U.S. patent application number 10/529266 was filed with the patent office on 2006-06-22 for glossy non-transfer composition comprising a sequenced polymer.
Invention is credited to Xavier Blin, Veronique Ferrari.
Application Number | 20060134051 10/529266 |
Document ID | / |
Family ID | 32045662 |
Filed Date | 2006-06-22 |
United States Patent
Application |
20060134051 |
Kind Code |
A1 |
Blin; Xavier ; et
al. |
June 22, 2006 |
Glossy non-transfer composition comprising a sequenced polymer
Abstract
The present invention relates to a cosmetic composition
containing a cosmetically acceptable organic liquid medium and a
film-forming linear ethylenic block 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,
and the transfer index of the said composition is less than or
equal to 40 out of 100.
Inventors: |
Blin; Xavier; (Paris,
FR) ; Ferrari; Veronique; (Maisons-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.: |
10/529266 |
Filed: |
September 26, 2003 |
PCT Filed: |
September 26, 2003 |
PCT NO: |
PCT/FR03/02847 |
371 Date: |
October 3, 2005 |
Current U.S.
Class: |
424/70.16 |
Current CPC
Class: |
A61K 8/922 20130101;
A61K 2800/594 20130101; A61Q 1/06 20130101; C08L 51/003 20130101;
C08F 293/005 20130101; Y10S 514/844 20130101; A61K 8/90 20130101;
A61Q 1/04 20130101; C08F 265/04 20130101; A61K 8/26 20130101; A61K
8/8182 20130101; C08F 265/06 20130101; A61K 8/8111 20130101; A61K
8/8152 20130101; Y10S 514/937 20130101; C08L 53/00 20130101; C08L
51/003 20130101; A61K 8/891 20130101; C08L 53/00 20130101; A61Q
1/10 20130101; C08F 291/00 20130101; A61K 8/927 20130101; Y10S
514/845 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 |
02/11949 |
Dec 20, 2002 |
FR |
02/16437 |
May 21, 2003 |
FR |
03/06121 |
Claims
1. Cosmetic composition containing a cosmetically acceptable
organic liquid medium and a film-forming linear ethylenic block
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, and the transfer index of
the said composition is less than or equal to 40 out of 100.
2. Cosmetic composition according to the preceding claim,
characterized in that the block polymer is a non-elastomeric
polymer.
3. Cosmetic composition according to either of the preceding
claims, 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 group-COO-- or
amide group --CON-- group.
4. Cosmetic composition according to one of the preceding claims,
characterized in that the block 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 claim 6, 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.
8. Composition according to claim 6 or 7, 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.
9. 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.
10. Composition according to one of the preceding claims,
characterized in that the transfer index is less than or equal to
30, preferably less than or equal to 20, preferably less than or
equal to 15, preferably less than or equal to 10, preferably less
than or equal to 5, and more preferably less than or equal to 2 out
of 100.
11. Cosmetic composition according to one of the preceding claims,
characterized in that the mean gloss measured at 20.degree. of the
composition, once spread onto a support, is 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, better still greater than or equal to 55 and better still
greater than or equal to 60.
12. Cosmetic 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
better still greater than or equal to 90 out of 100.
13. Cosmetic composition according to one of the preceding claims,
characterized in that the mean gloss of the composition, once
spread onto a support, measured at 20.degree. is greater than 35,
preferably 40, 45 or 50 out of 100, and/or the mean gloss of the
composition, once spread onto a support, measured at 60.degree. is
preferably greater than 65, 70 or 75 out of 100.
14. Cosmetic composition according to one of the preceding claims,
characterized in that the block polymer has a polydispersity index
I of greater than 2.
15. Composition according to claim 14, characterized in that the
block polymer has a polydispersity index of greater than or equal
to 2.5, preferably greater than or equal to 2.8 and preferably
between 2.8 and 6.
16. 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.
17. Composition according to claim 16, characterized in that the
weight-average mass (Mw) ranges from 35 000 to 200 000 and better
still from 45 000 to 150 000.
