but non-aromatic monocarboxylic acids:
petroselinic acid, vaccenic acid, elaidic acid, gondoic acid,
gadoleic acid, erucic acid, nervonic acid.
[0809] Preferably there may be used 2-ethylhexanoic acid,
isooctanoic acid, lauric acid, myristic acid, isoheptanoic acid,
isononanoic acid, nonanoic acid, palmitic acid, isostearic acid,
stearic acid, behenic acid and mixtures thereof, and even better
isostearic acid alone or stearic acid alone.
[0810] The said non-aromatic monocarboxylic acid or the mixture of
the said acids preferably represents 30 to 80% by weight,
especially 40 to 75% by weight, even 45 to 70% by weight, and
better 50 to 65% by weight of the total weight of the final
polycondensate.
[0811] Another constituent necessary for the preparation of the
polycondensates according to the invention is an aromatic
monocarboxylic acid comprising 7 to 11 carbon atoms, possibly
substituted in addition by 1 to 3 linear, branched and/or cyclic,
saturated or unsaturated alkyl radicals comprising 1 to 32 carbon
atoms, especially 2 to 12, even 3 to 8 carbon atoms. Quite
obviously a mixture of such aromatic monocarboxylic acids may be
used.
[0812] By aromatic monocarboxylic acid there is understood a
compound of formula R'COOH, in which R' is an aromatic hydrocarbon
radical comprising 6 to 10 carbon atoms, and in particular the
benzoic and naphthoic radicals. The said R' radical may be
substituted additionally by 1 to 3 linear, branched and/or cyclic,
saturated or unsaturated alkyl radicals comprising 1 to 32 carbon
atoms, especially 2 to 12, even 3 to 8 carbon atoms; and especially
chosen from among methyl, ethyl, propyl, isopropyl, butyl,
isobutyl, terbutyl, pentyl, isopentyl, neopentyl, cyclopentyl,
hexyl, cyclohexyl, heptyl, isoheptyl, octyl or isooctyl. Among the
aromatic monocarboxylic acids capable of being employed there may
be cited, alone or in mixtures, benzoic acid, o-toluic acid,
m-toluic acid, p-toluic acid, 1-naphthoic acid, 2-naphthoic acid,
4-tert-butylbenzoic acid, 1-methyl-2-naphthoic acid,
2-isopropyl-1-napthoic acid. Preferably there may be used benzoic
acid, 4-tert-butylbenzoic acid, o-toluic acid, m-toluic acid,
p-toluic acid, 1-naphthoic acid, alone or in mixtures; and even
better benzoic acid alone. The said aromatic monocarboxylic acid or
the mixture of the said acids preferably represents 0.1 to 10% by
weight, especially 0.5 to 9.95% by weight, still better 1 to 9.5%
by weight, even 1.5 to 8% by weight of the total weight of the
final polycondensate.
[0813] Another constituent necessary for the preparation of the
polycondensates according to the invention is a linear, branched
and/or cyclic, saturated or unsaturated, even aromatic
polycarboxylic acid comprising at least 2 carboxylic groups COOH,
especially 2 to 4 COOH groups; and/or a cyclic anhydride of such a
polycarboxylic acid. Quite obviously a mixture of such
polycarboxylic acids and/or anhydrides may be used. The said
polycarboxylic acid may be especially chosen from among the linear,
branched and/or cyclic, saturated or unsaturated, even aromatic
polycarboxylic acids comprising 2 to 50, especially 2 to 40 carbon
atoms, in particular 3 to 36, even 3 to 18, and still better 4 to
12 carbon atoms, even 4 to 10 carbon atoms; the said acid comprises
at least two carboxylic groups COOH, preferably 2 to 4 COOH
groups.
[0814] Preferably, the said polycarboxylic acid is linear,
saturated, aliphatic and comprises 2 to 36 carbon atoms, especially
3 to 18 carbon atoms, even 4 to 12 carbon atoms; or else it is
aromatic and comprises 8 to 12 carbon atoms. Preferably it
comprises 2 to 4 COOH groups. The said cyclic anhydride of such a
polycarboxylic acid may be represented in particular by one of the
following formulas:
##STR00029##
in which the groups A and B are, independently of one another:
[0815] a hydrogen atom, [0816] a linear, branched and/or cyclic,
saturated or unsaturated, aliphatic or else aromatic carbon
radical; comprising 1 to 16 carbon atoms, especially 2 to 10 carbon
atoms, even 4 to 8 carbon atoms, especially methyl or ethyl; [0817]
or else A and B taken together form a saturated or unsaturated,
even aromatic ring comprising in total 5 to 7, especially 6 carbon
atoms.
[0818] Preferably, A and B represent a hydrogen atom or together
form an aromatic ring comprising in total 6 carbon atoms.
[0819] Among the polycarboxylic acids or their anhydrides capable
of being employed there may be cited, alone or in mixtures. [0820]
the dicarboxylic acids, such as decanedioic acid, dodecanedioic
acid, cyclopropanedicarboxylic acid, cyclohexanedicarboxylic acid,
cyclobutanedicarboxylic acid, naphthalene-1,4-dicarboxylic acid,
naphthalene-2,3-dicarboxylic acid, naphthalene-2,6-dicarboxylic
acid, suberic acid, oxalic acid, malonic acid, succinic acid,
phthalic acid, terephthalic acid, isophthalic acid,
tetrahydrophthalic acid, hexahydrophthalic acid, pimelic acid,
sebacic acid, azelaic acid, glutaric acid, adipic acid, fumaric
acid, maleic acid, itaconic acid, the dimers of fatty acids
(especially with C36), such as the products sold under the trade
names Pripol 1006, 1009, 1013 and 1017 by Uniqema; [0821] the
tricarboxylic acids such as cyclohexanetricarboxylic acid,
trimellitic acid, 1,2,3-benzenetricarboxylic acid,
1,3,5-benzenetricarboxylic acid; [0822] the tetracarboxylic acids,
such as butanetetracarboxylic acid and pyromellitic acid, [0823]
the cyclic anhydrides of these acids and especially phthalic
anhydride, trimellitic anhydride, maleic anhydride and succinic
anhydride.
[0824] Preferably there may be used adipic acid, phthalic anhydride
and/or isophthalic acid, and even better isophthalic acid
alone.
[0825] The said polycarboxylic acid and/or its cyclic anhydride
preferably represents 5 to 40% by weight, especially 10 to 30% by
weight, and better 14 to 25% by weight of the total weight of the
final polycondensate.
[0826] The polycondensate according to the invention may
additionally comprise a silicone with hydroxyl (OH) and/or
carboxylic (COOH) function.
[0827] It may comprise 1 to 3 hydroxyl and/or carboxylic functions
and it preferably comprises two hydroxyl functions or else two
carboxylic functions.
[0828] These functions may be situated at the end of the chain or
in the chain, but advantageously at the end of the chain.
[0829] Preferably there are employed silicones having a
weight-average molecular weight (Mw) between 300 and 20,000,
especially 400 and 10,000, even 800 and 4,000.
[0830] This silicone may have the formula:
##STR00030##
in which: [0831] W and W' are, independently of one another, OH or
COOH; preferably W.dbd.W'; [0832] p and q are, independently of one
another, equal to 0 or 1, [0833] R and R' are, independently of one
another, a divalent linear, branched and/or cyclic, saturated or
unsaturated, even aromatic carbon, especially hydrocarbon radical;
comprising 1 to 12 carbon atoms, especially 2 to 8 carbon atoms,
and possibly additionally comprising 1 or more heteroatoms chosen
from among O, S and N, especially 0 (ether); in particular, R
and/or R' may have the formula --(CH.sub.2).sub.a-- with a=1-12,
and especially methylene, ethylene, propylene, phenylene; or else
the formula --[(CH.sub.2).sub.XO].sub.z-- with x=1, 2 or 3 and
z=1-10; in particular, x=2 or 3 and z=1-4; and better x=3 and z=1.
[0834] R1 to R6 are, independently of one another, a linear,
branched and/or cyclic, saturated or unsaturated, even aromatic
carbon radical comprising 1 to 20 carbon atoms, especially 2 to 12
carbon atoms; preferably R1 to R6 are saturated or else aromatic,
and they may be chosen in particular from among the alkyl radicals,
in particular the methyl, ethyl, propyl, isopropyl, butyl, pentyl,
hexyl, octyl, decyl, dodecyl and octadecyl radicals, the cycloalkyl
radicals, in particular the cyclohexyl radical, the aryl radicals,
especially phenyl and naphthyl, the arylalkyl radicals, especially
benzyl and phenylethyl, as well as the tolyl and xylyl radicals.
[0835] m and n are, independently of one another, integers between
1 and 140 and are such that the weight-average molecular weight
(Mw) of the silicone is between 300 and 20,000, especially between
400 and 10,000, even between 800 and 4,000.
[0836] There may be cited in particular the .alpha.,.omega.-diol or
.alpha.,.omega.-dicarboxylic polyalkylsiloxanes, and especially the
.alpha.,.omega.-diol polydimethylsiloxanes and the
.alpha.,.omega.-dicarboxylic polydimethylsiloxanes; the
.alpha.,.omega.-diol or am-dicarboxylic polyarylsiloxanes, and
especially the .alpha.,.omega.-diol or .alpha.,.omega.-dicarboxylic
polyphenylsiloxanes; the polyarylsiloxanes with silanol functions,
such as polyphenylsiloxane; the polyalkylsiloxanes with silanol
functions such as polydimethylsiloxane; the polyaryl/alkylsiloxanes
with silanol functions such as polyphenyl/methylsiloxane or else
polyphenyl/propylsiloxane.
[0837] More particularly, there will be used the
.alpha.,.omega.-diol polydimethylsiloxanes of weight-average
molecular weight (Mw) between 400 and 10,000, even between 500 and
5,000, and especially between 800 and 4,000.
[0838] When it is present, the said silicone may preferably
represent 0.1 to 15% by weight, especially 1 to 10% by weight, even
2 to 8% by weight of the weight of the polycondensate.
[0839] In a preferred embodiment of the invention, the aromatic
monocarboxylic acid is present in molar quantity smaller than or
equal to that of the non-aromatic monocarboxylic acid; in
particular the ratio between the number of moles of aromatic
monocarboxylic acid and the number of moles of non-aromatic
monocarboxylic acid is preferably between 0.08 and 0.70, especially
between 0.10 and 0.60, in particular between 0.12 and 0.40.
[0840] Preferentially, the polycondensate according to the
invention is capable of being obtained by reaction: [0841] of at
least one polyol chosen from among, alone or in mixtures,
1,2,6-hexanetriol, trimethylolethane, trimethylolpropane, glycerol;
pentaerythritol, erythritol, diglycerol, dimethylolpropane;
xylitol, sorbitol, mannitol, dipentaerythritol and/or triglycerol;
present preferably in a proportion of 10 to 30% by weight,
especially 12 to 25% by weight, and better 14 to 22% by weight,
relative to the total weight of the final polycondensate; [0842] of
at least one non-aromatic monocarboxylic acid chosen from among,
alone or in mixtures, caproic acid, caprylic acid, isoheptanoic
acid, 4-ethylpentanoic acid, 2-ethylhexanoic acid,
4,5-dimethylhexanoic acid, 2-heptylheptanoic acid,
3,5,5-trimethylhexanoic acid, octanoic acid, isooctanoic acid,
nonanoic acid, decanoic acid, isononanoic acid, lauric acid,
tridecanoic acid, myristic acid, palmitic acid, stearic acid,
isostearic acid, arachidic acid, behenic acid, cerotic
(hexacosanoic) acid; cyclopentanecarboxylic acid,
cyclopentaneacetic acid, 3-cyclopentylpropionic acid,
cyclohexanecarboxylic acid, cyclohexylacetic acid,
4-cyclohexylbutyric acid; present preferably in a proportion of 30
to 80% by weight, especially 40 to 75% by weight, and better 45 to
70% by weight, relative to the total weight of the final
polycondensate; [0843] of at least one aromatic monocarboxylic acid
chosen from among, alone or in mixtures, benzoic acid, o-toluic
acid, m-toluic acid, p-toluic acid, 1-naphthoic acid, 2-naphthoic
acid, 4-tert-butylbenzoic acid, 1-methyl-2-naphthoic acid,
2-isopropyl-1-napthoic acid; present preferably in a proportion of
0.1 to 10% by weight, especially 1 to 9.5% by weight, even 1.5 to
8% by weight, relative to the total weight of the final
polycondensate; and [0844] of at least one polycarboxylic acid or
one of its anhydrides chosen from among, alone or in mixtures,
decanedioic acid, dodecanedioic acid, cyclopropanedicarboxylic
acid, cyclohexanedicarboxylic acid, cyclobutanedicarboxylic acid,
naphthalene-1,4-dicarboxylic acid, naphthalene-2,3-dicarboxylic
acid, naphthalene-2,6-dicarboxylic acid, suberic acid, oxalic acid,
malonic acid, succinic acid, phthalic acid, terephthalic acid,
isophthalic acid, pimelic acid, sebacic acid, azelaic acid,
glutaric acid, adipic acid, fumaric acid, maleic acid;
cyclohexanetricarboxylic acid, trimellitic acid,
1,2,3-benzenetricarboxylic acid, 1,3,5-benzenetricarboxylic acid;
butanetetracarboxylic acid, pyromellitic acid, phthalic anhydride,
trimellitic anhydride, maleic anhydride and succinic anhydride;
present preferably in a proportion of 5 to 40% by weight,
especially 10 to 30% by weight, and better 14 to 25% by weight,
relative to the total weight of the final polycondensate.
[0845] Preferably, the polycondensate according to the invention is
capable of being obtained by reaction: [0846] of at least one
polyol chosen from among, alone or in mixtures, glycerol;
pentaerythritol, sorbitol and mixtures thereof, and still better
pentaerythritol alone; present in a proportion of 10 to 30% by
weight, especially 12 to 25% by weight, and better 14 to 22% by
weight, relative to the total weight of the final polycondensate;
[0847] of at least one non-aromatic monocarboxylic acid chosen from
among, alone or in mixtures, 2-ethylhexanoic acid, isooctanoic
acid, lauric acid, myristic acid, palmitic acid, isostearic acid,
isononanoic acid, stearic acid, behenic acid and mixtures thereof,
and even better isostearic acid alone or stearic acid alone;
present in a proportion of 30 to 80% by weight, especially 40 to
75% by weight, and better 45 to 70% by weight, relative to the
total weight of the final polycondensate; [0848] of at least one
aromatic monocarboxylic acid chosen from among, alone or in
mixtures, benzoic acid, o-toluic acid, m-toluic acid, 1-naphthoic
acid, and even better benzoic acid alone; present in a proportion
of 0.1 to 10% by weight, especially 1 to 9.5% by weight, even 1.5
to 8% by weight relative to the total weight of the final
polycondensate; and [0849] of at least one polycarboxylic acid or
one of its anhydrides chosen from among, alone or in mixtures,
phthalic anhydride and isophthalic acid, and even better
isophthalic acid alone; present in a proportion of 5 to 40% by
weight, especially 10 to 30% by weight, and better 14 to 25% by
weight, relative to the total weight of the final
polycondensate.
[0850] The polycondensate according to the invention may be
prepared by esterification/polycondensation methods usually
employed by those skilled in the art. By way of illustration, a
general preparation method consists in: [0851] mixing the polyol
and the aromatic and non-aromatic monocarboxylic acids, [0852]
heating the mixture under an inert atmosphere, at first up to the
melting point (generally 100-130.degree. C.) and then to a
temperature between 150 and 220.degree. C. until complete
consumption of the monocarboxylic acids (attained when the acid
index is smaller than or equal to 1), preferably by distilling off
water at the same rate as it is formed, then [0853] if necessary
cooling the mixture to a temperature between 90 and 150.degree. C.,
[0854] adding polycarboxylic acid and/or cyclic anhydride, and
optionally the silicone with hydroxyl or carboxylic functions, all
at once or in sequenced manner, then [0855] once again heating to a
temperature lower than or equal to 220.degree. C., especially
between 170 and 220.degree. C., preferably continuing to eliminate
the water formed, until there are obtained the required
characteristics in terms of acid index, viscosity, hydroxyl index
and solubility.
[0856] It is possible to add conventional esterification catalysts,
for example of sulfonic acid type (especially in a concentration
between 1 and 10% by weight) or of titanate type (especially in a
concentration between 5 and 100 ppm by weight).
[0857] It is also possible to carry out the reaction in its
entirety or in part in an inert solvent such as xylene and/or under
reduced pressure, to facilitate the elimination of water.
[0858] Advantageously neither catalyst nor solvent is used.
[0859] The said preparation method may also comprise a step of
addition of at least one antioxidant agent into the reaction
mixture, especially in a concentration between 0.01 and 1% by
weight relative to the total weight of monomers, so as to limit
possible degradation associated with prolonged heating.
[0860] The antioxidant agent may be of primary type or of secondary
type, and may be chosen from among the hindered phenols, the
secondary aromatic amines, the organophosphorus compounds, the
sulfur compounds, the lactones, the acryl bisphenols; and mixtures
thereof.
[0861] Mineral Lipophilic Structuring Agents
[0862] The fatty-phase thickening or gelling rheological agent may
be a mineral structuring lipophilic agent.
[0863] There may be cited especially the lipophilic clays, such as
the clays that have been modified if necessary, such as the
hectorites modified by a C.sub.10 to C.sub.22 fatty acid ammonium
chloride, such as hectorite modified by distearyldimethylammonium
chloride.
[0864] There may also be cited the hydrophobic silicas, such as
pyrogenic silica, which has been hydrophobically surface-treated if
necessary, whose particle size is smaller than 1 .mu.M. It is in
fact possible to modify the surface of the silica chemically, by
chemical reaction causing a decrease in the number of silanol
groups present at the surface of the silica. In particular, silanol
groups may be substituted by hydrophobic groups: a hydrophobic
silica is then obtained. The hydrophobic groups may be: [0865]
trimethylsiloxyl groups, which are obtained in particular by
treatment of pyrogenic silica in the presence of
hexamethyldisilazane. Silicas treated in this way are known as
"silica silylate" according to the CTFA (6.sup.th Edition, 1995).
For example, they are sold under the references "AEROSIL R812.RTM."
by the Degussa Company, "CAB-O-SIL TS-530.RTM." by the Cabot
Company. [0866] dimethylsilyloxyl or polydimethylsiloxane groups,
which are obtained in particular by treatment of pyrogenic silica
in the presence of polydimethylsiloxane or dimethyldichlorosilane.
Silicas treated in this way are known as "silica dimethyl silylate"
according to the CTFA (6.sup.th Edition, 1995). For example, they
are sold under the references "AEROSIL R972.RTM.", "AEROSIL
R974.RTM." by the Degussa Company, "CAB-O-SIL TS-6100", "CAB-O-SIL
TS 720.RTM." by the Cabot Company.
[0867] The hydrophobic pyrogenic silica preferably has a particle
size that may be nanometric to micrometric, for example ranging
approximately from 5 to 200 nm.
[0868] Lipophilic Polyamide Polymers
[0869] By polymer within the meaning of the invention there is
understood a compound having at least 2 repeating moieties,
preferably at least 3 repeating moieties and still better 10
repeating moieties.
[0870] As preferred lipophilic structuring polyamides that can be
used in the invention, there may be cited the polyamides branched
by pendant fatty chains and/or terminal fatty chains having 12 to
120 carbon atoms and especially 12 to 68 carbon atoms, the terminal
fatty chains being bonded to the polyamide skeleton by ester
groups. These polymers are more specially those described in the
document U.S. Pat. No. 5,783,657 of the Union Camp Company. Each of
these polymers satisfies especially the following formula (I):
##STR00031##
in which n denotes an integral number of amide moieties such that
the number of ester groups represents 10% to 50% of the total
number of ester and amide groups; R.sup.1, independently in each
occurrence, is an alkyl or alkenyl group having at least 4 carbon
atoms; R.sup.2, independently in each occurrence, represents a
C.sub.4 to C.sub.42 group, with the proviso that 50% of the R.sup.2
groups represent a C.sub.30 to C.sub.42 hydrocarbon group; R.sup.3,
independently in each occurrence, represents an organic group
provided with at least 2 carbon atoms, hydrogen atoms and
optionally one or more oxygen or nitrogen atoms; and R.sup.4,
independently in each occurrence, represents a hydrogen atom, a
C.sub.1 to C.sub.10 alkyl group or a direct bond to R.sup.3 or to
another R.sup.4, so that the nitrogen atom to which both R.sup.3
and R.sup.4 are bonded is part of a heterocyclic structure defined
by R.sup.4--N--R.sup.3, with at least 50% of the R.sup.4 groups
representing a hydrogen atom.
[0871] In particular, the ester groups of formula (I), which make
up part of the terminal and/or pendant fatty chains within the
meaning of the invention, represent 15 to 40% of the total number
of ester and amide groups and better 20 to 35%. In addition, n
advantageously represents an integral number ranging from 1 to 5.
Preferably, R.sup.1 is a C.sub.12 to C.sub.22 alkyl group, and
preferably C.sub.16 to C.sub.22. Advantageously, R.sup.2 may be a
C.sub.10 to C.sub.42 hydrocarbon group (especially alkyl or
alkenyl) having a polymerized fatty acid structure or a dimer
structure whose carboxylic acid groups have been removed (these
groups being used to form the amide). Preferably, at least 50% and
better 75% of the R groups are groups having 30 to 42 carbon atoms.
The other R.sup.2 groups are C.sub.4 to C.sub.19 and even C.sub.4
to C.sub.12 hydrogenated groups. Preferably, R.sup.3 represents a
C.sub.2 to C.sub.36 hydrocarbon group or a polyoxyalkylene group
and R.sub.4 represents a hydrogen atom. Preferably, R.sup.3
represents a C.sub.2 to C.sub.12 hydrocarbon group. The hydrocarbon
groups may be saturated or unsaturated, linear, cyclic or branched
groups. Furthermore, the alkyl and alkenyl groups may be linear or
branched groups.
[0872] Advantageously, the polymer of the composition of the
invention comprises a weight-average molecular weight ranging from
2,000 to 20,000 and better from 2,000 to 10,000.
[0873] According to the invention, structuring of the oil is
achieved by means of one or more polymers of formula (I). In
general, the polymers of formula (I) have the form of mixtures of
polymers, these mixtures additionally being able to contain a
synthetic product such that n is equal to 0, or in other words a
diester.
[0874] By way of example of structuring polymers that can be used
in the composition according to the invention there may be cited
the commercial products sold by the Bush Boake Allen Company under
the names Uniclear 80, Uniclear 100, Uniclear 80 V, Uniclear 100 V
and Uniclear 100 VG. They are sold respectively in the form of an
80% gel (in terms of active material) in a mineral oil and a 100%
gel (in terms of active material). They have a softening point of
88 to 94.degree. C. These commercial products are a mixture of
copolymer of a C.sub.36 diacid condensed on ethylenediamine, with
an average molecular weight of approximately 6,000. In addition,
the remaining terminal acid groups are esterified by cetylstearyl
alcohol.
[0875] As structuring polymer that can be used in the invention
there may also be cited the polyamide resins resulting from the
condensation of an aliphatic dicarboxylic acid and a diamine
(including compounds having more than 2 carbonyl groups and more
than 2 amine groups), the carbonyl and amine groups of adjacent
unitary moieties being condensed via an amide bond. These polyamide
resins are especially those sold under the brand Versamid.RTM. by
General Mills, Inc. and the Henkel Corp. (Versamid 930, 744 or
1655) or by Olin Mathieson Chemical Corp. under the brand
Onamid.RTM., especially Onamid S or C. These resins have a
weight-average molecular weight ranging from 6,000 to 9,000. For
more information about these polyamides, reference may be made to
the documents U.S. Pat. No. 3,645,705 and U.S. Pat. No. 3,148,125.
More especially, Versamid.RTM. 930 or 744 is used.
[0876] There may also be used the polyamides sold by Union Camp
Corp. under the references Uni-Rez (2658, 2931, 2970, 2621, 2613,
2624, 2665, 1554, 2623, 2662) and the product sold under the
reference Macromelt 6212 by the Henkel Company. For more
information about these polyamides, reference may be made to the
document U.S. Pat. No. 5,500,209.
[0877] The structuring polymers in the composition of the invention
advantageously have a softening temperature higher than 70.degree.
C. and possibly ranging up to 190.degree. C. Preferably, it has a
softening temperature ranging from 80 to 130.degree.. These
polymers are in particular non-waxy polymers.
