U.S. patent application number 10/538782 was filed with the patent office on 2006-06-22 for non-transfer cosmetic composition comprising a dispersion of a grafted ethylene polymer.
Invention is credited to Xavier Blin, Veronique Ferrari, Bertrand Lion.
Application Number | 20060134034 10/538782 |
Document ID | / |
Family ID | 32600653 |
Filed Date | 2006-06-22 |
United States Patent
Application |
20060134034 |
Kind Code |
A1 |
Blin; Xavier ; et
al. |
June 22, 2006 |
Non-transfer cosmetic composition comprising a dispersion of a
grafted ethylene polymer
Abstract
The invention provides a cosmetic lipcare and/or lip makeup
composition comprising at least one cosmetically acceptable organic
liquid medium and a dispersion of a grafted ethylenic polymer, the
said polymer being such that, when dispersed in sufficient amount
in the composition, the composition is able to form a deposit
having a transfer of less than or equal to 35%.
Inventors: |
Blin; Xavier; (Paris,
FR) ; Ferrari; Veronique; (Maisons-Alfort, FR)
; Lion; Bertrand; (Paris, FR) |
Correspondence
Address: |
FINNEGAN, HENDERSON, FARABOW, GARRETT & DUNNER;LLP
901 NEW YORK AVENUE, NW
WASHINGTON
DC
20001-4413
US
|
Family ID: |
32600653 |
Appl. No.: |
10/538782 |
Filed: |
December 12, 2003 |
PCT Filed: |
December 12, 2003 |
PCT NO: |
PCT/FR03/03710 |
371 Date: |
January 23, 2006 |
Current U.S.
Class: |
424/64 ;
424/70.16 |
Current CPC
Class: |
A61K 8/585 20130101;
C08F 290/06 20130101; A61Q 1/02 20130101; A61K 8/893 20130101; A61Q
19/04 20130101; A61K 8/04 20130101; C08L 51/003 20130101; C08F
265/00 20130101; C08F 265/04 20130101; A61Q 1/10 20130101; A61Q
1/08 20130101; A61Q 19/00 20130101; A61Q 17/04 20130101; C08F
283/06 20130101; C08L 51/003 20130101; C08L 2666/02 20130101; C08L
2666/02 20130101; A61Q 1/06 20130101; C08F 290/068 20130101; A61K
8/91 20130101; C08F 290/04 20130101; C08L 51/08 20130101; C08L
51/08 20130101 |
Class at
Publication: |
424/064 ;
424/070.16 |
International
Class: |
A61K 8/81 20060101
A61K008/81 |
Foreign Application Data
Date |
Code |
Application Number |
Dec 12, 2002 |
FR |
0215738 |
Dec 12, 2002 |
FR |
0215737 |
Dec 12, 2002 |
FR |
0215739 |
Claims
1. Cosmetic lipcare and/or lip makeup composition comprising a
dispersion, in a liquid fatty phase, of particles of a grafted
ethylenic polymer, the said polymer being such that, when dispersed
in sufficient amount in the composition, the latter is able to form
a deposit having a transfer of less than or equal to 35%.
2. Composition according to claim 1, characterized in that it is
able to form a deposit having a transfer of less than or equal to
30%, preferably less than or equal to 25%, preferably less than or
equal to 20%, preferably less than or equal to 15%, preferably less
than or equal to 10%, preferably less than or equal to 5%.
3. Composition according to either of the preceding claims,
characterized in that the grafted ethylenic polymer comprises an
ethylenic skeleton which is insoluble in the said liquid fatty
phase and side chains which are attached covalently to the said
skeleton and are soluble in the said liquid fatty phase.
4. Composition according to one of the preceding claims,
characterized in that the ethylenic polymer is dispersed in the
absence of additional stabilizer at the surface of the
particles.
5. Composition according to one of the preceding claims,
characterized in that the ethylenic polymer is a grafted acrylic
polymer.
6. Composition according to claims 3 and 5, characterized in that
the grafted ethylenic polymer in dispersion is a grafted acrylic
polymer obtainable by free-radical polymerization in an organic
polymerization medium: of at least one acrylic monomer, and
optionally of at least one additional non-acrylic vinyl monomer, to
form the said insoluble skeleton; and of at least one macromonomer
containing a polymerizable end group to form the side chains, the
said macromonomer having a weight-average molecular mass of greater
than or equal to 200 and the amount of polymerized macromonomer
representing from 0.05% to 20% by weight of the polymer.
7. Composition according to claim 6, characterized in that the
acrylic monomer is selected, alone or in a mixture, from the
following monomers, and also the salts thereof: (i) the
(meth)acrylates of formula: ##STR5## in which: R.sub.1 denotes a
hydrogen atom or a methyl group; R.sub.2 represents a group chosen
from: a linear or branched alkyl group containing from 1 to 6
carbon atoms, the said group possibly comprising in its chain one
or more heteroatoms chosen from O, N and S; and/or possibly
comprising one or more substituents chosen from --OH, halogen atoms
(F, Cl, Br or I) and --NR'R'' with R' and R'', which may be
identical or different, chosen from linear or branched
C.sub.1-C.sub.4 alkyls; and/or possibly being substituted with at
least one polyoxyalkylene group, especially polyoxyethylene and/or
polyoxypropylene, the said polyoxyalkylene group consisting of the
repetition of 5 to 30 oxyalkylene units; a cyclic alkyl group
containing from 3 to 6 carbon atoms, the said group possibly
comprising in its chain one or more heteroatoms chosen from O, N
and S, and/or possibly comprising one or more substituents chosen
from OH and halogen atoms (F, Cl, Br or I); (ii) the
(meth)acrylamides of formula: ##STR6## in which: R.sub.3 denotes a
hydrogen atom or a methyl group; R.sub.4 and R.sub.5, which may be
identical or different, represent a hydrogen atom or a linear or
branched alkyl group containing from 1 to 6 carbon atoms, which may
comprise one or more substituents chosen from --OH, halogen atoms
(F, Cl, Br or I) and --NR'R'' with R' and R'', which may be
identical or different, chosen from linear or branched
C.sub.1-C.sub.4 alkyls; or R.sub.4 represents a hydrogen atom and
R.sub.5 represents a 1,1-dimethyl-3-oxobutyl group; (iii) the
(meth)acrylic monomers comprising at least one carboxylic acid,
phosphoric acid or sulphonic acid function, such as acrylic acid,
methacrylic acid or acrylamidopropanesulphonic acid.
8. Composition according to claim 7, characterized in that the
acrylic monomer is selected from methyl, ethyl, propyl, butyl and
isobutyl (meth)acrylates; methoxyethyl or ethoxyethyl
(meth)acrylates; trifluoroethyl methacrylate; dimethylaminoethyl
methacrylate, diethylaminoethyl methacrylate, 2-hydroxypropyl
(meth)acrylate, 2-hydroxyethyl (meth)acrylate;
dimethylaminopropylmethacrylamide; methacrylic acid; and the salts
thereof.
9. Composition according to claim 7, characterized in that the
acrylic monomer is selected from methyl acrylate, methoxyethyl
acrylate, methyl methacrylate, 2-hydroxyethyl methacrylate,
methacrylic acid and dimethylaminoethyl methacrylate, and mixtures
thereof.
10. Composition according to claim 7, characterized in that the
acrylic monomer is acrylic acid.
11. Composition according to any one of claims 7 to 10,
characterized in that the grafted polymer comprises (meth)acrylic
acid.
12. Composition according to any one of claims 7 to 11,
characterized in that the acrylic monomers comprise at least
(meth)acrylic acid and at least one monomer selected from the
(meth)acrylates and (meth)acrylamides described in sections (i) and
(ii) in claim 8.
13. Composition according to any one of claims 7 to 12,
characterized in that the acrylic monomers comprise at least
(meth)acrylic acid and at least one monomer selected from
C.sub.1-C.sub.3 alkyl (meth)acrylates.
14. Composition according to any one of the preceding claims,
characterized in that the (meth)acrylic acid is present in an
amount of at least 5% by weight, relative to the total weight of
the polymer, in particular ranging from 5% to 80% by weight,
preferably at least 10% by weight, in particular ranging from 10%
by weight to 70% by weight, preferentially at least 15% by weight,
in particular ranging from 15% to 60% by weight.
15. Composition according to claim 6 or one of its dependent
claims, characterized in that the grafted acrylic polymer does not
contain any additional non-acrylic vinyl monomer.
16. Composition according to claim 6, or one of its dependent
claims, characterized in that the grafted acrylic polymer is
obtainable by free-radical polymerization of one or more acrylic
monomers and one or more additional non-acrylic vinyl monomers, and
of the said macromonomer.
17. Composition according to claim 16, characterized in that the
additional non-acrylic vinyl monomers are selected from: vinyl
esters of formula: R.sub.6--COO--CH.dbd.CH.sub.2 in which R.sub.6
represents a linear or branched alkyl group containing from 1 to 6
carbon atoms, or a cyclic alkyl group containing from 3 to 6 carbon
atoms and/or an aromatic group, for example of benzene, anthracene
or naphthalene type; non-acrylic vinyl monomers comprising at least
one carboxylic acid, phosphoric acid or sulphonic acid function,
such as crotonic acid, maleic anhydride, itaconic acid, fumaric
acid, maleic acid, styrenesulphonic acid, vinylbenzoic acid or
vinylphosphoric acid, and the salts thereof; non-acrylic vinyl
monomers comprising at least one tertiary amine function, such as
2-vinylpyridine or 4-vinylpyridine; and mixtures thereof.
18. Composition according to claim 6 or one of its dependent
claims, characterized in that the acrylic monomer represents from
50% to 100% by weight, preferably from 60% to 100% by weight,
preferentially from 70% to 100% by weight of the mixture of acrylic
monomer and of optional non-acrylic vinyl monomer.
19. Composition according to claim 6 or one of its dependent
claims, characterized in that the macromonomer comprises at one of
the ends of the chain a polymerizable end group selected from a
vinyl group or a (meth)acrylate group, and preferably a
(meth)acrylate group.
20. Composition according to claim 6 or one of its dependent
claims, characterized in that the weight-average molecular mass of
the macromonomer is greater than or equal to 300, preferentially
greater than or equal to 500, and more preferentially greater than
600.
21. Composition according to the preceding claim, characterized in
that the macromonomer has a weight-average molecular mass (Mw)
ranging from 300 to 100 000, preferably ranging from 500 to 50 000,
preferentially ranging from 800 to 20 000, more preferentially
ranging from 800 to 10 000, and more preferentially still ranging
from 800 to 6000.
22. Composition according to claim 6 or one of its dependent
claims, characterized in that the polymerized macromonomer
represents from 0.1% to 15% by weight of the total weight of the
polymer, preferably from 0.2% to 10% by weight, and preferentially
from 0.3% to 8% by weight.
23. Composition according to one of the preceding claims,
characterized in that the liquid fatty phase comprises a liquid
organic compound selected from liquid organic compounds having a
total solubility parameter according to the Hansen solubility space
of less than or equal to 18 (MPa).sup.1/2, preferably less than or
equal to 17 (MPa).sup.1/2.
24. Composition according to one of claims 1 to 22, characterized
in that the liquid fatty phase comprises a liquid organic compound
selected from monoalcohols having a total solubility parameter
according to the Hansen solubility space of less than or equal to
20 (MPa).sup.1/2.
25. Composition according to any one of the preceding claims,
characterized in that it comprises a volatile oil.
26. Composition according to the preceding claim, characterized in
that it comprises a volatile oil selected from
octamethylcyclotetrasiloxane, decamethylcyclopentasiloxane,
dodecamethylcyclohexasiloxane, heptamethylhexyltrisiloxane,
heptamethyloctyltrisiloxane, octamethyltrisiloxane,
decamethyltetrasiloxane, isododecane, isodecane and isohexadecane
and mixtures thereof.
27. Composition according to claim 25 or 26, characterized in that
the volatile oil is present in an amount ranging from 1% to 70% by
weight, relative to the total weight of the composition, preferably
ranging from 5% to 50% by weight and preferentially ranging from
10% to 35% by weight.
28. Composition according to one of the preceding claims,
characterized in that the liquid fatty phase is a
non-silicone-based liquid fatty phase.
29. Composition according to the preceding claim, characterized in
that the non-silicone-based liquid fatty phase is composed of at
least 50% by weight of at least one non-silicone-based organic
liquid compound selected from: non-silicone-based organic liquid
compounds having a total solubility parameter according to the
Hansen solubility space of less than or equal to 18 (MPa).sup.1/2;
liquid monoalcohols having a total solubility parameter according
to the Hansen solubility space of less than or equal to 20
(MPa).sup.1/2; and mixtures thereof.
30. Composition according to either of claims 28 and 29,
characterized in that the non-silicone-based liquid fatty phase
contains less than 50% by weight of silicone-based liquid organic
compounds having a total solubility parameter according to the
Hansen solubility space of less than or equal to 18
(MPa).sup.1/2.
31. Composition according to one of claims 28 to 30, characterized
in that the non-silicone-based liquid fatty phase does not contain
silicone-based liquid organic compounds.