18. Composition according to claim 17, characterized in that the
number-average mass (Mn) is less than or equal to 70 000.
19. Composition according to one of claims 16 to 18, the
number-average mass (Mn) of which ranges from 10 000 to 60 000 and
better still from 12 000 to 50 000.
20. 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.
21. Cosmetic composition according to one of the preceding claims,
characterized in that it contains less than 30%, preferably less
than 25%, less than 20% and better still less than 15% by weight of
at least one glossy oil.
22. Composition according to claim 6 or any of the preceding claims
dependent thereon, 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.
23. Composition according to claim 22, 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 4-0.degree.
C.
24. 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
alkyl group containing from 1 to 12 carbon atoms, 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.
25. Composition according to claim 23 or 24, 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.
26. Composition according to claim 25, characterized in that the
block with a Tg of less than or equal to 20.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 less than or equal to 20.degree. C.
27. Composition according to claim 26, 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.
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
alkyl acrylates whose alkyl chain contains from 1 to 10 carbon
atoms, with the exception of the tert-butyl group.
29. Composition according to claim 22, 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.
30. Composition according to claim 22, 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.
31. Composition according to claim 29 or 30, 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.
32. Composition according to one of claims 22 to 31, 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.
33. 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.
34. Composition according to claim 33, 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.
35. Composition according to claim 33 or 34, 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
alkyl group containing from 1 to 12 carbon atoms, 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.
36. Composition according to one of claims 33 to 35, 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.
37. Composition according to one of claims 33 to 36, 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.
38. Composition according to one of claims 32 to 37, 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.
39. Composition according to one of claims 32 to 38, 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.
40. Composition according to claim 38 or 39, 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.
41. Composition according to one of claims 38 to 40, 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.
42. Composition according to claim 41, 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
isobutyl acrylate, methyl acrylate and 2-ethylhexyl acrylate.
43. Composition according to one of claims 32 to 42, 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.
44. Composition according to one of claims 32 to 43, 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.
45. 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.
46. Composition according to claim 44 or 45, 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.
47. Composition according to one of claims 44 to 46, 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.
48. Composition according to one of claims 44 to 47, 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.
49. Composition according to any one of claims 44 to 47,
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.
50. Composition according to any one of claims 44 to 49,
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.
51. Composition according to either of claims 49 and 50,
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 alkyl group
containing from 1 to 12 carbon atoms, 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.
52. Composition according to one of claims 48 to 51, 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.
53. Composition according to one of claims 49 to 52, 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.
54. Composition according to one of claims 44 to 53, 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.
55. Composition according to one of claims 44 to 53, 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.
56. Composition according to claim 54 or 55, 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.
57. Composition according to one of claims 54 to 56, 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.
58. Composition according to one of claims 54 to 57, 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.
59. Cosmetic composition according to claim 5 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.
60. 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.
61. Composition according to claim 59 or 60, 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 from 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 methacryloxy-propyltrimethoxysilane and
methacryloxypropyl-tris(trimethylsiloxy)silane, and mixtures
thereof.
62. Composition according to either of claims 59 and 60,
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.
63. Composition according to either of claims 59 and 60,
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.
64. Composition according to either of claims 59 and 60,
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.
65. Composition according to one of claims 59 to 64, 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.
66. 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.
67. 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 paste, a mousse, a dispersion of vesicles, especially of ionic or
nonionic lipids, a two-phase or multi-phase lotion, a spray, a
powder or a paste, especially a soft paste or an anhydrous
paste.
68. Cosmetic composition according to any one of the preceding
claims, characterized in that it is in anhydrous form.
69. Cosmetic composition according to any one of the preceding
claims, characterized in that it is a makeup or care composition
for keratin materials.
70. Cosmetic composition according to one of the preceding claims,
characterized in that it is a lip makeup product.
71. Cosmetic composition according to one of the preceding claims,
characterized in that it is an eye 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.
Description
[0001] The present invention relates to a 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 or the eyebrows, comprising a cosmetically
acceptable organic liquid medium and a particular block
polymer.