[0878] Lipophilic Polyurea or Polyurethane Polymers
[0879] As fatty-phase rheological agent there may also be cited the
polyurethanes and the polyureas soluble or dispersible in the
hydrocarbon oil or oils, and containing: [0880] at least two
urethane groups or at least two urea groups or at least one
urethane group and one urea group in the chain, [0881] at least one
hydrocarbon sequence or graft or aliphatic polyester with a long
hydrocarbon chain, preferably branched.
[0882] By long hydrocarbon chain there is understood a linear or
branched hydrocarbon chain containing at least 8 carbon atoms and
preferably 10 to 500 carbon atoms.
[0883] The polymers preferred according to the invention are
defined by one of the following three formulas:
##STR00032##
in which n denotes an integral number from 1 to 10,000, and
preferably from 1 to 1,000, x represents, separately or together,
--O-- or --NH--, R is a divalent radical chosen from among the
alkylene, cycloalkylene, aromatic radicals and mixtures thereof, if
necessary functionalized, A.sub.1 and A.sub.2, be identical or
different, denote monovalent linear, branched or cyclic hydrocarbon
radicals, which may be saturated or contain unsaturations,
containing 1 to 80 carbon atoms,
D is
[0884] 1) a divalent saturated or unsaturated aliphatic and/or
cycloaliphatic hydrocarbon sequence, and/or aliphatic polyester
with long hydrocarbon chain, or 2) a graft
##STR00033##
[0885] in which Z is a trivalent hydrocarbon radical that may
contain one or more hetero atoms, and .phi. is a linear, branched
or cyclic aliphatic chain,
3) mixtures of sequences 1) and grafts 2).
[0886] Monovalent hydrocarbon radicals A.sub.1 and A.sub.2 are
preferably chosen from among the saturated or unsaturated
aliphatic, cycloaliphatic and aromatic radicals. Radicals A.sub.1
and A.sub.2 are derived from monoalcohols and/or monoamines, used
if necessary to consume the residual isocyanate groups at the end
of polymerization.
[0887] In the case that D is a saturated or unsaturated aliphatic
and/or cycloaliphatic hydrocarbon sequence, it is derived: [0888]
from a natural or synthetic oil, or [0889] from the addition
product (dimer, trimer or polymer) of at least two unsaturated
aliphatic chains, such as the aliphatic radicals derived from
"dimeric" fatty acids, such as, for example, the addition products
between oleic chains, or [0890] from polyenes, preferably
hydrogenated, such as polybutadiene, hydrogenated polyisoprene, or
the polyolefins or copolyolefins.
[0891] In the case that D is an aliphatic polyester sequence with a
long hydrocarbon chain, it is preferably derived from branched
polyesters with long hydrocarbon chains, such as, for example,
poly(12-hydroxystearate).
[0892] In the case that D is a graft, .phi. is a saturated or
unsaturated, linear, branched or cyclic aliphatic chain containing
8 to 40 carbon atoms. The possible hetero atoms of trivalent
radical Z are preferably --O--, --N--, and --S--.
[0893] The structuring polyurethanes and/or polyureas according to
the invention result from the polymerization reaction between:
1) at least one aliphatic, cycloaliphatic and/or aromatic
diisocyanate of the general formula
O.dbd.C.dbd.N--R--N.dbd.C.dbd.O, where R is such as defined in the
foregoing, 2) at least one difunctional derivative HX-D-XH having
two active hydrogens, each of which is capable of reacting with an
isocyanate group, where [0894] X denotes --O-- or --NH--, and
[0895] D is such as defined in the foregoing, and 3) possibly a
monofunctional derivative A.sub.1-XH, or two monofunctional
derivatives A.sub.1-XH and A.sub.2-XH having a single active
hydrogen that is capable of reacting with an isocyanate group, to
consume the residual isocyanate groups that may not have reacted
entirely with the difunctional reagents H--X-D-X--H, which
monofunctional derivatives A.sub.1-XH and A.sub.2-XH may be
identical or different, and A.sub.1 and A.sub.2 being such as
defined in the foregoing.
[0896] The isocyanates used in the polymerization reaction may be
aliphatic, cycloaliphatic or aromatic. Advantageously there will be
used hexamethylene diisocyanate, isophorone diisocyanate, toluene
diisocyanate, 4,4'-dicyclohexylmethane diisocyanate.
[0897] The difunctional derivatives H--X-D-X--H may be chosen from
among the dimer diols and their derivatives, the alkane diols, the
polydienes with hydroxyl ends, preferably hydrogenated, the
polyolefins with hydroxyl ends, the branched polyesters with long
alkyl chain carrying at least two reactive groups, the natural or
synthetic oils carrying two to three hydroxyl groups, and finally
the dimer diamines and the diamines with long aliphatic chain.
[0898] The dimer diols are C.sub.36 branched aliphatic and/or
alicyclic diols and/or a mixture of the said dimers. These diols
are prepared from "corresponding dimeric fatty acids".
[0899] By "corresponding dimeric fatty acids" there is understood
the dimeric fatty acids that have the same structure as these diols
but which possess two carboxylic acid ends instead of the diol
ends. The transformation of dimeric fatty acids into dimer diols
may be achieved either by hydrogenation of methyl esters of the
dimeric fatty acids or by direct dimerization of oleic alcohol. In
particular, there will be cited the dimer diols sold by the COGNIS
Company under the commercial names of SOVERMOL 908 (97% purity) and
SOVERMOL 650 NS (68% purity).
[0900] There may also be used the polyether-diol and the
polycarbonate-diol oligomers prepared by subsequent etherification
or esterification of these same C.sub.36 branched dimer diols.
These oligomers generally have a number-average molecular weight on
the order of 500 to 2,000 and possess two hydroxyl functions.
[0901] The polydienes with hydroxyl ends are, for example, those
defined in French Patent FR 2782723. They are chosen in the group
comprising the homopolymers and copolymers of polybutadiene,
polyisoprene and poly(1,3-pentadiene). These oligomers have a
number-average molecular weight smaller than 7,000, and preferably
1,000 to 5,000. They have a functionality of 1.8 to 3 and
preferably close to 2 at the end of the chain.
[0902] These polydienes with hydroxyl ends are, for example, the
hydroxylated polybutadienes sold by the ELF ATOCHEM Company under
the brands POLY BD-45H.RTM. and POLY BD R-20 LM.RTM.. These
products are preferably used in hydrogenated form.
[0903] There may also be used homopolymeric or copolymeric
polyolefins with .alpha.,.omega. hydroxyl ends, such as, for
example: [0904] the oligomers of polyisobutylene with
.alpha.,.omega. hydroxyl ends, or [0905] the copolymers sold by the
MITSUBISHI Company under the brand POLYTAIL.RTM., especially those
of the following structure:
##STR00034##
[0905] having a melting point of 60 to 70.degree. C.
[0906] As difunctional derivative H--X-D-X--H it is possible to use
a branched polyester having a long alkyl chain and containing at
least two reactive groups, such as, for example,
poly(12-hydroxystearate) with hydroxyl ends. This polyester is
obtained by auto-condensation of 1,2-hydroxystearic acid on itself,
then reaction with a polyol to consume the residual acid groups.
This oligomer has the structure
##STR00035##
where the sum m+n is such that the oligomer has a number-average
molecular weight on the order of 2,000 and a hydroxyl functionality
on the order of 1.8.
[0907] There may also be used as difunctional derivative
H--X-D-X--H natural or synthetic oils carrying two to three
hydroxyl groups.
[0908] In a particular embodiment of the invention, there will be
used the oils carrying two hydroxyl groups per chain, and
preferably the monoglycerides of the structure:
##STR00036##
R.sup.1 being a C.sub.8 to C.sub.30 linear or branched alkyl chain,
such as, for example, glycerol monostearate.
[0909] Such glycerol monoesters correspond, for example, to the
difunctional derivatives H--X-D-X--H, where: [0910] D
represents
[0910] ##STR00037## [0911] X represents --O--, and
##STR00038##
[0911] represents
##STR00039##
where R.sup.1 is defined as in the foregoing.
[0912] When these glycerol monoesters are reacted with a
diisocyanate, a solubilizing graft and not a sequence is introduced
into the polymer chain, as was the case with the difunctional
derivatives cited in the foregoing.
[0913] In a variant, there will be used a difunctional derivative
H--X-D-X--H chosen from among the oils carrying three hydroxyl
groups per chain, such as, for example, hydrogenated or
non-hydrogenated castor oil.
[0914] In this case, the polymerization reaction is carried out
with a deficit of diisocyanate compared with the stoichiometry of
the reaction, to avoid cross-linking of the polymer and to preserve
good solubility thereof.
[0915] There may also be used diols with long aliphatic chains.
Advantageously, there will be used the diols of structure HO-D-OH,
where D is a linear or branched alkyl chain containing 8 to 40
carbon atoms. These diols are sold by the ATOCHEM Company under the
trade name VIKINOL.RTM.. There will also be cited 1,12-dodecanediol
and 1,10-decanediol, the latter being sold by the COGNIS Company
under the commercial name of SOVERMOL 110.RTM..
[0916] There may also be used the diols of the structure
##STR00040##
where R.sup.2 is an alkyl chain containing 8 to 40 carbon
atoms.
[0917] These diols with long aliphatic chains are preferably used
with one or the other of the H--X-D-X--H derivatives cited in the
foregoing, to be used as chain couplers during synthesis of
polyurethanes and/or polyureas.
[0918] Finally, there may be used as difunctional H--X-D-X--H
derivative the dimer diamines or the diamines with long aliphatic
chain.
[0919] The use of such reagents in the polymerization reaction
makes it possible to introduce urea groups instead of urethane
groups into the polymer.
[0920] According to a particular embodiment of the invention, there
will be used dimer diamines having the same structure as the dimer
diols described in the foregoing, or in other words dimer diamines
containing two primary amine functions instead of hydroxyl
groups.
[0921] These dimer diamines may be obtained from the transformation
of dimeric fatty acids, such as the dimer diols.
[0922] In a variant, there may be used diamines of structure
H.sub.2N-D-NH.sub.2, where D is a linear or branched alkyl chain
containing 8 to 40 carbon atoms. These diamines are preferably used
in mixtures with a difunctional derivative H--X-D-X--H chosen from
among the dimer diols and their derivatives, the polydienes and
polyolefins with hydroxyl ends, the branched polyesters with long
alkyl chains, and the oils carrying 2 to 3 hydroxyl groups, cited
in the foregoing.
[0923] Among these diamines there may be cited: [0924]
1,10-diaminodecane and 1,12-diaminododecane, and [0925] the
following diamino oils sold by the AKZO NOBEL Company:
cocopropylene diamine (distilled or non-distilled) DUOMEEN.RTM. C
or CD, hydrogenated Tallowpropylene diamine DUOMEEN.RTM. HT,
C.sub.16-22 alkylpropylene diamine DUOMEEN.RTM. M, oleylpropylene
diamine DUOMEEN.RTM. O, Tallowpropylene diamine DUOMEEN.RTM. T.
[0926] As regards the monofunctional derivatives A.sub.1-XH and
A.sub.2-XH, they are advantageously chosen from among the
monoalcohols or monoamines having linear or branched alkyl chains
containing 1 to 80 carbon atoms, the natural or synthetic oils
carrying a single hydroxyl group per chain, such as, for example,
the diesters of glycerols or the triesters of citric acid and fatty
alcohol.
[0927] The envisioned polycondensation reactions are traditionally
carried out in an organic solvent capable of dissolving the
reagents and the formed polymer. This solvent is preferably easy to
eliminate at the end of the reaction, especially by distillation,
and it does not react with the isocyanate groups.
[0928] In general, each of the reagents is dissolved in a portion
of the organic solvent prior to the polymerization reaction.
[0929] It is often desired to use a catalyst to activate the
polymerization. This will generally be chosen from among the
catalysts commonly used in the chemistry of polyurethanes and
polyureas, such as, for example, tin 2-ethyl hexanoate.
[0930] The molar proportion between the main reagents of the
polymerization reaction depends on the chemical structure and
molecular weight of the polymers (polyurethanes and/or polyureas)
that are desired to be obtained, as is traditionally the case in
the chemistry of polyurethanes and polyureas. Similarly, the order
of introduction of the reagents will be adapted to this
chemistry.
[0931] Thus the reaction of two moles of functional derivative
H--X-D-X--H with one mole of isocyanate yields, after complete
consumption of the reagents, a polymer defined by formula I:
##STR00041##
[0932] This reaction will be advantageously carried out in the
following manner: [0933] the initial medium is a solution
comprising two moles of derivative H--X-D-X--H, for example two
moles of dimer diol, in a solvent, for example tetrahydrofuran,
[0934] to this initial solution there is added dropwise a solution
comprising one mole of diisocyanate dissolved in the same solvent,
such as, for example, toluene diisocyanate dissolved in
tetrahydrofuran.
[0935] Furthermore, the equimolar reaction of a difunctional
derivative H--X-D-X--H with a diisocyanate, with consumption of the
residual isocyanates by a monofunctional compound A.sub.1-XH,
yields a polymer defined by formula III:
##STR00042##
[0936] Preferably, this reaction will then be carried out by
simultaneous addition, into a reactor, of an organic solution of
one mole of H--X-D-X--H, such as, for example, a POLYTAIL.RTM.
described in the foregoing, and an organic solution of one mole of
diisocyanate, such as, for example, 4,4'-dicyclohexylmethane
diisocyanate. The simultaneous addition of these two organic
solutions is also known as "double decantation". At the end of
double decantation, the reaction mixture is heated to 60.degree. C.
for 5 hours. Then a sample of the reaction medium is withdrawn to
determine the residual isocyanates by using a method known to those
skilled in the art. Finally there is added to the reaction medium a
solution of a chosen monofunctional compound A.sub.1-X--H, in
quantity sufficient to consume the residual isocyanates, this
quantity having been estimated on the basis of the determination of
the residual isocyanates. Advantageously, 1-decanol will be used as
monofunctional derivative A.sub.1-X--H.
[0937] Finally, the reaction between [0938] one mole of compound
H--X-D-X--H, such as, for example, a dimer diol, [0939] there moles
of diisocyanate, such as, for example, 4,4'-dicyclohexyl methane
diisocyanate, and [0940] two moles of structure coupler
##STR00043##
[0940] where .phi. is a linear, branched or cyclic aliphatic chain
containing 8 to 20 carbon atoms, leads to the formation of a
polymer, both sequenced and grafted, of the structure:
##STR00044##
[0941] Any residual isocyanates being able to be consumed by
addition of an appropriate quantity of monofunctional reagent
A.sub.1-X--H.
[0942] Such a polymer is obtained in the following manner: [0943]
the initial reaction medium is composed of a solution comprising
one mole of a difunctional derivative H--X-D-X--H, [0944] a
solution of three moles of diisocyanate is added dropwise to this
medium, [0945] it is then allowed to react for 3 hours at
60.degree. C.; [0946] then there is decanted into this medium an
organic solution comprising two moles of a coupler defined by the
formula
##STR00045##
[0946] any residual isocyanates will be able to be consumed by
addition of an appropriate quantity of monofunctional reagent
A.sub.1-XH.
[0947] Lipophilic Silicone Polymers:
[0948] The lipophilic silicone polymer structuring agents are, for
example, polymers of the polyorganosiloxane type, such as those
described in the documents U.S. Pat. No. 5,874,069, U.S. Pat. No.
5,919,441, U.S. Pat. No. 6,051,216 and U.S. Pat. No. 5,981,680.
According to the invention, the polymers used as structuring agent
may belong to the following two families: [0949] 1)
polyorganosiloxanes containing at least two groups capable of
establishing hydrogen interactions, these two groups being situated
in the polymer chain, and/or [0950] 2) polyorganosiloxanes
containing at least two groups capable of establishing hydrogen
interactions, these two groups being situated on grafts or
branches.
[0951] The groups capable of establishing hydrogen interactions may
be chosen from among the ester, amide, sulfonamide, carbamate,
thiocarbamate, urea, urethane, thiourea, oxamido, guanidino,
biguanidino groups and combinations thereof.
[0952] According to a first variant, the silicone polymers are
polyorganosiloxanes such as defined above and whose moieties
capable of hydrogen interactions are disposed in the polymer
chain.
[0953] The silicone polymers may be more particularly polymers
comprising at least one moiety according to the general formula
I:
##STR00046##
[0954] in which
[0955] 1) R.sup.4, R.sup.5, R.sup.6 and R.sup.7, identical or
different, represent a group chosen from among: [0956] the
saturated or unsaturated, linear, branched or cyclic C.sub.1 to
C.sub.o hydrocarbon groups, which may contain one or more oxygen,
sulfur and/or nitrogen atoms in their chain and which may be
substituted partly or completely by fluorine atoms, [0957] the
C.sub.6 to C.sub.10 aryl groups, possibly substituted by one or
more C.sub.1 to C.sub.4 alkyl groups, [0958] the polyorganosiloxane
chains, which may or may not contain one or more oxygen, sulfur
and/or nitrogen atoms,
[0959] 2) the groups X, identical or different, represent a linear
or branched C.sub.1 to C.sub.30 di-yl alkylene group, which may
contain one or more oxygen and/or nitrogen atoms in its chain,
[0960] 3) Y is a saturated or unsaturated, linear or branched
divalent C.sub.1 to C.sub.50 alkylene, arylene, cycloalkylene,
alkylarylene or arylalkylene group. which may contain one or more
oxygen, sulfur and/or nitrogen atoms and/or carry as substituent
one of the following atoms or groups of atoms: fluorine, hydroxy,
C.sub.3 to C.sub.g cycloalkyl, C.sub.1 to C.sub.40 alkyl, C.sub.5
to C.sub.10 aryl, phenyl, possibly substituted by 1 to 3 C.sub.1 to
C.sub.3 alkyl groups, C.sub.1 to C.sub.3 hydroxyalkyl and C.sub.1
to C.sub.g aminoalkyl, or
[0961] 4) Y represents a group according to the formula:
##STR00047##
in which [0962] T represents a saturated or unsaturated, linear or
branched trivalent or tetravalent O.sub.3 to C.sub.24 hydrocarbon
group, possibly substituted by a polyorganosiloxane chain, which
may contain one or more atoms chosen from among O, N and S, or T
represents a trivalent atom chosen from among N, P and Al, and
[0963] R.sup.8 represents a linear or branched C.sub.1 to C.sub.50
alkyl group, or a polyorganosiloxane chain, which may contain one
or more ester, amide, urethane, thiocarbamate, urea, thiourea
and/or sulfonamide groups, which may or may not be bonded to
another chain of the polymer,
[0964] 5) the groups G, identical or different, represent the
divalent groups chosen from among:
##STR00048##
where R.sup.9 represents a hydrogen atom or a linear or branched
C.sub.1 to C.sub.20 alkyl group, with the proviso that at least 50%
of the R.sup.9 groups of the polymer represent a hydrogen atom and
that at least two of the groups G of the polymer are another group
such as:
##STR00049##
[0965] 6) n is an integral number ranging from 2 to 500, preferably
2 to 200, and m is an integral number ranging from 1 to 1,000,
preferably 1 to 700 and still better from 6 to 200. According to
the invention, 80% of the R.sup.4, R.sup.5, R.sup.6 and R.sup.7 of
the polymer are preferably chosen from among the methyl, ethyl,
phenyl and 3,3,3-trifluoropropyl groups.
[0966] According to the invention, Y may represent diverse divalent
groups, possibly containing one or two free valences to establish
bonds with other moieties of the polymer or copolymer. Preferably,
Y represents a group chosen from among:
[0967] a) the linear C.sub.1 to C.sub.20 alkylene groups,
preferably C.sub.1 to C.sub.10,
[0968] b) the branched C.sub.30 to C.sub.56 alkylene groups that
may contain rings and unconjugated unsaturations,
[0969] c) the C.sub.5-C.sub.6 cycloalkylene groups,
[0970] d) the phenylene groups, possibly substituted by one or more
C.sub.1 to C.sub.40 alkyl groups,
[0971] e) the C.sub.1 to C.sub.20 alkylene groups containing 1 to 5
amide groups,
[0972] f) the C.sub.1 to C.sub.20 alkylene groups containing one or
more substituents chosen from among the hydroxyl, C.sub.3 to
C.sub.8 cycloalkane, C.sub.1 to C.sub.3 hydroxyalkyl and C.sub.1 to
C.sub.6 alkylamine groups,
[0973] g) the polyorganosiloxane chains of formula:
##STR00050##
in which R.sup.4, R.sup.5, R.sup.6, R.sup.7, T and m are such as
defined hereinabove, and
[0974] h) the polyorganosiloxane chains of formula:
##STR00051##
[0975] According to the second variant, the polyorganosiloxanes may
be polymers comprising at least one moiety according to formula
(II):
##STR00052##
in which
[0976] R.sup.4 and R.sup.6, identical or different, are such as
defined hereinabove for formula (I),
[0977] R.sup.10 represents a group such as defined hereinabove for
R.sup.4 and R.sup.6, or represents the group of formula
--X-G-R.sup.12, in which X and G are as defined hereinabove for
formula (I) and R.sup.12 represents a hydrogen atom or a saturated
or unsaturated, linear, branched or cyclic C.sub.1 to C.sub.50
hydrocarbon group, possibly containing one or more atoms chosen
from among O, S and N in its chain, possibly substituted by one or
more fluorine atoms and/or one or more hydroxyl groups, or a phenyl
group, possibly substituted by one or more C.sub.1 to C.sub.4 alkyl
groups,
[0978] R.sup.11 represents the group of formula --X-G-R.sup.12, in
which X, G and R.sup.12 are such as defined hereinabove, [0979]
m.sub.1 is an integral number ranging from 1 to 998, and [0980]
m.sub.2 is an integral number ranging from 2 to 500.
[0981] According to the invention, the silicone polymer used as
structuring agent may be a homopolymer, or in other words a
copolymer containing several identical moieties, in particular
moieties of formula (I) or formula (II).
[0982] According to the invention, there may also be used a
silicone polymer constituted by a copolymer containing several
different moieties of formula (I), or in other words a polymer in
which at least one of R.sup.4, R.sup.5, R.sup.6, R.sup.7, X, G, Y,
m and n is different in one of the moieties. The copolymer may also
be formed from several moieties of formula (II), in which at least
one of R.sup.4, R.sup.6, R.sup.15, R.sup.11, m1 and m2 is different
in at least one of the moieties.
[0983] There may also be used a polymer containing at least one
moiety of formula (I) and at least one moiety of formula (II),
wherein the moieties of formula (I) and the moieties of formula
(II) may be identical to or different from one another.
[0984] According to a variant of the invention, there may also be
used a polymer comprising at least one hydrocarbon moiety
containing two groups capable of establishing hydrogen
interactions, chosen from among the ester, amide, sulfonamide,
carbamate, thiocarbamate, urea, urethane, thiourea, oxamido,
guanidino, biguanidino groups and combinations thereof. These
copolymers may be block polymers, sequenced polymers or graft
polymers.
[0985] According to an advantageous embodiment of the invention,
the groups capable of establishing hydrogen interactions are amide
groups of formula --C(O)NH-- and --HN--C(O)--. In this case, the
structuring agent may be a polymer comprising at least one moiety
of formula (III) or (IV):
##STR00053##
in which R.sup.4, R.sup.5, R.sup.6, R.sup.7, X, Y, m and n are such
as defined hereinabove.
[0986] Such a moiety may be obtained: [0987] either by a
condensation reaction between a silicone with
.alpha.,.omega.-carboxylic acid ends and one or more diamines,
according to the following reaction scheme:
[0987] ##STR00054## [0988] or by reaction of two molecules of
.alpha.-unsaturated carboxylic acid with a diamine according to the
following reaction scheme:
[0988]
CH.sub.2.dbd.CH--X'--COOH+H.sub.2N--Y--NH.sub.2--CH.sub.2--CH--X.-
sup.1--CO--NH--Y--NH--CO--X.sup.1--CH.dbd.CH.sub.2
followed by addition of a siloxane onto the ethylene unsaturations,
according to the following scheme:
##STR00055##
in which X.sup.1--(CH.sub.2).sub.2-- corresponds to X defined
hereinabove and Y, R.sup.4, R.sup.5, R.sup.6, R.sup.7 and m are
such as defined hereinabove, [0989] or by reaction of a silicone
with .alpha.,.omega.-NH.sub.2 ends and a diacid of formula
HOOC--Y--COOH according to the following reaction scheme:
##STR00056##
[0990] In these polyamides of formula (III) or (IV), m ranges from
1 to 700, in particular from 15 to 500 and especially from 50 to
200, and n ranges in particular from 1 to 500, preferably from 1 to
100 and still better from 4 to 25, [0991] X is preferably a linear
or branched alkylene chain having 1 to 30 carbon atoms, in
particular 1 to 20 carbon atoms, especially 5 to 15 carbon atoms
and more particularly 10 carbon atoms, and [0992] Y is preferably a
linear or branched alkylene chain or may contain rings and/or
unsaturations, having 1 to 40 carbon atoms, in particular 1 to 20
carbon atoms, and still better 2 to 6 carbon atoms, in particular 6
carbon atoms.