32. Composition according to one of claims 6 to 31, characterized
in that the macromonomer is a carbon-based macromonomer.
33. Composition according to the preceding claim, characterized in
that the carbon-based macromonomer is selected from: (i) linear or
branched C.sub.8-C.sub.22 alkyl acrylate or methacrylate
homopolymers and copolymers having a polymerizable end group
selected from vinyl or (meth)acrylate groups; (ii) polyolefins
having a polymerizable ethylenically unsaturated end group.
34. Composition according to claim 33, characterized in that the
carbon-based macromonomer is selected from: (i) poly(2-ethylhexyl
acrylate) macromonomers with a mono(meth)acrylate end group;
poly(dodecyl acrylate) macromonomers with a mono(meth)acrylate end
group; poly(dodecyl methacrylate) macromonomers; poly(stearyl
acrylate) macromonomers with a mono(meth)acrylate end group;
poly(stearyl methacrylate) macromonomers with a mono(meth)acrylate
end group; (ii) polyethylene macromonomers, polypropylene
macromonomers, macromonomers of polyethylene/polypropylene
copolymer, macromonomers of polyethylene/polybutylene copolymer,
polyisobutylene macromonomers, polybutadiene macromonomers,
polyisoprene macromonomers, polybutadiene macromonomers,
poly(ethylene/butylene)-polyisoprene macromonomers, these
macromonomers having a (meth)acrylate end group.
35. Composition according to claim 34, characterized in that the
carbon-based macromonomer is selected from: (i) poly(2-ethylhexyl
acrylate) macromonomers with a mono(meth)acrylate end group,
poly(dodecyl acrylate) macromonomers with a mono(meth)acrylate end
group; (ii) poly(ethylene/butylene) methacrylate.
36. Composition according to claim 35, characterized in that the
grafted polymer is selected from the polymers obtained by
polymerization: of methyl acrylate and of a
polyethylene/polybutylene macromonomer containing a methacrylate
end group, in particular in a solvent chosen from isododecane,
isononyl isononanoate, octyldodecanol, diisostearyl malate and a
C.sub.12-C.sub.15 alkyl benzoate; of methoxyethyl acrylate and of a
polyethylene/polybutylene macromonomer containing a methacrylate
end group, in particular in isododecane; of methyl acrylate/methyl
methacrylate monomers and of a polyethylene/polybutylene
macromonomer containing a methacrylate end group, in particular in
isododecane; of methyl acrylate/acrylic acid monomers and of a
polyethylene/polybutylene macromonomer containing a methacrylate
end group, in particular in isododecane; of methyl
acrylate/dimethylaminoethyl methacrylate monomers and of a
polyethylene/polybutylene macromonomer containing a methacrylate
end group, in particular in isododecane; of methyl
acrylate/2-hydroxyethyl methacrylate monomers and of a
polyethylene/polybutylene macromonomer containing a methacrylate
end group, in particular in isododecane.
37. Composition according to any one of claims 28 to 36,
characterized in that the grafted polymer is a non-silicone-based
grafted polymer.
38. Composition according to the preceding claim, characterized in
that the non-silicone-based grafted polymer contains predominantly
a carbon-based macromonomer and optionally contains not more than
7% by weight of silicone-based macromonomer.
39. Composition according to claim 37 or 38, characterized in that
the non-silicone-based grafted polymer is free of silicone-based
macromonomer.
40. Composition according to one of claims 1 to 27, characterized
in that the liquid fatty phase is a silicone-based liquid fatty
phase.
41. Composition according to claim 40, characterized in that the
silicone-based liquid fatty phase is composed of at least 50% by
weight of at least one silicone-based organic liquid compound
selected from silicone-based organic liquid compounds having a
total solubility parameter according to the Hansen solubility space
of less than or equal to 18 (MPa).sup.1/2.
42. Composition according to either of claims 40 and 41,
characterized in that the silicone-based organic liquid compound
comprises a volatile silicone oil.
43. Composition according to claim 42, characterized in that the
volatile silicone oil is selected from
octamethylcyclotetrasiloxane, decamethylcyclopentasiloxane,
dodecamethylcyclohexasiloxane, heptamethylhexyltrisiloxane,
heptamethyloctyltrisiloxane, octamethyltrisiloxane,
decamethyltetrasiloxane and mixtures thereof.
44. Composition according to one of claims 30 and 41 to 43,
characterized in that the silicone-based organic liquid compound
comprises a non-volatile silicone oil.
45. Composition according to the preceding claim, characterized in
that the non-volatile silicone oil is selected from non-volatile
polydialkylsiloxanes; polydimethylsiloxanes comprising alkyl,
alkoxy or phenyl groups, which are pendent or at the end of a
silicone chain, these groups containing from 2 to 24 carbon atoms;
phenyl silicones; polysiloxanes modified with fatty acids
(especially of C.sub.8-C.sub.20), fatty alcohols (especially of
C.sub.8-C.sub.20) or polyoxyalkylenes (especially polyoxyethylene
and/or polyoxypropylene); amino polysiloxanes; polysiloxanes
containing hydroxyl groups; fluoro polysiloxanes comprising a
fluorinated group that is pendent or at the end of a silicone
chain, containing from 1 to 12 carbon atoms, all or some of the
hydrogen atoms of which are replaced with fluorine atoms; and
mixtures thereof.
46. Composition according to one of the preceding claims,
characterized in that the liquid fatty phase contains less than 50%
by weight of non-silicone-based liquid organic compounds.
47. Composition according to claim 29 or 46, characterized in that
the non-silicone-based organic liquid compound having a total
solubility parameter according to the Hansen solubility space of
less than or equal to 18 (MPa).sup.1/2 is selected from
carbon-based oils, hydrocarbon-based oils and fluoro oils, alone or
in a mixture; linear, branched and/or cyclic alkanes, optionally
volatile; esters, and especially linear, branched or cyclic esters
having at least 6 carbon atoms; ketones, and especially ketones
having at least 6 carbon atoms; ethers, and especially ethers
having at least 6 carbon atoms.
48. Composition according to claim 29, characterized in that the
monoalcohols having a total solubility parameter according to the
Hansen solubility space of less than or equal to 20 (MPa).sup.1/2
are selected from aliphatic fatty monoalcohols having 6 to 30
carbon atoms, the hydrocarbon chain containing no substitution
group, and especially oleyl alcohol, octyldodecanol, decanol and
linoleyl alcohol.
49. Composition according to claims 40 to 45, characterized in that
the liquid fatty phase contains no non-silicone-based liquid
organic compounds.
50. Composition according to one of claims 6 and 40 to 48,
characterized in that the macromonomer is a silicone-based
macromonomer.
51. Composition according to claim 50, characterized in that the
silicone-based macromonomer is an organopolysiloxane macromonomer,
preferably a polydimethylsiloxane macromonomer.
52. Composition according to claim 50 or 51, characterized in that
the silicone-based macromonomer is selected from the macromonomers
of formula (II) below: ##STR7## in which R.sub.8 denotes a hydrogen
atom or a methyl group; R.sub.9 denotes a divalent hydrocarbon
group having from 1 to 10 carbon atoms and optionally contains one
or two ether bonds --O--; R.sub.10 denotes an alkyl group having
from 1 to 10 carbon atoms, in particular from 2 to 8 carbon atoms;
n denotes an integer ranging from 1 to 300, preferably ranging from
3 to 200 and preferentially ranging from 5 to 100.
53. Composition according to claim 5 and either of claims 50 to 51,
characterized in that the grafted acrylic polymer is obtainable by
free-radical polymerization in the polymerization medium: of a main
acrylic monomer selected from C.sub.1-C.sub.3 alkyl
(meth)acrylates, alone or in a mixture, and optionally one or more
additional acrylic monomers selected from acrylic acid, methacrylic
acid and alkyl (meth)acrylates of formula (I): ##STR8## in which:
R.sub.11 denotes a hydrogen atom or a methyl group; R.sub.12
represents a linear or branched alkyl group containing from 1 to 6
carbon atoms, the said group containing in its chain one or more
oxygen atoms and/or containing one or more substituents selected
from --OH, halogen atoms (F, Cl, Br, I) and --NR'R'', where R' and
R'', which are identical or different, are selected from
C.sub.1-C.sub.3 linear or branched alkyls; a cyclic alkyl group
containing from 3 to 6 carbon atoms, it being possible for the said
group to contain in its chain one or more oxygen atoms and/or to
contain one or more substituents selected from OH and halogen atoms
(F, Cl, Br, I); and salts thereof, to form the said insoluble
skeleton; and of a silicone-based macromonomer.
54. Composition according to the preceding claim, characterized in
that R.sub.12 denotes a group selected from methoxyethyl,
ethoxyethyl, trifluoroethyl, 2-hydroxyethyl, 2-hydroxypropyl,
dimethylaminoethyl, diethylaminoethyl and dimethylaminopropyl
groups.
55. Composition according to claim 50 or 51, characterized in that
the main acrylic monomer is selected from methyl (meth)acrylate,
ethyl (meth)acrylate, n-propyl (meth)acrylate, isopropyl
(meth)acrylate and mixtures thereof.
56. Composition according to claim 50, characterized in that the
main acrylic monomer is selected from methyl acrylate, methyl
methacrylate, ethyl acrylate and mixtures thereof.
57. Composition according to one of claims 50 to 53, characterized
in that the additional acrylic monomer is selected from
(meth)acrylic acid, methoxyethyl (meth)acrylate, ethoxyethyl
(meth)acrylate, trifluoroethyl methacrylate, dimethylaminoethyl
methacrylate, diethylaminoethyl methacrylate, 2-hydroxypropyl
(meth)acrylate, 2-hydroxyethyl (meth)acrylate and salts
thereof.
58. Composition according to the preceding claim, characterized in
that the additional acrylic monomer is selected from acrylic acid
and methacrylic acid.
59. Composition according to claim 49, characterized in that the
macromonomer is selected from polydimethylsiloxanes containing a
mono(meth)acrylate end group, and especially
monomethacryloyloxypropyl polydimethylsiloxanes.
60. Composition according to one of claims 5 and 37 to 56,
characterized in that the grafted acrylic polymer is selected from
the polymers obtained by polymerization: of methyl acrylate and a
monomethacryloyloxypropyl polydimethylsiloxane macromonomer having
a weight-average molecular weight ranging from 800 to 6000, in
particular in decamethylcyclopentasiloxane or phenyl trimethicone;
of methyl acrylate, acrylic acid and a monomethacryloyloxypropyl
polydimethylsiloxane macromonomer having a weight-average molecular
weight ranging from 800 to 6000, in particular in
decamethylcyclopentasiloxane or phenyl trimethicone.
61. Composition according to any one of claims 40 to 60,
characterized in that the grafted polymer is a silicone-based
grafted polymer.
62. Composition according to the preceding claim, characterized in
that the silicone-based grafted polymer contains predominantly a
silicone-based macromonomer and optionally contains not more than
7% by weight of carbon-based macromonomer.
63. Composition according to claim 61 or 62, characterized in that
the silicone-based grafted polymer is free of carbon-based
macromonomer.
64. Composition according to one of the preceding claims,
characterized in that the grafted ethylenic polymer has a
weight-average molecular mass (Mw) of between 10 000 and 300 000,
especially between 20 000 and 200 000, more preferably between 25
000 and 150 000.
65. Composition according to one of the preceding claims,
characterized in that the particles of grafted ethylenic polymer
have an average size ranging from 10 to 400 nm, preferably ranging
from 20 to 200 nm.
66. Composition according to one of the preceding claims,
characterized in that the grafted ethylenic polymer is a
film-forming polymer.
67. Lipcare and/or lip makeup composition comprising a dispersion
of particles of a grafted ethylenic polymer in a liquid fatty phase
and at least one pulverulent colorant selected in particular from
pigments, nacres or other fillers having an optical effect and
mixtures thereof.
68. Composition according to the preceding claim, characterized in
that it comprises a dispersion of particles of a grafted ethylenic
polymer in a liquid fatty phase as defined according to one of
claims 3 to 60.
69. Composition according to any one of the preceding claims,
characterized in that the grafted ethylenic polymer is present in
the composition in an amount, in terms of solids content, ranging
from 1% to 66.5% by weight relative to the total weight of the
composition, preferably ranging from 6% to 45% and better still
ranging from 8% to 40% by weight.
70. Composition according to any one of the preceding claims,
characterized in that it contains from 0.1% to 50% by weight of
waxes, relative to the total weight of the composition, and
preferably from 1% to 30% by weight.
71. Composition according to any one of the preceding claims,
characterized in that it comprises a cosmetic ingredient selected
from vitamins, trace elements, softeners, sequestrants, perfumes,
alkalifying or acidifying agents, preservatives, surfactants,
sunscreens, antioxidants and mixtures thereof.
72. Cosmetic composition according to any one of the preceding
claims, characterized in that it is in the form of a paste or
stick.
73. Cosmetic composition according to any one of the preceding
claims, characterized in that it is in anhydrous form.