[0002] "Transfer-resistant" lip and skin makeup compositions are
compositions that have the advantage of forming a deposit that does
not transfer or that does not leave traces or marks, at least
partially, on the supports with which they come into contact
(glass, clothing, cigarette or fabrics).
[0003] Known transfer-resistant compositions are based on silicone
resins and volatile silicone oils and, although having improved
staying power properties, have the drawback of leaving on the skin
and the lips, after the volatile silicone oils have evaporated off,
a film that becomes uncomfortable over time (sensation of drying
out and of tautness) and is barely glossy.
[0004] However, women are nowadays seeking products, especially for
colouring the lips or the eyelids, which are glossy while at the
same time being transfer-resistant.
[0005] There is still a need for a cosmetic product that not only
has good staying power, but is also transfer-resistant and
glossy.
[0006] A method has been proposed in the prior art, in patent
application WO-A-97/17057 from the company Procter & Gamble,
for increasing the gloss and the comfort of transfer-resistant
compositions, which consists in applying two compositions, one over
the other. However, these products remain uncomfortable. In
addition, the application of two compositions may be unacceptable
for certain consumers.
[0007] The aim of the present invention is to propose a novel route
for formulating a cosmetic product, in particular a makeup product,
which allows good "transfer-resistance" and gloss properties.
[0008] This product especially has the advantage of comprising only
one composition, in contrast with the product of patent application
WO-A-97/17057.
[0009] The product obtained according to the invention, especially
when it is a product for the lips, has good properties of migration
resistance, staying power and absence of a sensation of drying
out.
[0010] One subject of the invention is a glossy, transfer-resistant
composition for caring for or making up the skin and/or the lips
and/or integuments, containing a film-forming linear block
ethylenic polymer. The inventors have found, surprisingly, that the
use of such a block polymer makes it possible to obtain a glossy,
transfer-resistant composition. The composition according to the
invention also has the advantage of having good staying power.
[0011] The composition of the invention may in particular
constitute a haircare product or a makeup product for human body,
lips or integuments having care and/or treating properties. It
especially constitutes a lipstick or a lipgloss, an eyeshadow,
attack to product, a mascara, an eyeliner, a product for
artificially tanning the skin, an optionally tinted care or
protecting cream, a hair-colouring product or a haircare
product.
[0012] A subject of the invention is, more specifically, a cosmetic
composition containing a cosmetically acceptable organic liquid
medium and a film-forming linear ethylenic block polymer, the said
polymer being such that, when it is in sufficient amount in the
composition: [0013] 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, and [0014] the transfer index is less
than or equal to 40 out of 100.
[0015] Preferably, the composition according to the invention is a
leave-in composition.
[0016] The invention also relates to a cosmetic composition
comprising an organic liquid medium and at least one block polymer
as described below.
Mean Gloss of the Composition
[0017] The term "mean gloss" means the gloss as may be
conventionally measured using a glossmeter by the following
method.
[0018] 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.
[0019] 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.
[0020] 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, 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, and better still greater than or equal to 60.
[0021] 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 better
still greater than or equal to 90 out of 100.
[0022] 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.
[0023] 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.
[0024] 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.
[0025] 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.
Transfer Index of the Composition
[0026] The transfer index of the composition according to the
invention is preferably less than or equal to 40 out of 100. More
preferably, the transfer index is less than or equal to 30,
preferably less than or equal to 20, more preferably less than or
equal to 15, preferably less than or equal to 10, preferably less
than or equal to 5 out of 100, and preferably less than or equal to
2 out of 100.
[0027] The transfer index may be measured according to the
following method.
[0028] A support (rectangle of 40 mm.times.70 mm and 3 mm thick) of
polyethylene foam that is adhesive on one of the faces, having a
density of 33 kg/m.sup.3 (sold under the name RE40X70EP3 from the
company Joint Technique Lyonnais Ind) is preheated on a hotplate
maintained at a temperature of 40.degree. C. in order for the
surface of the support to be maintained at a temperature of
33.degree. C..+-.1.degree. C.