[0993] In formulas (III) and (IV), the alkylene group representing
X or Y may possibly contain, in its alkylene part, at least one of
the following elements:
[0994] 1) 1 to 5 amide, urea, urethane or carbamate groups,
[0995] 2) a C.sub.5 or C.sub.g cycloalkyl group, and
[0996] 3) a phenylene group, possibly substituted by 1 to 3
identical or different C.sub.1 to C.sub.3 alkyl groups.
[0997] In formulas (III) and (IV), the alkylene groups may also be
substituted by at least one element chosen in the group constituted
by: [0998] a hydroxy group, [0999] a C.sub.3 to C.sub.8 cycloalkyl
group, [1000] one to three C.sub.1 to C.sub.40 alkyl groups, [1001]
a phenyl group, possibly substituted by one to three C.sub.1 to
C.sub.3 alkyl groups, [1002] a C.sub.1 to C.sub.3 hydroxyalkyl
group, and [1003] a C.sub.1 to C.sub.6 aminoalkyl group.
[1004] In these formulas (III) and (IV), Y may also represent:
##STR00057##
where R.sup.8 represents a polyorganosiloxane chain and T
represents a group of the following formula:
##STR00058##
in which a, b and c are, independently, integral numbers ranging
from 1 to 10, and R.sup.13 is a hydrogen atom or a group such as
those defined for R.sup.4, R.sup.5, R.sup.6 and R.sup.7.
[1005] In formulas (III) and (IV), R.sup.4, R.sup.5, R.sup.6 and
R.sup.7 preferably represent, independently, a linear or branched
C.sub.1 to C.sub.40 alkyl group, preferably a CH.sub.3,
C.sub.2H.sub.5, n-C.sub.3H.sub.7 or isopropyl group, a
polyorganosiloxane chain or a phenyl group, possibly substituted by
one to three methyl or ethyl groups.
[1006] As has been seen in the foregoing, the polymer may comprise
identical or different moieties of formula (III) or (IV).
[1007] Thus the polymer may be a polyamide containing several
moieties of formula (III) or (IV) of different lengths, or in other
words a polyamide according to formula (V):
##STR00059##
in which X, Y, n, R.sup.4 to R.sup.7 have the meanings given
hereinabove, m.sub.l and m.sub.2, which are different, are chosen
in the interval ranging from 1 to 1,000, and p is an integral
number ranging from 2 to 300.
[1008] In this formula, the moieties may be structured so as to
form either a block copolymer or a random copolymer or an
alternating copolymer. In this copolymer, the moieties may be not
only of different lengths but also of different chemical
structures, for example having different Y groups. In this case,
the polymer may be represented by formula VI:
##STR00060##
in which R.sup.4 to R.sup.7, X, Y, m.sub.1, m.sub.2, n and p have
the meanings given hereinabove and Y.sup.1 is different from Y but
is chosen from among the groups defined for Y. As in the foregoing,
the different moieties may be structured so as to form either a
block copolymer or a random copolymer or an alternating
copolymer.
[1009] In this first embodiment of the invention, the structuring
agent may also be constituted by a graft copolymer. Thus the
polyamide containing silicone units may be grafted and possibly
cross-linked by silicone chains containing amide groups. Such
polymers may be synthesized with trifunctional amines.
[1010] In this case, the polymer may comprise at least one moiety
of formula (VII):
##STR00061##
in which X.sup.1 and X.sup.2, which are identical or different,
have the meaning given for X in formula (I), n is such as defined
in formula (I), Y and T are such as defined in formula (I),
R.sup.14 to R.sup.21 are groups chosen in the same group as R.sup.4
to R.sup.7, m.sub.1 and m.sub.2 are numbers in the interval ranging
from 1 to 1,000, and p is an integral number ranging from 2 to
500.
[1011] In formula (VII), it is preferred that [1012] p range from 1
to 25, still better from 1 to 7, [1013] R.sup.14 to R.sup.21 be
methyl groups, [1014] T be represented by one of the following
formulas:
##STR00062##
[1014] in which R.sup.22 is a hydrogen atom or a group chosen from
among the groups defined for R.sup.4 to R.sup.7, and R.sup.23,
R.sup.24 and R.sup.25 are, independently, linear or branched
alkylene groups, more preferably, with the formula:
##STR00063##
in particular with R.sup.23, R.sup.24 and R.sup.25 representing
--CH.sub.2--CH.sub.2--, [1015] m.sub.1 and m.sub.2 range from 15 to
500, and still better from 15 to 45, [1016] X.sub.1 and X.sub.2
represent --(CH.sub.2).sub.10--, and [1017] Y represents
--CH.sub.2--.
[1018] These polyamides with grafted silicone moiety of formula
(VII) may be copolymerized with silicone polyamides of formula (II)
to form block copolymers, alternating copolymers or random
copolymers. The percentage by weight of grafted silicone moieties
(VII) in the copolymer may range from 0.5 to 30% by weight.
[1019] According to the invention, as has been seen in the
foregoing, the siloxane units may be in the main chain or skeleton
of the polymer, but they may also be present in grafted or pendant
chains. In the main chain, the siloxane units may be in the form of
segments as described hereinabove. In the pendant or grafted
chains, the siloxane units may be present individually or in
segments.
[1020] According to an embodiment variant of the invention, there
may be used a copolymer of silicone polyamide and hydrocarbon
polyamide, or a copolymer containing moieties of formula (III) or
(IV) and hydrocarbon polyamide moieties. In this case, the silicone
polyamide moieties may be disposed at the ends of the hydrocarbon
polyamide.
[1021] Preferably, the preferred compounds are those of formula
III, whose INCI name is Nylon 611/dimethicone copolymers. According
to this embodiment, the groups R.sup.4, R.sup.5, R.sup.6 and
R.sup.7 represent methyl groups, one of X and Y represents an
alkylene group with 6 carbon atoms and the other an alkylene group
groups of 11 carbon atoms.
[1022] By way of example there may be cited the compounds sold by
the Dow Corning Company under the name DC 2-8179 (DP 100) and DC
2-8178 (DP 15). The degree of polymerization DP of these compounds
corresponds to n in formula III.
[1023] Advantageously, the composition according to the invention
comprises at least one polydimethylsiloxane block polymer of
general formula (I) possessing an index m whose value is
approximately 15.
[1024] More preferably, the composition according to the invention
comprises at least one polymer comprising at least one moiety of
formula (III), where m ranges from 5 to 100, in particular from 10
to 75 and more particularly is on the order of 15; more preferably,
R.sup.4, R.sup.5, R.sup.6 and R.sup.7 represent, independently, a
linear or branched C.sub.1 to C.sub.40 alkyl group, preferably a
CH.sub.3, C.sub.2H.sub.5, n-C.sub.3H.sub.7 or isopropyl group in
formula (III).
[1025] By way of example of a usable silicone polymer there may be
cited one of the silicone polyamides obtained in conformity with
Examples 1 to 3 of the document U.S. Pat. No. 5,981,680.
[1026] According to an embodiment variant of the invention, the
polymer is constituted by a homopolymer or copolymer containing
urethane or urea groups. These polymers are described in detail in
Application WO 2003/106614, published 24 Dec. 2003.
[1027] As in the foregoing, such a polymer may contain
polyorganosiloxane moieties containing two or more urethane and/or
urea groups, either in the polymer skeleton or on side chains or as
pendant groups. The polymers containing at least two urethane
and/or urea groups in the skeleton may be polymers comprising at
least one moiety according to the following formula (VIII):
##STR00064##
in which R.sup.4, R.sup.5, R.sup.8, R.sup.7, X, Y, m and n have the
meanings given hereinabove for formula (I), and U represents --O--
or --NH--, in order that:
##STR00065##
corresponds to a urethane or urea group.
[1028] In this formula (VIII), Y may be a linear or branched
C.sub.1 to C.sub.40 alkylene group, possibly substituted by a
C.sub.1 to C.sub.15 alkyl group or a C.sub.5 to C.sub.10 aryl
group. Preferably there will be used a --(CH.sub.2).sub.6--
group.
[1029] Y may also represent a C.sub.5 to C.sub.12 cycloaliphatic or
aromatic group, which may be substituted by a C.sub.1 to C.sub.15
alkyl group or a C.sub.5 to C.sub.10 aryl group, for example a
radical chosen from among the methylene-4-4-biscyclohexyl radical,
the radical derived from isophorone diisocyanate, 2,4 and
2,6-tolylenes, 1,5-naphthylene, p-phenylene and 4,4'-biphenylene
methane. In general, Y preferably represents a linear or branched
C.sub.1 to C.sub.40 alkylene radical, or a C.sub.4 to C.sub.12
cycloalkylene radical.
[1030] Y may also represent a polyurethane or polyurea sequence
corresponding to the condensation of several diisocyanate molecules
with one or more coupler molecules or the diol or diamine type. In
this case, Y comprises several urethane or urea groups in the
alkylene chain.
[1031] It may be represented by formula (IX):
##STR00066##
in which B.sup.1 is a group chosen from among the groups given
hereinabove for Y, U is --O-- or --NH--, and B.sup.2 is chosen from
among: [1032] the linear or branched C.sub.1 to C.sub.40 alkylene
groups, [1033] the C.sub.5 to C.sub.12 cycloalkylene groups,
possibly carrying alkyl substituents, for example one to three
methyl or ethyl groups, or alkylene, for example the diol radical:
cyclohexane dimethanol, [1034] the phenylene groups, which may
possibly carry C.sub.1 to C.sub.3 alkyl substituents, and [1035]
the groups of formula:
##STR00067##
[1035] in which T is a trivalent hydrocarbon radical, which may
contain one or more hetero atoms such as oxygen, sulfur and
nitrogen, and R.sup.8 is a polyorganosiloxane chain or a linear or
branched C.sub.1 to C.sub.50 alkyl chain.
[1036] As an example, T may represent:
##STR00068##
where w is an integral number ranging from 1 to 10 and R.sup.8 is a
polyorganosiloxane chain.
[1037] When Y is a linear or branched C.sub.1 to C.sub.40 alkylene
group, the --(CH.sub.2).sub.2-- and --(CH.sub.2).sub.6-- groups are
preferred.
[1038] In the formula given above for Y, d may be an integer
ranging from 0 to 5, preferably from 0 to 3, more preferably equal
to 1 or 2.
[1039] Preferably, B.sup.2 is a linear or branched C.sub.1 to
C.sub.40 alkylene, in particular --(CH.sub.2).sub.2-- or
--(CH.sub.2).sub.6--, or the group:
##STR00069##
where R.sup.8 is a polyorganosiloxane chain.
[1040] As in the foregoing, the polymer constituting the
texturizing copolymer may be formed from urethane silicone and/or
urea silicone moieties of different length and/or constitution, and
may have the form of block, sequenced or statistical (random)
copolymers.
[1041] The polymers of formula (VIII) containing urea or urethane
groups in the silicone polymer chain may be obtained by reaction
between a silicone with .alpha.,.omega.-NH.sub.2 or OH terminal
groups, of formula:
##STR00070##
in which m, R.sup.4, R.sup.5, R.sup.6, R.sup.7 and X are such as
defined for formula (I), and a diisocyanate OCN--Y--NCO, where Y
has the meaning given in formula (I); and possibly a diol or
diamine coupler of formula H.sub.2N--B.sup.2--NH.sub.2 or
HO--B.sup.2--OH, where B.sup.2 is such as defined in formula
(IX).
[1042] Depending on the stoichiometric proportions between the two
reagents, diisocyanate and coupler, Y will be able to have formula
(IX) with d equal to 0 or d equal to 1 to 5.
[1043] As in the case of the silicone polyamides of formula (IV),
(II) or (III), there may be used in the invention silicone
polyurethanes or polyureas having moieties of different length and
structure, in particular moieties of different lengths due to the
number of silicone units. In this case, the copolymer may be
represented, for example, by the formula:
##STR00071##
in which R.sup.4, R.sup.5, R.sup.6, R.sup.7, X, Y and U are such as
defined for formula (VIII) and m.sub.1, m.sub.2, n and p are such
as defined for formula (V).
[1044] According to the invention, the silicone may also contain
urethane and/or urea groups no longer in the skeleton but in side
branches. In this case, the polymer may comprise at least one
moiety of the following formula:
##STR00072##
in which R.sup.4, R.sup.6, R.sup.5, m.sub.1 and m.sub.2 have the
meanings given hereinabove for formula (II) and R.sup.5 for formula
(I), [1045] U represents O or NH, [1046] R.sup.26 represents a
C.sub.1 to C.sub.40 alkylene group, possibly containing one or more
hetero atoms chosen from among O and N, or a phenylene group, and
[1047] R.sup.27 is chosen from among the saturated or unsaturated,
linear, branched or cyclic C.sub.1 to C.sub.50 alkyl groups, and
the phenyl groups, possibly substituted by one to three C.sub.1 to
C.sub.3 alkyl groups.
[1048] The polymers containing at least one moiety of formula (X)
contain siloxane units and urea or urethane groups, and they may be
used as texturizing copolymer in the compositions of the
invention.
[1049] The siloxane polymers may have a single urea or urethane
group per branch or may have branches with two urea or urethane
groups, or even contain a mixture of branches with one urea or
urethane group and branches with two urea or urethane groups.
[1050] They may be obtained from branched polysiloxanes, containing
one or two amino groups per branch, by reacting these polysiloxanes
with monoisocyanates.
[1051] By way of examples of starting polymers of this type having
amino and diamino branches there may be cited the polymers
according to the following formulas:
##STR00073##
[1052] In these formulas, the "/" symbol indicates that the
segments may be of different lengths and in a random order, and R
represents a linear aliphatic group having preferably 1 to 6 carbon
atoms and still better 1 to 3 carbon atoms.
[1053] Such branched polymers may be formed by reacting a siloxane
polymer having at least three amino groups per polymer molecule
with a compound having a single monofunctional group (for example,
an acid, an isocyanate or isothiocyanate), thus causing this
monofunctional group to react with one of the amino groups and to
form the groups capable of establishing hydrogen interactions. The
amino groups may be on side chains extending from the main chain of
the siloxane polymer such that the groups capable of establishing
hydrogen interactions are formed on these side chains, or else the
amino groups may be at the ends of the main chain such that the
groups capable of hydrogen interaction will be terminal groups of
the polymer.
[1054] As a mode of operation for forming a polymer containing
siloxane units and groups capable of establishing hydrogen
interactions there may be cited the reaction of a diamine siloxane
and of a diisocyanate in a silicone solvent so as to produce a gel
directly. The reaction may be carried out in a silicone fluid, the
resulting product being dissolved in the silicone fluid at elevated
temperature, the temperature of the system then being lowered to
form the gel.
[1055] The polymers preferred for incorporation into the
compositions according to the present invention are urea-siloxane
copolymers that are linear and that contain urea groups as groups
capable of establishing hydrogen interactions in the skeleton of
the polymer.
[1056] By way of illustration of a polysiloxane terminated by four
urea groups there may be cited the polymer of formula:
##STR00074##
where Ph is a phenyl group and n is a number from 0 to 300, in
particular from 0 to 100, for example 50.
[1057] This polymer is obtained by reacting the following
polysiloxane having amino groups:
##STR00075##
with phenyl isocyanate.
[1058] Branched silicone polyurethanes or polyureas may also be
obtained by using, instead of the diisocyanate OCN--Y--NCO, a
triisocyanate of the following formula:
##STR00076##
[1059] In this way there is obtained a silicone polyurethane or
polyurea having branches containing an organosiloxane chain with
groups capable of establishing hydrogen interactions. Such a
polymer comprises, for example, a moiety according to the
formula:
##STR00077##
in which X.sup.1 and X.sup.2, which are identical or different,
have the meaning given for X in formula (I), n is such as defined
in formula (I), Y and T are such as defined in formula (I),
R.sup.14 to R.sup.21 are groups chosen in the same group as R.sup.4
to R.sup.7, m.sub.1 and m.sub.2 are numbers in the interval ranging
from 1 to 1,000, and p is an integral number ranging from 2 to
500.
[1060] As in the case of polyamides, silicone polyurethane or
polyurea or hydrocarbon polyurethane or polyurea copolymers may be
used in the invention by carrying out the reaction of synthesis of
the polymer in the presence of a difunctional .alpha.,.omega.
sequence of non-silicone nature, for example a polyester, a
polyether or a polyolefin.
[1061] As has been seen in the foregoing, the copolymers of the
invention may have siloxane moieties in the main chain of the
polymer and groups capable of establishing hydrogen interactions
either in the main chain of the polymer or at the ends thereof, or
on side chains or branches of the main chain. This may correspond
to the following five arrangements:
##STR00078##
in which the continuous line is the main chain of the siloxane
polymer and the squares represent the groups capable of
establishing hydrogen interactions.
[1062] In case (1), the groups capable of establishing hydrogen
interactions are disposed at the ends of the main chain. In case
(2), two groups capable of establishing hydrogen interactions are
disposed at each of the ends of the main chain.
[1063] In case (3), the groups capable of establishing hydrogen
interactions are disposed in the interior of the main chain, in
repetitive moieties.
[1064] Cases (4) and (5) correspond to copolymers in which the
groups capable of establishing hydrogen interactions are disposed
on branches of the main chain of a first series of moieties that
are copolymerized with moieties not containing groups capable of
establishing hydrogen interactions.
[1065] The polymers and copolymers used in the composition of the
invention advantageously have a solid-liquid transition temperature
of 45.degree. C. to 190.degree. C. Preferably they have a
solid-liquid transition temperature ranging from 70.degree. C. to
130.degree. C. and better from 80.degree. C. to 105.degree. C.
[1066] Organo Gelling Agents:
[1067] The oil-type structuring agent may also be chosen from among
the non-polymeric molecular organic gelling agents, also referred
to as organo gelling agents, which are compounds whose molecules
are capable of establishing physical interactions between one
another, leading to auto-aggregation of the molecules with
formation of a supra-molecular 3D network, which is responsible for
the gelling of the oil or oils (also referred to as liquid fatty
phase).
[1068] The supra-molecular network may result from the formation of
a network of fibrils (due to stacks or aggregations of molecules of
organo gelling agent), immobilizing the molecules of the liquid
fatty phase.
[1069] The ability to form this network of fibrils, and therefore
to gelify, depends on the nature (or chemical class) of the organo
gelling agent, on the nature of the substituents carried by its
molecules for a given chemical class, and on the nature of the
liquid fatty phase.
[1070] The physical interactions are diverse but exclude
co-crystallization. These physical interactions are in particular
interactions of the auto-complementary hydrogen interaction type,
.pi. interactions between unsaturated rings, dipole interactions,
coordination bonds with organometallic derivatives and their
associations. In general, each molecule of an organo gelling agent
may establish several types of physical interactions with a
neighboring molecule. Thus the molecules of organo gelling agents
according to the invention advantageously contain at least one
group capable of establishing hydrogen bonds and better at least
two groups capable of establishing hydrogen bonds, at least one
aromatic ring and better at least two aromatic rings, at least one
or more ethylenically unsaturated bonds and/or at least one or more
asymmetric carbons. Preferably, the groups capable of forming
hydrogen bonds are chosen from among the hydroxyl, carbonyl, amine,
carboxylic acid, amide, urea, benzyl groups and associations
thereof.
[1071] The organo gelling agent or agents according to the
invention are soluble in the liquid fatty phase after heating until
a transparent homogeneous liquid phase is obtained. They may be
solid or liquid at room temperature and atmospheric pressure.
[1072] The molecular organo gelling agent or agents that can be
used in the composition according to the invention are in
particular those described in the document "Specialist
Surfactants", edited by D. Robb, 1997, pp. 209-263, Chapter 8 by P.
Terech, European Applications EP A 1068854 and EP A 1086945, or
else in Application WO A 02/47031.
[1073] Among these organo gelling agents there may be cited in
particular the amides of carboxylic acids, particularly the
tricarboxylic acids, such as the cyclohexanetricarboxamides (see
European Patent Application EP A 1068854), the diamides having
hydrocarbon chains that each contain 1 to 22 carbon atoms, for
example 6 to 18 carbon atoms, the said chains being non-substituted
or substituted with at least one substituent chosen from among the
ester, urea and fluoro groups (see Application EP A 1086945) and
especially the diamides resulting from the reaction of
diaminocyclohexane, in particular of diaminocyclohexane in trans
form, and of an acid chloride such as, for example,
N,N'-bis(dodecanoyl)-1,2-diaminocyclohexane, the amides of
N-acylamino acids, such as the diamides resulting from the action
of an N-acylamino acid with amines containing 1 to 22 carbon atoms,
such as, for example, those described in the document WO-93/23008,
and especially the amides of N-acyl glutamic acid, in which the
acyl group represents a C.sub.8 to C.sub.22 alkyl chain, such as
the dibutylamide of N-lauroyl-L-glutamic acid, manufactured or sold
by the Ajinomoto Company under the trade name GP-1, and mixtures
thereof.
[1074] As organo gelling agents there may also be used compounds of
bis-urea type of the following general formula:
##STR00079##
in which [1075] A is a group of formula (II)
##STR00080##
[1075] where R1 is a linear or branched C.sub.1 to C.sub.4 alkyl
radical and the * symbolize the points of attachment of group A to
each of the two nitrogen atoms of the rest of the compound of
general formula (I), and [1076] R and R', identical or different,
are chosen from among: [1077] i) the radicals of formula (III):
##STR00081##
[1077] in which: [1078] L is a single bond or a divalent carbon
radical, especially a saturated or unsaturated, linear, branched
and/or cyclic hydrocarbon (alkylene), comprising 1 to 18 carbon
atoms, which may comprise 1 to 4 hetero atoms chosen from among N,
O and S; [1079] Ra is a) a carbon radical, especially a saturated
or unsaturated, linear, branched and/or cyclic hydrocarbon (alkyl),
comprising 1 to 18 carbon atoms, which may comprise 1 to 8 hetero
atoms chosen from among N, O, Si and S; or else b) a silicone
radical of formula:
##STR00082##
[1079] where n is between 0 and 100, especially between 1 and 80,
even 2 to 20; and R2 and R6 are, independently of one another,
carbon radicals, especially linear or branched hydrocarbons
(alkyl), having 1 to 12, especially 1 to 6 carbon atoms, which may
comprise 1 to 4 hetero atoms, especially 0; [1080] Rb and Rc are,
independently of one another, chosen from among: a) the carbon
radicals, especially saturated or unsaturated, linear, branched
and/or cyclic hydrocarbons (alkyl), comprising 1 to 18 carbon
atoms, which may comprise 1 to 4 hetero atoms chosen from among N,
O, Si and S; b) the radicals of formula:
##STR00083##
[1080] where n is between 0 and 100, especially between 1 and 80,
even 2 to 20; and R'2 and R'6 are, independently of one another,
carbon radicals, especially linear or branched hydrocarbons
(alkyl), having 1 to 12, especially 1 to 6 carbon atoms, which may
comprise 1 to 4 hetero atoms, especially O. and [1081] ii) the
saturated or unsaturated, linear, branched and/or cyclic C.sub.1 to
C.sub.30 alkyl radicals, possibly comprising 1 to 3 hetero atoms
chosen from among O, S, F and N; its being understood that at least
one of the radicals R and/or R' is of formula (III).
[1082] In particular, group A may be of formula:
##STR00084##
where R1 and the * are as defined in the foregoing. In particular,
R1 may be a methyl group, thus leading to a group A of formula:
##STR00085##
in which the * are as defined in the foregoing. In particular, the
compounds according to the invention may be in the form of a
mixture associated with the fact that A may be a mixture of
2,4-tolylene and 2,6-tolylene, especially in proportions of (2,4
isomer)/2,6 isomer) varying from 95/5 to 80/20.
