U.S. patent application number 10/529218 was filed with the patent office on 2006-06-01 for glossy liquid composition comprising a sequenced polymer.
Invention is credited to Xavier Blin, Veronique Ferrari.
Application Number | 20060115444 10/529218 |
Document ID | / |
Family ID | 32045662 |
Filed Date | 2006-06-01 |
United States Patent
Application |
20060115444 |
Kind Code |
A1 |
Blin; Xavier ; et
al. |
June 1, 2006 |
Glossy liquid composition comprising a sequenced polymer
Abstract
The present invention relates to a liquid cosmetic composition
containing a cosmetically acceptable organic liquid medium and a
non-elastomeric film-forming linear ethylenic block polymer in a
sufficient amount such that the mean gloss of a deposit of the
composition, once spread onto a support, is greater than or equal
to 30 out of 100.
Inventors: |
Blin; Xavier; (Paris,
FR) ; Ferrari; Veronique; (Maison-Alfort,
FR) |
Correspondence
Address: |
FINNEGAN, HENDERSON, FARABOW, GARRETT & DUNNER;LLP
901 NEW YORK AVENUE, NW
WASHINGTON
DC
20001-4413
US
|
Family ID: |
32045662 |
Appl. No.: |
10/529218 |
Filed: |
September 26, 2003 |
PCT Filed: |
September 26, 2003 |
PCT NO: |
PCT/FR03/02842 |
371 Date: |
October 3, 2005 |
Current U.S.
Class: |
424/70.16 |
Current CPC
Class: |
Y10S 514/937 20130101;
A61K 8/922 20130101; C08F 265/04 20130101; A61K 8/891 20130101;
C08L 53/00 20130101; C08L 51/003 20130101; C08F 265/06 20130101;
C08L 51/003 20130101; A61K 8/927 20130101; A61K 8/8111 20130101;
A61K 8/26 20130101; C08F 291/00 20130101; C08L 53/00 20130101; A61K
8/90 20130101; Y10S 514/844 20130101; A61Q 1/04 20130101; A61K
2800/594 20130101; A61Q 1/06 20130101; A61K 8/8182 20130101; Y10S
514/845 20130101; A61Q 1/10 20130101; C08F 293/005 20130101; A61K
8/8152 20130101; A61Q 3/02 20130101; C08L 2666/02 20130101; C08L
2666/02 20130101 |
Class at
Publication: |
424/070.16 |
International
Class: |
A61K 8/81 20060101
A61K008/81 |
Foreign Application Data
Date |
Code |
Application Number |
Sep 26, 2002 |
FR |
0211949 |
Dec 20, 2002 |
FR |
0216437 |
May 21, 2003 |
FR |
0306121 |
Claims
1. Liquid cosmetic composition containing a cosmetically acceptable
organic liquid medium and a non-elastomeric film-forming linear
block ethylenic polymer, the said polymer being such that, when it
is in sufficient amount in the composition, the mean gloss at
20.degree. of a deposit of the said composition, once spread onto a
support, is greater than or equal to 30 out of 100.
2. Liquid cosmetic composition containing a cosmetically acceptable
organic liquid medium and a film-forming linear block ethylenic
polymer free of styrene units, the polymer being such that, when it
is in sufficient amount in the composition, the mean gloss at
20.degree. of a deposit of the said composition, once spread onto a
support, is greater than or equal to 30 out of 100.
3. Cosmetic composition according to claim 1 or 2, characterized in
that the block polymer is an ethylenic polymer derived from
aliphatic ethylenic monomers comprising a carbon-carbon double bond
and at least one ester --COO-- or amide --CON-- group.
4. Cosmetic composition according to one of the preceding claims,
characterized in that the polymer is not soluble at an active
material content of at least 1% by weight in water or in a mixture
of water and of linear or branched lower monoalcohols containing
from 2 to 5 carbon atoms, without pH modification, at room
temperature (25.degree. C.).
5. Cosmetic composition according to one of the preceding claims,
characterized in that the block polymer contains first and second
blocks linked together via an intermediate segment comprising at
least one constituent monomer of the first block and at least one
constituent monomer of the second block.
6. Cosmetic composition according to one of the preceding claims,
characterized in that the block polymer contains first and second
blocks with different glass transition temperatures (Tg).
7. Composition according to the preceding claim, characterized in
that the first and second blocks are linked together via an
intermediate segment with a glass transition temperature that is
between the glass transition temperatures of the first and second
blocks.
8. Cosmetic composition according to any one of the preceding
claims, characterized in that the block polymer contains first and
second blocks that are incompatible in the said organic liquid
medium.
9. Cosmetic composition according to one of the preceding claims,
characterized in that the block polymer has a polydispersity index
I of greater than 2.
10. Composition according to claim 6, characterized in that the
first block of the polymer is chosen from: a) a block with a Tg of
greater than or equal to 40.degree. C., b) a block with a Tg of
less than or equal to 20.degree. C., c) a block with a Tg of
between 20 and 40.degree. C., and the second block is chosen from a
category a), b) or c) different from the first block.
11. Composition according to claim 10, characterized in that the
block with a Tg of greater than or equal to 40.degree. C. is
totally or partially derived from one or more monomers, which are
such that the homopolymer prepared from these monomers has a glass
transition temperature of greater than or equal to 40.degree.
C.
12. Composition according to the preceding claim, characterized in
that the monomers whose corresponding homopolymer has a glass
transition temperature of greater than or equal to 40.degree. C.
are chosen from the following monomers: methacrylates of formula
CH.sub.2.dbd.C(CH.sub.3)--COOR.sub.1 in which R.sub.1 represents a
linear or branched unsubstituted alkyl group containing from 1 to 4
carbon atoms, such as a methyl, ethyl, propyl or isobutyl group or
R.sub.1 represents a C.sub.4 to C.sub.12 cycloalkyl group,
acrylates of formula CH.sub.2.dbd.CH--COOR.sub.2 in which R.sub.2
represents a C.sub.4 to C.sub.12 cycloalkyl group such as isobornyl
acrylate or a tert-butyl group, (meth)acrylamides of formula:
##STR2## in which R.sub.7 and R.sub.8, which may be identical or
different, each represent a hydrogen atom or a linear or branched
C.sub.1 to C.sub.12 alkyl group such as an n-butyl, t-butyl,
isopropyl, isohexyl, isooctyl or isononyl group; or R.sub.7
represents H and R.sub.8 represents a 1,1-dimethyl-3-oxobutyl
group, and R' denotes H or methyl, and mixtures thereof.
13. Composition according to claim 11 or 12, characterized in that
the monomers whose corresponding homopolymer has a glass transition
temperature of greater than or equal to 40.degree. C. are chosen
from methyl methacrylate, isobutyl (meth)acrylate and isobornyl
(meth)acrylate, and mixtures thereof.
14. Composition according to claim 10, characterized in that the
block with a Tg of less than or equal to 20.degree. C. is derived
totally or partially from one or more monomers, which are such that
the homopolymer prepared from these monomers has a glass transition
temperature of less than or equal to 20.degree. C.
15. Composition according to claim 14, characterized in that the
monomers whose corresponding homopolymer has a glass transition
temperature of less than or equal to 20.degree. C. are chosen from
the following monomers: acrylates of formula
CH.sub.2.dbd.CHCOOR.sub.3, R.sub.3 representing a linear or
branched C.sub.1 to C.sub.12 unsubstituted alkyl group, with the
exception of the tert-butyl group, in which one or more hetero
atoms chosen from O, N and S is (are) optionally intercalated;
methacrylates of formula CH.sub.2.dbd.C(CH.sub.3)--COOR.sub.4,
R.sub.4 representing a linear or branched C.sub.6 to C.sub.12
unsubstituted alkyl group, in which one or more hetero atoms chosen
from O, N and S is (are) optionally intercalated; vinyl esters of
formula R.sub.5--CO--O--CH.dbd.CH.sub.2 in which R.sub.5 represents
a linear or branched C.sub.4 to C.sub.12 alkyl group; C.sub.4 to
C.sub.12 alkyl vinyl ethers, N--(C.sub.4 to C.sub.12)alkyl
acrylamides, such as N-octylacrylamide, and mixtures thereof.
16. Composition according to claim 14 or 15, characterized in that
the monomers whose corresponding homopolymer has a glass transition
temperature of less than or equal to 20.degree. C. are chosen from
alkyl acrylates whose alkyl chain contains from 1 to 10 carbon
atoms, with the exception of the tert-butyl group.
17. Composition according to claim 10, characterized in that the
block with a Tg of between 20 and 40.degree. C. is totally or
partially derived from one or more monomers, which are such that
the homopolymer prepared from these monomers has a glass transition
temperature of between 20 and 40.degree. C.
18. Composition according to claim 10, characterized in that the
block with a Tg of between 20 and 40.degree. C. is totally or
partially derived from monomers which are such that the
corresponding homopolymer has a Tg of greater than or equal to
40.degree. C. and from monomers which are such that the
corresponding homopolymer has a Tg of less than or equal to
20.degree. C.
19. Composition according to claim 17 or 18, characterized in that
the block with a Tg of between 20 and 40.degree. C. is totally or
partially derived from monomers chosen from methyl methacrylate,
isobornyl acrylate and methacrylate, butyl acrylate and
2-ethylhexyl acrylate, and mixtures thereof.
20. Composition according to one of claims 10 to 19, characterized
in that it comprises a block polymer comprising at least one first
block and at least one second block, the first block having a glass
transition temperature (Tg) of greater than or equal to 40.degree.
C. and the second block having a glass transition temperature of
less than or equal to 20.degree. C.
21. Composition according to the preceding claim, characterized in
that the first block is totally or partially derived from one or
more monomers which are such that the homopolymer prepared from
these monomers has a glass transition temperature of greater than
or equal to 40.degree. C.
22. Composition according to claim 21, characterized in that the
first block is a copolymer derived from monomers which are such
that the homopolymer prepared from these monomers has a glass
transition temperature of greater than or equal to 40.degree.
C.
23. Composition according to claim 21 or 22, characterized in that
the monomers whose corresponding homopolymer has a glass transition
temperature of greater than or equal to 40.degree. C. are chosen
from the following monomers: methacrylates of formula
CH.sub.2.dbd.C(CH.sub.3)--COOR.sub.1 in which R.sub.1 represents a
linear or branched unsubstituted alkyl group containing from 1 to 4
carbon atoms, such as a methyl, ethyl, propyl or isobutyl group or
R.sub.1 represents a C.sub.4 to C.sub.12 cycloalkyl group,
acrylates of formula CH.sub.2.dbd.CH--COOR.sub.2 in which R.sub.2
represents a C.sub.4 to C.sub.12 cycloalkyl group such as isobornyl
acrylate or a tert-butyl group, (meth)acrylamides of formula:
##STR3## in which R.sub.7 and R.sub.8, which may be identical or
different, each represent a hydrogen atom or a linear or branched
C.sub.1 to C.sub.12 alkyl group such as an n-butyl, t-butyl,
isopropyl, isohexyl, isooctyl or isononyl group; or R.sub.7
represents H and R.sub.8 represents a 1,1-dimethyl-3-oxobutyl
group, and R' denotes H or methyl, and mixtures thereof.
24. Composition according to one of claims 21 to 23, characterized
in that the monomers whose corresponding homopolymer has a glass
transition temperature of greater than or equal to 40.degree. C.
are chosen from methyl methacrylate, isobutyl methacrylate and
isobornyl (meth)acrylate, and mixtures thereof.
25. Composition according to one of claims 21 to 24, characterized
in that the proportion of the first block ranges from 20% to 90%,
better still from 30% to 80% and even better from 50% to 70% by
weight of the polymer.
26. Composition according to one of claims 20 to 25, characterized
in that the second block is totally or partially derived from one
or more monomers which are such that the homopolymer prepared from
these monomers has a glass transition temperature of less than or
equal to 20.degree. C.
27. Composition according to one of claims 20 to 26, characterized
in that the second block is a homopolymer derived from monomers
which are such that the homopolymer prepared from these monomers
has a glass transition temperature of less than or equal to
20.degree. C.
28. Composition according to claim 26 or 27, characterized in that
the monomers whose corresponding homopolymer has a glass transition
temperature of less than or equal to 20.degree. C. are chosen from
the following monomers: acrylates of formula
CH.sub.2.dbd.CHCOOR.sub.3, R.sub.3 representing a linear or
branched C.sub.1 to C.sub.12 unsubstituted alkyl group, with the
exception of the tert-butyl group, in which one or more hetero
atoms chosen from O, N and S is (are) optionally intercalated;
methacrylates of formula CH.sub.2.dbd.C(CH.sub.3)--COOR.sub.4,
R.sub.4 representing a linear or branched C.sub.6 to C.sub.12
unsubstituted alkyl group, in which one or more hetero atoms chosen
from O, N and S is (are) optionally intercalated; vinyl esters of
formula R.sub.5--CO--O--CH.dbd.CH.sub.2 in which R.sub.5 represents
a linear or branched C.sub.4 to C.sub.12 alkyl group; C.sub.4 to
C.sub.12 alkyl vinyl ethers, N--(C.sub.4 to C.sub.12)alkyl
acrylamides, such as N-octylacrylamide, and mixtures thereof.