74. Cosmetic assembly comprising: a) a container delimiting at
least one compartment, the said container being closed by a closing
member; and b) a composition disposed within the said compartment,
the composition being in accordance with any one of the preceding
claims.
75. Cosmetic assembly according to claim 74, characterized in that
the container is formed, at least in part, of at least one
thermoplastic material.
76. Cosmetic assembly according to claim 74, characterized in that
the container is formed, at least in part, of at least one
non-thermoplastic material, in particular of glass or of metal.
77. Assembly according to any one of claims 74 to 76, characterized
in that, with the container in its closed position, the closing
member is screwed onto the container.
78. Assembly according to any one of claims 74 to 77, characterized
in that, with the container in its closed position, the closing
member is coupled to the container other than by screwing, in
particular by snap fastening, adhesive bonding or welding.
79. Cosmetic method of making up or non-therapeutically caring for
the lips, comprising the application to the lips of a composition
according to any one of claims 1 to 73.
80. Use of a composition according to any one of claims 1 to 73 to
give a non-transfer deposit, in particular a non-transfer makeup
deposit on the lips.
81. Use of a sufficient amount of a dispersion, in a liquid fatty
phase, of a grafted ethylenic polymer in a cosmetic composition to
give a deposit on the lips that has a transfer of less than or
equal to 35%.
Description
[0001] The present invention relates to a cosmetic lipcare and/or
lip makeup composition comprising a dispersion of a grafted
ethylenic polymer in a liquid fatty phase, intended for application
to lips.
[0002] The composition according to the invention may be a makeup
composition or a care composition, preferably a makeup
composition.
[0003] Lipstick compositions are commonly employed to provide an
aesthetic colour to the lips. These makeup products generally
include fatty phases such as waxes and oils, pigments and/or
fillers, and, optionally, additives such as cosmetic or
dermatological actives.
[0004] These compositions, when applied to the lips, exhibit the
drawback of transferring: that is, of at least partly depositing,
leaving marks on certain substrates with which they may be brought
into contact, and in particular a glass, cup, cigarette, item of
clothing or the skin. One consequence is a mediocre persistence of
the applied film, necessitating regular renewal of application of
the lipstick composition.
[0005] "No-transfer" lip makeup compositions are therefore sought
which have the advantage of forming a deposit which does not
undergo at least partial deposition on the substrates with which
they are brought into contact (glass, clothing, cigarette,
fabrics).
[0006] In order to limit the transfer of cosmetic compositions it
is known to employ volatile oils, in particular in amounts greater
than 40% by weight. When present in large amount, these volatile
oils make the makeup product, in particular the lipstick,
uncomfortable for the user: the makeup deposit confers a sensation
of drying and of tautening.
[0007] Likewise known are products in the form of two separate
compositions to be applied one over the other to the lips to give a
no-transfer makeup. For example, the Lipfinity product from Max
Factor, as described in patent application WO 97/17057, is a
product comprising two compositions to be applied successively: the
base composition contains a silicone resin and volatile oils, and
the surface (or topcoat) composition contains a sucrose ester.
However, applying two compositions to make themselves up may be
prohibitive for certain users.
[0008] It is an object of the present invention to provide a new
formulation pathway for a cosmetic composition, in particular a lip
makeup composition, which allows a deposit having good non-transfer
properties to be obtained, in particular without the use of a
substantial proportion of volatile oils, the said deposit being
obtainable with this single composition.
[0009] It is another object of the invention to provide a cosmetic
composition, in particular a lip makeup composition, which allows a
comfortable deposit to be obtained on the lips.
[0010] The inventors have found that it is possible to obtain such
a composition using a dispersion of a specific grafted polymer in a
liquid fatty phase. The composition allows a deposit to be
obtained, in particular a lip makeup, which exhibits good
non-transfer properties. Moreover, the deposit obtained on the lips
does not give rise to a sensation of drying or tautening for the
user: the deposit is therefore comfortable.
[0011] More specifically, therefore, the present invention has as
its object a cosmetic composition comprising a polymer dispersion
as described below, the composition being in particular as defined
below.
[0012] The invention firstly provides a cosmetic lipcare and/or lip
makeup composition comprising a dispersion, in a liquid fatty
phase, of particles, preferably solid particles, of a grafted
ethylenic polymer, the said polymer being such that, when dispersed
in sufficient amount in the composition, the latter is able to form
advantageously a deposit having a transfer of less than or equal to
35%.
[0013] With further advantage, the composition according to the
invention is able to form a deposit having a transfer of less than
or equal to 30%, preferably less than or equal to 25%, preferably
less than or equal to 20%, preferably less than or equal to 15%,
preferably less than or equal to 10%, preferably less than or equal
to 5%. The invention also provides a cosmetic method of making up
or non-therapeutically caring for the lips, comprising the
application to the lips of a composition as defined above.
[0014] The invention additionally provides for the use of a
composition as defined above to give a non-transfer deposit, in
particular non-transfer makeup on the lips.
[0015] The invention further provides for the use of a grafted
ethylenic polymer, dispersed in a liquid fatty phase, in a cosmetic
composition to give a non-transfer deposit, in particular
non-transfer makeup on lips.
[0016] The invention additionally provides for the use, in a
cosmetic composition, of a sufficient amount of a dispersion, in a
liquid fatty phase, of a grafted ethylenic polymer to give a
deposit on the lips that has a transfer of less than or equal to
35%.
[0017] The transfer of the deposit obtained with the composition
according to the invention is determined according to the protocol
described below.
[0018] A substrate (a rectangle of 40 mm.times.70 mm with a
thickness of 3 mm) made of polyethylene foam that is adhesive on
one of the faces, having a density of 33 kg/m.sup.3 (sold under the
name RE40X70EP3 from Joint Technique Lyonnais Ind.), is preheated
on a hotplate which is 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.
[0019] With the substrate left on the hotplate, the composition is
applied over the entire non-adhesive surface of the substrate, by
spreading it with the aid of a fine brush to give a deposit of the
composition of approximately 15 .mu.m, and is then left to dry for
30 minutes.
[0020] After drying, the support is bonded via its adhesive face to
an anvil which has a diameter of 20 mm and is equipped with a screw
pitch. The substrate/deposit assembly is then cut by means of a
punch with a diameter of 18 mm. The anvil is subsequently screwed
onto a press (Statif Manuel Imada SV-2 from Someco) which is
equipped with a dynamometer (Imada DPS-20 from Someco).
[0021] White photocopier paper, 80 g/m.sup.2, is placed on the bed
of the press and then the substrate/deposit assembly is pressed on
the paper at a pressure of 2.5 kg for 30 seconds. After the
substrate/deposit assembly has been removed, some of the deposit
has undergone transfer to the paper. The colour of the deposit
transferred to the paper is then measured by means of a Minolta
CR300 colorimeter, the colour being characterized by the
colorimetric parameters L*, a* and b*. The colorimetric parameters
L*.sub.0, a*.sub.0 and b*.sub.0 of the colour of the uncoated paper
used are measured.
[0022] A determination is then made of the colour difference
.DELTA.E1 between the colour of the transferred deposit relative to
the colour of the uncoated paper, in accordance with the following
relationship: .DELTA.E1= {square root over
((L*-L.sub.0*).sup.2+(a*-a.sub.0*).sup.2+(b*-b.sub.0*).sup.2)}
[0023] Furthermore, a total transfer reference is prepared by
applying the composition directly to paper identical to that used
before, at ambient temperature (25.degree. C.), the composition
being spread by means of a fine brush to give a deposit of the
composition of approximately 15 .mu.m, and then left to dry for 30
minutes at ambient temperature (25.degree. C.). After the deposit
has dried, the colorimetric parameters L*', a*' and b*' of the
colour of the deposit placed on the paper are measured directly,
corresponding to the total transfer reference colour. The
colorimetric parameters L*'.sub.0, a*'.sub.0 and b*'.sub.0 of the
colour of the uncoated paper used are measured.
[0024] A determination is then made of the colour difference
.DELTA.E2 between the total transfer reference colour relative to
the colour of the uncoated paper, in accordance with the following
relationship: .DELTA.E2= {square root over
((L*'-L.sub.0*').sup.2+(a*'-a.sub.0*').sup.2+(b*'-b*'))}.sup.2
[0025] The transfer of the composition, expressed as a percentage,
is equal to the following ratio: 100.times..DELTA.E1/.DELTA.E2
[0026] The measurement is carried out on 4 substrates in succession
and the transfer value corresponds to the average of the 4
measurements obtained with the 4 substrates.
[0027] The composition according to the invention comprises a
dispersion of particles, preferably solid particles, of a grafted
ethylenic polymer in a liquid fatty phase.
[0028] The term "ethylenic" polymer means a polymer obtained by
polymerization of ethylenically unsaturated monomers.
[0029] The dispersion of grafted ethylenic polymer is especially
free of stabilizing polymer different from the said grafted
polymer, such as those described in EP 749 747 and the particles of
grafted ethylenic polymer are therefore not surface-stabilized with
such additional stabilizing polymers. The grafted polymer is
therefore dispersed in the liquid fatty phase in the absence of
additional surface stabilizer for the particles.
[0030] The term "grafted" polymer means a polymer having a skeleton
comprising at least one side chain that is pendent or located at
the end of a chain, and preferably pendent.
[0031] Advantageously, the grafted ethylenic polymer comprises an
ethylenic skeleton which is insoluble in the said liquid fatty
phase, and side chains which are attached covalently to the said
skeleton and are soluble in the said fatty phase.
[0032] The grafted ethylenic polymer is especially a
non-crosslinked polymer. In particular, the polymer is obtained by
polymerization of monomers comprising only one polymerizable
group.
[0033] Preferably, the grafted ethylenic polymer is a film-forming
polymer.
[0034] The term "film-forming" polymer means a polymer capable of
forming, by itself or in the presence of an auxiliary film-forming
agent, a film which is continuous, in particular to the touch
and/or to the naked eye, and which is adherent to a substrate, in
particular to keratin materials.
[0035] According to one embodiment of the invention, the grafted
ethylenic polymer is a grafted acrylic polymer.
[0036] The grafted ethylenic polymer is especially obtainable by
free-radical polymerization in an organic polymerization medium:
[0037] of at least one ethylenic monomer, in particular of at least
one acrylic monomer and optionally of at least one additional
non-acrylic vinyl monomer, to form the said insoluble skeleton; and
[0038] of at least one macromonomer containing a polymerizable end
group to form the side chains, the said macromonomer having a
weight-average molecular mass of greater than or equal to 200 and
the proportion of the polymerized macromonomer representing from
0.05% to 20% by weight of the polymer.
[0039] The medium in which the grafted polymer is supplied for its
formulation, called organic liquid dispersion medium, may be
identical to the polymerization medium.
[0040] However, the polymerization medium may be totally or
partially replaced with another organic liquid medium. This other
organic liquid medium may be added, after polymerization, to the
polymerization medium. The said polymerization medium is then
totally or partially evaporated.
[0041] The liquid fatty phase of the cosmetic composition may
contain the organic polymerization medium.
[0042] The liquid fatty phase may contain liquid organic compounds
other than those present in the dispersion medium. These other
compounds are chosen such that the grafted polymer remains in the
dispersed state in the liquid fatty phase.
[0043] The organic liquid dispersion medium is present in the
liquid fatty phase of the composition according to the invention
owing to the introduction into the composition of the dispersion of
grafted polymer obtained.
[0044] The liquid fatty phase:
[0045] The liquid fatty phase comprises, preferably predominantly,
one or more liquid organic compounds (or oils) as defined
below.
[0046] In particular, the liquid fatty phase is a non-aqueous
liquid organic phase that is immiscible with water at room
temperature (25.degree. C.).
[0047] The term "liquid organic compound" means a non-aqueous
compound that is in liquid form at room temperature (25.degree. C.)
and therefore flows under its own weight.
[0048] The term "silicone compound" means a compound containing at
least one silicon atom.
[0049] The composition according to the invention advantageously
contains a volatile oil as described below.
[0050] The term "volatile oil" means an oil capable of evaporating
from the skin or the lips in less than one hour, especially having
a vapour pressure, at room temperature and atmospheric pressure,
ranging from 10.sup.-3 to 300 mmHg (0.13 Pa to 40 000 Pa).
[0051] The volatile oil may be silicone-based or
non-silicone-based. It may be selected especially from
octamethylcyclotetrasiloxane, decamethylcyclopentasiloxane,
dodecamethylcyclohexasiloxane, heptamethylhexyltrisiloxane,
heptamethyloctyltrisiloxane, octamethyltrisiloxane,
decamethyltetrasiloxane, isododecane, isodecane and isohexadecane,
and mixtures thereof.
[0052] The volatile oil is advantageously present in an amount
ranging from 1% to 70% by weight, relative to the total weight of
the composition, preferably ranging from 5% to 50% by weight and
preferentially ranging from 10% to 35% by weight.