[0029] The composition is applied over the entire non-adhesive
surface of the support, by spreading it using a fine brush to
obtain a deposit of about 15 .mu.m of the composition, while
leaving the support on the hotplate, and the support is then left
to dry for 30 minutes.
[0030] After drying, the support is bonded via its adhesive face
onto an anvil 20 mm in diameter and equipped with a screw pitch.
The support/deposit assembly is then cut up using a punch 18 mm in
diameter. The anvil is then screwed onto a press (Statif Manuel
Imada SV-2 from the company Someco) equipped with a tensile testing
machine (Imada DPS-20 from the company Someco).
[0031] White photocopier paper of 80 g/m.sup.2 is placed on the bed
of the press and the support/deposit assembly is then pressed on
the paper at a pressure of 2.5 kg for 30 seconds. After removing
the support/deposit assembly, some of the deposit is transferred
onto the paper. The colour of the deposit transferred onto the
paper is then measured using a Minolta CR300 calorimeter, the
colour being characterized by the L*, a*, b* calorimetric
parameters. The calorimetric parameters L*.sub.0, a*.sub.0 and
b*.sub.0 of the colour of the plain paper used is determined.
[0032] The difference in colour .DELTA.E1 between the colour of the
deposit transferred relative to the colour of the plain paper is
then determined by means of the following relationship. .DELTA.E1=
{square root over
((L*-L.sub.0*).sup.2+(a*-a.sub.0*).sup.2+(b*-b.sub.0*).sup.2)}
[0033] Moreover, a total transfer reference is prepared by applying
the composition directly onto a paper identical to the one used
previously, at room temperature (25.degree. C.), by spreading the
composition using a fine brush and so as to obtain a deposit of
about 15 .mu.m of the composition, and the deposit is then left to
dry for 30 minutes at room temperature (25.degree. C.). After
drying, the calorimetric parameters L*', a*' and b*' of the colour
of the deposit placed on the paper, corresponding to the reference
colour of total transfer, is measured directly. The calorimetric
parameters L*'.sub.0, a*'.sub.0 and b*'.sub.0 of the colour of the
plain paper used are determined.
[0034] The difference in colour .DELTA.E2 between the reference
colour of total transfer relative to the colour of the plain paper
are then determined by means of the following relationship.
.DELTA.E2= {square root over
((L*'-L.sub.0*').sup.2+(a*'-a.sub.0*).sup.2+(b*'-b.sub.0*').sup-
.2)}
[0035] The transfer of the composition, expressed as a percentage,
is equal to the ratio: 100.times..DELTA.E1/.DELTA.E2
[0036] The measurement is performed on 4 supports in succession and
the transfer value corresponds to the mean of the 4 measurements
obtained with the 4 supports. The transfer index is equal to the
mean of these four measurements.
[0037] The invention also relates to a process for making up the
skin and/or the lips and/or integuments, which consists in applying
to the skin and/or the lips and/or integuments the composition as
defined above.
[0038] 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 and the inside of the lower
eyelids, and integuments, for instance the eyelashes, the hair, the
eyebrows, or even body hairs.
[0039] The invention also relates to the use of a block polymer in
a sufficient amount in a cosmetic composition to impart gloss and
transfer resistance to a deposit of the said composition.
[0040] 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.
[0041] The composition advantageously contains a small proportion
of oils conventionally used to impart gloss, these oils generally
being tacky. The composition according to the invention
advantageously contains less than 30%, less than 25%, less than 20%
and better still less than 15% of at least one glossy oil.
[0042] 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).
[0043] The glossy oil has, for example, a molar mass ranging from
650 to 10 000 g/mol and preferably from 750 to 7500 g/mol.