29. Composition according to one of claims 26 to 28, characterized
in that the monomers whose corresponding homopolymer has a glass
transition temperature of less than or equal to 20.degree. C. are
chosen from alkyl acrylates whose alkyl chain contains from 1 to 10
carbon atoms, with the exception of the tert-butyl group.
30. Composition according to one of claims 20 to 29, characterized
in that the proportion of the second block with a Tg of less than
or equal to 20.degree. C. ranges from 5% to 75%, better still from
15% to 50% and even better from 25% to 45% by weight of the
polymer.
31. Composition according to one of claims 10 to 19, characterized
in that it comprises a block polymer comprising at least one first
block and at least one second block, the first block having a glass
transition temperature (Tg) of between 20 and 40.degree. C. and the
second block having a glass transition temperature of less than or
equal to 20.degree. C. or a glass transition temperature of greater
than or equal to 40.degree. C.
32. Composition according to the preceding claim, characterized in
that the first block with a Tg of between 20 and 40.degree. C. is
totally or partially derived from one or more monomers which are
such that the homopolymer prepared from these monomers has a glass
transition temperature of between 20 and 40.degree. C.
33. Composition according to claim 31 or 32, characterized in that
the first block with a Tg of between 20 and 40.degree. C. is a
copolymer derived from monomers which are such that the
corresponding homopolymer has a Tg of greater than or equal to
40.degree. C. and from monomers which are such that the
corresponding homopolymer has a Tg of less than or equal to
20.degree. C.
34. Composition according to one of claims 31 to 33, characterized
in that the first block with a Tg of between 20 and 40.degree. C.
is derived from monomers chosen from methyl methacrylate, isobornyl
acrylate and methacrylate, butyl acrylate and 2-ethylhexyl
acrylate, and mixtures thereof.
35. Composition according to one of claims 31 to 34, characterized
in that the proportion of the first block with a Tg of between 20
and 40.degree. C. ranges from 10% to 85%, better still from 30% to
80% and even better from 50% to 70% by weight of the polymer.
36. Composition according to any one of claims 31 to 34,
characterized in that the second block has a Tg of greater than or
equal to 40.degree. C. and is totally or partially derived from one
or more monomers which are such that the homopolymer prepared from
these monomers has a glass transition temperature of greater than
or equal to 40.degree. C.
37. Composition according to any one of claims 31 to 36,
characterized in that the second block has a Tg of greater than or
equal to 40.degree. C. and is a homopolymer derived from monomers
which are such that the homopolymer prepared from these monomers
has a glass transition temperature of greater than or equal to
40.degree. C.
38. Composition according to either of claims 36 and 37,
characterized in that the monomers whose corresponding homopolymer
has a glass transition temperature of greater than or equal to
40.degree. C. are chosen from the following monomers: methacrylates
of formula CH.sub.2.dbd.C(CH.sub.3)--COOR.sub.1 in which R.sub.1
represents a linear or branched unsubstituted alkyl group
containing from 1 to 4 carbon atoms, such as a methyl, ethyl,
propyl or isobutyl group or R.sub.1 represents a C.sub.4 to
C.sub.12 cycloalkyl group, acrylates of formula
CH.sub.2.dbd.CH--COOR.sub.2 in which R.sub.2 represents a C.sub.4
to C.sub.12 cycloalkyl group such as isobornyl acrylate or a
tert-butyl group, (meth)acrylamides of formula: ##STR4## in which
R.sub.7 and R.sub.8, which may be identical or different, each
represent a hydrogen atom or a linear or branched C.sub.1 to
C.sub.12 alkyl group such as an n-butyl, t-butyl, isopropyl,
isohexyl, isooctyl or isononyl group; or R.sub.7 represents H and
R.sub.8 represents a 1,1-dimethyl-3-oxobutyl group, and R' denotes
H or methyl, and mixtures thereof.
39. Composition according to one of claims 35 to 38, characterized
in that the monomers whose corresponding homopolymer has a glass
transition temperature of greater than or equal to 40.degree. C.
are chosen from methyl methacrylate, isobutyl methacrylate and
isobornyl (meth)acrylate, and mixtures thereof.
40. Composition according to one of claims 36 to 39, characterized
in that the proportion of the second block with a Tg of greater
than or equal to 40.degree. C. ranges from 10% to 85%, preferably
from 20% to 70% and better still from 30% to 70% by weight of the
polymer.
41. Composition according to one of claims 31 to 40, characterized
in that the second block has a Tg of less than or equal to
20.degree. C. and is totally or partially derived from one or more
monomers which are such that the homopolymer prepared from these
monomers has a glass transition temperature of less than or equal
to 20.degree. C.
42. Composition according to one of claims 31 to 40, characterized
in that the second block has a Tg of less than or equal to
20.degree. C. and is a homopolymer derived from monomers which are
such that the homopolymer prepared from these monomers has a glass
transition temperature of less than or equal to 20.degree. C.
43. Composition according to claim 41 or 42, characterized in that
the monomers whose corresponding homopolymer has a glass transition
temperature of less than or equal to 20.degree. C. are chosen from
the following monomers: acrylates of formula
CH.sub.2.dbd.CHCOOR.sub.3, R.sub.3 representing a linear or
branched C.sub.1 to C.sub.12 unsubstituted alkyl group, with the
exception of the tert-butyl group, in which one or more hetero
atoms chosen from O, N and S is (are) optionally intercalated;
methacrylates of formula CH.sub.2.dbd.C(CH.sub.3)--COOR.sub.4,
R.sub.4 representing a linear or branched C.sub.6 to C.sub.12
unsubstituted alkyl group, in which one or more hetero atoms chosen
from O, N and S is (are) optionally intercalated; vinyl esters of
formula R.sub.5--CO--O--CH.dbd.CH.sub.2 in which R.sub.5 represents
a linear or branched C.sub.4 to C.sub.12 alkyl group; C.sub.4 to
C.sub.12 alkyl vinyl ethers, N--(C.sub.4 to C.sub.12)alkyl
acrylamides, such as N-octylacrylamide, and mixtures thereof.
44. Composition according to one of claims 41 to 43, characterized
in that the monomers whose homopolymers have glass transition
temperatures of less than or equal to 20.degree. C. are chosen from
alkyl acrylates whose alkyl chain contains from 1 to 10 carbon
atoms, with the exception of the tert-butyl group.
45. Composition according to one of claims 41 to 44, characterized
in that the proportion of the block with a glass transition
temperature of greater than or equal to 40.degree. C. ranges from
20% to 90%, better still from 30% to 80% and even better from 50%
to 70% by weight of the polymer.
46. Cosmetic composition according to one of claims 5 to 8 or any
of the preceding claims dependent thereon, characterized in that
the first block and/or the second block comprises at least one
additional monomer.
47. Composition according to the preceding claim, characterized in
that the additional monomer is chosen from hydrophilic monomers and
ethylenically unsaturated monomers comprising one or more silicon
atoms, and mixtures thereof.
48. Composition according to claim 46 or 47, characterized in that
the additional monomer is chosen from: a) hydrophilic monomers such
as: ethylenically unsaturated monomers comprising at least one
carboxylic or sulfonic acid function, for instance: acrylic acid,
methacrylic acid, crotonic acid, maleic anhydride, itaconic acid,
fumaric acid, maleic acid, acrylamidopropanesulfonic acid,
vinylbenzoic acid, vinylphosphoric acid, and salts thereof,
ethylenically unsaturated monomers comprising at least one tertiary
amine function, for instance 2-vinylpyridine, 4-vinylpyridine,
dimethylaminoethyl methacrylate, diethylaminoethyl methacrylate and
dimethylaminopropylmethacrylamide, and salts thereof, methacrylates
of formula CH.sub.2.dbd.C(CH.sub.3)--COOR.sub.6 in which R.sub.6
represents a linear or branched alkyl group containing from 1 to 4
carbon atoms, such as a methyl, ethyl, propyl or isobutyl group,
the said alkyl group being substituted with one or more
substituents chosen from hydroxyl groups (for instance
2-hydroxypropyl methacrylate and 2-hydroxyethyl methacrylate) and
halogen atoms (Cl, Br, I or F), such as trifluoroethyl
methacrylate, methacrylates of formula
CH.sub.2.dbd.C(CH.sub.3)--COOR.sub.9, R.sub.9 representing a linear
or branched C.sub.6 to C.sub.12 alkyl group in which one or more
hetero atoms chosen from O, N and S is (are) optionally
intercalated, the said alkyl group being substituted with one or
more substituents chosen from hydroxyl groups and halogen atoms
(Cl, Br, I or F); acrylates of formula CH.sub.2.dbd.CHCOOR.sub.10,
R.sub.10 representing a linear or branched C.sub.1 to C.sub.12
alkyl group substituted with one or more substituents chosen from
hydroxyl groups and halogen atoms (Cl, Br, I or F), such as
2-hydroxypropyl acrylate and 2-hydroxyethyl acrylate, or R.sub.10
represents a C.sub.1 to C.sub.12 alkyl-O-POE (polyoxyethylene) with
repetition of the oxyethylene unit 5 to 30 times, for example
methoxy-POE, or R.sub.10 represents a polyoxyethylenated group
comprising from 5 to 30 ethylene oxide units, and b) ethylenically
unsaturated monomers comprising one or more silicon atoms, such as
methacryloxypropyltrimethoxysilane and
methacryloxypropyl-tris(trimethylsiloxy)silane, and mixtures
thereof.
49. Composition according to either of claims 46 and 47,
characterized in that each of the first and second blocks comprises
at least one additional monomer chosen from acrylic acid,
(meth)acrylic acid and trifluoroethyl methacrylate, and mixtures
thereof.
50. Composition according to either of claims 46 and 47,
characterized in that each of the first and second blocks comprises
at least one monomer chosen from (meth)acrylic acid esters and
optionally at least one additional monomer such as (meth)acrylic
acid, and mixtures thereof.
51. Composition according to either of claims 46 and 47,
characterized in that each of the first and second blocks is
totally derived from at least one monomer chosen from (meth)acrylic
acid esters and optionally from at least one additional monomer
such as (meth)acrylic acid, and mixtures thereof.
52. Composition according to one of claims 46 to 51, characterized
in that the additional monomer(s) represent(s) from 1% to 30% by
weight relative to the total weight of the first and/or second
blocks.
53. Composition according to claim 6 or any one of the preceding
claims dependent thereon, characterized in that the difference
between the glass transition temperatures (Tg) of the first and
second blocks is greater than 10.degree. C., better still greater
than 20.degree. C., preferably greater than 30.degree. C. and
better still greater than 40.degree. C.
54. Composition according to claim 9, characterized in that the
block polymer has a polydispersity index of greater than or equal
to 2.5 and preferably greater than or equal to 2.8.
55. Composition according to claim 54, characterized in that it has
a polydispersity index of between 2.8 and 6.
56. Composition according to one of the preceding claims,
characterized in that the block polymer has a weight-average mass
(Mw) of less than or equal to 300 000.
57. Composition according to claim 56, characterized in that the
weight-average mass (Mw) ranges from 35 000 to 200 000 and better
still from 45 000 to 150 000.
58. Composition according to claim 57, characterized in that the
number-average mass (Mn) is less than or equal to 70 000.
59. Composition according to one of claims 56 to 58, the
number-average mass (Mn) of which ranges from 10 000 to 60 000 and
better still from 12 000 to 50 000.
60. Composition according to one of the preceding claims,
characterized in that the mean gloss of the composition measured at
20.degree. is greater than or equal to 30, even better greater than
or equal to 35, better still greater than or equal to 40, better
still greater than or equal to 45, better still greater than or
equal to 50 out of 100, better still greater than or equal to 55,
better still greater than or equal to 60, better still greater than
or equal to 65, better still greater than or equal to 70, or even
better still greater than or equal to 75 out of 100.
61. Composition according to one of the preceding claims,
characterized in that the mean gloss of the composition, once
spread onto a support, measured at 60.degree., is greater than or
equal to 50, better still greater than or equal to 60, better still
greater than or equal to 65, better still greater than or equal to
70, better still greater than or equal to 75, better still greater
than or equal to 80, better still greater than or equal to 85 or
even better still greater than or equal to 90 out of 100.
62. Composition according to one of the preceding claims,
characterized in that the mean gloss of the composition measured at
20.degree. is greater than or equal to 35, preferably 40, 45 or 50
out of 100, and/or the gloss of the composition measured at
60.degree. is greater than or equal to 65, 70 or 75 out of 100.
63. Composition according to one of the preceding claims,
characterized in that the gloss of the composition measured at
20.degree. is greater than or equal to 60, preferably 65, 70 or 75
out of 100, and/or the gloss of the composition measured at
60.degree. is greater than or equal to 80, 85 or 90 out of 100.
64. Composition according to one of the preceding claims,
characterized in that it comprises from 0.1% to 60% by weight of
active material, preferably from 5% to 50% by weight and more
preferably from 10% to 40% by weight, of polymer.
65. Cosmetic composition according to any one of the preceding
claims, characterized in that it also comprises one or more
dyestuffs chosen from water-soluble dyes and pulverulent dyestuffs,
such as pigments, nacres and flakes.