[0053] The liquid fatty phase may contain a non-volatile oil as
described below. The non-volatile oil is advantageously present in
an amount ranging from 1% to 80% by weight, relative to the total
weight of the composition, preferably ranging from 5% to 60% by
weight and preferentially ranging from 10% to 50% by weight.
[0054] Among the liquid organic compounds or oils that may be
present in the liquid fatty phase, mention may be made of liquid
organic compounds, especially silicone-based or non-silicone-based,
having a total solubility parameter according to the Hansen
solubility space of less than or equal to 18 (MPa).sup.1/2,
preferably 17 (MPa).sup.1/2. When the liquid organic compounds are
chosen from monoalcohols, their total solubility parameter
according to the Hansen solubility space may be greater than 17
(MPa).sup.1/2 while remaining less than or equal to 20
(MPa).sup.1/2.
[0055] The total solubility parameter 6 according to the Hansen
solubility space is defined in the article "Solubility parameter
values" by Eric A. Grulke in the work "Polymer Handbook", 3rd
Edition, Chapter VII, p. 519-559, by the relationship:
.delta.=(.delta..sub.D.sup.2+.delta..sub.P.sup.2+.delta..sub.H.sup.2).sup-
.1/2 in which
[0056] .delta..sub.D characterizes the London dispersion forces
arising from the formation of dipoles induced during molecular
impacts,
[0057] .delta..sub.P characterizes the Debye interaction forces
between permanent dipoles, and
[0058] .delta..sub.H characterizes the forces of specific
interactions (such as hydrogen bonds, acid/base, donor/acceptor,
etc.).
[0059] The definition of solvents in the solubility space according
to Hansen is described in the article by C. M. Hansen: "The
three-dimensional solubility parameters", J. Paint Technol. 39, 105
(1967).
[0060] Among the liquid organic compounds, especially
silicone-based or non-silicone-based, having a total solubility
parameter according to the Hansen solubility space of less than or
equal to 18 (MPa).sup.1/2, preferably less than or equal to 17
(MPa).sup.1/2, mention may be made of liquid fatty substances,
especially oils, which may be chosen from natural or synthetic,
carbon-based, hydrocarbon-based, fluoro and silicone oils, which
are optionally branched, alone or as a mixture.
[0061] Among these oils, mention may be made of plant oils formed
from fatty acid esters and from polyols, in particular
triglycerides, such as sunflower oil, sesame oil or rapeseed oil,
or esters derived from acids or alcohols containing a long chain
(i.e. a chain containing from 6 to 20 carbon atoms), in particular
the esters of formula RCOOR' in which R represents a higher fatty
acid residue containing from 7 to 19 carbon atoms and R' represents
a hydrocarbon-based chain containing from 3 to 20 carbon atoms,
such as palmitates, adipates and benzoates, in particular
diisopropyl adipate.
[0062] Mention may also be made of linear, branched and/or cyclic
alkanes which may be volatile, and in particular liquid paraffin,
liquid petroleum jelly or hydrogenated polyisobutylene, isododecane
or "Isopars", volatile isoparaffins. Mention may also be made of
esters, ethers and ketones.
[0063] Mention may also be made of silicone oils such as
polydimethylsiloxanes and polymethylphenylsiloxanes, optionally
substituted with aliphatic and/or aromatic groups, which are
optionally fluorinated, or with functional groups such as hydroxyl,
thiol and/or amine groups, and volatile silicone oils, which are
especially cyclic.
[0064] In particular, mention may be made of volatile and/or
non-volatile, optionally branched silicone oils.
[0065] As volatile silicone oils that may be used in the invention,
mention may be made of linear or cyclic silicones containing from 2
to 7 silicon atoms, these silicones optionally comprising alkyl or
alkoxy groups containing from 1 to 10 carbon atoms. Mention may be
made in particular of octamethylcyclotetrasiloxane,
decamethylcyclopentasiloxane, dodecamethylcyclohexasiloxane,
heptamethylhexyltrisiloxane, heptamethyloctyltrisiloxane,
octamethyltrisiloxane, decamethyltetrasiloxane, and mixtures
thereof.
[0066] As the non-volatile silicone oils that may be mentioned are
non-volatile polydialkylsiloxanes, such as non-volatile
polydimethylsiloxanes (PDMS); polydimethylsiloxanes comprising
alkyl, alkoxy or phenyl groups, which are pendent or at the end of
a silicone chain, these groups containing from 2 to 24 carbon
atoms; phenyl silicones, for instance phenyl trimethicones, phenyl
dimethicones, phenyl trimethylsiloxy diphenylsiloxanes, diphenyl
dimethicones, diphenyl methyldiphenyltrisiloxanes and
polymethylphenylsiloxanes; polysiloxanes modified with fatty acids
(especially of C.sub.8-C.sub.20), fatty alcohols (especially of
C.sub.8-C.sub.20) or polyoxyalkylenes (especially polyoxyethylene
and/or polyoxypropylene); amino polysiloxanes; polysiloxanes
containing hydroxyl groups; fluoro polysiloxanes comprising a
fluorinated group that is pendent or at the end of a silicone
chain, containing from 1 to 12 carbon atoms, all or some of the
hydrogen atoms of which are replaced with fluorine atoms; and
mixtures thereof.
[0067] As non-silicone-based liquid organic compounds with a total
solubility parameter according to the Hansen solubility space of
less than or equal to 18 (MPa) .sup.1/2, mention may be made in
particular of:
[0068] linear, branched or cyclic esters containing at least 6
carbon atoms, especially 6 to 30 carbon atoms;
[0069] ethers containing at least 6 carbon atoms, especially 6 to
30 carbon atoms; and
[0070] ketones containing at least 6 carbon atoms, especially 6 to
30 carbon atoms.
[0071] The liquid monoalcohols having a total solubility parameter
according to the Hansen solubility space of less than or equal to
20 (MPa).sup.1/2 that may be mentioned include aliphatic fatty
liquid monoalcohols containing from 6 to 30 carbon atoms, the
hydrocarbon-based chain not comprising a substitution group.
Monoalcohols according to the invention that may be mentioned
include oleyl alcohol, octyldodecanol, decanol and linoleyl
alcohol.
[0072] Non-Silicone-Based Medium
[0073] According to a first embodiment of the invention, the liquid
fatty phase may be a non-silicone-based liquid fatty phase.
[0074] The term "non-silicone-based liquid fatty phase" means a
fatty phase comprising one or more non-silicone-based liquid
organic compound(s) or oil(s), such as those mentioned above, the
said non-silicone-based compounds being predominantly present in
the liquid fatty phase, i.e. to at least 50% by weight, especially
from 50% to 100% by weight, preferably from 60% to 100% by weight
(for example from 60% to 99% by weight), or alternatively from 65%
to 100% by weight (for example from 65% to 95% by weight), relative
to the total weight of the liquid fatty phase.
[0075] The non-silicone-based liquid organic compounds may
especially be chosen from: non-silicone-based liquid organic
compounds having a total solubility parameter according to the
Hansen solubility space of less than or equal to 18 (MPa).sup.1/2,
preferably less than or equal to 17 (MPa).sup.12. When the liquid
organic compounds are chosen from monoalcohols, their total
solubility parameter according to the Hansen solubility space may
be greater than 17 (MPa).sup.1/2 while remaining less than or equal
to 20 (MPa).sup.1/2,
[0076] The said non-silicone-based liquid fatty phase may thus
optionally comprise silicone-based liquid organic compounds or
oils, such as those mentioned previously, which may be present in
an amount of less than 50% by weight, especially ranging from 0.1%
to 40% by weight, or even ranging from 1% to 35% by weight, or
alternatively ranging from 5% to 30% by weight, relative to the
total weight of the liquid fatty phase.
[0077] According to one particular embodiment of the invention, the
non-silicone-based liquid fatty phase does not contain
silicone-based liquid organic compounds or oils.
[0078] When the liquid fatty phase is a non-silicone-based liquid
fatty phase, the macromonomers present in the grafted polymer are
advantageously carbon-based macromonomers as described below.
[0079] In particular, when the liquid fatty phase is a
non-silicone-based liquid fatty phase, the grafted polymer present
in the composition is advantageously a non-silicone-based grafted
polymer.
[0080] The term "non-silicone-based grafted polymer" means a
grafted polymer predominantly containing a carbon-based
macromonomer and optionally containing not more than 7% by weight
and preferably not more than 5% by weight of silicone macromonomer,
or even being free of silicone macromonomer.
[0081] Silicone-Based Medium
[0082] According to a second embodiment of the invention, the
liquid fatty phase may be a silicone-based liquid fatty phase.
[0083] The term "silicone-based liquid fatty phase" means a fatty
phase comprising one or more silicone-based liquid organic
compound(s) or silicone oil(s) such as those described previously,
the said silicone compounds being predominantly present in the
liquid fatty phase, i.e. to at least 50% by weight, especially from
50% to 100% by weight, preferably from 60% to 100% by weight (for
example from 60% to 99% by weight), or else from 65% to 100% by
weight (for example from 65% to 95% by weight), relative to the
total weight of the liquid fatty phase.
[0084] The silicone-based liquid organic compounds may especially
be chosen from liquid organic compounds which are silicone-based
and have an overall solubility parameter according to the Hansen
solubility space of less than or equal to 18 (MPa).sup.1/2,
preferably less than or equal to 17 (MPa).sup.1/2.
[0085] The said silicone-based liquid fatty phase may thus
optionally comprise non-silicone-based liquid organic compounds or
oils, as described previously, which may be present in an amount of
less than 50% by weight, especially ranging from 0.1% to 40% by
weight, or even ranging from 1% to 35% by weight, or else ranging
from 5% to 30% by weight, relative to the total weight of the
liquid fatty phase.
[0086] According to one particular embodiment of the invention, the
silicone-based liquid fatty phase does not contain any
non-silicone-based liquid organic compounds.
[0087] When the liquid fatty phase is a silicone-based liquid fatty
phase, the macromonomers present in the grafted polymer are
advantageously silicone-based macromonomers as described below.
[0088] In particular, when the liquid fatty phase is a
silicone-based liquid fatty phase, the grafted polymer present in
the composition is advantageously a silicone-based grafted
polymer.
[0089] The term "silicone-based grafted polymer" means a grafted
polymer predominantly containing a silicone-based macromonomer and
optionally containing up to 7% by weight and preferably up to 5% by
weight of carbon-based macromonomer, or even being free of
carbon-based macromonomer.
[0090] The Grafted Polymer
[0091] The choice of monomers constituting the skeleton of the
polymer, of the macromonomers, the molecular weight of the polymer,
and the proportion of the monomers and macromonomers may be made as
a function of the liquid organic dispersion medium so as
advantageously to obtain a dispersion of particles of grafted
polymers, in particular a stable dispersion, this choice possibly
being made by a person skilled in the art.
[0092] The term "stable dispersion" means a dispersion that is not
liable to form a solid deposit or to undergo liquid/solid phase
separation, especially after centrifugation, for example, at 4000
rpm for 15 minutes.
[0093] The grafted ethylenic polymer forming the particles in
dispersion thus comprises a skeleton that is insoluble in the said
fatty phase and a portion that is soluble in the said fatty
phase.
[0094] The grafted ethylenic polymer may be a random polymer.
[0095] According to the invention, the term "grafted ethylenic
polymer" means a polymer that may be obtained by free-radical
polymerization:
[0096] of one or more ethylenic monomer(s);
[0097] with one or more macromonomer(s), in an organic
polymerization medium.
[0098] According to the invention, the term "grafted acrylic
polymer" means a polymer that may be obtained by free-radical
polymerization:
[0099] of at least one acrylic monomer, and optionally of at least
one additional non-acrylic vinyl monomer; and
[0100] of at least one macromonomer, in an organic polymerization
medium.
[0101] Advantageously, the acrylic monomers represent from 50% to
100% by weight, preferably from 55% to 100% by weight (especially
from 55% to 95% by weight) and preferentially from 60% to 100% by
weight (especially from 60% to 90% by weight) of the mixture of
acrylic monomers+optional non-acrylic vinyl monomers.
[0102] Preferably, the acrylic monomers are chosen from monomers
whose homopolymer is insoluble in the dispersion medium under
consideration, i.e. the homopolymer is in solid (or non-dissolved)
form at a concentration of greater than or equal to 5% by weight at
ambient temperature (20.degree. C.) in the said dispersion
medium.
[0103] Macromonomers:
[0104] According to the invention, the expression "macromonomer
containing a polymerizable end group" means any polymer comprising
on only one of its ends a polymerizable end group capable of
reacting during the polymerization reaction with acrylic monomers
and optionally the additional non-acrylic vinyl monomers
constituting the skeleton. The macromonomer makes it possible to
form the side chains of the grafted acrylic polymer. The
polymerizable group of the macromonomer may advantageously be an
ethylenically unsaturated group capable of free-radical
polymerization with the monomers constituting the skeleton.
[0105] The term "carbon-based macromonomer" means a
non-silicone-based macromonomer and especially an oligomeric
macromonomer obtained by polymerization of ethylenically
unsaturated non-silicone-based monomer(s), and mainly by
polymerization of acrylic and/or non-acrylic vinyl monomers.