[1083] According to the invention, at least one of the radicals R
and/or R' must be of formula (III):
##STR00086##
[1084] In this formula, L is preferably a divalent carbon radical,
especially a saturated or unsaturated, linear, branched and/or
cyclic hydrocarbon (alkylene), comprising 1 to 18 carbon atoms,
which may comprise 1 to 4 hetero atoms chosen from among N, O and
S.
[1085] In the radical L, the carbon chain may be interrupted by the
hetero atom or atoms and/or may comprise a substituent comprising
the said hetero atom or atoms.
[1086] In particular, L may be of --(CH.sub.2).sub.n-- structure,
where n=1 to 18, especially 2 to 12, even 3 to 8.
[1087] Preferably, L is chosen from among the methylene, ethylene,
propylene, butylene radicals and especially n-butylene or
octylene.
[1088] The radical L may also be branched, for example of the
--CH.sub.2--CH(CH.sub.3)-- type, which leads to the following
radical of formula III):
##STR00087##
[1089] The radical Ra may be a carbon radical, especially a
saturated or unsaturated, linear, branched and/or cyclic
hydrocarbon (alkyl), comprising 1 to 18 carbon atoms, which may
comprise 1 to 8 hetero atoms chosen from among N, O, Si and S. The
carbon chain may be interrupted by the hetero atom or atoms and/or
may comprise a substituent comprising the said hetero atom or
atoms; in particular the hetero atoms may form one or more --SiO--
(or --OSi)-- groups.
[1090] Thus the radical Ra may be of --(CH.sub.2)n'-CH.sub.3
structure, where n'=0 to 17, especially 1 to 12, even 1 to 6. In
particular, Ra may be methyl, ethyl, propyl or butyl.
[1091] It may also be of --(CH.sub.2)x-O--(CH.sub.2)z-CH.sub.3 or
else --(CH.sub.2)x-O--(CH.sub.2)y-O--(CH.sub.2)z-CH.sub.3
structure, where x=1 to 10, preferably 2; y=1 to 10, preferably 2,
and z=1 to 10, preferably 0 or 1.
[1092] The radical Ra may also be of --SiR.sub.4R.sub.5R.sub.6
structure (case where n=0), in which R4, R5 and R6 are,
independently of one another, preferably alkyl radicals having 1 to
12 carbon atoms, especially 1 to 6 carbon atoms; in particular, R4,
R5 and/or R6 may be chosen from among methyl, ethyl, propyl,
butyl.
[1093] The radical Ra may also be a silicone radical of
formula:
##STR00088##
in which R2 to R6 are, independently of one another, preferably
alkyl radicals having 1 to 12 carbon atoms, especially 1 to 6
carbon atoms; in particular, R2 to R6 may be chosen from among
methyl, ethyl, propyl, butyl; and in particular a radical:
##STR00089##
where n=1 to 100; and even more particularly a radical:
##STR00090##
The radicals Rb and Rc, identical or different, may be carbon
radicals, especially saturated or unsaturated, linear, branched
and/or cyclic hydrocarbons (alkyl), comprising 1 to 18 carbon
atoms, which may comprise 1 to 8 hetero atoms chosen from among N,
O, Si and S. In these radicals, the carbon chain may be interrupted
by the hetero atom or atoms and/or may comprise a substituent
comprising the said hetero atom or atoms; in particular the hetero
atoms may form one or more --SiO-- (or --OSi)-- groups.
[1094] Thus they may be of --(CH.sub.2)m-CH.sub.3 structure, where
m=0 to 17, especially 1 to 12, even 2 to 5. In particular, Rb
and/or Rc may be methyl, ethyl, propyl or butyl;
[1095] They may also be of --O--(CH.sub.2)m'-CH.sub.3 structure,
where m'=0 to 5, especially 1 to 4, and in particular methoxy or
ethoxy.
[1096] They may also be of --(CH.sub.2)x-O--(CH.sub.2)z-CH.sub.3 or
else --(CH.sub.2)x-O--(CH.sub.2)y-O--(CH.sub.2)z-CH.sub.3
structure, where x=1 to 10, preferably 2; y=1 to 10, preferably 2,
and z=1 to 10, preferably 0 or 1.
[1097] They may also be of structure:
##STR00091##
where n is between 0 and 100, especially between 1 and 80, even 2
to 20; and R'2 to R'6 are, independently of one another, preferably
alkyl radicals having 1 to 12 carbon atoms, especially 1 to 6
carbon atoms; in particular, R'2 to R'6 may be chosen from among
methyl, ethyl, propyl, butyl.
[1098] When they are of formula (III), the radicals R and/or R' are
preferably chosen from among the following radicals:
##STR00092##
and also those of formula:
##STR00093##
where n varies from 0 to 100 and in particular
##STR00094##
and
##STR00095##
or else
##STR00096##
in which x=1 to 10, preferably 2; and y=1 to 10, preferably 2; and
L is such as defined hereinabove.
[1099] In these formulas, L is preferably a linear or branched
C1-C8 alkylene radical, especially methylene, ethylene, propylene,
butylene and especially n-butylene, octylene or of formula
--CH.sub.2--CH(CH.sub.3)--.
[1100] In a particular embodiment, R and R', identical or
different, are both of formula (III).
[1101] In another embodiment, one of the radicals R or R'
represents a saturated or unsaturated, linear, branched and/or
cyclic C.sub.1 to C.sub.30 alkyl radical, possibly comprising 1 to
3 hetero atoms chosen from among O, S, F and N.
[1102] This proves particularly advantageous for conferring a
universal character on the compounds of formula (I), or in other
words permitting them to texturize, equally well, polar or apolar
carbon media, linear or cyclic silicone media, mixed oils, or in
other words carbon media that are part silicone, as well as
mixtures thereof.
[1103] The carbon chain may be interrupted by the hetero atom or
atoms and/or may comprise a substituent comprising the said hetero
atom or atoms, especially in the form of carbonyl groups (--CO--),
of one or more hydroxy radicals (--OH), and/or of an ester radical
--COOR'', where R''=linear or branched alkyl radical having 1 to 8
carbon atoms.
[1104] Thus the said radical R or R' may be a group chosen from
among:
##STR00097##
where * has the definition given hereinabove.
[1105] In a preferred embodiment, R or R' represents a saturated or
unsaturated, preferably non-cyclic, branched, especially singly
branched alkyl radical comprising 3 to 16 carbon atoms, especially
4 to 12, even 4 to 8 carbon atoms, and possibly comprising 1 to 3
hetero atoms chosen from among O, S, F and/or N, preferably O
and/or N.
[1106] In particular, R or R' may be tert-butyl or 2-ethylhexyl
radicals or of formula:
##STR00098##
[1107] When the compound of formula (I) comprises a radical R that
is an alkyl radical, and therefore a radical R' that is of formula
(III), the ratio between n.sub.R and n.sub.R' is preferably between
5/95 and 95/5, for example between 10/90 and 90/10, in particular
between 40/60 and 85/15, especially between 50/50 and 80/20, even
between 60/40 and 75/25;
where n.sub.R is the number of moles of NH.sub.2--R amine and
n.sub.R' is the number of moles of NH.sub.2--R' amine used to
prepare the compound of formula (I).
[1108] The compounds according to the invention may have the form
of salts and/or isomers of compounds of formula (I).
[1109] In general, the compounds of general formula (I) according
to the invention may be prepared as described in Application FR
2910809.
[1110] The compounds of silicone bis-urea type described in the
foregoing may be in a mixture with other non-silicone bis-urea
compounds. According to a first aspect, the non-silicone bis-urea
compounds may correspond to the following general formula (II):
##STR00099##
in which: [1111] A is a group of formula:
##STR00100##
[1111] where R' is a linear or branched C.sub.1 to C.sub.4 alkyl
radical and the * symbolize the points of attachment of the group A
to each of the two nitrogen atoms of the rest of the compound of
general formula (II), and [1112] R is a saturated or unsaturated,
singly branched, non-cyclic, C.sub.6 to C.sub.15 alkyl radical,
whose hydrocarbon chain is possibly interrupted by 1 to 3 hetero
atoms chosen from among O, S and N, or one of the salts or isomers
thereof.
[1113] According to a preferred embodiment of the invention, the
group represented by A is a group of formula:
##STR00101##
where R' and the * are such as defined in the foregoing.
[1114] In particular, R' may be a methyl group, and the group A is
then more particularly a group of formula:
##STR00102##
where the * are such as defined in the foregoing.
[1115] According to a first embodiment of the invention, R may be
chosen from among the singly branched radicals of general formula
C.sub.nH.sub.2n+1, where n is an integer varying from 6 to 15,
particularly from 7 to 9, even equal to 8.
[1116] Thus the two groups R of the compound of formula (II) may
respectively represent a group:
##STR00103##
where * symbolizes the point of attachment of each of the groups R
to each of the nitrogen atoms of the rest of the compound of
general formula (II).
[1117] According to a second embodiment of the invention, R may be
chosen from among the singly branched radicals of general formula
C.sub.m-pH.sub.2m+1-2pX.sub.p, where p is equal to 1, 2 or 3,
preferably equal to 1, m is an integer varying from 6 to 15,
preferably from 10 to 14, in particular from 10 to 12, even equal
to 11, and X represents sulfur and/or oxygen atoms, in particular
oxygen atoms.
[1118] More particularly, R may be a radical of formula
C.sub.m'H.sub.2m'X--(C.sub.p'H.sub.2p'X').sub.r--C.sub.xH.sub.2x+1,
in which X and X' are, independently of one another, an oxygen or
sulfur atom, preferably oxygen, r is equal to 0 or 1, m', p' and x
are integers such that their sum varies from 6 to 15, in particular
from 10 to 12, is even equal to 11, and its being understood that
at least one of the carbon chains C.sub.m'H.sub.2m',
C.sub.p'H.sub.2p' or C.sub.xH.sub.2x+1 is branched.
[1119] Preferably the C.sub.xH.sub.2x+1 chain is branched,
preferably r is equal to 0, preferably m' is an integer varying
from 1 to 10, especially from 2 to 6, in particular equal to 3,
and/or preferably x is an integer varying from 4 to 16, especially
from 6 to 12, in particular equal to 8.
[1120] Thus the two groups R of the compound of formula (I) may
respectively represent a group:
##STR00104##
where * symbolizes the point of attachment of each of the groups R
to each of the nitrogen atoms of the rest of the compound of
general formula (I).
[1121] Such compounds may be present in the compositions according
to the invention in mixtures with isomers, especially position
isomers on group A, especially in proportions of 95/5 or 80/20.
[1122] As becomes evident from the examples hereinafter, the
presence of one or the other of its radicals in the molecule of
general formula (II) proves particularly advantageous for
conferring universal character within the meaning of the invention
upon the corresponding non-silicone bis-urea derivatives.
[1123] As representative and non-limitative compounds that are
quite particularly suitable for the invention there may be cited
more particularly the following compounds, used in pure or mixed
form:
##STR00105##
and the salts thereof.
[1124] According to another aspect of the invention, the
non-silicone bis-urea derivatives following formula (III):
##STR00106##
in which: [1125] A is a group of formula:
##STR00107##
[1125] where [1126] R.sub.3 is a hydrogen atom or a linear or
branched C.sub.1 to C.sub.4 alkyl radical, [1127] n and m are,
independently of one another, equal to 0 or 1, and [1128] *
symbolize the point of attachment of the group A to the two
nitrogen atoms of the rest of the compound of general formula
(III), [1129] R.sub.1 is a saturated or unsaturated, branched,
non-cyclic C.sub.3 to C.sub.15 carbon radical, possibly containing
1 to 3 hetero atoms chosen from among O, S, F and N and/or a
carbonyl, and combinations thereof, [1130] R.sub.2 is different
from R.sub.1 and is chosen from among the linear, branched or
cyclic, saturated or unsaturated C.sub.1-C.sub.24 alkyl radicals,
possibly containing 1 to 3 hetero atoms chosen from among O, S, F
and N, and possibly substituted by: [1131] 1, 2 or 3 hydroxy
radicals, [1132] an ester radical (--COOR.sub.4), where R is a
linear or branched alkyl radical having 1 to 8, especially 1 to 6,
even 2 to 4 carbon atoms; [1133] a saturated, unsaturated cyclic or
aromatic radical having 5 to 12 carbon atoms, in particular a
phenyl radical, possibly substituted by one or more identical or
different radicals chosen from among the C.sub.1-C.sub.4 alkyl
radicals, trifluoromethyl, or a morpholine derivative, and/or
[1134] one or more linear or branched C.sub.1-C.sub.4 alkyl
radicals or one of the salts or isomers thereof.
[1135] In particular, n and m are equal, and more particularly are
equal to zero, and R.sub.3 is a radical R'.sub.3 such as defined
below. Thus A preferably represents a group
##STR00108##
where R.sub.3' is a linear or branched C.sub.1 to C.sub.4 alkyl
radical and * symbolize the point of attachment of the group A to
the two nitrogen atoms of the rest of the compound of general
formula (III).
[1136] According to a variant of the invention, the compound of
general formula (III) comprises, by way of A, at least one group
chosen from among:
##STR00109##
where R.sub.3' and * are such as defined in the foregoing.
[1137] In particular R.sub.3' may be a methyl group, and in this
case group A represents a group
##STR00110##
where * are defined as in the foregoing.
[1138] In particular, the compounds are such that A is a mixture of
2,4-tolylene and 2,6-tolylene, especially in proportions of (2,4
isomer)/2,6 isomer) varying from 95/5 to 80/20.
[1139] According to one embodiment of the invention, the compound
of general formula (III) comprises, by way of R.sub.1, a branched
C.sub.6-C.sub.15 radical.
[1140] According to one embodiment of the invention, the compound
of general formula (III) comprises, by way of R.sub.1, a compound
chosen from among:
##STR00111##
where * symbolize the point of attachment of the group R.sub.1 to
the nitrogen of the rest of the compound of general formula
(III).
[1141] As becomes evident from the examples hereinafter, the
presence of one and/or the other of its two radicals in the
molecule of general formula (III) proves particularly advantageous
for conferring universal character within the meaning of the
invention upon the corresponding asymmetric bis-urea
derivatives.
[1142] As regards R.sub.2, which is different from R.sub.1, it may
be advantageously chosen from among the following groups:
##STR00112## ##STR00113##
where * symbolize the point of attachment of the group R.sub.1 to
the nitrogen of the rest of the compound of general formula
(III).
[1143] In general, the described compounds may be prepared as
described in Application FR 2910809.
Fatty-Phase Gelling Silicone Elastomers
[1144] By "elastomer" there is understood a deformable, flexible
solid material having viscoelastic properties, and especially the
consistency of a sponge. This elastomer is formed from polymeric
chains of high molecular weight, whose mobility is limited by a
uniform network of cross-linking points.
[1145] The elastomeric organopolysiloxanes used in the composition
according to the invention are preferably partly or completely
cross-linked. They have the form of particles.
[1146] In particular, the elastomeric organopolysiloxane particles
have a size ranging from 0.1 to 500 .mu.m preferably from 3 to 200
.mu.m and better from 3 to 50 .mu.m. These particles may have any
shape and for example may be spherical, flat or amorphous.
[1147] When they are included in an oil phase, these elastomeric
organopolysiloxanes become transformed, depending on the proportion
of the oil phase used, into a product of spongy appearance when
they are used in the presence of low contents of oil phase, or into
a homogeneous gel in the presence of higher quantities of oil
phase. The gelling of the oil phase by these elastomers may be
total or partial.
[1148] Thus the elastomers of the invention may be conveyed in the
form of anhydrous gel composed of an elastomeric organopolysiloxane
and of an oil phase. The oil phase used during the manufacture of
the anhydrous elastomeric organopolysiloxane gel contains one or
more oils that are liquid at room temperature (25.degree. C.),
chosen from among the hydrocarbon oils and/or the silicone oils.
Advantageously, the oil phase is a silicone liquid phase containing
one or more oils chosen from among the linear chain or cyclic
polydimethylsiloxanes that are liquid at room temperature, possibly
containing an alkyl or aryl chain of pendant type or at the end of
the chain, the alkyl chain having 1 to 6 carbon atoms.
[1149] According to one embodiment, the elastomeric
organopolysiloxanes used according to the invention may be obtained
by addition and cross-linking reaction, in the presence of a
catalyst, preferably a catalyst of platinum type, of at least:
[1150] (i) an organopolysiloxane having two vinyl groups in
.alpha.-.omega. position of the silicone chain per molecule; and
[1151] (ii) an organopolysiloxane having at least two hydrogen
atoms bonded to one silicon atom per molecule.
[1152] The first organopolysiloxane (i) is chosen from among the
polydimethylsiloxanes; it is preferably an
.alpha.-.omega.-dimethylvinyl polydimethylsiloxane.
[1153] The organopolysiloxane is preferably in a gel obtained
according to the following steps: [1154] (a) mixing of the first
and second organopolysiloxanes (i) and (ii); [1155] (b) addition of
an oil phase to the mixture of step (a); [1156] (c) polymerization
of the first and second organopolysiloxanes (i) and (ii) in the oil
phase in the presence of a catalyst, preferably a platinum
catalyst.
[1157] According to one embodiment, the cross-linked
organopolysiloxane may be obtained by a polymeric addition reaction
of an organohydrogenopolysiloxane of formula (I) with an
organopolysiloxane of formula (II) and/or an unsaturated hydrogen
chain of formula (III).
[1158] According to one variant, the cross-linked
organopolysiloxane is obtained by a polymeric reaction of an
organohydrogenopolysiloxane of formula (I) with an
organopolysiloxane of formula (II).
Organohydrogenopolysiloxane of Formula (I)
[1159] The organohydrogenopolysiloxane of formula (I) comprises at
least one structural unit chosen in the group composed of an
SiO.sub.2 unit, an HSiO.sub.1.5 unit, an RSiO.sub.1.5 unit, an
RHSiO unit, an R.sub.2SiO unit, an R.sub.3SiO.sub.0.5 unit and an
R.sub.2HSiO.sub.0.5 unit, wherein the group R in these units is a
monovalent hydrocarbon chain containing 1 to 16 carbon atoms and
may or may not be substituted, but is different from an unsaturated
aliphatic group and possesses on average at least 1.5 hydrogen
atoms bonded to a silicon atom.
[1160] The group R in the organohydrogenopolysiloxane of formula
(I) may be an alkyl group containing 1 to 16, preferably 10 to 16
carbon atoms. This group R may be, for example, a methyl group, an
ethyl group, a propyl group, a lauryl group, a myristyl group and a
palmityl group.
[1161] The group R in the organohydrogenopolysiloxane of formula
(I) may also be an aryl group such as a phenyl or tolyl group.
[1162] The group R, still in the organohydrogenopolysiloxane of
formula (I), may also be a monovalent hydrocarbon chain comprising
a cycloalkyl group such as cyclohexyl or else a hydrocarbon chain
substituted by one, two or more groups chosen from among a halogen
atom such as chlorine, bromine, fluorine and a cyano group, for
example an .alpha.-trifluoropropyl or chloromethyl group.
[1163] In particular, the group R preferably represents at least 30
mol % of methyl groups and from 5 to 50 mol %, preferably from 10
to 40 mol % of hydrocarbon chains containing 10 to 16 carbon
atoms.
[1164] The hydrocarbon chain may then advantageously contain at
least one lauryl group, and even the majority of the groups R may
be lauryl groups.
[1165] The organohydrogenopolysiloxane of formula (I) may be
linear, branched or cyclic.
[1166] The organohydrogenopolysiloxane of formula (I) preferably
contains 2 to 50 and even more preferably 2 to 10 hydrogen atoms
bonded to a silicon atom (Si--H). The content of hydrogen atoms
bonded to a silicon atom in this compound of formula (I)
traditionally varies from 0.5 to 50 mol %, and even more preferably
from 1 to 20 mol % relative to the total sum of the hydrogen atoms
and of all the organic groups bonded to a silicon atom.
Organopolysiloxane of Formula (II)
[1167] The organopolysiloxane of formula (II) comprises at least
one structural unit chosen in the group composed of an SiO.sub.2
unit, a (CH.sub.2.dbd.CH)SiO.sub.1.5 unit, an RSiO.sub.1.5 unit, an
R(CH.sub.2.dbd.CH)SiO unit, an R.sub.2SiO unit, an
R.sub.3SiO.sub.0.5 unit and an R.sub.2(CH.sub.2.dbd.CH)SiO.sub.0.5
unit, wherein the group R is such as defined in formula (I) and
possesses on average at least 1.5 vinyl groups bonded to a silicon
atom.
[1168] This compound preferably contains 2 to 50 vinyl groups
bonded to a silicon atom.
[1169] The mean number of vinyl groups bonded to a silicon atom
preferably varies from 2 to 10 and even more preferably from 2 to
5.
[1170] Preferably, at least 30 mol % of the groups R are methyl
groups and 5 to 50 mol %, preferably from 10 to 40 mol % of the
groups R are a hydrocarbon chain containing 10 to 16 carbon
atoms.
[1171] The organopolysiloxane of formula (II) may be linear,
branched or cyclic.
[1172] The content of vinyl groups in the compound of formula (II)
preferably varies between 0.5 and 50 mol %, and even more
preferably from 1 to 20 mol % relative to all the organic groups
bonded to a silicon atom.
Optional Unsaturated Hydrocarbon Chain of Formula (III)
[1173] The unsaturated hydrocarbon chain of formula (III)
corresponds to the following formula:
C.sub.mH.sub.2m-1(CH.sub.2).sub.xC.sub.mH.sub.2m-1
in which m is an integer varying from 2 to 6 and x is an integer
equal to at least 1. x is preferably an integer varying from 1 to
20.
[1174] By way of example of this compound of formula (III) there
may be cited pentadiene, hexadiene, heptadiene, octadiene,
pentadecadiene, heptadecadiene and pentatriacontadiene.
[1175] The polymeric addition reactions are described in detail in
the document US 2004/0234477.
[1176] Among the cross-linked organopolysiloxanes there are
preferred the cross-linked polyalkyl dimethylsiloxanes. By
polyalkyl dimethylsiloxane there is understood a linear
organopolysiloxane of formula (IV)
##STR00114##
containing grafts, bonded in monovalent or divalent manner, of
formula (V)
##STR00115##
in which: Ra is an alkyl group containing 10 to 16 carbon atoms,
and preferably it may be a lauryl group, ya is an integer from 1 to
100; za is an integer from 1 to 100, yb is an integer from 1 to
100, zb is an integer from 1 to 100.
[1177] By "bonded in divalent manner" there is understood bonded to
two separate organopolysiloxanes of formula (IV). In other words,
this means a bridge between two linear chains such as defined in
formula (IV).
[1178] As non-emulsifying elastomers that can be used according to
the invention there are preferably used the dimethicone/vinyl
dimethicone copolymers (INCI name: Dimethicone/Vinyldimethicone
crosspolymer), and the vinyl dimethicone/alkyl dimethicone
copolymers, such as the vinyl dimethicone/lauryl dimethicone
copolymers (INCI name: Vinyl Dimethicone/Lauryl Dimethicone
Crosspolymer).
[1179] As non-emulsifying elastomers that can be used according to
the invention there may be cited: [1180] those of INCI name
Dimethicone/Vinyldimethicone Crosspolymer (and) C12-14 Pareth-12:
such as those sold under the name "DC 9509" by the Dow Corning
Company, [1181] those of INCI name Dimethicone/Vinyldimethicone
Crosspolymer: such as those sold under the name "DC9505", or "DC
9506" by the Dow Corning Company, those of INCI name Cyclomethicone
(and) Dimethicone/Vinyldimethicone Crosspolymer: such as those sold
under KSG-15.RTM. by Shin-Etsu, Methyl Trimethicone (and)
Dimethicone/Vinyldimethicone Crosspolymer: such as those sold by
Shin-Etsu under KSG-1610.RTM., [1182] those of INCI name
Dimethicone (and) Dimethicone/Vinyldimethicone Crosspolymer: such
as those sold under KSG-16.RTM. by Shin-Etsu, Isododecane (and)
Dimethicone/Vinyldimethicone Crosspolymer: such as those sold under
USG-106.RTM. by Shin-Etsu, [1183] those of INCI name: Vinyl
Dimethicone/Lauryl Dimethicone Crosspolymer: KSG-41.RTM. (in a
mineral oil), KSG-42.RTM. (in isododecane), KSG-43.RTM. (in
triethylhexanoin) and KSG-44.RTM. (in squalane), sold by
Shin-Etsu.