66. Cosmetic composition according to any one of the preceding
claims, characterized in that it is in the form of a suspension, a
dispersion, a solution, a gel, an emulsion, especially an
oil-in-water (O/W) or water-in-oil (W/O) emulsion, or a multiple
emulsion (W/O/W or polyol/O/W or O/w/O), or in the form of a cream,
a mousse, a dispersion of vesicles, especially of ionic or nonionic
lipids, a two-phase or multi-phase lotion, or a paste, especially a
soft paste or an anhydrous paste.
67. Cosmetic composition according to any one of the preceding
claims, characterized in that it is in anhydrous form.
68. Cosmetic composition according to any one of the preceding
claims, characterized in that it is a makeup or care composition
for keratin materials.
69. Cosmetic composition according to one of the preceding claims,
characterized in that it is a lip makeup product.
70. Cosmetic composition according to one of the preceding claims,
characterized in that it is an eye makeup product.
71. Cosmetic composition according to one of the preceding claims,
characterized in that it is a nail makeup product.
72. Cosmetic assembly comprising: a) a container delimiting at
least one compartment, the said container being closed by a closing
member; and b) a composition placed inside the said compartment,
the composition being in accordance with any one of the preceding
claims.
73. Cosmetic assembly according to claim 72, characterized in that
the container is at least partially formed from at least one
thermoplastic material.
74. Cosmetic assembly according to claim 72, characterized in that
the container is at least partially formed from at least one
non-thermoplastic material, especially from glass or metal.
75. Assembly according to any one of claims 72 to 74, characterized
in that, in the closed position of the container, the closing
member is screwed onto the container.
76. Assembly according to any one of claims 72 to 74, characterized
in that, in the closed position of the container, the closing
member is coupled to the container other than by screwing,
especially by click-fastening, bonding or welding.
77. Assembly according to any one of claims 72 to 76, characterized
in that the composition is substantially at atmospheric pressure
inside the compartment.
78. Assembly according to any one of claims 72 to 76, characterized
in that the composition is pressurized inside the container.
79. Cosmetic process for making up or caring for keratin materials,
comprising the application to the keratin materials of a cosmetic
composition according to one of claims 1 to 71.
Description
[0001] The present invention relates to a liquid cosmetic
composition for making up or caring for the skin, including the
scalp, of both the human face and body, and human lips or
integuments, for instance the hair, the eyelashes, the eyebrows or
the nails, comprising a cosmetically acceptable medium containing a
particular block polymer.
[0002] There are many cosmetic compositions for which the gloss
properties of the deposited film, after application to keratin
materials (skin, lips or integuments) are very substantial.
Examples that may be mentioned include lipsticks, nail varnishes or
certain hair products and certain mascaras.
[0003] It is known to cosmetic product formulators that this gloss
property is promoted when used is made of oils characterized by a
high viscosity and a high refractive index and which also have good
pigment or filler dispersing properties when the latter are present
in the composition.
[0004] In this perspective, the formulator has available several
types of raw material, for instance oily polymers such as
polybutenes, sold especially under the reference Indopol H100, H300
and H1500 by the company Amoco, which have a very high viscosity
but, however, have the drawback of being both very tacky and of
having relatively poor pigment dispersing properties, which limits
their use.
[0005] The aim of the present invention is to propose a novel route
for formulating a cosmetic product, in particular a makeup product,
which has good gloss properties.
[0006] In particular, the product of the invention makes it
possible to obtain continuous deposits on the skin or the lips,
which shows good coverage, having a very glossy appearance that
meets the desires of consumers, which does not migrate, does not
transfer, has good staying power, is not oily, and does not dry out
the skin, the hair or the lips to which it is applied, either
during the application or over time. It also has good stability
properties and thus allows a homogeneous and aesthetic
application.
[0007] One subject of the invention is a glossy liquid composition
for caring for or making up the skin and/or the lips and/or
integuments, containing a block polymer, which makes it possible to
overcome the drawbacks of the known glossy compositions. The
inventors have found, surprisingly, that the use of a sufficient
amount of a particular block polymer makes it possible to obtain a
glossy composition that also has good staying power.
[0008] The composition of the invention may in particular
constitute a haircare product or a makeup product for the human
body, lips or integuments that has care and/or treating properties.
It especially constitutes a lipstick or a lip gloss, an eyeshadow,
a tattoo product, a mascara, an eyeliner, a nail varnish, a product
for artificially tanning the skin, an optionally tinted care or
protecting cream, or a hair-colouring or haircare product.
[0009] More specifically, the invention relates to a liquid
cosmetic composition containing a cosmetically acceptable organic
liquid medium, and a non-elastomeric film-forming linear ethylenic
block polymer, the said polymer being such that, when it is in
sufficient amount in the composition, the mean gloss measured at
20.degree. of a deposit of the said composition, once spread onto a
support, is preferably greater than or equal to 30 out of 100.
[0010] A subject of the invention is also a liquid cosmetic
composition containing a cosmetically acceptable organic liquid
medium, and a film-forming linear ethylenic block polymer free of
styrene units, the said polymer being such that, when it is in
sufficient amount in the composition, the mean gloss measured at
20.degree. of a deposit of the said composition, once spread onto a
support, is preferably greater than or equal to 30 out of 100.
[0011] The term "liquid composition" means a composition which, at
25.degree. C. and atmospheric pressure, takes the shape of the
container into which it is poured.
[0012] Preferably, the composition according to the invention is a
leave-in composition.
Mean Gloss of the Composition
[0013] The term "mean gloss" means the gloss as may be
conventionally measured using a glossmeter by the following
method.
[0014] A coat of between 50 .mu.m and 150 .mu.m in thickness of the
composition is spread using an automatic spreader onto a Leneta
brand contrast card of reference Form 1A Penopac. The coat covers
at least the white background of the card. The deposit is left to
dry for 24 hours at a temperature of 30.degree. C., and the gloss
at 20.degree. is then measured on the white background using a Byk
Gardner brand glossmeter of reference microTri-Gloss.
[0015] This measurement (between 0 and 100) is repeated at least
three times, and the mean gloss is the mean of the at least three
measurements taken.
[0016] The mean gloss of the composition measured at 20.degree. is
advantageously greater than or equal to 30, better still greater
than or equal to 35, even better still greater than or equal to 40,
even better still greater than or equal to 45, even better still
greater than or equal to 50 out of 100, even better still greater
than or equal to 55, even better still greater than or equal to 60,
even better still greater than or equal to 65, even better still
greater than or equal to 70 or, even better still, greater than or
equal to 75 out of 100. For certain compositions according to the
invention, such as nail varnishes, the gloss measured at 20.degree.
may be greater than or equal to 70, or even 80 out of 100.
[0017] Preferably, the mean gloss of the composition, once spread
onto a support, measured at 60.degree. is greater than or equal to
50, better still greater than or equal to 60, better still greater
than or equal to 65, better still greater than or equal to 70,
better still greater than or equal to 75, better still greater than
or equal to 80, better still greater than or equal to 85 or, even
better still, greater than or equal to 90 out of 100.
[0018] The mean gloss at 60.degree. is measured as follows. The
gloss may be measured using a glossmeter, in a conventional manner,
by the following method.
[0019] A coat of between 50 .mu.m and 150 .mu.m in thickness of the
composition is spread using an automatic spreader onto a Leneta
brand contrast card of reference Form 1A Penopac. The coat covers
at least the white background of the card. The deposit is left to
dry for 24 hours at a temperature of 30.degree. C., and the gloss
at 60.degree. is then measured on the white background using a Byk
Gardner brand glossmeter of reference microTri-Gloss.
[0020] This measurement (between 0 and 100) is repeated at least
three times, and the mean gloss is the mean of the at least three
measurements taken.
[0021] According to one embodiment, the mean gloss of the
composition measured at 20.degree. is preferably greater than or
equal to 35, preferably 40, 45 or 50 out of 100, and/or the mean
gloss of the composition measured at 60.degree. is preferably
greater than or equal to 65, 70 or 75 out of 100. In this
embodiment, the composition advantageously constitutes a liquid
lipstick.
[0022] According to one embodiment, the mean gloss of the
composition measured at 20.degree. is preferably greater than or
equal to 60, preferably 65, 70 or 75 out of 100, and/or the mean
gloss of the composition measured at 60.degree. is preferably
greater than or equal to 80, 85 or 90 out of 100. In this
embodiment, the composition advantageously constitutes a nail
varnish.
[0023] The invention also relates to a cosmetic composition
comprising an organic liquid medium and at least one block polymer
as described below.
[0024] The invention also relates to a process for making up the
skin and/or the lips and/or the integuments, which consists in
applying the composition as defined above to the skin and/or the
lips and/or the integuments.
[0025] The composition according to the invention may be applied to
the skin of both the face and the scalp, and of the body, mucous
membranes, for instance the lips, the inside of the lower eyelids,
and integuments, for instance the nails, the eyelashes, the hair,
the eyebrows, or even body hairs.
[0026] The invention also relates to the use of a block polymer in
a sufficient amount in a cosmetic composition to give gloss and/or
staying power to a deposit of the said composition.
[0027] The invention also relates to the cosmetic use of the
composition defined above to improve the gloss of the makeup on the
skin and/or the lips and/or integuments.
[0028] The composition advantageously contains a small proportion
of oils conventionally used to impart gloss, these oils generally
being tacky.
[0029] The composition according to the invention advantageously
contains less than 30%, preferably less than 25%, less than 20% and
better still less than 15% of at least one glossy oil.
[0030] The term "oil" means a compound that is immiscible with
water in all proportions, and which is liquid at room temperature
(25.degree. C.) and atmospheric pressure (760 mmHg).
[0031] The term "glossy oil" means an oil whose molar mass
preferably ranges from 650 to 10 000 g/mol and preferably from 750
to 7500 g/mol.
[0032] The oil with a molar mass ranging from 650 to 10 000 g/mol
may be chosen from: [0033] lipophilic polymers such as: [0034]
polybutylenes such as Indopol H-100 (molar mass or MM=965 g/mol),
Indopol H-300 (MM=1340 g/mol) and Indopol H-1500 (MM=2160 g/mol)
sold or manufactured by the company Amoco, [0035] hydrogenated
polyisobutylenes such as Panalane H-300 E sold or manufactured by
the company Amoco (M=1340 g/mol), Viseal 20000 sold or manufactured
by the company Synteal (MM=6000 g/mol) and Rewopal PIB 1000 sold or
manufactured by the company Witco (MM=1000 g/mol), [0036]
polydecenes and hydrogenated polydecenes such as: Puresyn 10
(MM=723 g/mol) and Puresyn 150 (MM=9200 g/mol) sold or manufactured
by the company Mobil Chemicals, [0037] vinylpyrrolidone copolymers
such as: vinylpyrrolidone/1-hexadecene copolymer, Antaron V-216
sold or manufactured by the company ISP (MM=7300 g/mol), [0038]
esters such as: [0039] linear fatty acid esters with a total carbon
number ranging from 35 to 70, for instance pentaerythrityl
tetrapelargonate (MM=697.05 g/mol), [0040] hydroxylated esters such
as polyglyceryl-2 triisostearate (MM=965.58 g/mol), [0041] aromatic
esters such as tridecyl trimellitate (MM=757.19 g/mol), [0042]
esters of branched C.sub.24-C.sub.28 fatty alcohols or fatty acids
such as those described in patent application EP-A-0 955 039, and
especially triisoarachidyl citrate (MM=1033.76 g/mol),
pentaerythrityl tetraisononanoate (MM=697.05 g/mol), glyceryl
triisostearate (MM=891.51 g/mol), glyceryl
tris(2-decyl)tetradecanoate (MM=1143.98 g/mol), pentaerythrityl
tetraisostearate (MM=1202.02 g/mol), polyglyceryl-2
tetraisostearate (MM=1232.04 g/mol) or pentaerythrityl
tetrakis(2-decyl)tetradecanoate (MM=1538.66 g/mol), [0043] silicone
oils such as phenylsilicones, for instance Belsil PDM 1000 from the
company Wacker (MM=9000 g/mol), [0044] oils of plant origin, such
as sesame oil (820.6 g/mol), [0045] and mixtures thereof. Block
Polymer:
[0046] The composition according to the present invention contains
at least one block polymer. The term "block polymer" means a
polymer comprising at least two different blocks and preferably at
least three different blocks.
[0047] According to one embodiment, the block polymer of the
composition according to the present invention is an ethylenic
polymer. The term "ethylenic polymer" means a polymer obtained by
polymerizing monomers comprising an ethylenic unsaturation.
[0048] According to one embodiment, the block polymer of the
composition according to the present invention is a linear polymer.
In contrast, a polymer of non-linear structure is, for example, a
polymer of branched, starburst or grafted structure, or the
like.
[0049] According to one embodiment, the block polymer of the
composition according to the present invention is a film-forming
polymer. The term "film-forming polymer" means a polymer capable of
forming, by itself or in the presence of an auxiliary film-forming
agent, a continuous film that adheres to a support and especially
to keratin materials.
[0050] According to one embodiment, the block polymer of the
composition according to the invention is a non-elastomeric
polymer.
[0051] The term "non-elastomeric polymer" means a polymer which,
when it is subjected to a constraint intended to stretch it (for
example by 30% relative to its initial length), does not return to
a length substantially identical to its initial length when the
constraint ceases.