[0106] The term "silicone-based macromonomer" means an
organopolysiloxane macromonomer and in particular a
polydimethylsiloxane macromonomer.
[0107] Preferably, the macromonomer is chosen from macromonomers
whose homopolymer is soluble in the dispersion medium under
consideration, i.e. fully dissolved at a concentration of greater
than or equal to 5% by weight and at room temperature in the said
dispersion medium.
[0108] Thus, the grafted acrylic polymer comprises a skeleton (or
main chain) consisting of a sequence of acrylic units resulting
from the polymerization especially of one or more acrylic monomers
and of side chains (or grafts) derived from the reaction of the
macromonomers, the said side chains being covalently bonded to the
said main chain.
[0109] The skeleton (or main chain) is insoluble in the dispersion
medium under consideration, whereas the side chains (or grafts) are
soluble in the said dispersion medium.
[0110] The monomers:
[0111] In the present patent application, the term "acrylic
monomer" means monomers chosen from (meth)acrylic acid,
(meth)acrylic acid esters (also known as (meth)acrylates), and
(meth)acrylic acid amides (also known as (meth)acrylamides).
[0112] As acrylic monomers that may be used to constitute the
insoluble skeleton of the polymer, mention may be made, alone or as
a mixture, of the following monomers, and also the salts
thereof:
[0113] (i) the (meth)acrylates of formula: ##STR1## in which:
[0114] R.sub.1 denotes a hydrogen atom or a methyl group;
[0115] R.sub.2 represents a group chosen from: [0116] a linear or
branched alkyl group containing from 1 to 6 carbon atoms, the said
group possibly comprising in its chain one or more heteroatoms
chosen from O, N and S; and/or possibly comprising one or more
substituents chosen from --OH, halogen atoms (F, Cl, Br or I) and
--NR'R'' with R' and R'', which may be identical or different,
chosen from linear or branched C.sub.1-C.sub.4 alkyls; and/or
possibly being substituted with at least one polyoxyalkylene group,
in particular with C.sub.2-C.sub.4 alkylene, especially
polyoxyethylene and/or polyoxypropylene, the said polyoxyalkylene
group consisting of the repetition of 5 to 30 oxyalkylene units;
[0117] a cyclic alkyl group containing from 3 to 6 carbon atoms,
the said group possibly comprising in its chain one or more
heteroatoms chosen from O, N and S, and/or possibly comprising one
or more substituents chosen from OH and halogen atoms (F, Cl, Br or
I).
[0118] Examples of R.sub.2 that may be mentioned include the
methyl, ethyl, propyl, butyl, isobutyl, methoxyethyl, ethoxyethyl,
methoxypolyoxyethylene (350 OE), trifluoroethyl, 2-hydroxyethyl,
2-hydroxypropyl, dimethylaminoethyl, diethylaminoethyl or
dimethylaminopropyl group;
[0119] (ii) the (meth)acrylamides of formula: ##STR2## in
which:
[0120] R.sub.3 denotes a hydrogen atom or a methyl group;
[0121] R.sub.4 and R.sub.5, which may be identical or different,
represent a hydrogen atom or a linear or branched alkyl group
containing from 1 to 6 carbon atoms, which may comprise one or more
substituents chosen from --OH, halogen atoms (F, Cl, Br or I) and
--NR'R'' with R' and R'', which may be identical or different,
chosen from linear or branched C.sub.1-C.sub.4 alkyls; or
[0122] R.sub.4 represents a hydrogen atom and R.sub.5 represents a
1,1-dimethyl-3-oxobutyl group.
[0123] As examples of alkyl groups that can constitute R.sub.4 and
R.sub.5, mention may be made of n-butyl, t-butyl, n-propyl,
dimethylaminoethyl, diethylaminoethyl and dimethylaminopropyl;
[0124] (iii) the (meth)acrylic monomers comprising at least one
carboxylic acid, phosphoric acid or sulphonic acid function, such
as acrylic acid, methacrylic acid or acrylamidopropanesulphonic
acid.
[0125] Among these acrylic monomers, those that may be mentioned
most particularly are methyl, ethyl, propyl, butyl and isobutyl
(meth)acrylates; methoxyethyl or ethoxyethyl (meth)acrylates;
trifluoroethyl methacrylate; dimethylaminoethyl methacrylate,
diethylaminoethyl methacrylate, 2-hydroxypropyl methacrylate,
2-hydroxyethyl methacrylate, 2-hydroxypropyl acrylate,
2-hydroxyethyl acrylate; dimethylaminopropylmethacrylamide;
methacrylic acid; and the salts thereof; and mixtures thereof.
[0126] Preferably, the acrylic monomers are selected from methyl
acrylate, methoxyethyl acrylate, methyl methacrylate,
2-hydroxyethyl methacrylate, methacrylic acid and
dimethylaminoethyl methacrylate, and mixtures thereof.
[0127] According to one embodiment, the grafted acrylic polymer is
obtainable by free-radical polymerization of one or more acrylic
monomers and of one or more additional non-acrylic vinyl monomers,
and of the said macromonomer.
[0128] Among the additional non-acrylic vinyl monomers that may be
mentioned are:
[0129] vinyl esters of formula: R.sub.6--COO--CH.dbd.CH.sub.2 in
which R.sub.6 represents a linear or branched alkyl group
containing from 1 to 6 carbon atoms, or a cyclic alkyl group
containing from 3 to 6 carbon atoms and/or an aromatic group, for
example of benzene, anthracene or naphthalene type;
[0130] non-acrylic vinyl monomers comprising at least one
carboxylic acid, phosphoric acid or sulphonic acid function, such
as crotonic acid, maleic anhydride, itaconic acid, fumaric acid,
maleic acid, styrenesulphonic acid, vinylbenzoic acid or
vinylphosphoric acid, and the salts thereof;
[0131] non-acrylic vinyl monomers comprising at least one tertiary
amine function, such as 2-vinylpyridine or 4-vinylpyridine;
[0132] and mixtures thereof.
[0133] The acrylic monomer preferably represents from 50% to 100%
by weight, preferably from 60% to 100% by weight, preferentially
from 70% to 100% by weight of the mixture of acrylic monomer and of
optional non-acrylic vinyl monomer.
[0134] Advantageously, the acrylic monomers present in the grafted
polymer comprise at least (meth)acrylic acid and at least one
monomer selected from the (meth)acrylates and (meth)acrylamides
described previously in sections (i) and (ii). Preferably, the
acrylic monomers comprise at least (meth)acrylic acid and at least
one monomer selected from C.sub.1-C.sub.3 alkyl (meth)acrylates.
(Meth)acrylic acid may be present in a content of at least 5% by
weight (especially ranging from 5% to 80% by weight), preferably of
at least 10% by weight (especially ranging from 10% to 70% by
weight), and preferentially of at least 15% by weight (especially
ranging from 15% to 60% by weight), relative to the total weight of
the polymer.
[0135] Among the salts that may be mentioned are those obtained by
neutralization of acid groups with mineral bases such as sodium
hydroxide, potassium hydroxide or ammonium hydroxide, or organic
bases such as alkanolamines, for instance monoethanolamine,
diethanolamine, triethanolamine or 2-methyl-2-amino-1-propanol.
[0136] Mention may also be made of the salts formed by
neutralization of tertiary amine units, for example using a mineral
or organic acid. Among the mineral acids that may be mentioned are
sulphuric acid, hydrochloric acid, hydrobromic acid, hydriodic
acid, phosphoric acid and boric acid. Among the organic acids that
may be mentioned are acids comprising one or more carboxylic,
sulphonic or phosphonic groups. They may be linear, branched or
cyclic aliphatic acids, or alternatively aromatic acids. These
acids may also comprise one or more heteroatoms chosen from O and
N, for example in the form of hydroxyl groups. Acetic acid or
propionic acid, terephthalic acid, and citric acid and tartaric
acid may especially be mentioned.
[0137] According to one embodiment of the invention, the grafted
acrylic polymer does not contain any additional non-acrylic vinyl
monomers as described above. In this embodiment, the insoluble
skeleton of the grafted ethylenic polymer is formed solely from
acrylic monomers as described previously.
[0138] It is understood that these non-polymerized acrylic monomers
may be soluble in the dispersion medium under consideration, but
the polymer formed with these monomers is insoluble in the
dispersion medium.
[0139] According to one particular embodiment of the invention, the
grafted ethylenic polymer may be obtained by free-radical
polymerization in an organic polymerization medium:
[0140] of a main acrylic monomer chosen from C.sub.1-C.sub.3 alkyl
(meth)acrylates, alone or as a mixture, and optionally of one or
more additional acrylic monomers chosen from acrylic acid,
methacrylic acid and alkyl(meth)acrylates of formula (I) defined
below, and salts thereof, to form the said insoluble skeleton;
and
[0141] of at least one silicone-based macromonomer comprising a
polymerizable end group, as defined previously.
[0142] Main acrylic monomers that may be used include methyl
acrylate, methyl methacrylate, ethyl acrylate, ethyl methacrylate,
n-propyl acrylate, n'-propyl methacrylate, isopropyl acrylate and
isopropyl methacrylate, and mixtures thereof.
[0143] Methyl acrylate, methyl methacrylate and ethyl methacrylate
are most particularly preferred.
[0144] The additional acrylic monomers may be chosen from:
[0145] (meth)acrylic acid and its salts,
[0146] the (meth)acrylates of formula (I), and salts thereof:
##STR3## in which:
[0147] R.sub.11 denotes a hydrogen atom or a methyl group;
[0148] R.sub.12 represents [0149] a linear or branched alkyl group
containing from 1 to 6 carbon atoms, the said group comprising in
its chain one or more oxygen atoms and/or comprising one or more
substituents chosen from [0150] --OH, halogen atoms (F, Cl, Br or
I) and --NR'R'', with R' and R'', which may be identical or
different, being chosen from linear or branched C.sub.1-C.sub.3
alkyls; [0151] a cyclic alkyl group containing from 3 to 6 carbon
atoms, the said group possibly comprising in its chain one or more
oxygen atoms and/or possibly comprising one or more substituents
chosen from OH and halogen atoms (F, Cl, Br or I); [0152] and
mixtures thereof.
[0153] Examples of R'.sub.2 that may be mentioned include the
methoxyethyl, ethoxyethyl, trifluoroethyl; 2-hydroxyethyl,
2-hydroxypropyl, dimethylaminoethyl, diethylaminoethyl and
dimethylaminopropyl groups.
[0154] Among these additional acrylic monomers, mention may be made
most particularly of (meth)acrylic acid, methoxyethyl or
ethoxyethyl (meth)acrylates; trifluoroethyl methacrylate;
dimethylaminoethyl methacrylate, diethylaminoethyl methacrylate,
2-hydroxypropyl methacrylate, 2-hydroxyethyl methacrylate,
2-hydroxypropyl acrylate and 2-hydroxyethyl acrylate, the salts
thereof, and mixtures thereof.
[0155] Acrylic acid and methacrylic acid are most particularly
preferred.
[0156] The macromonomers comprise at one of the ends of the chain a
polymerizable end group capable of reacting during the
polymerization with the acrylic monomers and optionally the
additional vinyl monomers, to form the side chains of the grafted
ethylenic polymer. The said polymerizable end group may in
particular be a vinyl or (meth)acrylate (or (meth)acryloyloxy)
group, and preferably a (meth)acrylate group.
[0157] The macromonomers are preferably chosen from macromonomers
whose homopolymer has a glass transition temperature (Tg) of less
than or equal to 25.degree. C., especially ranging from
-100.degree. C. to 25.degree. C. and preferably ranging from
-80.degree. C. to 0.degree. C.
[0158] The macromonomers have a weight-average molecular mass of
greater than or equal to 200, preferably greater than or equal to
300, preferentially greater than or equal to 500, and more
preferentially greater than 600.
[0159] Preferably, the macromonomers have a weight-average
molecular mass (Mw) ranging from 300 to 100 000, preferably ranging
from 500 to 50 000, preferentially ranging from 800 to 20 000, more
preferentially ranging from 800 to 10 000, and more preferentially
still ranging from 800 to 6000.
[0160] In the present patent application, the weight-average (Mw)
and number-average (Mn) molar masses are determined by liquid gel
permeation chromatography (THF solvent, calibration curve
established with linear polystyrene standards, refractometric
detector).
[0161] Carbon-based macromonomers that may in particular be
mentioned include:
[0162] (i) linear or branched alkyl acrylate or methacrylate
C.sub.8-C.sub.22 homopolymers and copolymers having a polymerizable
end group selected from vinyl or (meth)acrylate groups, among which
mention may be made in particular of: poly(2-ethylhexyl acrylate)
macromonomers with a mono(meth)acrylate end group; poly(dodecyl
acrylate) or poly(dodecyl methacrylate) macromonomers with a
mono(meth)acrylate end group; poly(stearyl acrylate) or
poly(stearyl methacrylate) macromonomers with a mono(meth)acrylate
end group.