[1184] As non-emulsifying elastomer there may also be cited
spherical non-emulsifying silicone elastomers in the form of
elastomeric cross-linked organopolysiloxane powder coated with
silicone resin, especially silsesquioxane resin, such as described,
for example, in U.S. Pat. No. 5,538,793. Such elastomers are sold
under the trade names `KSP-100", KSP-101", "KSP-102", "KSP-103",
"KSP-104", "KSP-105" by the Shin Etsu Company.
[1185] Other elastomeric cross-linked organopolysiloxanes in the
form of spherical powders may be hybrid silicone powders
functionalized by fluoroalkyl groups, especially sold under the
trade name "KSP-200" by the Shin Etsu Company; hybrid silicone
powders functionalized by phenyl groups, especially sold under the
trade name "KSP-300" by the Shin Etsu Company.
[1186] There may also be used, in the compositions according to the
invention, silicone elastomers with MQ groups, such as those sold
by the Wacker Company under the trade names Belsil RG100, Belsil
RPG33 and preferably RG80. These particular elastomers, when they
are in association with the resins according to the invention, may
make it possible to improve the non-transfer properties of
compositions comprising them.
[1187] Cholesteric Liquid Crystal Agents:
[1188] By liquid crystal agents there is understood compounds
generating a mesomorphic state, or in other words a state for which
melting of the crystals makes it possible to obtain liquids
possessing optical properties comparable to those of certain
crystals. These compounds are defined more precisely in the Liquid
Crystals chapter of Ullmann's Encyclopedia.
[1189] These liquid crystal agents are described in particular in
the patents or patent applications EP 545409, WO 94109086, EP
709445, GB 2282145, GB 2276883, WO 95132247, WO 95132248, EP
686674, EP 711780.
[1190] These liquid crystal agents may react in response to
vibrations by a change in viscosity and/or by a change of color.
More particularly, the compounds generating a mesomorphic state are
compounds with cholesteric function, whose structure is the
following:
##STR00116##
[1191] R is an alkyl, alkylcarbonyl group comprising 1 to 30 carbon
atoms, which may or may not be substituted by cyclic, aromatic,
halogen groups, which may or may not be branched.
[1192] On a non-limitative basis there may be cited as liquid
crystals satisfying this definition: cholesterol erucyl carbonate,
cholesterol methyl carbonate, cholesterol oleyl carbonate,
cholesterol para-nonylphenyl carbonate, cholesterol phenyl
carbonate, cholesterol acetate, cholesterol benzoate, cholesterol
butyrate, cholesterol isobutyrate, cholesterol chloride,
cholesterol chloroacetate, cholesterol cinnamate, cholesterol
crotanoate, cholesterol decanoate, cholesterol erucate, cholesterol
heptanoate, cholesterol hexanoate, cholesterol myristate,
cholesterol nonanoate, cholesterol octanoate, cholesterol oleate,
cholesterol propionate, cholesterol valerate, dicholesteryl
carbonate.
[1193] The composition according to the invention may contain a
continuous aqueous phase or a continuous oil phase.
[1194] By composition of continuous aqueous phase there is
understood that the composition has a conductivity, measured at
25.degree. C., greater than or equal to 23 S/cm (microSiemens/cm),
the conductivity being measured, for example, by means of an MPC227
conductimeter of Mettler Toledo and an Inlab730 conductivity
measuring cell. The measuring cell is immersed in the composition,
in such a way as to eliminate the air bubbles that tend to form
between the 2 electrodes of the cell. The conductivity reading is
taken as soon as the value of the conductimeter has stabilized. A
mean is established over at least 3 successive measurements.
[1195] By composition of continuous oil phase there is understood
that the composition has a conductivity, measured at 25.degree. C.,
greater than or equal to 23 .mu.S/cm (microSiemens/cm), the
conductivity being measured, for example, by means of an MPC227
conductimeter of Mettler Toledo and an Inlab730 conductivity
measuring cell. The measuring cell is immersed in the composition,
in such a way as to eliminate the air bubbles that tend to form
between the 2 electrodes of the cell. The conductivity reading is
taken as soon as the value of the conductimeter has stabilized. A
mean is established over at least 3 successive measurements.
[1196] The compositions may contain 1 to 60% of fatty-phase
rheological agent. Preferably, the composition contains 2% to 50%
by weight, better 5% to 40% of fatty-phase rheological agent.
[1197] In the case that the composition comprises a fatty-phase
rheological agent, it contains a continuous oil phase.
Waxes
[1198] The composition according to the invention may comprise at
least one wax.
[1199] The compositions according to the invention may therefore
comprise at least one wax, and mixture 1) described
hereinabove.
[1200] By wax within the meaning of the present invention there is
understood a lipophilic compound, solid at room temperature
(25.degree. C.), with reversible change of state between solid and
liquid, having a melting point higher than or equal to 30.degree.
C. and possibly up to 120.degree. C.
[1201] The melting point of the wax may be measured by means of a
differential scanning calorimeter (D.S.C.), for example the
calorimeter sold under the trade name DSC 30 by the METTLER
Company.
[1202] The waxes may be hydrocarbon, fluoro and/or silicone and be
of vegetable, mineral, animal and/or synthetic origin. In
particular, the waxes have a melting temperature higher than
25.degree. C. and better higher than 45.degree. C.
[1203] The wax or the mixture of waxes is present in a content at
least equal to 7% by weight. Preferably, it is present in a content
ranging from 10 to 40% by weight relative to the total weight of
the composition, better from 15 to 35% and even better from 16 to
30% by weight.
[1204] In particular, there may be used hydrocarbon waxes such as
beeswax, lanolin wax, and Chinese insect waxes; rice wax, carnauba
wax, ouricurry wax, esparto grass wax, cork fiber wax, sugar cane
wax, Japan wax and sumac wax; montan wax, microcrystalline waxes,
paraffins; polyethylene waxes, waxes obtained by Fisher-Tropsch
synthesis and the waxy copolymers as well as the esters
thereof.
[1205] There may also be cited the waxes obtained by catalytic
hydrogenation of animal or vegetable oils having linear or branched
C8-C32 fatty chains.
[1206] Among those, there may be cited in particular hydrogenated
jojoba oil, hydrogenated sunflower seed oil, hydrogenated castor
oil, hydrogenated copra oil and hydrogenated lanolin oil,
di-(trimethylol-1,1,1-propane) tetrastearate sold under the trade
name "HEST 2T-4S" by the HETERENE Company,
di-(trimethylol-1,1,1-propane) tetrabehenate sold under the trade
name HEST 2T-4B by the HETERENE Company.
[1207] There may also be cited the fluoro waxes.
[1208] There may also be used the wax obtained by hydrogenation of
olive oil esterified with stearyl alcohol sold under the trade name
"PHYTOWAX Olive 18 L 57" or else the waxes obtained by
hydrogenation of castor oil esterified with cetyl alcohol sold
under the trade name "PHYTOWAX ricin 16L64 and 22L73" by the SOPHIM
Company. Such waxes are described in Application FR A 2792190.
[1209] According to a particular embodiment, the compositions
according to the invention may comprise at least one wax referred
to as tacky wax, or in other words possessing a tack greater than
or equal to 0.7 Ns and a hardness smaller than or equal to 3.5
MPa.
[1210] The use of a tacky wax especially may make it possible to
obtain a cosmetic composition that is applied easily on the
eyelashes, clings well to the eyelashes and leads to the formation
of a smooth, homogeneous and thickening makeup.
[1211] The tacky wax used may possess especially a tack ranging
from 0.7 Ns to 30 Ns, in particular greater than or equal to 1 Ns,
especially ranging from 1 Ns to 20 Ns, in particular greater than
or equal to 2 Ns, especially ranging from 2 Ns to 10 Ns and in
particular ranging from 2 Ns to
[1212] 5Ns.
[1213] The tack of the wax is determined by measuring the evolution
of force (compression force or stretching force) as a function of
time at 20.degree. C. by means of the texturometer sold under the
trade name "TA-TX2i.RTM." by the RHEO Company, equipped with an
acrylic polymer traveler in the form of a cone having an angle of
45.degree..
[1214] The measurement protocol is the following:
[1215] The wax is melted at a temperature equal to the melting
point of the wax+10.degree. C. The molten wax is cast in a
receptacle of 25 mm diameter and 20 mm depth. The wax is
recrystallized at room temperature (25.degree. C.) for 24 hours, in
such a way that the surface of the wax is plane and smooth, then
the wax is kept for at least 1 hour at 20.degree. C. before the
measurement of the tack is carried out.
[1216] The traveler of the texturometer is displaced at a speed of
0.5 mm/s, then penetrates into the wax as far as a penetration
depth of 2 mm. When the traveler has penetrated to a depth of 2 mm
into the wax, the traveler is maintained in fixed position for 1
second (corresponding to the relaxation time) then is withdrawn at
a speed of 0.5 mm/s.
[1217] During the relaxation time, the force (compression force)
decreases rapidly to zero, then during withdrawal of the traveler,
the force (stretching force) becomes negative then increases again
to the value 0. The tack corresponds to the integral of the curve
of force as a function of time for the part of the curve
corresponding to the negative values of force (stretching force).
The value of the tack is expressed in Ns.
[1218] The tacky wax that may be used generally has a hardness of
smaller than or equal to 3.5 MPa, in particular ranging from 0.01
MPa to 3.5 MPa, especially ranging from 0.05 MPa to 3 MPa, even
better ranging from 0.1 MPa to 2.5 MPa.
[1219] The hardness is measured according to the protocol described
in the foregoing.
[1220] As tacky wax there may be used a C20-C40 alkyl
(hydroxystearyloxy) stearate (the alkyl group comprising 20 to 40
carbon atoms) alone or in a mixture, in particular a C20-C40 alkyl
12-(12'-hydroxystearyloxy) stearate of formula (II):
##STR00117##
in which m is an integer ranging from 18 to 38, or a mixture of
compounds of formula (II).
[1221] Such a wax is sold in particular under the trade names
"Kester Wax K 82 P.RTM." and "Kester Wax K 80 P.RTM." by the KOSTER
KEUNEN Company.
[1222] The waxes cited above generally have a starting melting
point lower than 45.degree. C.
[1223] There may also be used the microcrystalline wax sold under
the reference SP18 by the STRAHL and PITSCH Company, which wax has
a hardness of approximately 0.46 MPa and a tack value of
approximately 1 Ns.
[1224] The wax or waxes may be present in the form of an aqueous
microdispersion of wax. By aqueous microdispersion of wax there is
understood an aqueous dispersion of wax particles in which the size
of the said wax particles is smaller than or equal to approximately
1 .mu.m.
[1225] The microdispersions of wax are stable dispersions of
colloidal particles of wax, and are described in particular in
"Microemulsions Theory and Practice", L. M. Prince Ed., Academic
Press (1977) pages 21-32.
[1226] In particular, these wax microdispersions may be obtained by
melting the wax in the presence of a surfactant and possibly a
portion of water, then progressively adding hot water with
agitation.
[1227] There is observed the intermediate formation of an emulsion
of water-in-oil type, followed by a phase inversion that finally
yields a microemulsion of the oil-in-water type. Upon cooling,
there is obtained a stable microdispersion of solid colloidal
particles of wax.
[1228] The wax microdispersions may also be obtained by agitation
of the mixture of wax, surfactant and water using agitation means
such as ultrasound, high-pressure homogenizer, turbines.
[1229] The particles of the wax microdispersion preferably have
mean dimensions smaller than 1 .mu.m (in particular ranging from
0.02 .mu.m to 0.99 .mu.m), preferably smaller than 0.5 .mu.m (in
particular ranging from 0.06 .mu.m to 0.5 .mu.m).
[1230] These particles are composed substantially of a wax or of a
mixture of waxes. Nevertheless, they may comprise a minority
proportion of fatty oil and/or paste additives, a surfactant and/or
a common fat-soluble additive/active substance.
Hydrophilic Gelling Agents:
[1231] The composition according to the invention may comprise at
least one hydrophilic gelling agent, also referred to as
hydrophilic thickening agent hereinafter.
[1232] These thickening agents may be used alone or in association.
These thickening agents may be chosen in particular from among the
gums and the cellulose polymers.
[1233] By hydrophilic thickening agent there is understood a
thickening agent that is soluble or dispersible in water.
[1234] As hydrophilic thickening agents there may be cited in
particular the water-soluble or water-dispersible thickening
polymers. These may be chosen in particular from among: [1235]
polyvinylpyrrolidone, [1236] polyvinyl alcohol, [1237] the modified
or non-modified carboxyvinyl polymers, such as the products sold
under the trade names Carbopol (CFTA name: carbomer) by the
Goodrich Company; [1238] the acrylic or methacrylic homopolymers or
copolymers or their salts and their esters, and in particular the
products sold under the trade names VERSICOL F.RTM. or VERSICOL
K.RTM. or Salcare SC95 by the ALLIED COLLOID Company, ULTRAHOLD
8.RTM. by the CIBA-GEIGY Company, the polyacrylates and
polymethacrylates such as the products sold under the trade names
of Lubragel and Norgel by the GUARDIAN Company or under the trade
name Hispagel by the HISPANO CHIMICA Company, the polyacrylic acids
of SYNTHALEN K type; [1239] the polyacrylamides; [1240] the
copolymers of acrylic acid and acrylamide sold in the form of their
sodium salt under the trade names RETEN.RTM. by the HERCULES
Company, the sodium polymethacrylate sold under the trade name
DARVAN No. 7.RTM. by the VANDERBILT Company, the sodium salts of
polyhydroxycarboxylic acids sold under the trade name HYDAGEN
F.RTM. by the HENKEL Company; [1241] the polymers and copolymers of
2-acrylamido-2-methylpropanesulfonic acid, possibly cross-linked
and/or neutralized, such as the
poly(2-acrylamido-2-methylpropanesulfonic acid) sold by the
CLARIANT Company under the trade name "Hostacerin AMPS" (CTFA name:
ammonium polyacryldimethyltauramide); [1242] the cross-linked
anionic copolymers of acrylamide and AMPS, having the form of a
water-in-oil emulsion, such as those sold under the name of SEPIGEL
305 (C.T.F.A. name: Polyacrylamide/C13-14 isoparaffin/Laureth-7)
and under the name of SIMULGEL 600 (C.T.F.A. name:
Acrylamide/Sodium acryloyldimethyl taurate
copolymer/Isohexadecane/Polysorbate 80) by the SEPPIC Company;
[1243] the polyacrylic acid/alkyl acrylate copolymers of PEMULEN
type; [1244] the polysaccharide biopolymers such as xanthan gum,
guar gum, gum arabic, carob gum, acacia gum, the scleroglucans, the
derivatives of chitin and chitosan, the carrageenans, the gellans,
the alginates, the celluloses such as microcrystalline cellulose,
carboxymethyl cellulose, hydroxymethyl cellulose, hydroxyethyl
cellulose and hydroxypropyl cellulose; [1245] the hydrophilic
pyrogenic silicas obtained by hydrolysis at high temperature of a
volatile silicon compound in an oxyhydrogen flame, producing a
finely divided silica. The hydrophilic silicas have a large number
of silanol groups at their surface. Such hydrophilic silicas are
sold, for example, under the trade names "AEROSIL 130.RTM.",
"AEROSIL 200.RTM.", "AEROSIL 255.RTM.", "AEROSIL 300.RTM.",
"AEROSIL 380.RTM." by the Degussa Company, "CAB-O-SIL HS-5.RTM.",
"CAB-O-SIL EH-5.RTM.", "CAB-O-SIL LM-130.RTM.", "CAB-O-SIL
MS-55.RTM.", "CAB-O-SIL M-5.RTM." by the Cabot Company. They
preferably have a particle size that may be nanometric to
micrometric, for example ranging approximately from 5 to 200 nm;
[1246] the hydrophilic clays; [1247] the associative polymers such
as PEG-150/STEARYL ALCOHOL/SMDI COPOLYMER sold under the name
Aculyn 46 by Rohm & Haas, or STEARETH-100/PEG-136/HDI COPOLYMER
sold under the name Rheolate FX 1100 by Elementis); [1248] and
mixtures thereof.
[1249] The hydrophilic thickening agent may be chosen from among
the associative polymers. By "associative polymer" within the
meaning of the present invention there is understood any
amphiphilic polymer containing in its structure at least one fatty
chain and at least one hydrophilic portion. The associative
polymers according to the present invention may be anionic,
cationic, non-ionic or amphoteric.
[1250] Among the associative anionic polymers there may be cited
those containing at least one hydrophilic moiety and at least one
fatty-chain allyl ether moiety, more particularly from among those
whose hydrophilic moiety is composed of an ethylenically
unsaturated anionic monomer, more particularly of a vinyl
carboxylic acid and very particularly of an acrylic acid, a
methacrylic acid or mixtures thereof, and whose fatty-chain allyl
ether moiety corresponds to the monomer of the following formula
(I):
CH.sub.2.dbd.C(R)CH.sub.2OB.sub.nR (I)
in which R' denotes H or CH.sub.3, B denotes the ethyleneoxy
radical, n is zero or denotes an integer ranging from 1 to 100, R
denotes a hydrocarbon radical chosen from among the alkyl,
arylalkyl, aryl, alkylaryl, cycloalkyl radicals comprising 8 to 30
carbon atoms, preferably 10 to 24, and still more particularly 12
to 18 carbon atoms.
[1251] Anionic amphiphilic polymers of this type are described and
prepared according to an emulsion polymerization method in EP
Patent 0216479.
[1252] As associative anionic polymers there may also be cited the
anionic polymers containing at least one hydrophilic moiety of
olefinically unsaturated carboxylic acid type, and at least one
hydrophobic moiety exclusively of the type (C.sub.10-C.sub.30)
alkyl ester of unsaturated carboxylic acid. By way of example there
may be cited the anionic polymers described and prepared according
to U.S. Pat. Nos. 3,915,921 and 4,509,949.
[1253] As cationic associative polymers there may be cited the
quaternized cellulose derivatives and the polyacrylates with amino
side groups.
[1254] The non-ionic associative polymers may be chosen from among:
[1255] the celluloses modified by groups containing at least one
fatty chain, such as, for example, the hydroxyethyl celluloses
modified by groups containing at least one fatty chain, such as
alkyl groups, especially with C.sub.8-C.sub.22, arylalkyl,
alkylaryl groups, such as NATROSOL PLUS GRADE 330 CS(C.sub.16
alkyl) sold by the AQUALON Company, [1256] the celluloses modified
by polyalkylene glycol alkylphenol ether groups, [1257] the guars
such as hydroxypropyl guar, modified by groups containing at least
one fatty chain, such as an alkyl chain [1258] the copolymers of
vinylpyrrolidone and fatty-chain hydrophobic monomers; [1259] the
copolymers of C.sub.1-C.sub.6 alkyl methacrylates or acrylates and
amphiphilic monomers containing at least one fatty chain, [1260]
the copolymers of hydrophilic methacrylates or acrylates and
hydrophobic monomers containing at least one fatty chain, such as,
for example, the polyethylene glycol methacrylate/lauryl
methacrylate copolymer, [1261] the associative polyurethanes,
[1262] mixtures thereof.
[1263] Preferably, the associative polymer is chosen from among the
associative polyurethanes. The associative polyurethanes are
non-ionic sequenced copolymers containing, in the chain, both
hydrophilic sequences, most often of polyoxyethylene nature, and
hydrophobic sequences, which may be aliphatic chains alone and/or
cycloaliphatic and/or aromatic chains.
[1264] In particular, these polymers contain at least two
lipophilic hydrocarbon chains having C.sub.6 to C.sub.30 carbon
atoms, separated by a hydrophilic sequence, wherein the hydrocarbon
chains may be pendant chains or chains at the end of the
hydrophilic sequence. In particular, it is possible to provide one
or more pendant chains. In addition, the polymer may contain a
hydrocarbon chain at one end or at both ends of a hydrophilic
sequence. The associative polyurethanes may be sequenced in
triblock or multiblock form. The hydrophobic sequences may
therefore be at each end of the chain (for example: triblock
copolymer with hydrophilic central sequence) or distributed both at
the ends and in the chain (multisequenced copolymer, for example).
These polymers may also be grafts or star polymers. Preferably, the
associative polyurethanes are triblock copolymers whose hydrophilic
sequence is a polyoxyethylene chain containing 50 to 1,000
oxyethylene groups. In general, the associative polyurethanes
contain a urethane bond between the hydrophilic sequences, thus
explaining the origin of the name.
[1265] By way of example of associative polymers that can be used
in the invention there may be cited the polymer
C.sub.16--OC.sub.120--C.sub.16 of the SERVO DELDEN Company (under
the name SER AD FX1100, a molecule with urethane function and
weight-average molecular weight of 1300), OE being one oxyethylene
moiety. As an associative polymer there may also be used Rheolate
205 with urea function sold by the RHEOX Company or else Rheolate
208 or 204 or even Rheolate FX 1100 by Elementis. These associative
polyurethanes are sold in pure form. The product DW 1206B of ROHM
& HAAS with C.sub.20 alkyl chain and urethane bond, sold as 20%
dry material in water, may also be used.
[1266] There may also be used solutions or dispersions of these
polymers, especially in water or in aqueous alcohol media. By way
of examples of such polymers there may be cited SER AD FX1010, SER
AD FX1035 and SER AD 1070 of the SERVO DELDEN Company, Rheolate
255, Rheolate 278 and Rheolate 244 sold by the RHEOX Company. There
may also be used the product Aculyn 46, DW 1206F and DW 1206J, as
well as Acrysol RM 184 or Acrysol 44 of the ROHM & HAAS
Company, or else Borchigel LW 44 of the BORCHERS Company.
Fillers:
[1267] The composition according to the invention may comprise at
least one filler.
[1268] The filler or fillers may be present in a content ranging
from 0.01% to 50% by weight relative to the total weight of the
composition, preferably ranging from 0.01 to 30% by weight.
[1269] By fillers there must be understood particles of any shape,
colorless or white, mineral or synthetic, insoluble in the medium
of the composition regardless of the temperature at which the
composition is manufactured. These fillers are used in particular
to modify the rheology or the texture of the composition.
[1270] The fillers may be mineral or organic of any platelet,
spherical or oblong shape, regardless of the crystallographic form
(for example layered, cubic, hexagonal, orthorhombic, etc.). There
may be cited talc, mica, silica, kaolin, polyamide powders
(Nylon.RTM.) (Orgasol.RTM. of Atochem), the powders of polymethyl
methacrylate, the powders of acrylic polymers, poly-.beta.-alanine
and polyethylene, the powders of tetrafluoroethylene polymers
(Teflon.RTM.), lauroyl lysine powders, starch powders, the powders
of cellulose, boron nitride, the hollow microspheres of organic
polymers, especially the polymeric hollow microspheres of
polyvinylidine chloride/acrylonitrile, such as Expancel.RTM. (Nobel
Industrie), of acrylic acid copolymers (Polytrap of the Dow Corning
Company) and the microbeads of silicone resin (Tospearls.RTM. of
Toshiba, for example), the particles of elastomeric
polyorganosiloxanes, precipitated calcium carbonate, magnesium
carbonate and bicarbonate, hydroxyapatite, the microspheres of
hollow silica (Silica Beads.RTM. of Maprecos), the microcapsules of
glass or ceramic, clay, quartz, the powder of natural diamond, the
metal soaps derived from organic carboxylic acids having 8 to 22
carbon atoms, preferably 12 to 18 carbon atoms, for example zinc,
magnesium or lithium stearate, zinc laurate, magnesium
myristate.
[1271] As mineral fillers there may be cited in particular talc,
mica, silica, kaolin, boron nitride, precipitated calcium
carbonate, magnesium carbonate and bicarbonate, hydroxyapatite, the
microspheres of hollow silica (Silica Beads.RTM. of Maprecos), the
microcapsules of glass or ceramic, clay, quartz, the powder of
natural diamond or mixtures thereof.
[1272] As silica powder there may be cited: [1273] the microspheres
of porous silica sold under the trade name SILICA BEADS SB-700 by
the MYOSHI Company; "SUNSPHERE.RTM. H51", "SUNSPHERE.RTM. H33" by
the ASAHI GLASS Company; [1274] the microspheres of amorphous
silica coated with polydimethylsiloxane sold under the trade name
"SA SUNSPHERE.RTM. H 33", "SA SUNSPHERE.RTM. H53" by the ASAHI
GLASS Company.
[1275] Preferably, the mineral filler is silica, talc or a mixture
thereof.