[0052] More specifically, the term "non-elastomeric polymer"
denotes a polymer with an instantaneous recovery R.sub.i<50% and
a delayed recovery R.sub.2h<70% after having been subjected to a
30% elongation. Preferably, R.sub.i is <30% and
R.sub.2h<50%.
[0053] More specifically, the non-elastomeric nature of the polymer
is determined according to the following protocol:
[0054] A polymer film is prepared by pouring a solution of the
polymer in a Teflon-coated mould, followed by drying for 7 days in
an environment conditioned at 23.+-.5.degree. C. and 50.+-.10%
relative humidity.
[0055] A film about 100 .mu.m thick is thus obtained, from which
are cut rectangular specimens (for example using a punch) 15 mm
wide and 80 mm long.
[0056] This sample is subjected to a tensile stress using a machine
sold under the reference Zwick, under the same temperature and
humidity conditions as for the drying.
[0057] The specimens are pulled at a speed of 50 mm/min and the
distance between the jaws is 50 mm, which corresponds to the
initial length (l.sub.0) of the specimen.
[0058] The instantaneous recovery R.sub.i is determined in the
following manner: [0059] the specimen is pulled by 30% (max), i.e.
about 0.3 times its initial length (l.sub.0) [0060] the constraint
is released by applying a return speed equal to the tensile speed,
i.e. 50 mm/min, and the residual elongation of the specimen is
measured as a percentage, after returning to zero constraint
(.epsilon..sub.i).
[0061] The percentage instantaneous recovery (R.sub.i) is given by
the following formula:
R.sub.i=((.epsilon..sub.max-.epsilon..sub.i)/.epsilon..sub.max).times.100
[0062] To determine the delayed recovery, the percentage residual
elongation of the specimen (.epsilon..sub.2h) is measured, 2 hours
after returning to zero constraint.
[0063] The percentage delayed recovery (R.sub.2h) is given by the
following formula:
R.sub.2h=((.epsilon..sub.max-.epsilon..sub.2h)/.epsilon..sub.max).times.1-
00
[0064] Purely as a guide, a polymer according to one embodiment of
the invention has an instantaneous recovery R.sub.i of 10% and a
delayed recovery R.sub.2h of 30%.
[0065] According to another embodiment, the block polymer of the
composition according to the invention does not comprise any
styrene units. The expression "polymer free of styrene units" means
a polymer comprising less than 10%, preferably less than 5%,
preferentially less than 2% and more preferentially less than 1% by
weight i) of styrene units of formula
--CH(C.sub.6H.sub.5)--CH.sub.2-- or ii) of substituted styrene
units, for instance methylstyrene, chlorostyrene or
chloromethylstyrene.
[0066] According to one embodiment, the block polymer of the
composition according to the invention is derived from aliphatic
ethylenic monomers. The term "aliphatic monomer" means a monomer
comprising no aromatic groups.
[0067] According to one embodiment, the block polymer is an
ethylenic polymer derived from aliphatic ethylenic monomers
comprising a carbon-carbon double bond and at least one ester group
--COO-- or amide group --CON--. The ester group may be linked to
one of the two unsaturated carbons via the carbon atom or the
oxygen atom. The amide group may be linked to one of the two
unsaturated carbons via the carbon atom or the nitrogen atom.
[0068] According to one embodiment, the block polymer comprises at
least one first block and at least one second block.
[0069] The term "at least one block" means one or more blocks.
[0070] It is pointed out that, in the text herein-above and
hereinbelow, the terms "first" and "second" blocks do not in any
way condition the order of the said blocks in the polymer
structure.
[0071] According to one embodiment, the block polymer comprises at
least one first block and at least one second block that have
different glass transition temperatures (Tg).
[0072] In this embodiment, the first and second blocks may be
linked together via an intermediate segment with a glass transition
temperature between the glass transition temperatures of the first
and second blocks.
[0073] According to one embodiment, the block polymer comprises at
least one first block and at least one second block linked together
via an intermediate segment comprising at least one constituent
monomer of the first block and at least one constituent monomer of
the second block.
[0074] Preferably, the intermediate block is derived essentially
from constituent monomers of the first block and of the second
block.
[0075] The term "essentially" means at least 85%, preferably at
least 90%, better still 95% and even better still 100%.
[0076] Advantageously, the intermediate segment comprising at least
one constituent monomer of the first block and at least one
constituent monomer of the second block of the polymer is a random
polymer.
[0077] According to one embodiment, the block polymer comprises at
least one first block and at least one second block that are
incompatible in the organic liquid medium of the composition of the
invention.
[0078] The term "mutually incompatible blocks" means that the
mixture formed from the polymer corresponding to the first block
and from the polymer corresponding to the second block is not
miscible in the liquid that is in major amount by weight contained
in the organic liquid medium of the composition, at room
temperature (25.degree. C.) and atmospheric pressure (10.sup.5 Pa),
for a content of the polymer mixture of greater than or equal to 5%
by weight, relative to the total weight of the mixture (polymers
and major organic liquid), it being understood that: [0079] i) the
said polymers are present in the mixture in a content such that the
respective weight ratio ranges from 10/90 to 90/10, and [0080] ii)
each of the polymers corresponding to the first and second blocks
has an average (weight-average or number-average) molecular mass
equal to that of the block polymer.+-.15%.
[0081] When the organic liquid medium comprises a mixture of
organic liquids, in the case of two or more liquids present in
identical mass proportions, the said polymer mixture is immiscible
in at least one of them.
[0082] When the organic liquid medium comprises only one organic
liquid, this liquid obviously constitutes the liquid that is in
major amount by weight.
[0083] The term "organic liquid medium" means a medium containing
at least one organic liquid, i.e. at least one organic compound
that is liquid at room temperature (25.degree. C.) and atmospheric
pressure (10.sup.5 Pa). According to one embodiment, the major
liquid of the organic liquid medium is a volatile or non-volatile
oil (fatty substance). Preferably, the organic liquid is
cosmetically acceptable (acceptable tolerance, toxicology and
feel). The organic liquid medium is cosmetically acceptable, in the
sense that it is compatible with keratin materials, for instance
the oils or organic solvents commonly used in cosmetic
compositions.
[0084] According to one embodiment, the major liquid of the organic
liquid medium is the polymerization solvent or one of the
polymerization solvents of the block polymer, as are described
below.
[0085] The term "polymerization solvent" means a solvent or a
mixture of solvents. The polymerization solvent may be chosen
especially from ethyl acetate, butyl acetate, alcohols such as
isopropanol and ethanol, aliphatic alkanes such as isododecane, and
mixtures thereof. Preferably, the polymerization solvent is a
mixture of butyl acetate and isopropanol, or isododecane.
[0086] In general, the block polymer may be incorporated into the
composition to a high solids content, typically greater than 10%,
greater than 20%, more preferably greater than 30% and more
preferentially greater than 45% by weight relative to the total
weight of the composition, while at the same time being easy to
formulate.
[0087] Preferably, the block polymer comprises no silicon atoms in
its skeleton. The term "skeleton" means the main chain of the
polymer, as opposed to the pendent side chains.
[0088] Preferably, the polymer according to the invention is not
water-soluble, i.e. the polymer is not soluble in water or in a
mixture of water and linear or branched lower monoalcohols
containing from 2 to 5 carbon atoms, for instance ethanol,
isopropanol or n-propanol, without pH modification, at an active
material content of at least 1% by weight, at room temperature
(25.degree. C.).
[0089] According to one embodiment, the block polymer has a
polydispersity index I of greater than 2.
[0090] Advantageously, the block polymer used in the compositions
according to the invention has a polydispersity index I of greater
than 2, for example ranging from 2 to 9, preferably greater than or
equal to 2.5, for example ranging from 2.5 to 8 and better still
greater than or equal to 2.8, and especially ranging from 2.8 to
6.
[0091] The polydispersity index I of the polymer is equal to the
ratio of the weight-average mass Mw to the number-average mass
Mn.
[0092] The weight-average molar mass (Mw) and number-average molar
mass (Mn) are determined by gel permeation liquid chromatography
(THF solvent, calibration curve established with linear polystyrene
standards, refractometric detector).
[0093] The weight-average mass (Mw) of the block polymer is
preferably less than or equal to 300 000; it ranges, for example,
from 35 000 to 200 000 and better still from 45 000 to 150 000.
[0094] The number-average mass (Mn) of the block polymer is
preferably less than or equal to 70 000; it ranges, for example,
from 10 000 to 60 000 and better still from 12 000 to 50 000.
[0095] Each block of the block polymer is derived from one type of
monomer or from several different types of monomer.
[0096] This means that each block may consist of a homopolymer or a
copolymer; this copolymer constituting the block may in turn be
random or alternating.
[0097] The glass transition temperatures indicated for the first
and second blocks may be theoretical Tg values determined from the
theoretical Tg values of the constituent monomers of each of the
blocks, which may be found in a reference manual such as the
Polymer Handbook, 3rd Edition, 1989, John Wiley, according to the
following relationship, known as Fox's law: 1 / Tg = i .times. (
.PI. i / Tg i ) , ##EQU1## {overscore (.omega.)} .sub.i being the
mass fraction of the monomer i in the block under consideration and
Tg.sub.i being the glass transition temperature of the homopolymer
of the monomer i.
[0098] Unless otherwise indicated, the Tg values indicated for the
first and second blocks in the present patent application are
theoretical Tg values.
[0099] The difference between the glass-transition temperatures of
the first and second blocks is generally greater than 10.degree.
C., preferably greater than 20.degree. C. and better still greater
than 30.degree. C.
[0100] In particular, the block polymer comprises at least one
first block and at least one second block such that the first block
may be chosen from: [0101] a) a block with a Tg of greater than or
equal to 40.degree. C., [0102] b) a block with a Tg of less than or
equal to 20.degree. C., [0103] c) a block with a Tg of between 20
and 40.degree. C., and the second block can be chosen from a
category a), b) or c) different from the first block.
[0104] In the present invention, the expression: "between . . . and
. . . " is intended to denote a range of values for which the
limits mentioned are excluded, and "from . . . to . . . " and
"ranging from . . . to . . . " are intended to denote a range of
values for which the limits are included.
a) Block with a Tg of Greater Than or Equal to 40.degree. C.
[0105] The block with a Tg of greater than or equal to 40.degree.
C. has, for example, a Tg ranging from 40 to 150.degree. C.,
preferably greater than or equal to 50.degree. C., for example
ranging from 50.degree. C. to 120.degree. C. and better still
greater than or equal to 60.degree. C., for example ranging from
60.degree. C. to 120.degree. C.
[0106] The block with a Tg of greater than or equal to 40.degree.
C. may be a homopolymer or a copolymer.
[0107] The block with a Tg of greater than or equal to 40.degree.
C. may be totally or partially derived from one or more monomers,
which are such that the homopolymer prepared from these monomers
has a glass transition temperature of greater than or equal to
40.degree. C.
[0108] In the case where this block is a homopolymer, it is derived
from monomers which are such that the homopolymers prepared from
these monomers have glass transition temperatures of greater than
or equal to 40.degree. C. This first block may be a homopolymer
consisting of only one type of monomer (for which the Tg of the
corresponding homopolymer is greater than or equal to 40.degree.
C.).
[0109] In the case where the first block is a copolymer, it may be
totally or partially derived from one or more monomers, the nature
and concentration of which are chosen such that the Tg of the
resulting copolymer is greater than or equal to 40.degree. C. The
copolymer may comprise, for example: [0110] monomers which are such
that the homopolymers prepared from these monomers have Tg values
of greater than or equal to 40.degree. C., for example a Tg ranging
from 40 to 150.degree. C., preferably greater than or equal to
50.degree. C., for example ranging from 50.degree. C. to
120.degree. C. and better still greater than or equal to 60.degree.
C., for example ranging from 60.degree. C. to 120.degree. C., and
[0111] monomers which are such that the homopolymers prepared from
these monomers have Tg values of less than 40.degree. C., chosen
from monomers with a Tg of between 20 and 40.degree. C. and/or
monomers with a Tg of less than or equal to 20.degree. C., for
example a Tg ranging from -100 to 20.degree. C., preferably less
than 15.degree. C., especially ranging from -80.degree. C. to
15.degree. C. and better still less than 10.degree. C., for example
ranging from -50.degree. C. to 0.degree. C., as described
later.
[0112] The monomers whose homopolymers have a glass transition
temperature of greater than or equal to 40.degree. C. are chosen,
preferably, from the following monomers, also known as the main
monomers: [0113] methacrylates of formula
CH.sub.2.dbd.C(CH.sub.3)--COOR.sub.1 in which R.sub.1 represents a
linear or branched unsubstituted alkyl group containing from 1 to 4
carbon atoms, such as a methyl, ethyl, propyl or isobutyl group or
R.sub.1 represents a C.sub.4 to C.sub.12 cycloalkyl group, [0114]
acrylates of formula CH.sub.2.dbd.CH--COOR.sub.2 in which R.sub.2
represents a C.sub.4 to C.sub.12 cycloalkyl group such as isobornyl
acrylate or a tert-butyl group, [0115] (meth)acrylamides of
formula: ##STR1## [0116] in which R.sub.7 and R.sub.8, which may be
identical or different, each represent a hydrogen atom or a linear
or branched C.sub.1 to C.sub.12 alkyl group such as an n-butyl,
t-butyl, isopropyl, isohexyl, isooctyl or isononyl group; or
R.sub.7 represents H and R.sub.8 represents a
1,1-dimethyl-3-oxobutyl group, and R' denotes H or methyl. Examples
of monomers that may be mentioned include N-butylacrylamide,
N-t-butylacrylamide, N-isopropylacrylamide, N,N-dimethylacrylamide
and N,N-dibutylacrylamide, [0117] and mixtures thereof.