[0163] Such macromonomers are described in particular in the
patents EP 895 467 and EP 96 459, and in the article by Gillman K.
F., Polymer Letters, Vol 5, page 477-481 (1967).
[0164] Mention may be made in particular of macromonomers based on
poly(2-ethylhexyl acrylate) or poly(dodecyl acrylate) with a
mono(meth)acrylate end group;
[0165] (ii) polyolefins having an ethylenically unsaturated end
group, in particular containing a (meth)acrylate end group.
Examples of such polyolefins that may be mentioned in particular
include the following macromonomers, it being understood that they
have a (meth)acrylate end group: polyethylene macromonomers,
polypropylene macromonomers, macromonomers of
polyethylene/polypropylene copolymer, macromonomers of
polyethylene/polybutylene copolymer, polyisobutylene macromonomers;
polybutadiene macromonomers; polyisoprene macromonomers;
polybutadiene macromonomers; poly(ethylene/butylene)-polyisoprene
macromonomers.
[0166] Such macromonomers are described in particular in U.S. Pat.
No. 5,625,005, which mentions ethylene/butylene and
ethylene/propylene macromonomers containing a (meth)acrylate
reactive end group.
[0167] Mention may be made in particular of the
poly(ethylene/butylene) methacrylate such as that sold under the
name Kraton Liquid L-1253 by Kraton Polymers.
[0168] Silicone-based macromonomers that may be mentioned in
particular include polydimethylsiloxanes containing
mono(meth)acrylate end groups, and especially those of formula (II)
below: ##STR4## in which R.sub.8 denotes a hydrogen atom or a
methyl group; R.sub.9 denotes a divalent hydrocarbon-based group
containing from 1 to 10 carbon atoms and optionally contains one or
two ether bonds --O--; R.sub.10 denotes an alkyl group containing
from 1 to 10 carbon atoms and especially from 2 to 8 carbon atoms;
n denotes an integer ranging from 1 to 300, preferably ranging from
3 to 200 and preferentially ranging from 5 to 100.
[0169] Silicone-based macromonomers that may be used include
monomethacryloyloxypropyl polydimethylsiloxanes such as those sold
under the name PS560-K6 by the company United Chemical Technologies
Inc. (UCT) or under the name MCR-M17 by the company Gelest Inc.
[0170] Preferably, the polymerized macromonomer (constituting the
side chains of the grafted polymer) represents from 0.05% to 20% by
weight of the total weight of the polymer, preferably from 0.1% to
15% by weight, preferentially from 0.2% to 10% by weight and more
preferentially from 0.3% to 8% by weight.
[0171] As particularly preferred grafted ethylenic polymer
dispersed in a non-silicone-based liquid fatty phase, it is
possible to use those obtained by polymerization:
[0172] of methyl acrylate and of a polyethylene/polybutylene
macromonomer containing a methacrylate end group (especially Kraton
L-1253), in particular in a solvent chosen from isododecane,
isononyl isononanoate, octyldodecanol, diisostearyl malate or a
C.sub.12-C.sub.15 alkyl benzoate (such as Finsolv TN);
[0173] of methoxyethyl acrylate and of a polyethylene/polybutylene
macromonomer containing a methacrylate end group (especially Kraton
L-1253), in particular in isododecane;
[0174] of methyl acrylate/methyl methacrylate monomers and of a
polyethylene/polybutylene macromonomer containing a methacrylate
end group (especially Kraton L-1253), in particular in
isododecane;
[0175] of methyl acrylate/acrylic acid monomers and of a
polyethylene/polybutylene macromonomer containing a methacrylate
end group (especially Kraton L-1253), in particular in
isododecane;
[0176] of methyl acrylate/dimethylaminoethyl methacrylate monomers
and of a polyethylene/polybutylene macromonomer containing a
methacrylate end group (especially Kraton L-1253), in particular in
isododecane;
[0177] of methyl acrylate/2-hydroxyethyl methacrylate monomers and
of a polyethylene/polybutylene macromonomer containing a
methacrylate end group (especially Kraton L-1253), in particular in
isododecane.
[0178] As particularly preferred grafted acrylic polymer dispersed
in a silicone-based liquid fatty phase, it is possible to use those
obtained by polymerization:
[0179] of methyl acrylate and of the monomethacryloyloxypropyl
polydimethylsiloxane macromonomer with a weight-average molecular
weight ranging from 800 to 6000, in particular in
decamethylcyclopentasiloxane or phenyl trimethicone;
[0180] of methyl acrylate, acrylic acid and the
monomethacryloxypropyl polydimethylsiloxane macromonomer with a
weight-average molecular weight ranging from 800 to 6000, in
particular in decamethylcyclopentasiloxane or phenyl
trimethicone.
[0181] The weight-average molecular mass (Mw) of the grafted
polymer is preferably between 10 000 and 300 000, especially
between 20 000 and 200 000 and better still between 25 000 and 150
000.
[0182] By virtue of the abovementioned characteristics, in a given
organic dispersion medium, the polymers have the capacity of
folding over on themselves, thus forming particles of substantially
spherical shape, the periphery of these particles having the
deployed side chains, which ensure the stability of these
particles. Such particles resulting from the characteristics of the
grafted polymer have the particular feature of not aggregating in
the said medium and thus of being self-stabilized and of forming a
particularly stable polymer particle dispersion.
[0183] In particular, the grafted ethylenic polymers of the
dispersion are capable of forming nanometre-sized particles, with a
mean size ranging from 10 to 400 nm and preferably from 20 to 200
nm.
[0184] As a result of this very small size, the grafted polymer
particles in dispersion are particularly stable and therefore have
little susceptibility to form agglomerates.
[0185] The dispersion of grafted polymer may thus be a dispersion
that is stable and does not form sediments when it is placed at
room temperature (25.degree. C.) for an extended period (for
example 24 hours).
[0186] Preferably, the dispersion of grafted polymer particles has
a solids content (or dry extract) of polymer of from 40% to 70% by
weight of solids and especially from 45% to 65% by weight.
[0187] The dispersion of grafted polymer particles may be prepared
by a process comprising a free-radical copolymerization step, in an
organic polymerization medium, of one or more acrylic monomers as
defined above with one or more macromonomers as defined above.
[0188] As mentioned previously, the liquid organic dispersion
medium may be identical to or different from the polymerization
medium.
[0189] The copolymerization may be performed conventionally in the
presence of a polymerization initiator. The polymerization
initiators may be free-radical initiators. In general, such a
polymerization initiator may be chosen from organic peroxide
compounds such as dilauroyl peroxide, dibenzoyl peroxide or
tert-butyl peroxy-2-ethylhexanoate; diazo compounds such as
azobisisobutyronitrile or azobisdimethylvaleronitrile.
[0190] The reaction may also be initiated using photoinitiators or
with radiation such as UV or neutrons, or with plasma.
[0191] In general, to perform this process, at least a portion of
the organic polymerization medium, a portion of the additional
acrylic and/or vinyl monomers, which will constitute the insoluble
skeleton after polymerization, all of the macromonomer (which will
constitute the side chains of the polymer) and a portion of the
polymerization initiator are introduced into a reactor whose size
is suitable for the amount of polymer to be prepared. At this stage
of introduction, the reaction medium forms a relatively homogeneous
medium.
[0192] The reaction medium is then stirred and heated up to a
temperature to obtain polymerization of the monomers and
macromonomers. After a certain time, the initially homogeneous and
clear medium leads to a dispersion of milky appearance. A mixture
consisting of the remaining portion of monomers and of the
polymerization initiator is then added. After an adequate time
during which the mixture is heated with stirring, the medium
stabilizes in the form of a milky dispersion, the dispersion
comprising polymer particles stabilized in the medium in which they
have been created, the said stabilization being due to the
presence, in the polymer, of side chains that are soluble in the
said dispersion medium.
[0193] The polymer dispersion may be present in a proportion of
from 3% to 95% by weight in the composition, in particular from 4%
to 90% by weight, or even from 20% to 70% by weight.
[0194] The grafted polymer may be present in the composition
according to the invention in an amount in terms of solids content
(or active substance) ranging from 1% to 66.5% by weight relative
to the total weight of the composition, preferably ranging from 6%
to 45% and more preferably ranging from 8% to 40% by weight.
[0195] The present examples illustrate the preparation of polymers
in accordance with the invention and capable of forming a
dispersion of particles in an organic medium under
consideration.
[0196] In these examples, following preparation of the said
dispersion, determinations are made of the weight-average (Mw) and
number-average (Mn) molar masses of the polymer, the glass
transition temperature of the polymer, the solids content (or dry
extract) of the dispersion, and the size of the polymer
particles.
[0197] The weight-average (Mw) and number-average (Mn) molar masses
are determined by liquid gel-permeation chromatography (THF
solvent, calibration curve established with linear polystyrene
standards, refractometric detector).
[0198] The glass transition temperature (Tg) is measured in
accordance with standard ASTM D3418-97, by differential enthalpy
analysis (DSC "Differential Scanning Calorimetry") on a
calorimeter, over a temperature range of between -100.degree. C.
and +150.degree. C. at a heating rate of 10.degree. C./min in 150
.mu.l aluminium crucibles.
[0199] The crucibles are prepared as follows: 1001 .mu.l of the
dispersion obtained are introduced into a 150 .mu.l aluminium
crucible and the solvent is allowed to evaporate over 24 hours at
ambient temperature and at 50% relative humidity. The operation is
repeated and the crucible is then introduced into the Mettler DSC30
calorimeter.
[0200] The solids content (or dry extract), in other words the
amount of non-volatile matter, may be measured in a variety of
ways: mention may be made, for example, of the methods involving
oven drying or the methods involving drying by exposure to infrared
radiation.
[0201] The solids content is preferably measured by heating the
sample with infrared rays with a wavelength of from 2 .mu.m to 3.5
.mu.m. The substances present in the composition that have a high
vapour pressure evaporate under the effect of this radiation.
Measuring the weight loss from the sample allows the dry extract of
the composition to be determined. These measurements are performed
by means of a commercial infrared desiccator LP16 from Mettler.
This technique is fully described in the documentation for the
instrument supplied by Mettler.
[0202] The measurement protocol is as follows: approximately 1 g of
the composition is spread onto a metal cup. After this cup has been
introduced into the desiccator, it is subjected to a setpoint
temperature of 120.degree. C. for an hour. The wet mass of the
sample, corresponding to the initial mass, and the dry mass of the
sample, corresponding to the mass after radiation exposure, are
measured by means of a precision balance. The solids content is
calculated as follows: Dry extract=100.times.(dry mass/wet
mass).
[0203] The particle sizes may be measured by a variety of
techniques: mention may be made, in particular, of light scattering
techniques (dynamic and static), Coulter counter methods,
sedimentation rate measurements (related to the size via Stokes'
law) and microscopy. These techniques allow a particle diameter
and, in certain cases, a particle size distribution to be
measured.
[0204] The sizes and size distributions of the particles in the
compositions according to the invention are preferably measured by
static light scattering using a commercial granulometer of type
MasterSizer 2000 from Malvern. The data are processed on the basis
of the Mie scattering theory. This theory, which is exact for
isotropic particles, makes it possible to determine an "effective"
particle diameter in the case of non-spherical particles. This
theory is described in particular in the work by Van de Hulst, H.
C., "Light Scattering by Small Particles," Chapters 9 and 10,
Wiley, New York, 1957.
[0205] The composition is characterized by its "effective" mean
diameter by volume D[4.3], which is defined as follows: D .times. [
4.3 ] = i .times. .times. V i d i i .times. .times. V i ##EQU1## in
which V.sub.i represents the volume of particles with an effective
diameter d.sub.i. This parameter is described in particular in the
technical documentation accompanying the granulometer.
[0206] The measurements are carried out at 25.degree. C. on a
dilute particle dispersion obtained from the composition as
follows: 1) dilution by a factor of 100 with water, 2)
homogenization of the solution, 3) standing of the solution for 18
hours, 4) recovery of the whitish uniform supernatant.
EXAMPLE 1
Polymer Obtained by Polymerizing Methyl Acrylate and the
Macromonomer Corresponding to a Polyethylene/Polybutylene Copolymer
Containing Methacrylate End Groups (Kraton L-1253).
[0207] A reactor is charged with 2 kg of heptane, 2 kg of
isododecane, 2.8 kg of methyl acrylate and 1.2 kg of a macromonomer
of the type constituting a polyethylene/polybutylene copolymer
containing methacrylate end groups (Kraton L-1253) and 320 g of
tert-butyl peroxy-2-ethylhexanoate (Trigonox 21S).
[0208] The reaction mixture is stirred and heated at ambient
temperature to 90.degree. C. over 1 hour. After 15 minutes at
90.degree. C., a change is observed in the appearance of the
reaction medium, which passes from transparent to milky in
appearance. Heating with stirring is maintained for a further 15
minutes, and then a mixture consisting of 16 kg of methyl acrylate
and 200 g of Trigonox 12S is added dropwise over 1 hour.
[0209] Heating takes place subsequently at 90.degree. C. for 4
hours and then the heptane is distilled from the reaction medium.