[0044] The oil with a molar mass ranging from 650 to 10 000 g/mol
may be chosen from:
[0045] lipophilic polymers such as: [0046] 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, [0047] 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), [0048] 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, [0049] vinylpyrrolidone copolymers such as:
vinylpyrrolidone/1-hexadecene copolymer, Antaron V-216 sold or
manufactured by the company ISP (MM=7300 g/mol),
[0050] esters such as: [0051] linear fatty acid esters with a total
carbon number ranging from 35 to 70, for instance pentaerythrityl
tetrapelargonate (MM=697.05 g/mol), [0052] hydroxylated esters such
as polyglyceryl-2 triisostearate (MM=965.58 g/mol), [0053] aromatic
esters such as tridecyl trimellitate (MM=757.19 g/mol), [0054]
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),
[0055] silicone oils such as phenylsilicones, for instance Belsil
PDM 1000 from the company Wacker (MM 9000 g/mol),
[0056] oils of plant origin, such as sesame oil (820.6 g/mol),
[0057] and mixtures thereof.
Block Polymer:
[0058] 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.
[0059] According to one embodiment, the block polymer of the
composition according to the invention is an ethylenic polymer. The
term "ethylenic" polymer means a polymer obtained by polymerizing
monomers comprising an ethylenic unsaturation.
[0060] According to one embodiment, the block polymer of the
composition according to the 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.
[0061] 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.
[0062] According to one embodiment, the block polymer of the
composition according to the invention is a non-elastomeric
polymer.
[0063] 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.
[0064] 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%.
[0065] More specifically, the non-elastomeric nature of the polymer
is determined according to the following protocol:
[0066] 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.
[0067] 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.
[0068] 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.
[0069] 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.
[0070] The instantaneous recovery R.sub.i is determined in the
following manner: [0071] the specimen is pulled by 30%
(.epsilon..sub.max), i.e. about 0.3 times its initial length
(l.sub.0) [0072] 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.1).
[0073] The percentage instantaneous recovery (R.sub.i) is given by
the following formula:
R.sub.i=(.epsilon..sub.max-.DELTA..sub.1)/.epsilon..sub.max).times.100
[0074] To determine the delayed recovery, the percentage residual
elongation of the specimen (.epsilon..sub.2h) is measured, 2 hours
after returning to zero constraint.
[0075] 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.10-
0
[0076] Purely as a guide, a block 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%.
[0077] 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.
[0078] 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.
[0079] 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.
[0080] According to one embodiment, the block polymer comprises at
least one first block and at least one second block.
[0081] The term "at least one block" means one or more blocks.
[0082] 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.
[0083] 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)
[0084] 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.
[0085] 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.
[0086] Preferably, the intermediate block is derived essentially
from constituent monomers of the first block and of the second
block.
[0087] The term "essentially" means at least 85%, preferably at
least 90%, better still 95% and even better still 100%.
[0088] 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.
[0089] 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.
[0090] 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: [0091] i) the
said polymers are present in the mixture in a content such that the
respective weight ratio ranges from 10/90 to 90/10, and that [0092]
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%.
[0093] 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.
[0094] When the organic liquid medium comprises only one organic
liquid, this liquid obviously constitutes the liquid that is in
major amount by weight.
[0095] 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.
[0096] 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.
[0097] 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.
[0098] 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.
[0099] 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.
[0100] 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.).
[0101] According to one embodiment, the block polymer has a
polydispersity index I of greater than 2.
[0102] 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.
[0103] The polydispersity index I of the polymer is equal to the
ratio of the weight-average mass Mw to the number-average mass
Mn.
[0104] 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).
[0105] 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.
[0106] 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.
[0107] Each block of the block polymer is derived from one type of
monomer or from several different types of monomer.
[0108] 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.
[0109] 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## .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.
[0110] Unless otherwise indicated, the Tg values indicated for the
first and second blocks in the present patent application are
theoretical Tg values.
[0111] 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.
[0112] 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: [0113] a) a block with a Tg of greater than or
equal to 40.degree. C., [0114] b) a block with a Tg of less than or
equal to 20.degree. C., [0115] 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.
[0116] 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.
[0117] 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.
[0118] The block with a Tg of greater than or equal to 40.degree.
C. may be a homopolymer or a copolymer.
[0119] 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.
[0120] 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.).
[0121] 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:
[0122] 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
[0123] 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.