[0118] Main monomers that are particularly preferred are methyl
methacrylate, isobutyl (meth)acrylate and isobornyl (meth)acrylate,
and mixtures thereof.
b) Block with a Tg of Less Than or Equal to 20.degree. C.
[0119] The block with a Tg of less than or equal to 20.degree. C.
has, for example, a Tg ranging from -100 to 20.degree. C.,
preferably less than or equal to 15.degree. C., especially ranging
from -80.degree. C. to 15.degree. C. and better still less than or
equal to 10.degree. C., for example ranging from -50.degree. C. to
0.degree. C.
[0120] The block with a Tg of less than or equal to 20.degree. C.
may be a homopolymer or a copolymer.
[0121] The block with a Tg of less than or equal to 20.degree. C.
may be totally or partially derived from one or more monomers,
which are such that the homopolymer prepared from these monomers
has a glass transition temperature of less than or equal to
20.degree. C.
[0122] In the case where this block is a homopolymer, it is derived
from monomers which are such that the homopolymers prepared from
these monomers have glass transition temperatures of less than or
equal to 20.degree. C. This second block may be a homopolymer
consisting of only one type of monomer (for which the Tg of the
corresponding homopolymer is less than or equal to 20.degree.
C.).
[0123] In the case where the block with a Tg of less than or equal
to 20.degree. C. is a copolymer, it may be totally or partially
derived from one or more monomers, the nature and concentration of
which are chosen such that the Tg of the resulting copolymer is
less than or equal to 20.degree. C.
[0124] It may comprise, for example [0125] one or more monomers
whose corresponding homopolymer has a Tg of less than or equal to
20.degree. C., for example a Tg ranging from -100.degree. C. to
20.degree. C., preferably less than 15.degree. C., especially
ranging from -80.degree. C. to 15.degree. C. and better still less
than 10.degree. C., for example ranging from -50.degree. C. to
0.degree. C., and [0126] one or more monomers whose corresponding
homopolymer has a Tg of greater than 20.degree. C., such as
monomers with a Tg of greater than or equal to 40.degree. C., for
example a Tg ranging from 40 to 150.degree. C., preferably greater
than or equal to 50.degree. C., for example ranging from 50.degree.
C. to 120.degree. C. and better still greater than or equal to
60.degree. C., for example ranging from 60.degree. C. to
120.degree. C. and/or monomers with a Tg of between 20 and
40.degree. C., as described above.
[0127] Preferably, the block with a Tg of less than or equal to
20.degree. C. is a homopolymer.
[0128] The monomers whose homopolymer has a Tg of less than or
equal to 20.degree. C. are preferably chosen from the following
monomers, or main monomer: [0129] acrylates of formula
CH.sub.2.dbd.CHCOOR.sub.3, R.sub.3 representing a linear or
branched C.sub.1 to C.sub.12 unsubstituted alkyl group, with the
exception of the tert-butyl group, in which one or more hetero
atoms chosen from O, N and S is (are) optionally intercalated,
[0130] methacrylates of formula
CH.sub.2.dbd.C(CH.sub.3)--COOR.sub.4, R.sub.4 representing a linear
or branched C.sub.6 to C.sub.12 unsubstituted alkyl group, in which
one or more hetero atoms chosen from O, N and S is (are) optionally
intercalated; [0131] vinyl esters of formula
R.sub.5--CO--O--CH.dbd.CH.sub.2 in which R.sub.5 represents a
linear or branched C.sub.4 to C.sub.12 alkyl group; [0132] C.sub.4
to C.sub.12 alkyl vinyl ethers, [0133] N--(C.sub.4 to
C.sub.12)alkyl acrylamides, such as N-octylacrylamide, [0134] and
mixtures thereof.
[0135] The main monomers that are particularly preferred for the
block with a Tg of less than or equal to 20.degree. C. are alkyl
acrylates whose alkyl chain contains from 1 to 10 carbon atoms,
with the exception of the tert-butyl group, such as methyl
acrylate, isobutyl acrylate and 2-ethylhexyl acrylate, and mixtures
thereof.
c) Block with a Tg of Between 20 and 40.degree. C.
[0136] The block with a Tg of between 20 and 40.degree. C. may be a
homopolymer or a copolymer.
[0137] The block with a Tg of between 20 and 40.degree. C. may be
totally or partially derived from one or more monomers, which are
such that the homopolymer prepared from these monomers has a glass
transition temperature of between 20 and 40.degree. C.
[0138] The block with a Tg of between 20 and 40.degree. C. may be
totally or partially derived from monomers, which are such that the
corresponding homopolymer has a Tg of greater than or equal to
40.degree. C. and from monomers which are such that the
corresponding homopolymer has a Tg of less than or equal to
20.degree. C.
[0139] In the case where this block is a homopolymer, it is derived
from monomers (or main monomer) which are such that the
homopolymers prepared from these monomers have glass transition
temperatures of between 20 and 40.degree. C. This first block may
be a homopolymer, consisting of only one type of monomer (for which
the Tg of the corresponding homopolymer ranges from 20.degree. C.
to 40.degree. C.).
[0140] The monomers whose homopolymer has a glass transition
temperature of between 20 and 40.degree. C. are preferably chosen
from n-butyl methacrylate, cyclodecyl acrylate, neopentyl acrylate
and isodecylacrylamide, and mixtures thereof.
[0141] In the case where the block with a Tg of between 20 and
40.degree. C. is a copolymer, it is totally or partially derived
from one or more monomers (or main monomer) whose nature and
concentration are chosen such that the Tg of the resulting
copolymer is between 20 and 40.degree. C.
[0142] Advantageously, the block with a Tg of between 20 and
40.degree. C. is a copolymer totally or partially derived from:
[0143] main monomers whose corresponding homopolymer has a Tg of
greater than or equal to 40.degree. C., for example a Tg ranging
from 40.degree. C. to 150.degree. C., preferably greater than or
equal to 50.degree. C., for example ranging from 50 to 120.degree.
C. and better still greater than or equal to 60.degree. C., for
example ranging from 60.degree. C. to 120.degree. C., as described
above, and/or [0144] main monomers whose corresponding homopolymer
has a Tg of less than or equal to 20.degree. C., for example a Tg
ranging from -100 to 20.degree. C., preferably less than or equal
to 15.degree. C., especially ranging from -80.degree. C. to
15.degree. C. and better still less than or equal to 10.degree. C.,
for example ranging from -50.degree. C. to 0.degree. C., as
described above, the said monomers being chosen such that the Tg of
the copolymer forming the first block is between 20 and 40.degree.
C.
[0145] Such main monomers are chosen, for example, from methyl
methacrylate, isobornyl acrylate and methacrylate, butyl acrylate
and 2-ethylhexyl acrylate, and mixtures thereof.
[0146] Preferably, the proportion of the second block with a Tg of
less than or equal to 20.degree. C. ranges from 10% to 85%, better
still from 20% to 70% and even better still from 20% to 50% by
weight of the polymer.
[0147] Preferably, each of the first and second blocks comprises at
least one monomer chosen from acrylic acid, acrylic acid esters,
methacrylic acid and methacrylic acid esters, and mixtures
thereof.
[0148] Advantageously, each of the first and second blocks is
totally derived from at least one monomer chosen from acrylic acid,
acrylic acid esters, methacrylic acid and methacrylic acid esters,
and mixtures thereof.
[0149] However, each of the blocks may contain in small proportion
at least one constituent monomer of the other block.
[0150] Thus, the first block may contain at least one constituent
monomer of the second block, and vice versa.
[0151] Each of the first and/or second blocks may comprise, in
addition to the monomers indicated above, one or more other
monomers known as additional monomers, which are different from the
main monomers mentioned above.
[0152] The nature and amount of this or these additional monomer(s)
are chosen such that the block in which they are present has the
desired glass transition temperature.
[0153] This additional monomer is chosen, for example, from: [0154]
a) hydrophilic monomers such as: [0155] ethylenically unsaturated
monomers comprising at least one carboxylic or sulfonic acid
function, for instance: [0156] acrylic acid, methacrylic acid,
crotonic acid, maleic anhydride, itaconic acid, fumaric acid,
maleic acid, acrylamidopropanesulfonic acid, vinylbenzoic acid,
vinylphosphoric acid, and salts thereof, [0157] ethylenically
unsaturated monomers comprising at least one tertiary amine
function, for instance 2-vinylpyridine, 4-vinylpyridine,
dimethylaminoethyl methacrylate, diethylaminoethyl methacrylate and
dimethylaminopropylmethacrylamide, and salts thereof, [0158]
methacrylates of formula CH.sub.2.dbd.C(CH.sub.3)--COOR.sub.6
[0159] in which R.sub.6 represents a linear or branched alkyl group
containing from 1 to 4 carbon atoms, such as a methyl, ethyl,
propyl or isobutyl group, the said alkyl group being substituted
with one or more substituents chosen from hydroxyl groups (for
instance 2-hydroxypropyl methacrylate and 2-hydroxyethyl
methacrylate) and halogen atoms (Cl, Br, I or F), such as
trifluoroethyl methacrylate, [0160] methacrylates of formula
CH.sub.2.dbd.C(CH.sub.3)--COOR.sub.9, [0161] R.sub.9 representing a
linear or branched C.sub.6 to C.sub.12 alkyl group in which one or
more hetero atoms chosen from O, N and S is (are) optionally
intercalated, the said alkyl group being substituted with one or
more substituents chosen from hydroxyl groups and halogen atoms
(Cl, Br, I or F); [0162] acrylates of formula
CH.sub.2.dbd.CHCOOR.sub.10, [0163] R.sub.10 representing a linear
or branched C.sub.1 to C.sub.12 alkyl group substituted with one or
more substituents chosen from hydroxyl groups and halogen atoms
(Cl, Br, I or F), such as 2-hydroxypropyl acrylate and
2-hydroxyethyl acrylate, or R.sub.10 represents a C.sub.1 to
C.sub.12 alkyl-O-POE (polyoxyethylene) with repetition of the
oxyethylene unit 5 to 30 times, for example methoxy-POE, or [0164]
R.sub.10 represents a polyoxyethylenated group comprising from 5 to
30 ethylene oxide units [0165] b) ethylenically unsaturated
monomers comprising one or more silicon atoms, such as
methacryloxypropyltrimethoxysilane and
methacryloxypropyl-tris(trimethylsiloxy)silane, [0166] and mixtures
thereof.
[0167] Additional monomers that are particularly preferred are
acrylic acid, methacrylic acid and trifluoroethyl methacrylate, and
mixtures thereof.
[0168] According to one embodiment, each of the first and second
blocks of the block polymer comprises at least one monomer chosen
from (meth)acrylic acid esters and optionally at least one
additional monomer such as (meth)acrylic acid, and mixtures
thereof.
[0169] According to another embodiment, each of the first and
second blocks of the block polymer is totally derived from at least
one monomer chosen from (meth)acrylic acid esters and optionally at
least one additional monomer such as (meth)acrylic acid, and
mixtures thereof.
[0170] According to one preferred embodiment, the block polymer is
a non-silicone polymer, i.e. a polymer free of silicon atoms.
[0171] This or these additional monomer(s) generally represent(s)
an amount of less than or equal to 30% by weight, for example from
1% to 30% by weight, preferably from 5% to 20% by weight and more
preferably from 7% to 15% by weight, relative to the total weight
of the first and/or second blocks.
[0172] The block polymer may be obtained by free-radical solution
polymerization according to the following preparation process:
[0173] a portion of the polymerization solvent is introduced into a
suitable reactor and heated until the adequate temperature for the
polymerization is reached (typically between 60 and 120.degree.
C.), [0174] once this temperature is reached, the constituent
monomers of the first block are introduced in the presence of some
of the polymerization initiator, [0175] after a time T
corresponding to a maximum degree of conversion of 90%, the
constituent monomers of the second block and the rest of the
initiator are introduced, [0176] the mixture is left to react for a
time T' (ranging from 3 to 6 hours), after which the mixture is
cooled to room temperature, [0177] the polymer dissolved in the
polymerization solvent is obtained.
FIRST EMBODIMENT
[0178] According to a first embodiment, the block polymer comprises
a first block with a Tg of greater than or equal to 40.degree. C.,
as described above in a) and a second block with a Tg of less than
or equal to 20.degree. C., as described above in b).
[0179] Preferably, the first block with a Tg of greater than or
equal to 40.degree. C. is a copolymer derived from monomers which
are such that the homopolymer prepared from these monomers has a
glass transition temperature of greater than or equal to 40.degree.
C., such as the monomers described above.
[0180] Advantageously, the second block with a Tg of less than or
equal to 20.degree. C. is a homopolymer derived from monomers which
are such that the homopolymer prepared from these monomers has a
glass transition temperature of less than or equal to 20.degree.