At the end of this distillation operation, a stable dispersion is
obtained of particles of polymer thus prepared in isododecane.
[0210] The grafted polymer contains 6% by weight of macromonomer
relative to the weight of the polymer.
[0211] The characteristics of the polymer and of the particles
formed by the said polymer are as follows:
[0212] Weight-average molecular mass Mw=119 900
[0213] Number-average molecular mass Mn=16 300
[0214] Polydispersity index (Mw/Mn)=7.37
[0215] Glass transition: 10.degree. C. by Mettler DSC;
[0216] Dry extract: 52.4% in isododecane, carried out by
thermobalance;
[0217] Particle size: 46 nm with a polydispersity of 0.05,
performed on a Malvern Autosizer Lo-C at 25.degree. C.
[0218] The stability of the resulting dispersion is demonstrated by
implementing the following stability protocol: a haemolysis tube is
charged with 8 ml of the dispersion prepared and is centrifuged at
4000 rpm for 15 minutes with the aid of a Jouan C100-S5 centrifuge.
After 15 minutes it is found that there is no phase separation,
thereby demonstrating that the dispersion is stable.
EXAMPLE 2
Polymer Obtained by Polymerizing Methyl Acrylate, Acrylic Acid and
the Macromonomer Corresponding to a Polyethylene/Polybutylene
Copolymer (Kraton L-1253).
[0219] A 1 litre reactor is charged with 200 g of heptane, 200 g of
isododecane, 14 g of methyl acrylate, 10 g of acrylic acid and 16 g
of a macromonomer of the type constituting a
polyethylene/polybutylene copolymer containing methacrylate end
groups (Kraton L-1253) and 3.2 g of tert-butyl
peroxy-2-ethylhexanoate (Trigonox 21S).
[0220] The reaction mixture is stirred and heated at ambient
temperature to 90.degree. C. over 1 hour. After 15 minutes at
90.degree. C., a change is observed in the appearance of the
reaction medium, which passes from transparent to milky in
appearance. Heating with stirring is maintained for a further 15
minutes, and then a mixture consisting of 130 g of methyl acrylate,
30 g of acrylic acid and 2 g of Trigonox 12S is added dropwise over
1 hour.
[0221] Heating takes place subsequently at 90.degree. C. for 4
hours and then the heptane is distilled from the reaction medium.
At the end of this distillation operation, a stable dispersion is
obtained of particles of polymer thus prepared in isododecane.
[0222] The characteristics of the polymer and of the particles
formed by the said polymer are as follows:
[0223] Weight-average molecular mass Mw=175 294
[0224] Number-average molecular mass Mn=28 265
[0225] Polydispersity index (Mw/Mn)=6.2
[0226] Dry extract: 54.9% in isododecane;
[0227] Particle size: 85 nm with a polydispersity of 0.04,
performed on a Malvern Autosizer Lo-C at 25.degree. C.
[0228] The grafted polymer contains 8% by weight of macromonomer
relative to the weight of the polymer.
[0229] The stability of the resulting dispersion is demonstrated by
implementing the following stability protocol: a haemolysis tube is
charged with 8 ml of the dispersion prepared and is centrifuged at
4000 rpm for 15 minutes with the aid of a Jouan C100-S5 centrifuge.
After 15 minutes it is found that there is no phase separation,
thereby demonstrating that the dispersion is stable.
EXAMPLE 3
Polymer Obtained by Polymerizing Methyl Acrylate, Acrylic Acid and
the Monomethacryloyloxypropyl Polydimethylsiloxane Macromonomer
[0230] The macromonomer has a weight-average molecular weight of
5000 and is sold under the name MCR-M17 by Gelest Inc.
[0231] A 1 litre reactor is charged with 200 g of heptane, 200 g of
decamethylcyclopentasiloxane, 26 g of methyl acrylate, 14 g of
monomethacryloyloxypropyl polydimethylsiloxane MCR-M17 and 3.2 g of
tert-butyl peroxy-2-ethylhexanoate (Trigonox 21S).
[0232] The reaction mixture is stirred and heated to 90.degree. C.
over 1 hour. After 15 minutes at 90.degree. C., a change is
observed in the appearance of the reaction medium, which passes
from transparent to milky in appearance. Heating with stirring is
maintained for a further 15 minutes, and then a mixture consisting
of 120 g of methyl acrylate, 40 g of acrylic acid and 2 g of
Trigonox 21S is added dropwise over 1 hour. Heating takes place
subsequently at 90.degree. C. for 4 hours and then the heptane is
distilled from the reaction medium.
[0233] At the end of this distillation operation, a stable
dispersion is obtained of particles of polymer thus prepared in
decamethylcyclopentasiloxane.
[0234] The grafted polymer contains 7% by weight of macromonomer
(and therefore of side chains soluble in D5) relative to the weight
of the polymer.
[0235] The characteristics of the polymer and of the particles
formed by the said polymer are as follows:
[0236] Dry extract: 50% in decamethylcyclopentasiloxane, performed
by thermobalance
[0237] Glass transition: 12.degree. C. by Mettler DSC
[0238] Particle size: 170 nm with a polydispersity of 0.04,
performed on a Malvern Autosizer Lo-C at 25.degree. C.
EXAMPLE 4
Polymer Obtained by Polymerizing Methyl Acrylate, Acrylic Acid and
the Macromonomer Corresponding to a Polyethylene/Polybutylene
Copolymer Containing Methacrylate End Groups (Kraton L-1253).
[0239] A 1 litre reactor is charged with 200 g of heptane, 200 g of
isododecane, 28 g of methyl acrylate, 12 g of a macromonomer of the
type constituting a polyethylene/polybutylene copolymer containing
methacrylate end groups (Kraton L-1253) and 3.2 g of tert-butyl
peroxy-2-ethylhexanoate (Trigonox 21S).
[0240] The reaction mixture is stirred and heated at ambient
temperature to 90.degree. C. over 1 hour. After 15 minutes at
90.degree. C., a change is observed in the appearance of the
reaction medium, which passes from transparent to milky in
appearance. Heating with stirring is maintained for a further 15
minutes, and then a mixture consisting of 150 g of methyl acrylate,
10 g of acrylic acid and 2 g of Trigonox 12S is added dropwise over
1 hour.
[0241] Heating takes place subsequently at 90.degree. C. for 4
hours and then the heptane is distilled from the reaction medium.
At the end of this distillation operation, a stable dispersion is
obtained of particles of polymer thus prepared in isododecane.
[0242] The grafted polymer contains 6% by weight of macromonomer
relative to the weight of the polymer.
[0243] The characteristics of the polymer and of the particles
formed by the said polymer are as follows:
[0244] Weight-average molecular mass Mw=143 639
[0245] Number-average molecular mass Mn=23 965
[0246] Polydispersity index (Mw/Mn)=5.99
[0247] Theoretical dry extract: 51.3% in isododecane
[0248] Particle size: 48 nm with a polydispersity of 0.04,
performed on a Malvern Autosizer Lo-C at 25.degree. C.
[0249] After the stability protocol has been implemented in
accordance with Example 1, it is found that the resulting
dispersion is stable.
[0250] The composition according to the invention may also comprise
at least fatty substances that are solid at ambient temperature,
selected in particular from waxes, pasty fatty substances, gums and
mixtures thereof. These fatty substances may be of animal, plant,
mineral or synthetic origin.
[0251] By pasty fatty substance is meant a lipophilic fatty
compound comprising at a temperature of 23.degree. C. a liquid
fraction and a solid fraction.
[0252] The said 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.
[0253] The hardness is measured according to a method involving
penetration of a probe into a sample of compound, and in particular
by means of a texture analyser (for example the TA-XT2i from Rheo)
which is equipped with a stainless steel cylinder 2 mm in diameter.
The hardness measurement is performed at 20.degree. C. in the
centre of 5 samples. The cylinder is introduced into each sample at
a pre-speed of 1 mm/s and then at a measuring speed of 0.1 mm/s,
the depth of penetration being 0.3 mm. The value found for the
hardness is that of the maximum peak.
[0254] The liquid fraction of the pasty compound measured at
23.degree. C. represents preferably 9% to 97% by weight of the
compound. This fraction that is liquid at 23.degree. C. represents
preferably between 15% and 85%, more preferably between 40% and 85%
by weight. The liquid fraction by weight of the pasty compound at
23.degree. C. is equal to the ratio of the enthalpy of fusion
consumed at 23.degree. C. to the enthalpy of fusion of the pasty
compound.
[0255] The enthalpy of fusion of the pasty compound is the enthalpy
consumed by the compound in passing 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 crystalline form. The
pasty compound is said to be in the liquid state when the entirety
of its mass is in liquid form.
[0256] The enthalpy of fusion of the pasty compound is equal to the
area under the curve of the thermogram obtained by means of a
differential scanning calorimeter (DSC), such as the calorimeter
sold under the name MDSC 2920 by TA Instrument, with a temperature
rise of 5 or 10.degree. C. per minute, according to standard ISO
11357-3:1999. The enthalpy of fusion of the pasty compound is the
amount of energy required to cause the compound to pass from the
solid state to the liquid state. It is expressed in J/g.
[0257] The enthalpy of fusion consumed at 23.degree. C. is the
amount of energy absorbed by the sample in passing from the solid
state to the state in which it exists at 23.degree. C., composed of
a liquid fraction and a solid fraction.
[0258] The liquid fraction of the pasty compound measured at
32.degree. C. represents preferably from 30% to 100% by weight of
the compound, preferably from 80% to 100%, more preferably from 90%
to 100% by weight of the compound. When the liquid fraction of the
pasty compound measured at 32.degree. C. is 100%, the temperature
of the end of the melting range of the pasty compound is less than
or equal to 32.degree. C.
[0259] The liquid fraction of the pasty compound measured at
32.degree. C. is equal to the ratio of the enthalpy of fusion
consumed at 32.degree. C. to the enthalpy of fusion of the pasty
compound. The enthalpy of fusion consumed at 32.degree. C. is
calculated in the same way as for the enthalpy of fusion consumed
at 23.degree. C.
[0260] A wax for the purposes of the present invention is
understood to mean a lipophilic compound which is solid at ambient
temperature (25.degree. C.) and exhibits a reversible solid/liquid
state change, having a melting point of greater than or equal to
30.degree. C. and possibly as high as 120.degree. C.
[0261] The melting point of the wax can be measured by means of a
differential scanning calorimeter (DSC), an example being the
calorimeter sold under the name DSC 30 by the company Mettler.
[0262] The waxes may be hydrocarbon, fluoro and/or silicone waxes
and may be of plant, mineral, animal and/or synthetic origin. In
particular the waxes have a melting point greater than or equal to
30.degree. C. and better still greater than 45.degree. C.
[0263] As a wax which can be used in the composition of the
invention mention may be made of beeswax, carnauba wax or
candelilla wax, paraffin, microcrystalline waxes, ceresin or
ozokerite; synthetic waxes such as polyethylene or Fischer-Tropsch
waxes; and silicone waxes such as alkyl or alkoxy dimethicones
having from 16 to 45 carbon atoms.
[0264] The gums are generally high-molecular-weight
polydimethylsiloxanes (PDMS) or cellulose gums or polysaccharides,
and the pasty substances are generally hydrocarbon compounds such
as lanolins and derivatives thereof or else PDMSs.
[0265] The nature and amount of the solid substances depend on the
desired textures and mechanical properties. As a guide, the
composition may contain from 0.1% to 50% by weight of waxes,
relative to the total weight of the composition, and better still
from 1% to 30% by weight.
[0266] The composition may therefore include water or a mixture of
water and hydrophilic organic solvent(s) such as alcohols, and
especially linear or branched lower monoalcohols having from 2 to 5
carbon atoms, such as ethanol, isopropanol or n-propanol, and
polyols, such as glycerol, diglycerol, propylene glycol, sorbitol,
pentylene glycol, and polyethylene glycols, or else C.sub.2 ethers
and C.sub.2-C.sub.4 aldehydes which are hydrophilic.
[0267] The water or the mixture of water and hydrophilic organic
solvents may be present in the composition according to the
invention in an amount ranging from 0.1% to 99% by weight, relative
to the total weight of the composition, and preferably from 1% to
80%, and more preferably from 10% to 80% by weight.
[0268] The composition according to the invention may further
comprise one or more colorants selected from water-soluble dyes and
pulverulent colorants such as pigments, nacres and mixtures
thereof. The colorants may be present in the composition in an
amount ranging from 0.01% to 50% by weight, relative to the weight
of the composition, preferably from 0.01% to 30% by weight.
[0269] One of the subjects of the invention is a lipcare and/or lip
makeup composition comprising a dispersion of particles of a
grafted ethylenic polymer in a liquid fatty phase and at least one
pulverulent colorant selected in particular from pigments, nacres
or other filler having an optical effect, and mixtures thereof. The
Applicant has found, in effect, that pulverulent materials,
especially pigments, disperse readily in the dispersion of
particles of grafted ethylenic polymer as described above, without
employing substantial amounts of dispersant or even without adding
any dispersant at all.