[1276] Among the spherical fillers there are preferred the silicas,
such as the hollow silica microspheres, in particular the
SB700.RTM. of Miyoshi Kasei.
[1277] According to a preferred embodiment. the composition
according to the invention additionally comprises at least one
other filler. The said at least one other filler may be mineral or
organic. It may therefore be a mixture of mineral and organic
fillers.
[1278] According to one alternative, the composition according to
the invention may contain a mineral filler and one other mineral
filler, the said mineral fillers being such as defined hereinabove,
and possibly at least one organic filler such as defined below.
[1279] According to another alternative, the composition according
to the invention may contain one mineral filler and one organic
filler.
[1280] As organic fillers there may be cited in particular the
polyamide powders (Nylon.RTM. or Orgasol.RTM. of Arkema), the
powders of acrylic polymers, especially the powders of polymethyl
methacrylate, polymethyl methacrylate/ethylene glycol
dimethacrylate, allyl polymethacrylate/ethylene glycol
dimethacrylate, ethylene glycol dimethacrylate/lauryl methacrylate
copolymer, the powders of cellulose, poly-.beta.-alanine and
polyethylene, the powders of tetrafluoroethylene polymers
(Teflon.RTM.), lauroyl lysine, starch, the polymeric hollow
microspheres such as those of polyvinylidine
chloride/acrylonitrile, such as Expancel.RTM. (Nobel Industrie), of
acrylic acid copolymers (Polytrap of the Dow Corning Company) and
the microbeads of silicone resin (Tospearls.RTM. of Toshiba, for
example), the particles of elastomeric polyorganosiloxanes,
especially 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 with ethylenic
unsaturation (especially two vinyl groups) in the presence of a
platinum catalyst, or also the metal soaps derived from organic
carboxylic acids having 8 to 22 carbon atoms, preferably 12 to 18
carbon atoms, for example zinc, magnesium or lithium stearate, zinc
laurate, magnesium myristate.
Ionic Surfactants
[1281] The composition according to the invention may comprise at
least one ionic surfactant.
[1282] The compositions according to the invention may therefore
comprise at least one ionic surfactant and mixture 1) described
hereinabove.
[1283] The surfactant may be lipophilic and/or hydrophilic, used
alone or in combination. The surfactant may be chosen from among
the anionic, cationic, amphoteric surfactants.
[1284] The surfactant may be present in the composition according
to the invention and in a content ranging from 0.1% to 10% by
weight relative to the total weight of the composition, and
preferably ranging from 0.5% to 8% by weight, and preferentially
ranging from 0.5% to 7% by weight.
[1285] When the ionic surfactant is an anionic surfactant, it is
chosen from among: [1286] the carboxylates, such as sodium
2-(2-hydroxyalkyloxy)acetate; [1287] the taurates and N-acyl
N-methyltaurates; [1288] the alkylsulfoacetates; [1289] the
polypeptides; [1290] the anionic derivatives of alkyl polyglycoside
(acyl-D-galactoside uronate); [1291] the salts of C16-C30 fatty
acids, especially those derived from amines, such as
triethanolamine stearate and/or 2-amino-2-methylpropane-1,3-diol
stearate; [1292] the salts of polyoxyethylenated fatty acids,
especially those derived from amines or the alkaline salts, and
mixtures thereof; [1293] the phosphoric esters and their salts such
as "DEA oleth-10 phosphate" (Crodafos N 10N of the CRODA Company)
or monopotassium monocetyl phosphate (Amphisol K of Givaudan);
[1294] the sulfosuccinates such as "Disodium PEG-5 citrate lauryl
sulfosuccinate" and "Disodium ricinoleamido MEA sulfosuccinate";
[1295] the alkyl sulfates; [1296] the isethionates and N-acryl
isethionates; [1297] the acyl glutamates such as "Disodium
hydrogenated tallow glutamate" (AMISOFT HS-21 R.RTM. sold by the
AJINOMOTO Company) and sodium stearyl glutamate (AMISOFT HS-11
PF.RTM. sold by the AJINOMOTO Company) and mixtures thereof; [1298]
the soy derivatives such as potassium soyate; [1299] the citrates,
such as glyceryl stearate citrate (Axol C 62 Pellets of Degussa);
[1300] the proline derivatives, such as sodium palmitoyl proline
(Sepicalm VG of Seppic), or the mixture of sodium palmitoyl
sarcosinate, magnesium palmitoyl glutamate, palmitic acid and
palmitoyl proline (Sepifeel One of Seppic); [1301] the lactylates,
such as sodium stearoyl lactylate (Akoline SL of Karlshamns AB);
[1302] the sarcosinates, such as sodium palmitoyl sarcosinate
(Nikkol sarcosinate PN) or the 75/25 mixture of stearoyl sarcosine
and myristoyl sarcosine (Crodasin SM of Croda); [1303] the
sulfonates, such as Sodium C14-17 alkyl sec sulfonate (Hostapur SAS
60 of Clariant); [1304] the glycinates, such as sodium cocoyl
glycinate (Amilite GCS-12 of Ajinomoto).
[1305] The compositions according to the invention may also contain
one or more amphoteric surfactants such as the N-acyl amino acids,
such as the N-alkyl aminoacetates and disodium cocoamphodiacetate
and the amine oxides such as stearamine oxide, the betaines, the
N-alkylamido betaines and their derivatives, the sultaines, the
alkyl polyaminocarboxylates, the alkylamphoacetates, or even the
silicone surfactants such as the dimethicone copolyol phosphates
such as that sold under the trade name PECOSIL PS 100.RTM. by the
PHOENIX CHEMICAL Company and mixtures thereof.
[1306] Preferably, the compositions according to the invention also
comprise an elastomer of amphiphilic silicone containing
polyalkylene, in particular polyoxyethylene and/or polyoxypropylene
hydrophilic groups, sequences or grafts, or polyglycerol
hydrophilic groups, sequences or grafts, which are capable in
addition of possessing alkyl side groups, in particular lauryl side
groups, especially an elastomer of polyglycerol silicone. By way of
example, there is used an elastomeric cross-linked
organopolysiloxane that may be obtained by cross-linking addition
reaction of diorganopolysiloxane containing at least one hydrogen
bonded to silicon and polyglycerol compounds having ethylenically
unsaturated groups, especially in the presence of platinum
catalyst.
[1307] As polyglycerol silicone elastomers there may be used those
sold under the trade names "KSG-710," "KSG-810," "KSG-820,"
"KSG-830," "KSG-840" by the Shin-Etsu Company.
Fibers
[1308] The composition may comprise fibers.
[1309] By "fiber" there is to be understood an object of length L
and of 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
inscribed. In particular, the L/D ratio (or form factor) is chosen
in the interval ranging from 3.5 to 2,500, preferably from 5 to
500, and better from 5 to 150.
[1310] The fibers that can be used in the composition of the
invention may be fibers of synthetic or natural, mineral or organic
origin. They may be short or long, individual or organized, for
example, in braids, hollow or solid. They may have any shape and in
particular be of circular or polygonal (square, hexagonal or
octagonal) cross section depending on the specific application
envisioned. In particular, their ends are blunted or polished to
avoid causing injury.
[1311] 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 from 0.3 mm to
3 mm. Their cross section may be contained in a circle of diameter
ranging from 2 nm to 500 .mu.l, preferably ranging from 100 nm to
100 .mu.m and better from 1 .mu.m to 50 .mu.m. The weight or titer
of the fibers is often expressed in denier or decitex and
represents the weight in grams for 9 km of filament. Preferably,
the fibers according to the invention have a titer chosen in the
interval ranging from 0.01 to 10 denier, preferably from 0.1 to 2
denier and better from 0.3 to 0.7 denier.
[1312] Such fibers are described in particular in Applications FR A
2844710, EP A 1201221, the contents of which are incorporated by
reference.
[1313] The fibers may be present in the composition in a content
ranging from 0.1% to 30% by weight relative 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.
Other Ingredients and/or Additives
[1314] The ingredients described below may be used alone or in
association with the resins of the invention or as additives to
supplement other aforementioned ingredients in association with the
said resins according to the invention.
Silicone Elastomers
[1315] The compositions according to the invention may additionally
comprise an amphiphilic silicone elastomer, preferably chosen from
among the polyoxyalkylene and polyglycerol silicone elastomers.
[1316] As polyoxyalkylene silicone elastomers there may be cited
those described in U.S. Pat. Nos. 5,236,986, 5,412,004, 5,837,793,
5,811,487.
[1317] As polyoxyalkylene silicone elastomers there may be used:
[1318] those of INCI name PEG-10 Dimethicone/Vinyl dimethicone
crosspolymer: such as those sold under the trade names "KSG-21",
"KSG-20" by Shin-Etsu; [1319] those of INCI name Lauryl PEG-15
Dimethicone/Vinyldimethicone
[1320] Crosspolymer: such as those sold under the trade names
"KSG-30" and "KSG-31", "KSG-32" (in isododecane), "KSG-33" (in
trioctanoin), "KSG-210", "KSG-310" (in a mineral oil), "KSG-320"
(in isododecane), "KSG-330", "KSG-340" by the Shin-Etsu
Company.
[1321] As elastomers of polyglycerol silicones there may be used:
[1322] those of INCI name Dimethicone (and)
Dimethicone/Polyglycerin-3 crosspolymer: such as those sold under
the trade names "KSG-710" by Shin-Etsu; [1323] those of INCI name
Lauryl Dimethicone/Polyglycerin-3 crosspolymer: such as those sold
under the trade names "KSG-840" (in squalene) by the Shin-Etsu
Company.
[1324] These particular elastomers, when they are in association
with the resins according to the invention, may make it possible to
improve the non-transfer and comfort (flexibility) properties of
compositions containing them.
Oils
[1325] The composition according to the invention may comprise at
least one oil.
[1326] The oil may be chosen from among the hydrocarbon oils, the
silicone oils, the fluoro oils.
[1327] The oil may be chosen from among the volatile oils, the
non-volatile oils, and mixtures thereof.
[1328] By hydrocarbon oil there is understood an oil formed
substantially, even constituted of carbon and hydrogen atoms, and
possibly of oxygen, nitrogen atoms, and not containing silicon or
fluorine atoms; it may contain ester, ether, amine, amide
groups.
[1329] By silicone oil there is understood an oil containing at
least one silicon atom, and especially containing Si--O groups.
[1330] By fluoro oil there is understood an oil containing at least
one fluorine atom.
[1331] The composition according to the invention may comprise at
least one volatile oil.
[1332] By "volatile oil" there is understood an oil (or non-aqueous
medium) capable of evaporating on contact with the skin in less
than one hour, at room temperature and atmospheric pressure. The
volatile oil is a volatile cosmetic oil, liquid at room
temperature, having especially a non-zero vapor pressure at room
temperature and atmospheric pressure, in particular having a vapor
pressure ranging from 0.13 Pa to 40,000 Pa (10.sup.-3 to 300 mm
Hg), in particular ranging from 1.3 Pa to 13,000 Pa (0.01 to 100 mm
Hg), and preferentially ranging from 1.3 Pa to 1,300 Pa (0.01 to 10
mm Hg).
[1333] In addition, the volatile oil generally has a boiling point,
measured at atmospheric pressure, ranging from 150.degree. C. to
260.degree. C., and preferably ranging from 170.degree. C. to
250.degree. C.
[1334] The composition according to the invention may comprise a
volatile hydrocarbon oil, in particular chosen from among the
hydrocarbon oils having a flash point ranging from 40.degree. C. to
102.degree. C., preferably ranging from 40.degree. C. to 55.degree.
C., and preferentially ranging from 40.degree. C. to 50.degree.
C.
[1335] As volatile hydrocarbon oil there may be cited the volatile
hydrocarbon oils having 8 to 16 carbon atoms and mixtures thereof,
and in particular the C.sub.8-C.sub.16 branched alkanes such as the
C8-C16 iso-alkanes (also referred to as isoparaffins), isododecane,
isodecane, isohexadecane and, for example the oils sold under the
commercial names of Isopars or Permethyls, the C8-C16 branched
esters such as isohexyl neopentanoate, and mixtures thereof.
Preferably, the volatile hydrocarbon oil is chosen from among the
volatile hydrocarbon oils having 8 to 16 carbon atoms and mixtures
thereof, in particular from among isododecane, isodecane,
isohexadecane, and in particular is isododecane.
[1336] For good properties of color staying power while preserving
a matt and comfortable deposit for coloring applications there will
be preferred volatile hydrocarbon solvents with 8 to 16 carbon
atoms, in particular from 9 to 13 carbon atoms. As C8 to C16
volatile hydrocarbon solvent there may be cited in particular the
linear or branched, in particular branched alkanes, such as the
C8-C16 iso-alkanes (also referred to as isoparaffins), isododecane,
isodecane, isohexadecane, and, for example, the oils sold under the
commercial names of Isopars or Permethyls, and mixtures thereof.
Preferably, the volatile hydrocarbon solvent having 8 to 16 carbon
atoms is chosen from among isododecane, isodecane, isohexadecane,
and mixtures thereof. According to a particular embodiment, the
volatile solvent is isododecane.
[1337] According to another particular embodiment the volatile
hydrocarbon solvent is a volatile linear alkane having a flash
point in the interval ranging from 70.degree. C. to 120.degree. C.,
and more particularly from 80.degree. C. to 100.degree. C., and
especially being around 89.degree. C.
[1338] A volatile linear alkane suitable for the invention is
liquid at room temperature (approximately 25.degree. C.).
[1339] According to one embodiment, an alkane suitable for the
invention may be a volatile linear alkane comprising 8 to 16 carbon
atoms in particular 10 to 15 carbon atoms, and more particularly 11
to 13 carbon atoms.
[1340] A volatile linear alkane suitable for the invention may
advantageously be of vegetable origin.
[1341] Such an alkane may be obtained directly or in several steps
from a vegetable raw material such as an oil, a butter, a wax,
etc.
[1342] By way of example of alkane suitable for the invention,
there may be mentioned the alkanes described in Patent Application
WO 2007/068371 of the Cognis Company.
[1343] These alkanes are obtained from fatty alcohols, themselves
obtained from copra or palm oil.
[1344] By way of example of linear alkane suitable for the
invention there may be cited n-nonane (C9), n-decane (C10),
n-undecane (C11), n-dodecane (C12), n-tridecane (C13),
n-tetradecane (C14), n-pentadecane (C15), n-hexadecane (C16) and
n-heptadecane (C17), and mixtures thereof, and in particular the
mixture of n-undecane (C11) and n-tridecane (C13) sold under the
reference CETIOL UT by the Cognis Company.
[1345] According to a particular embodiment, a volatile linear
alkane suitable for the invention may be chosen from among
n-nonane, n-undecane, n-dodecane, n-tridecane, n-heptadecane, and
mixtures thereof.
[1346] More particularly, a volatile linear alkane suitable for the
invention may be employed in the form of an n-undecane/n-tridecane
mixture.
[1347] Preferably, in such a mixture, the n-undecane:n-tridecane
weight ratio may be 50:50 to 90:10, preferably varying from 60:40:
to 80:20, preferably varying from 65:35 to 75:25.
[1348] In particular, a composition according to the invention may
comprise an n-undecane:n-tridecane mixture in a weight ratio of
70:30. Such a mixture is sold under the trade name CETIOL UT by the
COGNIS Company.
[1349] For skin makeup products, especially foundations and
lipsticks, there will advantageously be used volatile linear
hydrocarbon oils having 8 to 16 carbon atoms.
[1350] As volatile silicone oil there may be cited the linear or
cyclic silicones having 2 to 7 silicon atoms, these silicones
possibly containing alkyl or alkoxy groups having 1 to 10 carbon
atoms. As volatile silicone oil that can be used in the invention
there may be cited in particular octamethylcyclotetrasiloxane,
decamethylcyclopentasiloxane, dodecamethylcyclohexasiloxane,
heptamethylhexyltrisiloxane, heptamethyloctyltrisiloxane,
octamethyltrisiloxane, decamethyltetrasiloxane and mixtures
thereof.
[1351] The volatile oil may be present in the composition according
to the invention in a content ranging from 0.1% to 90% by weight
relative to the total weight of the composition, preferably ranging
from 1% to 70% by weight, and preferentially ranging from 5% to 50%
by weight.
[1352] The composition according to the invention may comprise at
least one non-volatile oil.
[1353] By "non-volatile oil", there is understood an oil that
remains on the horny tissues at room temperature and atmospheric
pressure for at least several hours, and having in particular a
vapor pressure lower than 10.sup.-3 mm Hg (0.13 Pa). A non-volatile
oil may also be defined as having an evaporation rate such that,
under the conditions defined in the foregoing, the quantity
evaporated at the end of 30 minutes is smaller than 0.07
mg/cm.sup.2.
[1354] As non-volatile hydrocarbon oil there may be used paraffin
oil (or vaseline), squalane, hydrogenated polyisobutylene (Parleam
oil), perhydrosqualene, mink, turtle, soy oil, sweet almond oil,
calophyllum, palm, grapeseed, sesame, corn, arara, colza, sunflower
seed, cotton, apricot, castor, avocado, jojoba, olive or cereal
germ oil; esters of lanolic acid, oleic acid, lauric acid, stearic
acid; the fatty esters, especially with C12-C36, such as isopropyl
myristate, isopropyl palmitate, butyl stearate, hexyl laurate,
diisopropyl adipate, isononyl isononanoate, 2-ethylhexyl palmitate,
2-hexyldecyl laurate, 2-octyldecyl palmitate, 2-octyldodecyl
myristate or lactate, di(2-ethylhexyl) succinate, diisostearyl
malate, glycerine or diglycerine triisostearate; behenic acid,
oleic acid, linoleic acid, linolenic acid or isostearic acid; the
higher fatty alcohols, especially with C16-C22, such as cetanol,
oleic alcohol, linoleic or linolenic alcohol, isostearic alcohol or
octyldodecanol; and mixtures thereof.
[1355] In particular, to obtain a makeup for achieving matt colors,
while preserving comfortable use, both during application and after
makeup, there will be used non-volatile C6-C22 hydrocarbon oils,
which may be chosen from among: [1356] the carbonates of the
following formula (1): R1-O--C(.dbd.O)--O--R'1, where R1 and R'1,
identical or different, represent a saturated or unsaturated
(preferably saturated), linear or branched, C4 to C12, and
preferentially C5 to C10 alkyl chain, possibly having at least one
saturated or unsaturated (preferably saturated) ring; [1357] which
oils of formula (I) may be dicaprylyl carbonate, sold under the
trade name Cetiol CC.RTM. by the COGNIS Company, di(2-ethylhexyl)
carbonate, sold under the trade name TEGOSOFT DEC.RTM. by the
Goldschmidt Company, di-isobutyryl carbonate; di-neopentyl
carbonate; dipentyl carbonate, di-neoheptyl carbonate; di-heptyl
carbonate; di-isononyl carbonate; or di-nonyl carbonate; [1358] the
monoesters of formula (II): R2-O--C(.dbd.O)--R'2, where R2 and R'2,
identical or different, represent a saturated or unsaturated
(preferably saturated), linear or branched, C4 to C12, and
preferentially C5 to C10 alkyl chain, possibly having at least one
saturated or unsaturated, preferably saturated ring; [1359] which
oils of formula (II) may be 2-ethylhexyl isobutyrate, 2-ethylhexyl
butyrate, caprylyl butyrate, isononyl isobutyrate, 2-ethylhexyl
hexanoate, isononyl hexanoate, neopentyl hexanoate, caprylyl
heptanoate, octyl octanoate, sold under the trade name DRAGOXAT
EH.RTM. by the SYMRISE Company, isononyl isononanoate, [1360] the
di-esters of the following formula (III):
R3-O--C(.dbd.O)--R'3-C(.dbd.O)--O--R''3, where R3 and R''3,
identical or different, represent a saturated or unsaturated
(preferably saturated), linear or branched C4 to C12 and
preferentially C5 to C10 alkyl chain, possibly having at least one
saturated or unsaturated, preferably saturated ring, and R'3
represents a saturated or unsaturated C1 to C4, preferably C2 to C4
alkylene chain, such as, for example, an alkylene chain derived
from succinate (in this case R'3 is a saturated C2 alkylene chain),
maleate (in this case R'3 is an unsaturated C2 alkylene chain),
glutarate (in this case R'3 is a saturated C3 alkylene chain), or
adipate (in this case R'3 is a saturated C4 alkylene chain); in
particular, R3 and R''3 are chosen from among isobutyl, pentyl,
neopentyl, hexyl, heptyl, neoheptyl, 2-ethylhexyl, octyl, nonyl,
isononyl; there may be cited preferentially dicaprylyl maleate,
especially sold by the ALZO Company; di(2-ethylhexyl) succinate;
[1361] the ethers of the following formula (IV): R4-O--R4', where
R4 and R'4, identical or different, represent a saturated or
unsaturated (preferably saturated), linear or branched C4 to C12
and preferentially C5 to C10 alkyl chain, possibly having at least
one saturated or unsaturated, preferably saturated ring; in
particular, R4 and R'4 are chosen from among isobutyl, pentyl,
neopentyl, hexyl, heptyl, neoheptyl, 2-ethylhexyl, octyl, nonyl,
isononyl; among the compounds of formula (IV) there may be cited
preferentially dicaprylyl ether, sold under the name of Cetiol
OE.RTM. by the COGNIS Company; [1362] the alkyl tri-esters of
formula (V): R5-O--C(O):CH2-CH[--O--C(O)--R'5]-CH2-O--C(O)--R''5,
where R5, R'5 and R''5, identical or different, represent a
saturated or unsaturated (preferably saturated), linear or branched
C4-C10, preferably C5-C8 alkyl chain, in particular, R5, R'5 and
R''5 are identical; preferably, R5, R'5 and R''5 (in particular
identical) are alkyl radicals of the following fatty acids:
caprylic, 2-ethylhexylic, neopentanoic, or neoheptanoic acid; as
compound of formula (V) there may be cited preferentially caprylic
capric triglyceride, sold in particular under the name MYRITOL
318.RTM. by the COGNIS Company; [1363] and mixtures thereof.
[1364] The C6-C22 non-volatile hydrocarbon oil advantageously used
in the said makeup and/or care compositions intended to impart matt
quality to the color is dicaprylyl carbonate, in particular sold
under the name of CETIOL CC by the COGNIS Company.
[1365] Advantageously, when the composition is intended for makeup
and/or care of the lips and comprises a non-volatile oil, this oil
is chosen from among the phenyl silicone oils. Such an oil is also
referred to as phenyl silicone.
[1366] By phenyl silicone there is understood an organopolysiloxane
substituted by at least one phenyl group.
[1367] The phenyl silicone is preferably non-volatile. By
"non-volatile" there is understood an oil whose vapor pressure at
room temperature and atmospheric pressure is non-zero and lower
than 0.13 Pa.
[1368] Preferably, the weight-average molecular weight of the
phenyl silicone oil is between 500 and 10,000 g/mol.
[1369] The silicone oil may be chosen from among the phenyl
trimethicones, the phenyl dimethicones, the phenyl trimethylsiloxy
diphenylsiloxanes, the diphenyl dimethicones, the diphenyl
methyldiphenyl trisiloxanes, the 2-phenylethyl
trimethylsiloxysilicates.
[1370] The silicone oil may be represented by the formula:
##STR00118##
in which the groups R, independently of one another, represent a
methyl or a phenyl. In this formula, the silicone oil preferably
comprises at least three phenyl groups, for example at least four,
at least five or at least six.
[1371] According to another embodiment, the silicone oil is
represented by the formula
##STR00119##
in which the groups R, independently of one another, represent a
methyl or a phenyl, In this formula, the said organopolysiloxane
preferably comprises at least three phenyl groups, for example at
least four or at least five.
[1372] Mixtures of the phenyl organopolysiloxanes described in the
foregoing may be used.
[1373] As examples there may be cited mixtures of triphenyl,
tetraphenyl or pentaphenyl organopolysiloxanes.
[1374] According to another embodiment, the silicone oil is
represented by the formula
##STR00120##
in which Me represents methyl, Ph represents phenyl. Such a phenyl
silicone is manufactured in particular by Dow Corning under the
reference Dow Corning 555 Cosmetic Fluid (INCI name: trimethyl
pentaphenyl trisiloxane). The reference Dow Corning 554 Cosmetic
Fluid may also be used.
[1375] According to another embodiment, the silicone oil is
represented by the formula
##STR00121##
in which Me represents methyl, y is between 1 and 1,000, and X
represents --CH2-CH(CH3)(Ph).