C., such as the monomers described above.
[0181] Preferably, the proportion of the block with a Tg of greater
than or equal to 40.degree. C. ranges from 20% to 90%, better still
from 30% to 80% and even better still from 50% to 70% by weight of
the polymer. Preferably, the proportion of the block with a Tg of
less than or equal to 20.degree. C. ranges from 5% to 75%,
preferably from 15% to 50% and better still from 25% to 45% by
weight of the polymer.
[0182] Thus, according to a first variant, the polymer according to
the invention may comprise: [0183] a first block with a Tg of
greater than or equal to 40.degree. C., for example having a Tg
ranging from 70 to 110.degree. C., which is a methyl
methacrylate/acrylic acid copolymer, [0184] a second block with a
Tg of less than or equal to 20.degree. C., for example ranging from
0 to 20.degree. C., which is a methyl acrylate homopolymer, and
[0185] an intermediate block which is a methyl methacrylate/acrylic
acid/methyl acrylate copolymer.
[0186] According to a second variant, the polymer according to the
invention may comprise: [0187] a first block with a Tg of greater
than or equal to 40.degree. C., for example ranging from 70 to
100.degree. C., which is a methyl methacrylate/acrylic
acid/trifluoroethyl methacrylate copolymer, [0188] a second block
with a Tg of less than or equal to 20.degree. C., for example
ranging from 0 to 20.degree. C., which is a methyl acrylate
homopolymer, and [0189] an intermediate block which is a methyl
methacrylate/acrylic acid/methyl acrylate/trifluoroethyl
methacrylate random copolymer.
[0190] According to a third variant, the polymer according to the
invention may comprise: [0191] a first block with a Tg of greater
than or equal to 40.degree. C., for example ranging from 85 to
115.degree. C., which is an isobornyl acrylate/isobutyl
methacrylate copolymer, [0192] a second block with a Tg of less
than or equal to 20.degree. C., for example ranging from -85 to
-55.degree. C., which is a 2-ethylhexyl acrylate homopolymer, and
[0193] an intermediate block, which is an isobornyl
acrylate/isobutyl methacrylate/2-ethylhexyl acrylate random
copolymer.
[0194] According to a fourth variant, the polymer according to the
invention may comprise: [0195] a first block with a Tg of greater
than or equal to 40.degree. C., for example ranging from 85 to
115.degree. C., which is an isobornyl acrylate/methyl methacrylate
copolymer, [0196] a second block with a Tg of less than or equal to
20.degree. C., for example ranging from -85 to -55.degree. C.,
which is a 2-ethylhexyl acrylate homopolymer, and [0197] an
intermediate block which is an isobornyl acrylate/methyl
methacrylate/2-ethylhexyl acrylate random copolymer.
[0198] According to a fifth variant, the polymer according to the
invention may comprise: [0199] a first block with a Tg of greater
than or equal to 40.degree. C., for example ranging from 95 to
125.degree. C., which is an isobornyl acrylate/isobornyl
methacrylate copolymer, [0200] a second block with a Tg of less
than or equal to 20.degree. C., for example ranging from -85 to
-55.degree. C., which is a 2-ethylhexyl acrylate homopolymer, and
[0201] an intermediate block which is an isobornyl
acrylate/isobornyl methacrylate/2-ethylhexyl acrylate random
copolymer.
[0202] According to a sixth variant, the polymer according to the
invention may comprise: [0203] a first block with a Tg of greater
than or equal to 40.degree. C., for example ranging from 85 to
115.degree. C., which is an isobornyl methacrylate/isobutyl
methacrylate copolymer, [0204] a second block with a Tg of less
than or equal to 20.degree. C., for example ranging from -35 to
-5.degree. C., which is an isobutyl acrylate homopolymer, and
[0205] an intermediate block which is an isobornyl
methacrylate/isobutyl methacrylate/isobutyl acrylate random
copolymer.
[0206] According to a seventh variant, the polymer according to the
invention may comprise: [0207] a first block with a Tg of greater
than or equal to 40.degree. C., for example ranging from 95 to
125.degree. C., which is an isobornyl acrylate/isobornyl
methacrylate copolymer, [0208] a second block with a Tg of less
than or equal to 20.degree. C., for example ranging from -35 to
-5.degree. C., which is an isobutyl acrylate homopolymer, and
[0209] an intermediate block which is an isobornyl
acrylate/isobornyl methacrylate/isobutyl acrylate random
copolymer.
[0210] According to an eighth variant, the polymer according to the
invention may comprise: [0211] a first block with a Tg of greater
than or equal to 40.degree. C., for example ranging from 60 to
90.degree. C., which is an isobornyl acrylate/isobutyl methacrylate
copolymer, [0212] a second block with a Tg of less than or equal to
20.degree. C., for example ranging from -35 to -5.degree. C., which
is an isobutyl acrylate homopolymer, and [0213] an intermediate
block which is an isobornyl acrylate/isobutyl methacrylate/isobutyl
acrylate random copolymer.
[0214] The examples that follow illustrate, in a non-limiting
manner, polymers corresponding to this first embodiment.
[0215] The amounts are expressed in grams.
EXAMPLE 1
Preparation of a poly(methyl methacrylate/acrylic acid/methyl
acrylate) Polymer
[0216] 100 g of butyl acetate are introduced into a 1 litre reactor
and the temperature is then raised so as to pass from room
temperature (25.degree. C.) to 90.degree. C. in 1 hour.
[0217] 180 g of methyl methacrylate, 30 g of acrylic acid, 40 g of
butyl acetate, 70 g of isopropanol and 1.8 g of
2,5-bis(2-ethylhexanoylperoxy)-2,5-dimethylhexane (Trigonox.RTM.
141 from Akzo Nobel) are then added at 90.degree. C. and over 1
hour.
[0218] The mixture is maintained at 90.degree. C. for 1 hour.
[0219] 90 g of methyl acrylate, 70 g of butyl acetate, 20 g of
isopropanol and 1.2 g of
2,5-bis(2-ethylhexanoylperoxy)-2,5-dimethylhexane are then
introduced into the above mixture, still at 90.degree. C. and over
1 hour.
[0220] The mixture is maintained at 90.degree. C. for 3 hours and
then diluted with 105 g of butyl acetate and 45 g of isopropanol,
and the mixture is then cooled.
[0221] A solution containing 40% polymer active material in a butyl
acetate/isopropanol mixture is obtained.
[0222] A polymer comprising a poly(methyl methacrylate/acrylic
acid) first block with a Tg of 100.degree. C., a polymethyl
acrylate second block with a Tg of 10.degree. C. and an
intermediate block which is a methyl methacrylate/acrylic
acid/polymethyl acrylate random polymer is obtained.
[0223] This polymer has a weight-average mass of 52 000 and a
number-average mass of 18 000, i.e. a polydispersity index I of
2.89.
EXAMPLE 2
Preparation of a poly(isobornyl acrylate/isobutyl
methacrylate/2-ethylhexyl acrylate) Polymer
[0224] 100 g of isododecane are introduced into a 1 litre reactor
and the temperature is then increased so as to pass from room
temperature (25.degree. C.) to 90.degree. C. over 1 hour.
[0225] 120 g of isobornyl acrylate, 90 g of isobutyl methacrylate,
110 g of isododecane and 1.8 g of
2,5-bis(2-ethylhexanoylperoxy)-2,5-dimethylhexane (Trigonox.RTM.
141 from Akzo Nobel) are then added, at 90.degree. C. and over 1
hour.
[0226] The mixture is maintained at 90.degree. C. for 1 hour 30
minutes.
[0227] 90 g of 2-ethylhexyl acrylate, 90 g of isododecane and 1.2 g
of 2,5-bis(2-ethylhexanoylperoxy)-2,5-dimethylhexane are then
introduced into the above mixture, still at 90.degree. C. and over
30 minutes.
[0228] The mixture is maintained at 90.degree. C. for 3 hours and
is then cooled.
[0229] A solution containing 50% polymer active material in
isododecane is obtained.
[0230] A polymer comprising a poly(isobornyl acrylate/isobutyl
methacrylate) first block with a Tg of 80.degree. C., a
poly-2-ethylhexyl acrylate second block with a Tg of -70.degree. C.
and an intermediate block which is an isobornyl acrylate/isobutyl
methacrylate/2-ethylhexyl acrylate random polymer is obtained.
[0231] This polymer has a weight-average mass of 77 000 and a
number-average mass of 19 000, i.e. a polydispersity index I of
4.05.
EXAMPLE 3
Preparation of a poly(isobornyl acrylate/isobornyl
methacrylate/2-ethylhexyl acrylate) Polymer
[0232] 100 g of isododecane are introduced into a 1 litre reactor
and the temperature is then increased so as to pass from room
temperature (25.degree. C.) to 90.degree. C. over 1 hour.
[0233] 105 g of isobornyl acrylate, 105 g of isobornyl
methacrylate, 110 g of isododecane and 1.8 g of
2,5-bis(2-ethylhexanoylperoxy)-2,5-dimethylhexane (Trigonox.RTM.
141 from Akzo Nobel) are then added, at 90.degree. C. and over 1
hour.
[0234] The mixture is maintained at 90.degree. C. for 1 hour 30
minutes.
[0235] 90 g of 2-ethylhexyl acrylate, 90 g of isododecane and 1.2 g
of 2,5-bis(2-ethylhexanoylperoxy)-2,5-dimethylhexane are then
introduced into the above mixture, still at 90.degree. C. and over
30 minutes.
[0236] The mixture is maintained at 90.degree. C. for 3 hours and
is then cooled.
[0237] A solution containing 50% polymer active material in
isododecane is obtained.
[0238] A polymer comprising a poly(isobornyl acrylate/isobornyl
methacrylate) first block with a Tg of 110.degree. C., a
poly-2-ethylhexyl acrylate second block with a Tg of -70.degree. C.
and an intermediate block which is an isobornyl acrylate/isobornyl
methacrylate/2-ethylhexyl acrylate random polymer is obtained.
[0239] This polymer has a weight-average mass of 103 900 and a
number-average mass of 21 300, i.e. a polydispersity index I of
4.89.
EXAMPLE 4
Preparation of a poly(isobornyl acrylate/isobutyl
methacrylate/isobutyl acrylate) Polymer
[0240] 100 g of isododecane are introduced into a 1 litre reactor
and the temperature is then increased so as to pass from room
temperature (25.degree. C.) to 90.degree. C. over 1 hour.
[0241] 120 g of isobornyl acrylate, 90 g of isobutyl methacrylate,
110 g of isododecane and 1.8 g of
2,5-bis(2-ethylhexanoylperoxy)-2,5-dimethylhexane (Trigonox.RTM.
141 from Akzo Nobel) are then added, at 90.degree. C. and over 1
hour.
[0242] The mixture is maintained at 90.degree. C. for 1 hour 30
minutes.
[0243] 90 g of isobutyl acrylate, 90 g of isododecane and 1.2 g of
2,5-bis(2-ethylhexanoylperoxy)-2,5-dimethylhexane are then
introduced into the above mixture, still at 90.degree. C. and over
30 minutes.
[0244] The mixture is maintained at 90.degree. C. for 3 hours and
is then cooled.
[0245] A solution containing 50% polymer active material in
isododecane is obtained.
[0246] A polymer comprising a poly(isobornyl acrylate/isobutyl
methacrylate) first block with a Tg of 75.degree. C., a
polyisobutyl acrylate second block with a Tg of -20.degree. C. and
an intermediate block which is an isobornyl acrylate/isobutyl
methacrylate/isobutyl acrylate random polymer is obtained.
EXAMPLE 5
Preparation of a poly(methyl methacrylate/methyl acrylate/acrylic
acid) Polymer
[0247] 100 g of butyl acetate are introduced into a 1 litre reactor
and the temperature is then increased so as to pass from room
temperature (25.degree. C.) to 90.degree. C. over 1 hour.
[0248] 50.4 g of methyl methacrylate, 21 g of acrylic acid, 138.6 g
of methyl acrylate, 40 g of butyl acetate, 70 g of isopropanol and
1.8 g of 2,5-bis(2-ethylhexanoylperoxy)-2,5-dimethylhexane
(Trigonox.RTM. 141 from Akzo Nobel) are then added, at 90.degree.
C. and over 1 hour.
[0249] The mixture is maintained at 90.degree. C. for 1 hour.
[0250] 90 g of methyl methacrylate, 70 g of butyl acetate, 20 g of
isopropanol and 1.2 g of
2,5-bis(2-ethylhexanoylperoxy)-2,5-dimethylhexane are then
introduced into the above mixture, still at 90.degree. C. and over
1 hour.
[0251] The mixture is maintained at 90.degree. C. for 3 hours and
is then diluted with 105 g of butyl acetate and 45 g of isopropanol
and cooled.
[0252] A solution containing 40% polymer active material in butyl
acetate/isopropanol is obtained.
[0253] The polymer obtained comprises a poly(methyl acrylate/methyl
methacrylate/acrylic acid) first block with a Tg of 35.degree. C.,
a poly(methyl methacrylate) second block with a Tg of 100.degree.
C. and an intermediate block which is a methyl methacrylate/acrylic
acid/polymethyl acrylate random polymer.