[0270] By pigments are meant particles of any form, white or
coloured, organic or inorganic, which are insoluble in the
physiological medium and are intended for colouring the
composition.
[0271] By nacres are meant particles of any form which are
iridescent and, in particular, are produced by certain molluscs in
their shell or else are synthesized.
[0272] The pigments may be white or coloured, organic and/or
inorganic. Among inorganic pigments mention may be made of titanium
dioxide, optionally with surface treatment, zirconium oxide or
cerium oxide, and also zinc oxide, iron oxide (black, yellow or
red) or chromium oxide, manganese violet, ultramarine blue,
chromium hydrate and ferric blue, and metal powders such as
aluminium powder and copper powder.
[0273] Among organic pigments mention may be made of carbon black,
D & C-type pigments, and lakes based on cochineal carmine,
barium, strontium, calcium or aluminium.
[0274] Mention may also be made of effect pigments, such as
particles comprising an organic or inorganic, natural or synthetic
substrate, for example glass, acrylic resins, polyester,
polyurethane, polyethylene terephthalate, ceramics or aluminas, the
said substrate being covered or not covered with metallic
substances such as aluminium, gold, silver, platinum, copper,
bronze, or with metal oxides such as titanium dioxide, iron oxide,
chromium oxide and mixtures thereof.
[0275] The nacreous pigments may be selected from white nacreous
pigments such as titanium-coated mica, or bismuth oxychloride,
coloured nacreous pigments such as titanium mica coated with iron
oxides, titanium mica coated with, in particular, ferric blue or
chromium oxide, titanium mica covered with an organic pigment of
the aforementioned type, and nacreous pigments based on bismuth
oxychloride. It is also possible to use interference pigments,
especially liquid-crystal or multilayer pigments.
[0276] The water-soluble dyes are, for example, beetroot juice and
methylene blue.
[0277] The composition according to the invention may comprise at
least one filler, in particular in an amount 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. By fillers are
meant particles of any shape, colourless or white, inorganic or
synthetic, which are insoluble in the medium of the composition
irrespective of the temperature at which the composition is
manufactured. These fillers serve in particular to modify the
rheology or texture of the composition.
[0278] The fillers may be organic or inorganic and of any shape,
platelet-like, spherical or oblong, whatever the crystallographic
form (for example sheet, cubic, hexagonal, orthorhombic, etc.).
Mention may be made of talc, mica, silica, kaolin, polyamide
(Nylon.RTM.) powders (orgasol.RTM. from Atochem),
poly-.beta.-alanine power and polyethylene powder, powders of
tetrafluoroethylene (Teflon.RTM.)) polymers, lauroyllysine, starch,
boron nitride, polymeric hollow microspheres such as those of
polyvinylidene chloride/acrylonitrile such as Expancel.RTM. (Nobel
Industries), acrylic acid copolymers (Polytrap.RTM. from the Dow
Corning company) and silicone resin microbeads (Tospearls.RTM. from
Toshiba, for example), particles of elastomeric
polyorganosiloxanes, precipitated calcium carbonate, magnesium
carbonate and hydrogencarbonate, hydroxyapatite, hollow silica
microspheres (Silica Beads.RTM. from Maprecos), ceramic or glass
microcapsules, and metal soaps derived from organic carboxylic
acids having from 8 to 22 carbon atoms, preferably from 12 to 18
carbon atoms, for example zinc stearate, magnesium stearate or
lithium stearate, zinc laurate and magnesium myristate.
[0279] The pigments, nacres or solid fillers may be dispersed in
the liquid fatty phase of the composition in the presence of a
dispersant.
[0280] The purpose of the dispersant is to protect the dispersed
particles against agglomeration or flocculation. This dispersant
may be a surfactant, an oligomer, a polymer or a mixture of two or
more thereof, carrying one or more functionalities having a high
affinity for the surface of the particles to be dispersed. In
particular, they may become physically or chemically attached to
the surface of the pigments. These dispersants additionally exhibit
at least one functional group which is compatible with or soluble
in the continuous medium. Use is made in particular of the esters
of 12-hydroxystearic acid, in particular, and of a C.sub.8 to
C.sub.20 fatty acid and a polyol such as glycerol, diglycerol, such
as poly(12-hydroxystearic) acid stearate with a molecular weight of
approximately 750 g/mol, such as that sold under the name Solsperse
21 000 by Avecia, polyglyceryl-2 dipolyhydroxystearate (CTFA name)
sold under the reference Dehymyls PGPH by Henkel, or else
polyhydroxystearic acid such as that sold under the reference
Arlacel P100 by Uniqema, and mixtures thereof.
[0281] As other dispersants which can be used in the composition of
the invention, mention may be made of quaternary ammonium
derivatives of polycondensed fatty acids, such as Solsperse 17 000,
sold by Avecia, and of mixtures of
polydimethylsiloxane/oxypropylene such as those sold by Dow Corning
under the references DC2-5185 and DC2-5225 C.
[0282] Polydihydroxystearic acid and the esters of
12-hydroxystearic acid are preferably intended for a
hydrocarbon-based or fluorine-based medium, whereas mixtures of
dimethylsiloxane oxyethylene/oxypropylene are preferably intended
for a silicone-based medium.
[0283] The pigments, nacres or fillers may be introduced into the
composition in the form of a particulate paste comprising the
particles, a liquid medium and the dispersant. The liquid medium of
the particulate paste is advantageously one of the oils whose use
is desired in the composition forming part of the liquid fatty
phase.
[0284] The composition according to the invention may additionally
comprise ingredients commonly used in cosmetology, such as
vitamins, trace elements, softeners, sequestrants, perfumes,
alkalifying or acidifying agents, preservatives, sunscreens,
surfactants, antioxidants or mixtures thereof.
[0285] It will be appreciated that the skilled person will take
care to select this or these optional additional compounds, and/or
their amount, in such a way that the advantageous properties of the
corresponding composition according to the invention are not, or
not substantially, adversely affected by the addition
envisaged.
[0286] The composition according to the invention may be in the
form in particular of a suspension, dispersion, solution, gel,
emulsion, especially an oil-in-water (O/W) or water-in-oil (W/O) or
multiple (W/O/W or polyol/O/W or O/W/O) emulsion, in the form of a
cream, paste, mousse, a dispersion of vesicles, especially of ionic
or nonionic lipids, or in the form of a two-phase or multiphase
lotion. The composition may be anhydrous; for example, it may
comprise an anhydrous stick or paste.
[0287] By "anhydrous" is meant a composition which may contain less
than 5% of water, better still less than 3% of water, and more
preferably 1% of water relative to the total weight of the
composition.
[0288] The skilled person will be able to select the appropriate
presentation form, and also the method of preparing it, on the
basis of his or her general knowledge, taking into account, first,
the nature of the constituents used, particularly their solubility
in the vehicle, and, secondly, the application intended for the
composition.
[0289] According to another aspect the invention also pertains to a
cosmetic assembly comprising: [0290] i) a container delimiting at
least one compartment, the said container being closed by a closing
member; and [0291] ii) a composition disposed within the said
compartment, the composition being in accordance with the
invention.
[0292] The container may be in any suitable form. It may in
particular be in the form of a bottle, tube, jar, case, box, sachet
or carton.
[0293] The closing member may be in the form of a removable
stopper, a lid, a cap, a tear-off strip or a capsule, particularly
of the type comprising a body attached to the container and a cover
cap articulated on the body. It may also be in the form of a member
for selectively closing the container, especially a pump, a valve
or a flap.
[0294] The container may be combined with an applicator. The
applicator may be in the form of a fine brush, as described for
example in patent FR 2 722 380. The applicator may be in the form
of a block of foam or of elastomer, a felt or a spatula. The
applicator may be free (a tuft or sponge) or may be securely
attached to a rod carried by the closing member, as described for
example in patent U.S. Pat. No. 5,492,426. The applicator may be
securely attached to the container, as described, for example, by
patent FR 2 761 959.
[0295] The product may be contained directly in the container or
indirectly. By way of example, the product may be disposed on an
impregnated support, especially in the form of a wipe or a pad, and
may be disposed (individually or in plurality) in a carton or in a
sachet. A support of this kind incorporating the product is
described for example in patent application WO 01/03538.
[0296] The closing member may be coupled to the container by
screwing. Alternatively the coupling between the closing member and
the container is accomplished other than by screwing, in particular
via a bayonet mechanism, by snap fastening, gripping, welding,
adhesive bonding, or magnetic attraction. By "snap fastening" is
meant, in particular, any system involving the crossing of a bead
or cord of material by elastic deformation of a portion, in
particular of the closing member, followed by return to the
elastically unconstrained position of the said portion after the
crossing of the bead or cord.
[0297] The container may be at least partly made of thermoplastic
material. Examples of thermoplastic materials that may be mentioned
include polypropylene and polyethylene.
[0298] Alternatively the container is made of non-thermoplastic
material, in particular of glass or of metal (or alloy).
[0299] The container may have rigid walls or deformable walls, in
the form in particular of a tube or a tubular bottle.
[0300] The container may comprise means intended for distributing
or facilitating the distribution of the composition. By way of
example, the container may have deformable walls so as to allow the
composition to exit in response to a positive pressure within the
container, this positive pressure being caused by elastic (or
non-elastic) squeezing of the walls of the container.
Alternatively, and particularly when the product is in the form of
a stick, the product may be driven out by a piston mechanism. Still
in the case of a stick, the container may comprise a mechanism, in
particular a rack mechanism, or a mechanism with a threaded rod, or
with a helical groove, and may be capable of moving a stick in the
direction of the said opening. A mechanism of this kind is
described for example in patent FR 2 806 273 or in patent FR 2 775
566. A mechanism of this kind for a liquid product is described in
patent FR 2 727 609.
[0301] The container may be composed of a carton with a base
delimiting at least one housing containing the composition and a
cover which is articulated, in particular, on the base and is able
to cover the said base at least partly. A carton of this kind is
described for example in patent application WO 03/013423 or in
patent FR 2 791 042.
[0302] The container may be equipped with a drainer arranged in the
region of the opening of the container. A drainer of this kind
allows the applicator to be wiped and, where appropriate, allows
the rod to which it may be securely attached to be wiped. A drainer
of this kind is described for example in patent FR 2 792 618.
[0303] The content of the patents or patent applications cited
above is incorporated by reference into the present
application.
[0304] The invention is illustrated in greater detail by the
examples described below.
EXAMPLE 5
Lipstick
[0305] TABLE-US-00001 Ingredients, INCI name % by mass
Octyldodecanol 11.75 VP-eicosene copolymer (Antaron V 220, ISP) 15
Polyethylene (Polywax 500, Bareco) 13 Pigments 10.25 Polymer of
Example 1 50
[0306] In a melting pot, the waxes, the oily phase and the pigments
in the form of a millbase are introduced into the oily phase
containing the PVP-eicosene. The mixture is melted at 100.degree.
C. with Rayneri stirring. When the preparation is liquid, the whole
is left at 100.degree. C. for 40 minutes. Then the volatile
ingredients, or ingredients containing volatile solvents, are
introduced. The pot is covered in order to limit evaporation, and
the mixture is left with stirring for 10 minutes. The formula is
then cast at 42.degree. C. before being placed in a freezer.
Demoulding is carried out when the mould temperature is
approximately 4.degree. C.
[0307] The transfer of this formula was measured in accordance with
the protocol described above. It is equal to 1.85.+-.0.1.
EXAMPLE 6
Lipstick
[0308] In a melting pot, with Rayneri stirring, the waxes, pigment
pastes and sucrose ester are introduced, the temperature is
stabilized at 105.degree. C., the mixture is turned for 30 minutes,
and then the nacres are added, followed by the polymer dispersion
and the perfume, after which the mixture is turned for 10 minutes
and then cast in a mould at 42.degree. C. The mould is placed in a
freezer and demoulding is carried out when the mould is at
approximately 4.degree. C.; TABLE-US-00002 Ingredients % by mass
Pigments 8.20 Hydrogenated polyisobutene (Parleam) 5.18
Polyhydroxystearic 0.21 acid (Octacare DSPOL300, Avecia) C30-C50
alcohols 2 (Performacol 550 Alcohol, New Phase Technologies)
Polyethylene (Polywax 500, Bareco) 10 Sucrose acetate isobutyrate 5
(Eastman SAIB Special, Eastman Chemical) Polymer of Example 1 68.82
Perfume qs
[0309] The transfer, measured according to the protocol described
above, is 1.2.
EXAMPLE 7
Lipstick
[0310] TABLE-US-00003 Pigments 8.20 Hydrogenated polyisobutene
(Parleam) 5.18 Polyhydroxystearic acid (Octacare DSPOL300, Avecia)
0.21 C30-C50 alcohols 2 (Performacol 550 Alcohol, New Phase
Technologies) Polyethylene (Polywax 500, Bareco) 10 Sucrose acetate
isobutyrate 5 (Eastman SAIB Special, Eastman Chemical) Polymer of
Example 4 68.82 Perfume qs
* * * * *