[0124] 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: [0125] 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, [0126]
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, [0127] (meth)acrylamides of
formula: ##STR1## 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, [0128] and mixtures thereof.
[0129] 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.
[0130] 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.
[0131] The block with a Tg of less than or equal to 20.degree. C.
may be a homopolymer or a copolymer.
[0132] 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.
[0133] 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.)
[0134] 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.
[0135] It may comprise, for example
[0136] 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
[0137] 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.
[0138] Preferably, the block with a Tg of less than or equal to
20.degree. C. is a homopolymer.
[0139] 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:
[0140] 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, [0141] 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; [0142] 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; [0143] C.sub.4
to C.sub.12 alkyl vinyl ethers, [0144] N--(C.sub.4 to
C.sub.12)alkyl acrylamides, such as N-octylacrylamide, [0145] and
mixtures thereof.
[0146] 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.
[0147] c) Block with a Tg of Between 20 and 40.degree. C.
[0148] The block with a Tg of between 20 and 40.degree. C. may be a
homopolymer or a copolymer.
[0149] 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.
[0150] 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.
[0151] 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.).
[0152] 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.
[0153] 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.
[0154] Advantageously, the block with a Tg of between 20 and
40.degree. C. is a copolymer totally or partially derived from:
[0155] 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
[0156] 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.
[0157] Such main monomers are chosen, for example, from methyl
methacrylate, isobornyl acrylate and methacrylate, butyl acrylate
and 2-ethylhexyl acrylate, and mixtures thereof.
[0158] Preferably, the proportion of the second block with a Tg of
less than or equal to 20.degree. C. ranges from 10% to 85% by
weight, better still from 20% to 70% and even better still from 20%
to 50% by weight of the polymer.
[0159] Preferably, each of the first and second blocks comprises at
least one monomer chosen from acrylic acid, acrylic acid esters,
(meth)acrylic acid and (meth)acrylic acid esters, and mixtures
thereof.
[0160] Advantageously, each of the first and second blocks is
totally derived from at least one monomer chosen from acrylic acid,
acrylic acid esters, (meth)acrylic acid and (meth)acrylic acid
esters, and mixtures thereof.
[0161] However, each of the blocks may contain in small proportion
at least one constituent monomer of the other block.
[0162] Thus, the first block may contain at least one constituent
monomer of the second block, and vice versa.
[0163] 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.
[0164] 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.
[0165] This additional monomer is chosen, for example, from:
[0166] a) hydrophilic monomers such as: [0167] ethylenically
unsaturated monomers comprising at least one carboxylic or sulfonic
acid function, for instance: [0168] acrylic acid, methacrylic acid,
crotonic acid, maleic anhydride, itaconic acid, fumaric acid,
maleic acid, acrylamidopropanesulfonic acid, vinylbenzoic acid,
vinylphosphoric acid, and salts thereof, [0169] ethylenically
unsaturated monomers comprising at least one tertiary amine
function, for instance 2-vinylpyridine, 4-vinylpyridine,
dimethylamino-ethyl methacrylate, diethylaminoethyl methacrylate
and dimethylaminopropylmethacrylamide, and salts thereof, [0170]
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, [0171] 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); [0172] 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 from 5 to 30 times, for example methoxy-POE, or
R.sub.10 represents a polyoxyethylenated group comprising from 5 to
30 ethylene oxide units b) ethylenically unsaturated monomers
comprising one or more silicon atoms, such as
methacryloxy-propyltrimethoxysilane and
methacryloxypropyl-tris(trimethylsiloxy)silane, [0173] and mixtures
thereof.
[0174] Additional monomers that are particularly preferred are
acrylic acid, methacrylic acid and trifluoroethyl methacrylate, and
mixtures thereof.
[0175] 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.
[0176] 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.
[0177] According to one preferred embodiment, the block polymer is
a non-silicone polymer, i.e. a polymer free of silicon atoms.
[0178] 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.