EXAMPLE 6
Preparation of a poly(isobornyl acrylate/isobornyl
methacrylate/isobutyl acrylate) Polymer
[0254] 100 g of isododecane are introduced into a 1 litre reactor
and the temperature is then increased so as to pass from room
temperature (25.degree. C.) to 90.degree. C. over 1 hour.
[0255] 105 g of isobornyl acrylate, 105 g of isobornyl
methacrylate, 110 g of isododecane and 1.8 g of
2,5-bis(2-ethylhexanoylperoxy)-2,5-dimethylhexane (Trigonox.RTM.
141 from Akzo Nobel) are then added, at 90.degree. C. and over 1
hour.
[0256] The mixture is maintained at 90.degree. C. for 1 hour 30
minutes.
[0257] 90 g of isobutyl acrylate, 90 g of isododecane and 1.2 g of
2,5-bis(2-ethylhexanoylperoxy)-2,5-dimethylhexane are then
introduced into the above mixture, still at 90.degree. C. and over
30 minutes.
[0258] The mixture is maintained at 90.degree. C. for 3 hours and
is then cooled.
[0259] A solution containing 50% polymer active material in
isododecane is obtained.
[0260] A polymer comprising a poly(isobornyl acrylate/isobornyl
methacrylate) first block with a Tg of 110.degree. C., a
polyisobutyl acrylate second block with a Tg of -20.degree. C. and
an intermediate block which is an isobornyl acrylate/isobornyl
methacrylate/isobutyl acrylate random polymer is obtained.
[0261] This polymer has a weight-average mass of 151 000 and a
number-average mass of 41 200, i.e. a polydispersity index I of
3.66.
EXAMPLE 7
Preparation of a poly(isobornyl methacrylate/isobutyl
methacrylate/isobutyl acrylate) Polymer
[0262] 100 g of isododecane are introduced into a 1 litre reactor
and the temperature is then increased so as to pass from room
temperature (25.degree. C.) to 90.degree. C. over 1 hour.
[0263] 120 g of isobornyl methacrylate, 90 g of isobutyl
methacrylate, 110 g of isododecane and 1.8 g of
2,5-bis(2-ethylhexanoylperoxy)-2,5-dimethylhexane (Trigonox.RTM.
141 from Akzo Nobel) are then added, at 90.degree. C. and over 1
hour.
[0264] The mixture is maintained at 90.degree. C. for 1 hour 30
minutes.
[0265] 90 g of isobutyl acrylate, 90 g of isododecane and 1.2 g of
2,5-bis(2-ethylhexanoylperoxy)-2,5-dimethylhexane are then
introduced into the above mixture, still at 90.degree. C. and over
30 minutes.
[0266] The mixture is maintained at 90.degree. C. for 3 hours and
is then cooled.
[0267] A solution containing 50% polymer active material in
isododecane is obtained.
[0268] A polymer comprising a poly(isobornyl methacrylate/isobutyl
methacrylate) first block with a Tg of 95.degree. C., a
polyisobutyl acrylate second block with a Tg of -20.degree. C. and
an intermediate block which is an isobornyl methacrylate/isobutyl
methacrylate/isobutyl acrylate random polymer is obtained.
[0269] This polymer has a weight-average mass of 100 700 and a
number-average mass of 20 800, i.e. a polydispersity index I of
4.85.
SECOND EMBODIMENT
[0270] According to a second embodiment, the block polymer
comprises a first block having a glass transition temperature (Tg)
of between 20 and 40.degree. C., in accordance with the blocks
described in c) and a second block having a glass transition
temperature of less than or equal to 20.degree. C., as described
above in b) or a glass transition temperature of greater than or
equal to 40.degree. C., as described in a) above.
[0271] Preferably, the proportion of the first block with a Tg of
between 20 and 40.degree. C. ranges from 10% to 85%, better still
from 30% to 80% and even better still from 50% to 70% by weight of
the polymer.
[0272] When the second block is a block with a Tg of greater than
or equal to 40.degree. C., it is preferably present in a proportion
ranging from 10% to 85%, better still from 20% to 70% and even
better still from 30% to 70% by weight of the polymer.
[0273] When the second block is a block with a Tg of less than or
equal to 20.degree. C., it is preferably present in a proportion
ranging from 10% to 85%, better still from 20% to 70% and even
better still from 20% to 50% by weight of the polymer.
[0274] Preferably, the first block with a Tg of between 20 and
40.degree. C. is a copolymer derived from monomers which are such
that the corresponding homopolymer has a Tg of greater than or
equal to 40.degree. C., and from monomers which are such that the
corresponding homopolymer has a Tg of less than or equal to
20.degree. C.
[0275] Advantageously, the second block with a Tg of less than or
equal to 20.degree. C. or with a Tg of greater than or equal to
40.degree. C. is a homopolymer.
[0276] Thus, according to a first variant of this second
embodiment, the block polymer may comprise: [0277] a first block
with a Tg of between 20 and 40.degree. C., for example with a Tg of
25 to 39.degree. C., which is a copolymer comprising at least one
methyl acrylate monomer, at least one methyl methacrylate monomer
and at least one acrylic acid monomer, [0278] a second block with a
Tg of greater than or equal to 40.degree. C., for example ranging
from 85 to 125.degree. C., which is a homopolymer composed of
methyl methacrylate monomers, and [0279] an intermediate block
comprising at least one methyl acrylate, methyl methacrylate
monomer, and [0280] an intermediate block comprising methyl
methacrylate, at least one acrylic acid monomer and at least one
methyl acrylate monomer.
[0281] According to a second variant of this second embodiment, the
block polymer may comprise: [0282] a first block with a Tg of
between 20 and 40.degree. C., for example with a Tg of 21 to
39.degree. C., which is a copolymer comprising isobornyl
acrylate/isobutyl methacrylate/2-ethylhexyl acrylate, [0283] a
second block with a Tg of less than or equal to 20.degree. C., for
example ranging from -65 to -35.degree. C., which is a methyl
methacrylate homopolymer, and [0284] an intermediate block which is
an isobornyl acrylate/isobutyl methacrylate/2-ethylhexyl acrylate
random copolymer.
[0285] According to a third variant of this second embodiment, the
block polymer may comprise: [0286] a first block with a Tg of
between 20 and 40.degree. C., for example with a Tg from 21 to
39.degree. C., which is an isobornyl acrylate/methyl
acrylate/acrylic acid copolymer, [0287] a second block with a Tg of
greater than or equal to 40.degree. C., for example ranging from 85
to 115.degree. C., which is an isobornyl acrylate homopolymer, and
[0288] an intermediate block which is an isobornyl acrylate/methyl
acrylate/acrylic acid random copolymer.
[0289] The composition of the invention advantageously contains
from 0.1% to 60% by weight of active material (or solids),
preferably from 0.5% to 50% by weight and more preferably from 1%
to 40% by weight, of block polymer.
[0290] The composition according to the invention may comprise a
hydrophilic medium comprising water or a mixture of water and of
hydrophilic organic solvent(s), for instance alcohols and
especially linear or branched lower monoalcohols containing from 2
to 5 carbon atoms, for instance ethanol, isopropanol or n-propanol,
and polyols, for instance glycerol, diglycerol, propylene glycol,
sorbitol, pentylene glycol and polyethylene glycols, or
alternatively hydrophilic C.sub.2 ethers and C.sub.2-C.sub.4
aldehydes.
[0291] The water or the mixture of water and of hydrophilic organic
solvents may be present in the composition according to the
invention in a content ranging from 0.1% to 99% by weight and
preferably from 10% to 80% by weight relative to the total weight
of the composition.
[0292] The composition according to the invention comprises a
cosmetically acceptable organic liquid medium (acceptable
tolerance, toxicology and feel).
[0293] According to one particularly preferred embodiment, the
organic liquid medium of the composition contains at least one
organic solvent, which is the or one of the polymerization
solvent(s) for the block polymer as described above.
Advantageously, the said organic solvent is the liquid that is in
majority amount by weight in the organic liquid medium of the
cosmetic composition.
[0294] According to one embodiment, the organic liquid medium
comprises at least one fatty substance that is liquid at room
temperature (in general 25.degree. C.). This liquid fatty substance
may be of animal, plant, mineral or synthetic origin.
[0295] As fatty substances that are liquid at room temperature,
often known as oils, which may be used in the invention, mention
may be made of: hydrocarbon-based oils of animal origin such as
perhydrosqualene; hydrocarbon-based plant oils such as liquid
triglycerides of fatty acids containing from 4 to 10 carbon atoms,
for instance heptanoic or octanoic acid triglycerides, or
alternatively sunflower oil, corn oil, soybean oil, grapeseed oil,
sesame seed oil, apricot oil, macadamia oil, castor oil, avocado
oil, caprylic/capric acid triglycerides, jojoba oil or shea butter;
linear or branched hydrocarbons, of mineral or synthetic origin,
such as liquid paraffins and derivatives thereof, petroleum jelly,
polydecenes, and hydrogenated polyisobutene such as parleam;
synthetic esters and ethers, especially of fatty acids, for
instance purcellin oil, isopropyl myristate, 2-ethylhexyl
palmitate, 2-octyldodecyl stearate, 2-octyldodecyl erucate or
isostearyl isostearate; hydroxylated esters, for instance
isostearyl lactate, octyl hydroxystearate, octyldodecyl
hydroxystearate, diisostearyl malate, triisocetyl citrate, and
fatty alkyl heptanoates, octanoates or decanoates; polyol esters,
for instance propylene glycol dioctanoate, neopentyl glycol
diheptanoate or diethylene glycol diisononanoate; and
pentaerythritol esters; fatty alcohols containing from 12 to 26
carbon atoms, for instance octyldodecanol, 2-butyloctanol,
2-hexyldecanol, 2-undecylpentadecanol or oleyl alcohol; partially
hydrocarbon-based and/or partially silicone-based fluoro oils;
silicone oils, for instance volatile or non-volatile, linear or
cyclic polymethylsiloxanes (PDMS), for instance cyclomethicones,
dimethicones optionally comprising a phenyl group, for instance
phenyl trimethicones, phenyltrimethylsiloxydiphenylsiloxanes,
diphenylmethyl dimethyl trisiloxanes, diphenyl dimethicones, phenyl
dimethicones and polymethylphenylsiloxanes; mixtures thereof.
[0296] These oils may be present in a content ranging from 0.01% to
90% and better still from 0.1% to 85% by weight relative to the
total weight of the composition.
[0297] The organic liquid medium of the composition according to
the invention may also comprise one or more cosmetically acceptable
organic solvents (acceptable tolerance, toxicology and feel).
[0298] These solvents may generally be present in a content ranging
from 0.1% to 90%, preferably from 10% to 90% and better still from
30% to 90% by weight relative to the total weight of the
composition.
[0299] As solvents that may be used in the composition of the
invention, mention may be made, besides the hydrophilic organic
solvents mentioned above, of ketones that are liquid at room
temperature, such as methyl ethyl ketone, methyl isobutyl ketone,
diisobutyl ketone, isophorone, cyclohexanone and acetone; propylene
glycol ethers that are liquid at room temperature, such as
propylene glycol monomethyl ether, propylene glycol monomethyl
ether acetate and dipropylene glycol mono-n-butyl ether;
short-chain esters (containing from 3 to 8 carbon atoms in total),
such as ethyl acetate, methyl acetate, propyl acetate, n-butyl
acetate and isopentyl acetate; ethers that are liquid at room
temperature, such as diethyl ether, dimethyl ether and
dichlorodiethyl ether; alkanes that are liquid at room temperature,
such as decane, heptane, dodecane, isododecane and cyclohexane;
cyclic aromatic compounds that are liquid at room temperature, such
as toluene and xylene; aldehydes that are liquid at room
temperature, such as benzaldehyde and acetaldehyde, and mixtures
thereof.
[0300] The composition may comprise, besides the block polymer
described above, an additional polymer such as a film-forming
polymer. According to the present invention, the term "film-forming
polymer" means a polymer that is capable of forming, by itself or
in the presence of an auxiliary film-forming agent, a continuous
film that adheres to a support, especially to keratin
materials.
[0301] Among the film-forming polymers that may be used in the
composition of the present invention, mention may be made of
synthetic polymers, of free-radical type or of polycondensate type,
polymers of natural origin, and mixtures thereof. Film-forming
polymers that may be mentioned in particular include acrylic
polymers, polyurethanes, polyesters, polyamides, polyureas and
cellulose-based polymers, for instance nitrocellulose.
[0302] The polymer may be combined with one or more auxiliary
film-forming agents. Such a film-forming agent may be chosen from
any compound known to those skilled in the art as being capable of
fulfilling the desired function, and may be chosen especially from
plasticizers and coalescers.
[0303] The composition according to the invention may comprise at
least one wax. For the purposes of the present invention, the term
"wax" means a lipophilic compound that is solid at room temperature
(25.degree. C.), which undergoes a reversible solid/liquid change
of state, and which has a melting point of greater than or equal to
30.degree. C., which may be up to 120.degree. C.
[0304] The melting point of the wax may be measured using a
differential scanning calorimeter (DSC), for example the
calorimeter sold under the name DSC 30 by the company Mettler.