[1376] According to another embodiment, the silicone oil is
represented by the formula
##STR00122##
in which --OR' represents --O--SiMe3, y is between 1 and 1,000 and
z is between 1 and 1,000.
[1377] The phenyl silicone oil may be chosen from among the phenyl
silicones of the following formula (VI):
##STR00123##
in which [1378] R1 to R10, independently of one another, are
saturated or unsaturated, linear, cyclic or branched C1-C30
hydrocarbon radicals, [1379] m, n, p and q are, independently of
one another, integral numbers between 0 and 900, with the proviso
that the sum of `m+n+q` is different from 0.
[1380] Preferably, the sum of `m+n+q` is between 1 and 100.
Preferably, the sum of `m+n+p+q` is between 1 and 900, still better
between 1 and 800. Preferably, q is equal to 0.
[1381] The phenyl silicone oil may be chosen from among the phenyl
silicones of the following formula (VII):
##STR00124##
in which [1382] R1 to R6, independently of one another, are
saturated or unsaturated, linear, cyclic or branched C1-C30
hydrocarbon radicals, [1383] m, n and p are, independently of one
another, integral numbers between 0 and 100, with the proviso that
the sum of `n+m` is between 1 and 100.
[1384] Preferably, R1 to R6, independently of one another,
represent a saturated, linear or branched C1-C30 hydrocarbon
radical, especially C1-C12, and in particular a methyl, ethyl,
propyl or butyl radical.
[1385] In particular, R1 to R6 may be identical, and in addition
may be a methyl radical.
[1386] Preferably, formula (VII) may be such that m=1, 2 or 3,
and/or n=0 and/or p=0 or 1.
[1387] There may be used a phenyl silicone oil of formula (VI)
having a viscosity at 25.degree. C. between 5 and 1,500 mm.sup.2/s
(or 5 to 1500 cSt), preferably having a viscosity between 5 and
1,000 mm.sup.2/s (or 5 to 1,000 cSt).
[1388] As phenyl silicone oil of formula (VII) there may be used in
particular the phenyltrimethicones such as DC556 of Dow Corning
(22.5 cSt), Silbione oil 70663V30 of Rhone Poulenc (28 cSt), or the
diphenyldimethicones such as the Belsil oils, especially Belsil
PDM1000 (1,000 cSt), Belsil PDM 200 (200 cSt) and Belsil PDM 20 (20
cSt) of Wacker. The values in parentheses represent the viscosities
at 25.degree. C.
[1389] The non-volatile silicone oil may be chosen from among the
silicones of formula:
##STR00125##
in which R.sub.1, R.sub.2, R.sub.5 and R.sub.6 are, together or
separately, an alkyl radical having 1 to 6 carbon atoms, R.sub.3
and R.sub.4 are, together or separately, an alkyl radical having 1
to 6 carbon atoms or an aryl radical,
[1390] X is an alkyl radical having 1 to 6 carbon atoms, a hydroxyl
radical or a vinyl radical,
[1391] n and p are chosen so as to confer on the oil a
weight-average molecular weight smaller than 200,000 g/mol,
preferably smaller that 150,000 g/mol and more preferably smaller
than 100,000 g/mol.
[1392] The non-volatile oil may be present in a content ranging
from 0.1% to 70% by weight relative to the total weight of the
non-volatile liquid fatty phase, preferably ranging from 0.5% to
60% by weight, and preferentially ranging from 1% to 50% by
weight.
[1393] For skin makeup products, especially foundations and
lipsticks, there will be used advantageously volatile or
non-volatile linear silicone oils. The association of resins
according to the invention and of a linear silicone oil may make it
possible in particular to improve the non-transfer property.
[1394] For skin makeup products, especially lipsticks, there will
be advantageously used phenyl silicone oils. The association of
resins according to the invention and of a phenyl silicone oil may
make it possible in particular to improve the gloss and comfort and
to reduce the tacky sensation.
Non-Ionic Surfactants
[1395] The composition according to the invention may comprise at
least one non-ionic surfactant.
[1396] In particular, there may be used an emulsifier possessing,
at 25.degree. C., an HLB balance (hydrophilic-lipophilic balance)
within the meaning of GRIFFIN that is specific to the composition
being sought.
[1397] The HLB value according to GRIFFIN is defined in J. Soc.
Cosm. Chem. 1954 (volume 5), pages 249-256.
[1398] The document "Encyclopedia of Chemical Technology,
KIRK-OTHMER, volume 22, p. 333-432, 3.sup.rd edition, 1979, WILEY,
may be consulted for the definition of properties and functions
(emulsifying) of surfactants, in particular pp. 347-377 of this
reference, for non-ionic surfactants.
[1399] The non-ionic surfactants used preferentially in the
composition according to the invention are chosen from among:
[1400] a) the non-ionic surfactants of HLB higher than or equal to
8 to 25.degree. C., used alone or in mixtures; there may be cited
in particular: [1401] the esters and ethers of oses such as the
mixture of cetylstearyl glucoside and of cetyl and stearyl alcohols
such as Montanov 68 of Seppic; [1402] the methylene and/or
oxypropylene ethers (which may contain 1 to 150 oxyethylene and/or
oxypropylene groups) of glycerol; [1403] the oxyethylene and/or
oxypropylene ethers (which may contain 1 to 150 oxyethylene and/or
oxypropylene groups) of fatty alcohols (especially of C8-C24 and
preferably C12-C18 alcohol) such as the oxyethylene ether of
cetearylic alcohol with 30 oxyethylene groups (CTFA name
"Ceteareth-30"), the oxyethylene ether of stearyl alcohol with 20
oxyethylene groups (CTFA name "Steareth-20"), and the oxyethylene
ether of the mixture of C12-C15 fatty alcohols containing 7
oxyethylene groups (CTFA name "C12-15 Pareth-7") sold under the
trade name NEODOL 25-7.RTM. by SHELL CHEMICALS, [1404] the esters
of fatty acid (especially C8-C24, and preferably C16-C22 acid) and
of polyethylene glycol (which may contain 1 to 150 ethylene glycol
moieties), such as PEG-50 stearate and PEG-40 monostearate sold
under the name MYRJ 52P.RTM. by the ICI UNIQUEMA Company, [1405]
the esters of fatty acid (especially C8-C24, and preferably C16-C22
acid) and of oxyethylene and/or oxypropylene glycerol ethers (which
may contain 1 to 150 oxyethylene and/or oxypropylene groups), such
as PEG-200 glyceryl monostearate sold under the trade name Simulsol
220 .TM..RTM. by the SEPPIC Company; polyethoxyl glyceryl stearate
with 30 ethylene oxide groups such as the product TAGAT S.RTM. sold
by the GOLDSCHMIDT Company, polyethoxyl glyceryl oleate with 30
ethylene oxide groups such as the product TAGAT O.RTM. sold by the
GOLDSCHMIDT Company, polyethoxyl glyceryl cocoate with 30 ethylene
oxide groups such as the product VARIONIC LI 13.RTM. sold by the
SHEREX Company, polyethoxyl glyceryl isostearate with 30 ethylene
oxide groups such as the product TAGAT L.RTM. sold by the
GOLDSCHMIDT Company and polyethoxyl glyceryl laurate with 30
ethylene oxide groups such as the product TAGAT I.RTM. of the
GOLDSCHMIDT Company, [1406] the esters of fatty acid (especially
C8-C24, and preferably C16-C22 acid) and of oxyethylene and/or
oxypropylene sorbitol ethers (which may contain 1 to 150
oxyethylene and/or oxypropylene groups), such as polysorbate 20
sold under the trade name Tween 20.RTM. by the CRODA Company,
polysorbate 60 sold under the trade name Tween 60.RTM. by the CRODA
Company, [1407] dimethicone copolyol, such as that sold under the
trade name Q2-5220.RTM. by the DOW CORNING Company, [1408]
dimethicone copolyol benzoate (FINSOLV SLB 101.RTM. and 201.RTM. of
the FINTEX Company), [1409] the copolymers of propylene oxide and
ethylene oxide, also referred to as OE/OP polycondensates, [1410]
and mixtures thereof.
[1411] The OE/OP polycondensates are more particularly copolymers
consisting of polyethylene glycol and polypropylene glycol blocks,
such as, for example, the polyethylene glycol/polypropylene
glycol/polyethylene glycol triblock polycondensates. These triblock
polycondensates have, for example, the following chemical
structure:
H--(O--CH.sub.2--CH.sub.2).sub.a--(O--CH(CH.sub.3)--CH.sub.2).sub.b--(O--
-CH.sub.2--CH.sub.2).sub.a--OH,
in which formula a ranges from 2 to 120, and b ranges from 1 to
100.
[1412] The OE/OP polycondensate preferably has a weight-average
molecular weight ranging from 1,000 to 15,000, and better ranging
from 2,000 to 13,000. Advantageously, the said OE/OP polycondensate
has a cloud point, at 10 g/L in distilled water, higher than or
equal to 20.degree. C., preferably higher than or equal to
60.degree. C. The cloud point is measured according to the ISO 1065
standard. As OE/OP polycondensate that can be used according to the
invention there may be cited the polyethylene glycol/polypropylene
glycol/polyethylene glycol triblock polycondensates sold under the
trade names SYNPERONIC.RTM. such as SYNPERONIC PE/L44.RTM. and
SYNPERONIC PE/F127.RTM. by the ICI Company.
[1413] b) the non-ionic surfactants of HLB lower than 8 to
25.degree. C., possibly associated with one or more non-ionic
surfactants of HLB higher than 8 to 25.degree. C., such as those
cited above, such as: [1414] the esters and ethers of oses such as
sucrose stearate, sucrose cocoate, sorbitan stearate and mixtures
thereof such as Arlatone 2121.RTM. sold by the ICI Company; [1415]
the oxyethylene and/or oxypropylene ethers (which may contain 1 to
150 oxyethylene and/or oxypropylene groups) of fatty alcohols
(especially of C8-C24 and preferably C12-C18 alcohol) such as the
oxyethylene ether of stearyl alcohol with 2 oxyethylene groups
(CTFA name "Steareth-2"); [1416] the esters of fatty acid
(especially C8-C24, and preferably C16-C22 acid) and of polyol,
especially of glycerol or sorbitol, such as glyceryl stearate,
glyceryl stearate such as the product sold under the trade name
TEGIN M.RTM. by the GOLDSCHMIDT Company, glyceryl laurate such as
the product sold under the trade name IMWITOR312.RTM. by the HULS
Company, polyglyceryl-2 stearate, sorbitan tristearate, glyceryl
ricinoleate; [1417] the lecithins, such as the soy lecithins (such
as Emulmetik 100 J of Cargill, or Biophilic H of Lucas Meyer);
[1418] the cyclomethicone/dimethicone copolyol mixture sold under
the trade name Q2-3225C.RTM. by the DOW CORNING Company.
[1419] The non-ionic surfactant may also be chosen from among a
C8-C22 alkyl dimethicone polyol, or in other words an oxypropylene
and/or oxyethylene polymethyl (C8-C22)alkyl dimethyl methyl
siloxane.
[1420] The C8-C22 dimethicone copolyol is advantageously a compound
of the following formula (I):
##STR00126##
in which [1421] PE represents (--C2H4O)x-(C3H6O)y-R, where R is
chosen from among a hydrogen atom and an alkyl radical with 1 to 4
carbon atoms, where x ranges from 1 to 100 and y ranges from 0 to
80, x and y not being simultaneously 0 [1422] m ranges from 1 to 40
[1423] n ranges from 10 to 200 [1424] o ranges from 1 to 100 [1425]
p ranges from 7 to 21 [1426] q ranges from 0 to 4 and
preferably:
R=H
[1427] m=1 to 10 n=10 to 100 o=1 to 30 p=15 q=3
[1428] As C8-C22 alkyl dimethicone copolyol there may be cited
cetyl dimethicone copolyol such as the product sold under the trade
name Abil EM-90 by the Goldschmidt Company.
[1429] According to a particular embodiment intended for
formulation of stable emulsions, having low viscosity permitting
easy application, while conferring on the makeup product staying
power of the makeup over time once it has been applied, there will
be used advantageously at least one non-ionic silicone surfactant,
possibly associated with at least one hydrocarbon surfactant and
possibly also at least one wax:
[1430] As non-ionic silicone surfactant there may be cited, for
example:
a) the polydialkyl silicones with hydrophilic polyoxyalkylene
(polyoxyethylene (or POE) and/or polyoxypropylene (or PPO)) side
and/or terminal groups. In addition, these silicone surfactants
preferably contain linear or branched C1 to C20 alkyl side groups,
preferably linear alkyl groups, such as lauryl or cetyl. These
surfactants may also carry organosiloxane side groups.
[1431] In particular, in this category there may be cited: [1432]
the polydimethyl siloxanes with POE side groups, such as, in
particular, KF-6011, KF-6012, KF-6013, KF-6015, KF-6016 and KF-6017
of the Shin Etsu Company; [1433] the polydimethyl siloxanes with
POE side groups and alkyl side groups, such as, in particular,
Cetyl PEG-PPG 10/1 dimethicone, sold under the trade name ABIL EM90
by the Evonik GOLDSCHMIDT Company; [1434] the branched
polydimethylsiloxanes with POE side groups, such as, in particular,
PEG-9 polydimethyl siloxyethyl dimethicone, sold under the trade
name KF-6028 by the Shin Etsu Company; [1435] the branched
polydimethyl siloxanes with alkyl side groups, such as, in
particular, lauryl PEG-9 polydimethylsiloxyethyl dimethicone, sold
under the trade name KF-6038 by the Shin Etsu Company; b) the
polydialkyl silicones with polyglycerol or glycerol side groups.
These silicone surfactants additionally contain preferably linear
or branched C1 to C20 alkyl side groups, and preferably also linear
alkyl groups, such as lauryl or cetyl. Similarly, these silicone
and glycerol surfactants may also carry organosiloxane side
groups.
[1436] In particular, in this category there may be cited: [1437]
the polydimethyl siloxanes with polyglycerol side groups, such as
polyglyceryl-3 disiloxane dimethicone, sold under the trade name
KF-6100 by the Shin Etsu Company; [1438] the branched polydimethyl
siloxanes that also have polyglycerol side groups, such as
polyglyceryl-3 polydimethylsiloxyethyl dimethicone, sold under the
trade name KF-6104 by the Shin Etsu Company; [1439] the branched
polydimethyl siloxanes, with polyglycerol side groups and with
alkyl side groups, such as lauryl polyglyceryl-3 polydimethyl
siloxyethyl dimethicone, sold under the trade name KF-6105 by the
Shin Etsu Company;
[1440] Among the non-ionic silicone surfactants there is preferred
Cetyl PEG/PPG-10/1 dimethicone, sold under the trade name ABIL EM90
by the EVONIK GOLDSCHMIDT Company.
[1441] The non-ionic silicone surfactant is advantageously in
association with at least one non-ionic organic surfactant.
[1442] As non-ionic organic surfactant there may be cited the
polyol esters of fatty acids, such as the mono-, di-, tri- or
sesqui-oleates or stearates of sorbitol or glycerol, the laurates
of glycerol or polyethylene glycol; the polyethylene glycol esters
of fatty acids (polyethylene glycol monostearate or monolaurate);
the polyoxyethylene sorbitol esters of fatty acids (stearate,
oleate); the polyoxyethylene alkyl (lauryl, cetyl, stearyl,
octyl)ethers.
[1443] Among the non-ionic organic surfactants there are preferred:
[1444] the polyglycerol esters of fatty acids containing at least
three glycerol ether moieties, such as polyglyceryl 3; [1445] the
polyoxyalkylene (polyoxyethylene and/or polyoxypropylene) esters of
fatty acids, preferably containing at least 3 oxyethylene groups;
[1446] the ethers of fatty alcohols and polyglycerols with at least
3 glyceryl ether moieties; [1447] the ethers of fatty alcohols and
polyoxyalkylene (POE and/or POE/PPO) with at least 3 POE
groups.
[1448] Among the non-ionic organic surfactants there is preferred
the polyglyceryl-4 isostearate sold under the trade name ISOLAN
GI348.RTM. by the EVONIK GOLDSCHMIDT Company.
[1449] In association with the non-ionic silicone surfactant and
the non-ionic organic surfactant there may be advantageously used
at least one wax.
[1450] Among the waxes there is preferred the mixture of acetyl
ethylene glycol stearate/glyceryl tri-stearate, in particular sold
under the trade name UNITWIX by the UNITED GUARDIAN Company.
Coloring Materials
[1451] The composition according to the invention may comprise at
least one coloring material.
[1452] The coloring material may be chosen from among the
pulverulent coloring materials (especially the pigments and the
nacres), the water-soluble or fat-soluble coloring materials.
[1453] By pigments there is to be understood particles of any
shape, white or colored, mineral or organic, insoluble in the
physiological medium, intended to color the composition.
[1454] By nacre there will be understood iridescent particles of
any iridescent form, especially produced by certain mollusks in
their shell, or else synthesized.
[1455] The pigments may be white or colored, mineral and/or
organic. Among the mineral pigments there may be cited titanium
dioxide, possibly surface-treated, the oxides of zirconium or
cerium, as well as the oxides of zinc, of iron (black, yellow or
red) or of chromium, manganese violet, ultramarine, chromium
hydrate and ferric blue, the metal powders such as aluminum powder,
copper powder.
[1456] Among the organic pigments there may be cited carbon black,
the pigments of D & C type, and the lakes based on cochineal
carmine, barium, strontium, calcium, aluminum.
[1457] There may also be cited the effect pigments such as the
particles containing an organic or mineral, natural or synthetic
substrate, for example glass, the acrylic resins, polyester,
polyurethane, polyethylene terephthalate, the ceramics or the
aluminas, wherein the said substrate may or may not be covered with
metallic substances, such as aluminum, gold, silver, platinum,
copper, bronze, or metal oxides such as titanium dioxide, iron
oxide, chromium oxide and mixtures thereof.
[1458] The nacreous pigments may be chosen from among the white
nacreous pigments such as mica covered with titanium, or bismuth
oxychloride, the colored nacreous pigments such as titanium mica
covered with iron oxides, titanium mica covered with especially
ferric blue or with chromium oxide, titanium mica covered with an
organic pigment of the aforesaid type as well as nacreous pigments
based on bismuth oxychloride. There may also be used interference
pigments, especially with liquid crystals or multilayers.
[1459] The term alkyl mentioned in the compounds cited in the
foregoing denotes in particular an alkyl group having 1 to 30
carbon atoms, preferably having 5 to 16 carbon atoms.
Hydrophobic-treated pigments are described in particular in
Application EP A 1086683.
[1460] The pulverulent coloring materials such as described in the
foregoing may be completely or partly surface-treated with a
hydrophobic agent, in particular a compound of silicone nature, a
compound of fluoro nature, a compound of fluorosilicone nature, a
fatty acid or amino acid or one of the mixtures thereof.
[1461] By silicone compound there is understood a compound
comprising at least one silicon atom.
[1462] By fluoro compound there is understood a compound comprising
at least one fluorine atom.
[1463] By fluorosilicone compound there is understood a compound
comprising at least one fluorine atom and at least one silicon
atom.
[1464] By way of example, the hydrophobic treatment agent may be
chosen from among the silicones such as the methicones, the
dimethicones, the perfluoroalkylsilanes, the perfluoroalkyl
silazanes, triethoxy caprylylsilane, triethoxysilylethyl
polydimethylsiloxyethyl hexyl dimethicone; the fatty acids such as
stearic acid, the metal soaps such as aluminum dimyristate, the
aluminum salt of hydrogenated suet glutamate; the perfluoroalkyl
phosphates, the polyoxides of hexafluoropropylene, the
polyorganosiloxanes comprising perfluoroalkyl perfluoro polyether
groups, the silicone-grafted acrylic polymers (especially described
in Application JP A 05-339125, the contents of which are
incorporated by reference); the amino acids; the N-acyl amino acids
or their salts; lecithin, isopropyl trisostearyl titanate,
isostearyl sebacate, and mixtures thereof.
[1465] The surface-treated pulverulent coloring materials may be
prepared according to surface-treatment techniques of chemical,
electronic, mechano-chemical or mechanical nature that are well
known to those skilled in the art. Commercial products may also be
used.
[1466] The surface agent may be absorbed or adsorbed on the
pulverulent coloring materials by solvent evaporation, chemical
reaction and creation of a covalent bond.
[1467] According to one variant, the surface treatment consists in
coating the pulverulent coloring materials.
[1468] The coating may represent 1 to 300% by weight of the weight
of the untreated pulverulent coloring materials, for example 5 to
200%, in particular 10 to 100% by weight of the weight of the
untreated pulverulent coloring materials.
[1469] The coating may represent 0.1 to 10% by weight, and in
particular 1 to 5% by weight of the total weight of the coated
pulverulent coloring material.
[1470] The coating may be applied, for example, by adsorption of a
liquid surface agent on the surface of the pulverulent coloring
materials by simply mixing the pulverulent coloring materials and
the said surface agent under agitation, possibly in the hot, prior
to incorporating the particles in the other ingredients of the
makeup or care composition.
[1471] The coating may be applied, for example, by chemical
reaction of a surface agent with the surface of the pulverulent
coloring materials and creation of a covalent bond between the
surface agent and the pulverulent coloring materials. This method
is described in particular in U.S. Pat. No. 4,578,266.
[1472] The chemical surface treatment may consist in diluting the
surface agent in a volatile solvent, dispersing the pulverulent
coloring materials in this mixture, then slowly evaporating the
volatile solvent, so that the surface agent is deposited on the
surface of the pulverulent coloring materials.
Fluoro Surface Went
[1473] The solid particles may be completely or partly
surface-treated with a compound of fluoro nature.
[1474] The fluoro surface agents may be chosen from among the
perfluoroalkyl phosphates, the perfluoro polyethers,
polytetrafluopolyethylene (PTFE) and the perfluoroalkanes.
[1475] The perfluoro polyethers are described in particular in
Patent Application EP A 486135, and are sold under the trade names
FOMBLIN by the MONTEFLUOS Company.
[1476] Perfluoroalkyl phosphates are described in particular in
Application JP H05-86984. The perfluoroalkyl diethanolamine
phosphate sold by Asahi Glass under the reference AsahiGuard AG530
may be used.
[1477] The perfluoroalkanes may be linear or cyclic
perfluoroalkanes. Among the linear perfluoroalkanes there may be
cited the series of linear alkanes, such as perfluorooctane,
perfluorononane or perfluorodecane. Among the cyclic
perfluoroalkanes there may be cited the perfluorocycloalkanes, the
perfluoro(alkylcycloalkanes), the perfluoropolycycloalkanes, the
perfluoro aromatic hydrocarbons (the perfluoroarenes). Among the
perfluoroalkanes there may also be cited the perfluoro
organohydrocarbon compounds containing at least one hetero
atom.
[1478] Among the perfluorocycloalkanes and the
perfluoro(alkylcycloalcanes) there may be cited perfluorodecalin
sold under the trade name of "FLUTEC PP5 GMP" by the RHODIA
Company, perfluoro(methyldecalin), the perfluoro(C3-C5
alkyl-cyclohexanes) such as perfluoro(butylcyclohexane).
[1479] Among the perfluoropolycycloalkanes there may be cited the
derivatives of bicyclo [3.3.1] nonane such as
perfluorotrimethylbicyclo [3.3.1] nonane, the derivatives of
adamantane, such as perfluorodimethyladamantane, and the perfluoro
derivatives of hydrogenated phenanthrene, such as
tetracosafluoro-tetradecahydrophenanthrene.
[1480] Among the perfluorearenes there may be cited the perfluoro
derivatives of naphthalene such as perfluoronaphthalene and
perfluoromethyl-1-naphthalene.