[0305] The waxes may be hydrocarbon-based waxes, fluoro waxes
and/or silicone waxes and may be of plant, mineral, animal and/or
synthetic origin. In particular, the waxes have a melting point of
greater than 25.degree. C. and better still greater than 45.degree.
C.
[0306] As waxes that may 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, for instance polyethylene waxes or
Fischer-Tropsch waxes, and silicone waxes, for instance alkyl or
alkoxy dimethicones containing from 16 to 45 carbon atoms.
[0307] The nature and amount of the solid fatty substances depend
on the desired mechanical properties and textures. As a guide, the
composition may contain from 0% to 50% by weight and better still
from 1% to 30% by weight of waxes, relative to the total weight of
the composition.
[0308] The composition according to the invention may also comprise
one or more dyestuffs chosen from water-soluble dyes and
pulverulent dyestuffs, for instance pigments, nacres and flakes
that are well known to those skilled in the art. The dyestuffs may
be present in the composition in a content ranging from 0.01% to
50% by weight and preferably from 0.01% to 30% by weight, relative
to the weight of the composition.
[0309] The term "pigments" should be understood as meaning white or
coloured, mineral or organic particles of any shape, which are
insoluble in the physiological medium and which are intended to
colour the composition.
[0310] The term "nacres" should be understood as meaning iridescent
particles of any shape, produced especially by certain molluscs in
their shell, or alternatively synthesized.
[0311] The pigments may be white or coloured, and mineral and/or
organic. Among the mineral pigments that may be mentioned are
titanium dioxide, optionally surface-treated, zirconium oxide or
cerium oxide, and also zinc oxide, iron oxide (black, yellow or
red) or chromium oxide, manganese violet, ultramarine blue,
chromium hydrate and ferric blue, and metal powders, for instance
aluminium powder or copper powder.
[0312] Among the organic pigments that may be mentioned are carbon
black, pigments of D & C type, and lakes based on cochineal
carmine or on barium, strontium, calcium or aluminium.
[0313] Mention may also be made of pigments with an effect, such as
particles comprising a natural or synthetic, organic or mineral
substrate, for example glass, acrylic resins, polyester,
polyurethane, polyethylene terephthalate, ceramics or aluminas, the
said substrate being uncoated or coated with metal substances, for
instance aluminium, gold, silver, platinum, copper or bronze, or
with metal oxides, for instance titanium dioxide, iron oxide or
chromium oxide, and mixtures thereof.
[0314] The nacreous pigments may be chosen from white nacreous
pigments such as mica coated with titanium or with bismuth
oxychloride, coloured nacreous pigments such as titanium mica
coated with iron oxides, titanium mica coated especially with
ferric blue or chromium oxide, titanium mica coated with an organic
pigment of the abovementioned type and also nacreous pigments based
on bismuth oxychloride. Interference pigments, especially
liquid-crystal pigments or multilayer pigments, may also be
used.
[0315] The water-soluble dyes are, for example, beetroot juice or
methylene blue.
[0316] The composition according to the invention may comprise one
or more fillers, especially in a content ranging from 0.01% to 50%
by weight and preferably ranging from 0.01% to 30% by weight,
relative to the total weight of the composition. The term "fillers"
should be understood as meaning colourless or white, mineral or
synthetic particles of any shape, which are insoluble in the medium
of the composition, irrespective of the temperature at which the
composition is manufactured. These fillers serve especially to
modify the rheology or the texture of the composition.
[0317] The fillers may be mineral or organic in any form,
platelet-shaped, spherical or oblong, irrespective of the
crystallographic form (for example leaflet, cubic, hexagonal,
orthorhombic, etc.). Mention may be made of talc, mica, silica,
kaolin, polyamide (Nylon.RTM.) powders (Orgasol.RTM. from Atochem),
poly-.beta.-alanine powder and polyethylene powder, powders of
tetrafluoroethylene polymers (Teflon.RTM.), lauroyllysine, starch,
boron nitride, hollow polymer microspheres such as those of
polyvinylidene chloride/acrylonitrile, for instance Exapancel.RTM.
(Nobel Industrie) or acrylic acid copolymers (Polytrap.RTM. from
the company Dow Corning) and silicone resin microbeads (for example
Tospearls.RTM. from Toshiba), elastomeric polyorganosiloxane
particles, precipitated calcium carbonate, magnesium carbonate,
magnesium hydrocarbonate, hydroxyapatite, hollow silica
microspheres (Silica Beads.RTM. from Maprecos), glass or ceramic
microcapsules, and metal soaps derived from organic carboxylic
acids containing from 8 to 22 carbon atoms and preferably from 12
to 18 carbon atoms, for example zinc, magnesium or lithium
stearate, zinc laurate or magnesium myristate.
[0318] The composition according to the invention may especially be
in the form of a suspension, a dispersion, a solution, a gel, an
emulsion, especially an oil-in-water (O/W) emulsion, a water-in-oil
(W/O) emulsion or a multiple emulsion (W/O/W or polyol/O/W or O/W/O
emulsion), in the form of a cream, a paste, a mousse, a dispersion
of vesicles, especially of ionic or nonionic lipids, a two-phase or
multi-phase lotion, a spray, a powder, a paste, especially a soft
paste (especially a paste with a dynamic viscosity at 25.degree. C.
of about from 0.1 to 40 Pas under a shear rate of 200 s.sup.-1,
after measurement for 10 minutes in cone/plate geometry). The
composition may be anhydrous; for example, it may be a soft
anhydrous paste.
[0319] A person skilled in the art may select the appropriate
galenical form, and also the method for preparing it, on the basis
of his general knowledge, taking into account firstly the nature of
the constituents used, especially their solubility in the support,
and secondly the intended application for the composition.
[0320] The composition according to the invention may be a makeup
composition, for instance products for the complexion
(foundations), makeup rouges, eyeshadows, liquid lipsticks,
concealer products, mascaras, eyeliners, eyebrow makeup products,
nail products, such as nail varnishes, body makeup products or hair
makeup products (hair mascara or hair lacquer).
[0321] The composition according to the invention may also be a
care product for body and facial skin, especially an antisun
product or a skin-colouring product (such as a self-tanning
product).
[0322] A subject of the present invention is also a cosmetic
assembly comprising:
i) a container delimiting at least one compartment, the said
container being closed by a closing member; and
ii) a composition as described above, placed inside the said
compartment.
[0323] The container may be in any adequate form. It may especially
be in the form of a bottle, a tube, a jar, a case, a box, a sachet
or a carton.
[0324] The closing member may be in the form of a removable
stopper, a lid, a cap, a tear-off strip or a capsule, especially of
the type comprising a body attached to the container and a cover
cap articulated on the body. It may also be in the form of a member
for selectively closing the container, especially a pump, a valve
or a flap valve.
[0325] The container may be combined with an applicator, especially
in the form of a brush comprising an arrangement of bristles
maintained by a twisted wire. Such a twisted brush is described
especially in patent U.S. Pat. No. 4,887,622. It may also be in the
form of a comb comprising a plurality of application members,
obtained especially by moulding. Such combs are described, for
example, in patent FR 2 796 529. The applicator may be in the form
of a fine brush, as described, for example, in patent FR 2 722 380.
The applicator may be in the form of a block of foam or of
elastomer, a felt or a spatula. The applicator may be free (tuft or
sponge) or securely fastened to a rod borne by the closing member,
as described, for example, in patent U.S. Pat. No. 5,492,426. The
applicator may be securely fastened to the container, as described,
for example, in patent FR 2 761 959.
[0326] The product may be contained directly in the container, or
indirectly. By way of example, the product may be arranged on an
impregnated support, especially in the form of a wipe or a pad, and
arranged (individually or in plurality) in a box or in a sachet.
Such a support incorporating the product is described, for example,
in patent application WO 01/03538.
[0327] The closing member may be coupled to the container by
screwing. Alternatively, the coupling between the closing member
and the container is done other than by screwing, especially via a
bayonet mechanism, by click-fastening, gripping, welding, bonding
or by magnetic attraction. The term "click-fastening" in particular
means any system involving the crossing of a bead or cord of
material by elastic deformation of a portion, especially of the
closing member, followed by return to the elastically unconstrained
position of the said portion after the crossing of the bead or
cord.
[0328] The container may be at least partially made of
thermoplastic material. Examples of thermoplastic materials that
may be mentioned include polypropylene or polyethylene.
[0329] Alternatively, the container is made of non-thermoplastic
material, especially glass or metal (or alloy).
[0330] The container may have rigid walls or deformable walls,
especially in the form of a tube or a tubular bottle.
[0331] The container may comprise means for distributing or
facilitating the distribution of the composition. By way of
example, the container may have deformable walls so as to allow the
composition to exit in response to a positive pressure inside the
container, this positive pressure being caused by elastic (or
non-elastic) squeezing of the walls of the container.
[0332] The container may consist of a carton with a base delimiting
at least one housing containing the composition, and a lid,
especially articulated on the base, and capable of at least
partially covering the said base. Such a carton is described, for
example, in patent application WO 03/018423 or in patent FR 2 791
042.
[0333] The container may be equipped with a drainer arranged in the
region of the aperture of the container. Such a drainer makes it
possible to wipe the applicator and possibly the rod to which it
may be securely fastened. Such a drainer is described, for example,
in patent FR 2 792 618.
[0334] The composition may be at atmospheric pressure inside the
container (at room temperature) or pressurized, especially by means
of a propellent gas (aerosol). In the latter case, the container is
equipped with a valve (of the type used for aerosols).
[0335] The content of the patents or patent applications mentioned
above are incorporated by reference into the present patent
application.
[0336] The examples that follow illustrate the compositions
according to the invention in a non-limiting manner.
EXAMPLES 8 TO 12
Lipsticks
[0337] TABLE-US-00001 Example 8 9 10 11 12 Polymer of Example 2
90.7 Polymer of Example 3 90.7 Polymer of Example 4 90.7 Polymer of
Example 6 90.7 Polymer of Example 7 90.7 Hydrogenated polyisobutene
2.1 2.1 2.1 2.1 2.1 Octyldodecanol 0.9 0.9 0.9 0.9 0.9 Phenyl
trimethicone 2.1 2.1 2.1 2.1 2.1 (DC 556, 20 cSt, Dow Corning)
Copolymer vinylpyrrolidone/1- 1.2 1.2 1.2 1.2 1.2 eicosene (Antaron
V-220, ISP) Pigments 3 3 3 3 3
Procedure [0338] 1. A ground pigmentary mixture of the pigments in
the oily phase is prepared by treating the mixture three times in a
three-roll mill. [0339] 2. The ground material required for the
composition and the other ingredients are weighed out in a beaker.
[0340] 3 The mixture is stirred using a Rayneri blender for 45
minutes at room temperature. [0341] 4. The formula is cast in
isododecane-leaktight cooling boxes. Gloss Measurement [0342] 1.
Films with a wet thickness of 50 and/or 150 .mu.m are prepared
using a mechanical applicator. The depositions are made on a Leneta
brand contrast card with reference Form 1A Penopac. [0343] 2 The
films are left to dry for 24 hours at a regulated temperature of
30.degree. C. [0344] 3 The gloss measurements are performed using a
Byk Gardner micro-tri-gloss glossmeter with measuring angles of
20.degree. and 60.degree. for each series of deposits.
[0345] The gloss results obtained in vivo are given in the table
below:
[0346] 150 .mu.m Deposit TABLE-US-00002 Angle Deposit Polymer Mean
(%) Standard deviation Angle of 150 .mu.m Example 8 54.2 2.0
20.degree. deposit Example 9 41.0 3.5 Angle 150 .mu.m Example 8
75.7 0.8 Example 9 73.6 1.6
[0347] 50 .mu.m Deposit TABLE-US-00003 Angle Deposit Polymer Mean
(%) Standard deviation Angle of 50 .mu.m Example 8 47.6 1.2
20.degree. deposit Example 9 42.6 5.2 Angle of 50 .mu.m Example 8
69.3 0.7 60.degree. deposit Example 9 74.8 1.0
[0348] The mean gloss obtained is greater than 40 out of 100 for a
measuring angle of 20.degree. and a thickness of 50 .mu.m or 150
.mu.m.
[0349] The mean gloss obtained is greater than 65 out of 100 for a
measuring angle of 60.degree. and a thickness of 50 .mu.m. The mean
gloss obtained is greater than 70 out of 100 for a measuring angle
of 60.degree. and a thickness of 150 .mu.m.
EXAMPLE 13
Nail Varnish
[0350] TABLE-US-00004 Polymer of Example 1 23.8 g AM Butyl acetate
24.99 g Isopropanol 10.71 g Hexylene glycol 2.5 g DC Red 7 Lake 1 g
Hectorite modified with distearyl- 1.3 g dimethylbenzylammonium
chloride (Bentone .RTM. 27V from Elementis)
EXAMPLE 14
Nail Varnish
[0351] TABLE-US-00005 Polymer of Example 5 23.8 g AM Butyl acetate
24.99 g Isopropanol 10.71 g Hexylene glycol 2.5 g DC Red 7 Lake 1 g
Hectorite modified with distearyl- 1.3 g dimethylbenzylammonium
chloride (Bentone .RTM. 27V from Elementis) Ethyl acetate qs 100
g
* * * * *