[1481] By way of example of commercial references of pigments
treated with a fluoro compound there may be cited: [1482] Yellow
iron oxide/perfluoroalkyl phosphate, sold in particular under the
reference PF 5 Yellow 601 by the Daito Kasei Company, [1483] Red
iron oxide/perfluoroalkyl phosphate, sold in particular under the
reference PF 5 Red R 516L by the Daito Kasei Company, [1484] Black
iron oxide/perfluoroalkyl phosphate, sold in particular under the
reference PF 5 Black BL 100 by the Daito Kasei Company, [1485]
Titanium dioxide/perfluoroalkyl phosphate, sold in particular under
the reference PF 5 TiO2 CR 50 by the Daito Kasei Company, [1486]
Yellow iron oxide/perfluoropolymethyl isopropyl ether, sold in
particular under the reference iron oxide yellow BF-25-3 by the
Toshiki Company, [1487] DC Red 7/perfluoropolymethyl isopropyl
ether, sold in particular under the reference D&C Red 7 FHC by
Cardre Inc., [1488] DC Red 6/PTFE, sold in particular under the
reference T 9506 by the Warner-Jenkinson Company,
Fatty Acid or Amino Acid Treatment Agent
[1489] The hydrophobic treatment agent may be chosen from among the
fatty acids, such as stearic acid; the metal soaps, such as
aluminum dimyristate, the aluminum salt of hydrogenated suet
glutamate; the amino acids; the N-acyl amino acids or their salts;
lecithin, isopropyl trisostearyl titanate (or also referred to as
ITT), and mixtures thereof.
[1490] The N-acyl amino acids may comprise an acyl group having 8
to 22 carbon atoms, such as, for example, a 2-ethylhexanoyl,
caproyl, lauroyl, myristoyl, palmitoyl, stearoyl, cocoyl group. The
salts of these compounds may be the aluminum, magnesium, calcium,
zirconium, zinc, sodium, potassium salts. The amino acid may be,
for example, lysine, glutamic acid, alanine.
[1491] The fatty acids in the present invention are in particular
acids with hydrocarbon chains having 1 to 30 carbon atoms,
preferably having 5 to 18 carbon atoms. The hydrocarbon chain may
be saturated, monounsaturated or polyunsaturated.
[1492] By way of example of pigments coated with fatty acids there
may be cited those sold under the commercial reference
NAI-TAO-77891, NAI-C33-8073-10, NAI-C33-8075, NAI-C47-051-10,
NAI-C33-115, NAI-C33-134, NAI-C33-8001-10, NAI-C33-7001-10,
NAI-C33-9001-10 of the MIYOSHI KASEI Company.
[1493] The water-soluble coloring agents are, for example beet
juice, Methylene Blue.
[1494] The synthetic or natural fat-soluble coloring agents 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, the carotenes
(.beta.-carotene, lycopene), the xanthophylls (capsanthin,
capsorubin, lutein), palm oil, Sudan Brown, Quinoline Yellow,
annatto, curcumin.
[1495] The coloring materials, in particular the pigments treated
with a hydrophobic agent, may be present in the composition in a
content ranging from 0.1% to 50% by weight relative to the total
weight of the composition, preferably ranging from 0.5% to 30% by
weight and preferentially ranging from 1% to 20% by weight.
[1496] The composition according to the invention may also contain
ingredients commonly used in cosmetics, such as vitamins, oligo
elements, softening agents, sequestering agents, fragrances,
alkalinizing or acidifying agents, preservatives, sunscreens,
anti-oxidants, anti-hair loss agents, anti-hair loss agents,
propellants, or mixtures thereof.
[1497] Of course, the person skilled in the art will take care to
choose this or these possible supplementary compounds and/or the
quantity thereof so that the advantageous properties of the
corresponding composition according to the invention are not or
substantially not altered by the envisioned addition.
[1498] According to a preferred embodiment, the composition
according to the invention is a lipstick.
[1499] According to a preferred embodiment, the composition
according to the invention is in liquid form at 25.degree. C.
[1500] According to another embodiment, the composition is in solid
form at 25.degree. C. In the case of a lipstick, it may be shaped
as a stick or cast in a small tub, for example.
[1501] According to another aspect, the invention also relates to a
method for makeup or cosmetic care of horny tissues comprising a
step of application of a composition according to the invention on
the said tissues.
[1502] According to another aspect, the invention also relates to a
cosmetic set comprising: [1503] i) a container defining at least
one compartment, the said container being closed by a closure
element; and [1504] ii) a composition disposed in the interior of
the said compartment, the composition being in conformity with the
invention.
[1505] The container may be in any appropriate form. In particular,
it may be in the form of a bottle, tube, jar, case, box, sachet or
casing.
[1506] The closure element may be in the form of a removable
stopper, cover, lid, tear-off strip, or capsule, especially of the
type containing a body fixed to the container and a cap hinged on
the body. It may also be in the form of an element assuring
selective closure of the container, especially a pump, a valve, or
a flap.
[1507] The container may be associated with an applicator,
especially in the form of a brush containing an arrangement of
bristles held by a twisted wire. Such a twisted brush is described
in particular in U.S. Pat. No. 4,887,622. It may also be in the
form of a comb containing a plurality of application elements,
obtained in particular by molding. Such combs are described, for
example, in French Patent 2796529. The applicator may be in the
form of a makeup brush, such as described, for example, in French
Patent 2722380. The applicator may be in the form of a block of
foam or elastomer, of a felt, or of a spatula. The applicator may
be unattached (puff or sponge) or integral with a rod carried by
the closure element, such as described, for example, in U.S. Pat.
No. 5,492,426. The applicator may be integral with the container,
such as described, for example, in French Patent FR 2761959.
[1508] The product may be contained directly in the container, or
indirectly. By way of example, the product may be disposed on an
impregnated substrate, especially in the form of a wipe or pad, and
disposed (as single or multiple pieces) in a box or in a sachet.
Such a substrate incorporating the product is described, for
example, in Application WO 01/03538.
[1509] The closure element may be coupled with the container by a
threaded connection. Alternatively, the coupling between the
closure element and the container is established by other than a
threaded connection, especially via a bayonet mechanism, by snap
fastening, clamping, welding, adhesive bonding, or by magnetic
attraction. By "snap fastening" there is understood in particular
any system in which one portion, especially the closure element, is
elastically deformed involving passage over a strip or rib of
material, then the said portion returns elastically to the
non-restrained position after passing over the strip or rib.
[1510] The container may be made at least partly of thermoplastic
material. By way of examples of thermoplastic materials there may
be cited polypropylene or polyethylene. Alternatively, the
container is made of non-thermoplastic material, especially of
glass or metal (or alloy).
[1511] The container may have rigid walls or deformable walls,
especially in the form of a tube or tubular bottle.
[1512] The container may comprise means intended to bring about or
facilitate distribution of the composition. By way of example, the
container may have deformable walls, so as to cause discharge of
the composition in response to overpressure in the interior of the
container, which overpressure is caused by elastic (or non-elastic)
squeezing of the walls of the container. Alternatively, especially
when the product is in the form of a stick, it may be entrained by
a piston mechanism. Also in the case of a stick, especially of
makeup product (lipstick, foundation, etc.), the container may
comprise a mechanism, especially with a rack, or with a threaded
rod, or with a helical ramp, and capable of displacing a stick in
the direction of the said opening. Such a mechanism is described,
for example, in French Patent 2806273 or in French Patent 2775566.
Such a mechanism for a liquid product is described in French Patent
2727609.
[1513] The container may consist of a casing with a bottom defining
at least one housing containing the composition, and a cover,
especially hinged on the bottom, and capable of covering the said
bottom at least partly. Such a casing is described, for example, in
Application WO 03/018423 or in French Patent 2791042.
[1514] The container may be equipped with a wiper arranged in the
vicinity of the opening of the container. Such a wiper makes it
possible to wipe the applicator and possibly the rod with which it
may be integral. Such a wiper is described, for example, in French
Patent 2792618.
[1515] The composition may be at atmospheric pressure inside the
container (at room temperature) or may be pressurized, especially
by means of a propellant gas (aerosol). In the latter case, the
container is equipped with a valve (of the type of those used for
aerosols). [1516] Another object of the present invention is a
method for makeup of the lips, comprising application of a
composition according to the invention on the said lips.
Protocol for Measuring the Staving Power:
[1517] The staying power index of the deposit obtained with the
composition according to the invention is determined according to
the measurement protocol described below.
[1518] There is prepared a substrate (rectangle of 40 mm.times.70
mm) composed of an acrylic lining (hypoallergenic acrylic adhesive
on polyethylene film sold under the trade name BLENDERME ref
FH5000-55113 by the 3M Sante Company) adhesively bonded onto a
layer of adhesive polyethylene foam on the face opposite to that on
which there is fixed the adhesive plaster (layer of foam sold under
the trade name RE40X70EP3 by the JOINT TECHNIQUE LYONNAIS IND
Company).
[1519] The color L*0a*0b*0 of the substrate on the side of the
acrylic-lined face is measured by means of a MINOLTA CR 300
colorimeter.
[1520] The substrate prepared in this way is preheated on a hot
plate maintained at a temperature of 40.degree. C., so that the
surface of the substrate is maintained at a temperature of
33.degree. C..+-.1.degree. C. While the substrate is left on the
hot plate, the composition is applied over the entire non-adhesive
surface of the substrate (or in other words over the acrylic-lined
surface) by spreading by means of a brush to obtain a deposit of
the composition of approximately 15 .mu.m, then it is left to dry
for 10 minutes.
[1521] After drying, the color L*a*b of the film obtained in this
way is measured.
[1522] The color difference .DELTA.E1 between the color of the film
relative to the color of the uncoated substrate is then determined
by the following relationship.
.DELTA.E1= {square root over
((L*-L.sub.o*).sup.2+(a*-a.sub.o*).sup.2+(b*-b.sub.o*).sup.2)}{square
root over
((L*-L.sub.o*).sup.2+(a*-a.sub.o*).sup.2+(b*-b.sub.o*).sup.2)}{-
square root over
((L*-L.sub.o*).sup.2+(a*-a.sub.o*).sup.2+(b*-b.sub.o*).sup.2)}
[1523] The substrate is then bonded via its adhesive face (adhesive
face of the foam layer) onto an anvil with a diameter of 20 mm,
equipped with a screw thread. A specimen of the substrate/deposit
assembly is then cut out by means of a hollow punch with a diameter
of 18 mm. The anvil is then screwed onto a press (STATIF MANUEL
IMADA SV-2 of the SOMECO Company) equipped with a dynamometer
(IMADA DPS-20 of the SOMECO Company).
[1524] On a white photocopier paper sheet of weight 80 g/m.sup.2
there is drawn a strip of 33 mm width and 29.7 cm length, a first
line is traced at 2 cm from the edge of the sheet, then a second
line at 5 cm from the edge of the sheet, the first and second lines
thus defining a box on the strip; then a first mark and a second
mark are made in the strip at coordinates of 8 cm and 16 cm
respectively from the second line. 20 .mu.L water is place on the
first mark and 10 .mu.L refined sunflower seed oil (sold by the
LESIEUR Company) on the second mark.
[1525] The white paper is placed on the base of the press then the
specimen placed on the box of the strip of paper is pressed at a
pressure of approximately 300 g/cm2 exerted for 30 seconds. Then
the press is relaxed and the specimen is replaced just after the
second line (therefore at the side of the box), a pressure of
approximately 300 g/cm2 is applied once again and, as soon as
contact is established, the paper is displaced in a straight line
at a speed of 1 cm/s over the entire length of the strip, in such a
way that the specimen traverses the deposits of water and oil.
[1526] After withdrawal of the specimen, part of the deposit has
transferred onto the paper. The color L*', a*', b*' of the deposit
remaining on the specimen is then measured.
[1527] The color difference .DELTA.E2 between the color of the
deposit remaining of the specimen relative to the color of the
uncoated substrate is then determined by the following
relationship.
.DELTA.E2= {square root over
((L*'-L.sub.o*).sup.2+(a*'-a.sub.o*).sup.2+(b*'-b.sub.o*).sup.2)}{square
root over
((L*'-L.sub.o*).sup.2+(a*'-a.sub.o*).sup.2+(b*'-b.sub.o*).sup.2-
)}{square root over
((L*'-L.sub.o*).sup.2+(a*'-a.sub.o*).sup.2+(b*'-b.sub.o*).sup.2)}
[1528] The staying power index of the composition, expressed as a
percentage, is equal to the ratio:
100.times..DELTA.E2/.DELTA.E1
[1529] The measurement is carried out on 6 substrates in succession
and the value of the staying power corresponds to the mean of the 6
measurements obtained with the 6 substrates.
[1530] In the Application, the contents are expressed in weight
relative to the total weight of the composition, unless otherwise
explicitly indicated.
[1531] The purpose of the following examples is to illustrate the
compositions and methods according to this invention, but in no
case are they limitative of the scope of the invention. All the
parts and percentages in the examples are by weight, and all the
measurements were obtained at approximately 23.degree. C., unless
otherwise indicated.
EXAMPLE NO. 1
Obtaining the Mixture of MQ and Propyl T Resins According to the
Invention
Materials
[1532] MQ resin=an MQ resin of formula M.sub.0.43Q.sub.0.57 and of
M.sub.n=3,230 dissolved in xylene with 70.8% by weight of solids.
The MQ resin was manufactured according to the techniques described
by Daudt in U.S. Pat. No. 2,676,182.
[1533] T-Propyl resin=a propyl silsesquioxane resin at 74.8% by
weight in toluene. The propyl silsesquioxane resin was obtained by
hydrolysis of propyl trichlorosilane.
[1534] Different solutions of MQ resin and propyl T resin are mixed
in a three-necked flask equipped with an agitator. Aliquots of each
mixture are placed in an aluminum cup of 2 inches diameter and
heated under vacuum at a temperature of 110.degree. C. for one
hour, followed by 1 hour 25 minutes at 140.degree. C. Visual
qualitative observations are made of the clarity and hardness of
the mixtures obtained (see Table 1 below):
TABLE-US-00003 TABLE 1 % by Propyl T Dried weight of Example # MQ
(g) (g) Aliquot (g) aliquot (g) MQ resin Clarity Hardness 1-a 0.00
13.46 2.0475 1.5361 0.0 Clear Gummy appearance; soft solid 1-b 1.40
12.03 2.0643 1.5415 9.9 Clear Soft solid 1-c 2.88 16.74 2.0840
1.5517 14.0 Clear Harder than 1-b 1-d 4.19 9.39 2.0746 1.5414 29.7
Clear Harder than 1-c 1-e 5.72 8.14 2.1066 1.5606 39.9 Clear Harder
than 1-d 1-f 7.11 6.82 2.0257 1.4968 49.6 Clear Harder than 1-e
[1535] The results obtained show the unexpected miscibility of the
MQ and propyl T resins, based on the clarity of the mixture without
solvent and the increase of hardness accompanying the increase in
proportion of MQ resin.
[1536] According to an alternative denoted 1-g, there is used the
mixture of resins described in Example 22 of Application WO
2005/075567, in which the weight ratio between the MQ resin and the
propyl T resin is 85/15.
[1537] According to an alternative denoted 1-h, there is used the
mixture described in Example 13 of Patent Application WO
2007/145765, in which the weight ratio between the MQ resin and the
propyl T resin is 60/40.
EXAMPLE NO. 2
Liquid Lipstick
[1538] The following formulas of liquid lipstick were prepared.
TABLE-US-00004 Composition Composition Comparative 1 according to 2
according to composition the invention the invention 3 (% by
Compound Commercial name (% by weight) (% by weight) weight) Butyl
acrylate copolymer containing DOW CORNING FA 31.25 31.25 37.5
dendritic silicone side chains: 4002 ID SILICONE
[TRI(TRIMETHYLSILOXY) ACRYLATE OF DOW SILOXYETHYL CORNING
DIMETHYLSILOXY] SILYLPROPYL METHACRYLATE IN ISODODECANE 40/60
MQ-PROPYL T (60:40) SILICONE (DOW CORNING MQ- -- 4.20 -- RESIN
(according to Example 1-h 1603 S of DOW hereinabove) AT 60.0% IN
CORNING) ISODODECANE MQ-PROPYL T (85:15) SILICONE (DOW CORNING MQ-
4.20 -- -- RESIN (according to Example 1-g 1603 H of DOW
hereinabove) AT 60.0% IN CORNING) ISODODECANE ISODODECANE
ISODODECANE OF 2.05 2.05 -- INEOS SQUALANE PHYTOSQUALAN 12.02 12.02
12.02 of SOPHIM OCTYLDODECANOL EUTANOL G of 13.62 13.62 13.62
COGNIS POLYBUTENE INDOPOL H 100 of 10.65 10.65 10.65 INEOS
ISOPROPYLPARABEN (and) LIQUAPAR OIL of 0.65 0.65 0.65
ISOBUTYLPARABEN (and) ISP BUTYLPARABEN RED 7 UNIPURE RED LC 0.23
0.23 0.23 3079 OR of LCW (SENSIENT) IRON OXIDES SUNPURO BLACK 0.05
0.05 0.05 IRON OXIDE C33-7001 of SUN MICA (and) TITANIUM CLOISONNE
SPARKLE 1.00 1.00 1.00 DIOXIDE (and) GOLD 222 J of IRON OXIDES
ENGELHARD CALCIUM ALUMINUM METASHINE ME 2040 2.50 2.50 2.50
BOROSILICATE (and) SILVER PS of NIPPON SHEET GLASS
TRIMETHYLSILOXYPHENYL WACKER-BELSIL PDM 15.98 15.98 15.98
DIMETHICONE 1000 of WACKER SILICA DIMETHYL SILYLATE AEROSIL R 972
of 5.00 5.00 5.00 EVONIK DEGUSSA SILICA AEROSIL 200 of 0.50 0.50
0.50 EVONIK DEGUSSA FRAGRANCE GOURMANDISE P106 0.30 0.30 0.30 347
of ROBERTET TOTAL: 100 100 100
Mode of Operation:
[1539] a. The fillers and pigments that may possibly be present are
ground in a part of the oil phase. [1540] b. The rest of the
fat-soluble ingredients are then mixed at a temperature on the
order of 100.degree. C. The ground mixture is then added to the oil
phase. [1541] c. The mixture is subjected to RAYNERI agitation for
45 minutes and the siloxane resin is added at room temperature.
[1542] d. The formula is poured into sealed boiling vessels
containing isododecane.
[1543] Comparative composition 3 contains substantially the same
proportion of dry material of film-forming polymer as compositions
1 and 2 according to the invention (siloxane resin+vinyl polymer
with moiety derived from carbosiloxane dendrimer).
[1544] For composition 1 according to the invention containing a
vinyl polymer comprising at least one moiety derived from
carbosiloxane dendrimer and an MQ-T propyl siloxane resin, a value
of 27.28.+-.3.17 is measured for the holding power.
[1545] For composition 2 according to the invention containing a
vinyl polymer comprising at least one moiety derived from
carbosiloxane dendrimer and an MQ-T propyl siloxane resin, a value
of 24.75.+-.2.24 is measured for the holding power.
[1546] For comparative composition 3, which does not contain
siloxane resin, a value of 18.32.+-.0.56 is measured for the
holding, power.
[1547] Thus a better holding power is obtained with the
compositions according to the invention.
Example 3
Preparation of a Poly(Isobornyl Acrylate/Isobornyl
Methacrylate/Isobutyl Acrylate/Acrylic Acid) Polymer
[1548] 300 g isododecane is introduced into a 1-liter reactor, then
the temperature is raised so as to change from room temperature
(25.degree. C.) to 90.degree. C. in 1 hour.
[1549] There is then added, at 90.degree. C. and in 1 hour, 105 g
isobornyl methacrylate (manufactured by Arkema), 105 g isobornyl
acrylate (manufactured by Arkema) and 1.8 g
2,5-bis(2-ethylhexanoylperoxy)-2,5-dimethylhexane (Trigonox.RTM. D
141 of Akzo Nobel).
[1550] The mixture is maintained at 90.degree. C. for 1 hour 30
minutes.
[1551] To the preceding mixture there is then added, again at
90.degree. C. and in 30 minutes, 75 g isobutyl acrylate
(manufactured by Fluka), 15 g acrylic acid and 1.2 g
2,5-bis(2-ethylhexanoylperoxy)-2,5-dimethylhexane.
[1552] The mixture is maintained at 90.degree. C. for 3 hours, then
the whole is cooled.
[1553] There is obtained a solution of 50% of polymer active
material in isododecane.
[1554] There is obtained a polymer comprising a rigid first
sequence of poly(isobornyl acrylate/isobornyl methacrylate) having
a Tg of 110.degree. C., a flexible second sequence of poly(isobutyl
acrylate/acrylic acid) having a Tg of -9.degree. C. and an
intermediate sequence, which is a statistical polymer of isobornyl
acrylate/isobornyl methacrylate/isobutyl acrylate/acrylic acid.
EXAMPLE NO. 4
Liquid Lipsticks
[1555] The following compositions 3 and 4 are prepared:
TABLE-US-00005 Composition 3 Composition 4 according to the
according to the invention invention Percentages in % Percentages
in % Compounds by weight by weight 2-OCTYL DODECANOL 9.43 9.43
REFINED VEGETABLE PERHYDROSQUALENE 5.05 5.05 (PHYTOSQUALAN of
SOPHIM) ALUMINUM LAKE OF BRILLIANT YELLOW FCF 2.58 2.58 ON ALUMINA
(42/58) (CI: 15985:1 + 77002 ALUMINUM LAKE OF BRILLIANT BLUE FCF
0.16 0.16 ON ALUMINA (12/88) (CI: 42090:2 + 77002) CALCIUM SALT OF
LITHOL RED B 0.59 0.59 RUTILE TITANIUM OXIDE TREATED WITH 2.74 2.74
ALUMINA/SILICA/TRI-METHYLOLPROPANE (CI: 77891) BLACK IRON OXIDE
(CI: 77499) 0.32 0.32 MIXTURE OF (40/30/30) ISO-PROPYL, ISO-BUTYL,
0.65 0.65 N-BUTYL P-HYDROXYBENZOATES (LIQUAPAR OIL OF ISP) POLY
PHENYLTRIMETHYLSILOXY 25.03 25.03 DIMETHYLSILOXANE (VISCOSITY: 1000
CST- MW: 3000-G/MOL) (BELSIL PDM 1000 of WACKER) MICA-TITANIUM
DIOXIDE-BROWN IRON OXIDE 2 2 (77/21/4) (SIZE: 16-128 MICRONS)
FRAGRANCE 0.3 0.3 POLYBUTENE (MONOOLEFINS/ISOPARAFFINS( 10.65 10.65
(MW: 920) (INDOPOL H 100 of INEOS) POLY(ISOBORNYL METHACRYLATE-CO-
30 30 ISOBORNYL ACRYLATE-CO-ISOBUTYL ACRYLATE-CO-ACRYLIC ACID such
as prepared in Example 2 hereinabove (50% polymer in 50%
isododecane) MQ-PROPYL T (60:40) SILICONE RESIN (according 5.1 --
to Example 1-h hereinabove) AT 60.0% IN ISODODECANE (DOW CORNING
MQ-1603 S OF DOW CORNING) MQ-PROPYL T (85:15) SILICONE RESIN
(according -- 5.1 to Example 1-g hereinabove) AT 60.0% IN
ISODODECANE (DOW CORNING MQ-1603 H OF DOW CORNING) HYDROPHILIC
PYROGENIC SILICA 0.5 0.5 (AEROSIL 200 OF EVONIK DEGUSSA)
HYDROPHOBIC PYROGENIC SILICA, SURFACE- 5 5 TREATED BY
DI-METHYLSILANE (AEROSIL R 972 OF EVONIK DEGUSSA) Total: 100
100
Mode of Operation:
[1556] e. The fillers and pigments that may possibly be present are
ground in a part of the oil phase. [1557] b. The rest of the
fat-soluble ingredients is then mixed at a temperature on the order
of 100.degree. C. The ground mixture is then added to the oil
phase. [1558] c. The mixture is subjected to RAYNERI agitation for
45 minutes and the siloxane resin is added at room temperature.
[1559] d. The formula is poured into sealed boiling vessels
containing isododecane.
[1560] Composition 3 according to the invention contains 15%
polymer (weight as dry extract) prepared according to Example 2 and
3.5% (weight as dry extract) of siloxane resin prepared according
to Example 1-C), or in other words a total of 18.5% of film-forming
polymer.
[1561] Comparative composition 4 contains 18.5% polymer (weight as
dry extract) prepared according to Example 2.
[1562] Comparative composition 4 is very viscous and tacky and is
very thick during application. It is uncomfortable on the lips,
because the film formed is very thick and tacky.
[1563] Composition 3 according to the invention is much more
agreeable (gliding) during application, and it forms a very much
thinner and more comfortable deposit.
[1564] The foregoing example is reproduced by replacing the 60:40
weight/weight MQ:T resin in the composition by the MQ:T resin such
as prepared in Example 1-f (which corresponds to a (51:49) MQ:T
resin), also solubilized in 60% isododecane. A result similar to
that obtained with the (60:40) MQ:T resin is obtained.
* * * * *