[0179] The block polymer may be obtained by free-radical solution
polymerization according to the following preparation process:
[0180] 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.), [0181] once this temperature is reached, the constituent
monomers of the first block are introduced in the presence of some
of the polymerization initiator, [0182] 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, [0183] 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,
[0184] the polymer dissolved in the polymerization solvent is
obtained.
FIRST EMBODIMENT
[0185] 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).
[0186] 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.
[0187] 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.
[0188] 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.
[0189] Thus, according to a first variant, the polymer according to
the invention may comprise:
[0190] 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,
[0191] 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
[0192] an intermediate block which is a methyl methacrylate/acrylic
acid/methyl acrylate copolymer.
[0193] According to a second variant, the polymer according to the
invention may comprise:
[0194] 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,
[0195] 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
[0196] an intermediate block which is a methyl methacrylate/acrylic
acid/methyl acrylate/trifluoroethyl methacrylate random
copolymer.
[0197] According to a third variant, the polymer according to the
invention may comprise:
[0198] 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,
[0199] 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
[0200] an intermediate block, which is an isobornyl
acrylate/isobutyl methacrylate/2-ethylhexyl acrylate random
copolymer.
[0201] According to a fourth variant, the polymer according to the
invention may comprise:
[0202] 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,
[0203] 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
[0204] an intermediate block which is an isobornyl acrylate/methyl
methacrylate/2-ethylhexyl acrylate random copolymer.
[0205] According to a fifth variant, the polymer according to the
invention may comprise:
[0206] 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,
[0207] 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
[0208] an intermediate block which is an isobornyl
acrylate/isobornyl methacrylate/2-ethylhexyl acrylate random
copolymer.
[0209] According to a sixth variant, the polymer according to the
invention may comprise:
[0210] 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,
[0211] 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
[0212] an intermediate block which is an isobornyl
methacrylate/isobutyl methacrylate/isobutyl acrylate random
copolymer.
[0213] According to a seventh variant, the polymer according to the
invention may comprise:
[0214] 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,
[0215] 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
[0216] an intermediate block which is an isobornyl
acrylate/isobornyl methacrylate/isobutyl acrylate random
copolymer.
[0217] According to an eighth variant, the polymer according to the
invention may comprise:
[0218] 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/isobornyl methacrylate copolymer,
[0219] 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
[0220] an intermediate block which is an isobornyl
acrylate/isobutyl methacrylate/isobutyl acrylate random
copolymer.
[0221] The examples that follow illustrate, in a non-limiting
manner, polymers corresponding to this first embodiment.
[0222] The amounts are expressed in grams.
EXAMPLE 1
Preparation of a poly(isobornyl acrylate/isobutyl
methacrylate/2-ethylhexyl acrylate) polymer
[0223] 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.
[0224] 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.
[0225] The mixture is maintained at 90.degree. C. for 1 hour 30
minutes.
[0226] 90 g of 2-ethylhexyl acrylate, 90 g of isododecane and 1.2 g
of 2,5-bis(2-ethylhexanoyl-peroxy)-2,5-dimethylhexane are then
introduced into the above mixture, still at 90.degree. C. and over
30 minutes.
[0227] The mixture is maintained at 90.degree. C. for 3 hours and
is then cooled.
[0228] A solution containing 50% polymer active material in
isododecane is obtained.
[0229] 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 that is an isobornyl acrylate/isobutyl
methacrylate/2-ethylhexyl acrylate random polymer is obtained.
[0230] 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 2
Preparation of a poly(isobornyl acrylate/isobornyl
methacrylate/2-ethylhexyl acrylate) polymer
[0231] 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.
[0232] 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.
[0233] The mixture is maintained at 90.degree. C. for 1 hour 30
minutes.
[0234] 90 g of 2-ethylhexyl acrylate, 90 g of isododecane and 1.2 g
of 2,5-bis(2-ethylhexanoyl-peroxy)-2,5-dimethylhexane are then
introduced into the above mixture, still at 90.degree. C. and over
30 minutes.
[0235] The mixture is maintained at 90.degree. C. for 3 hours and
is then cooled.
[0236] A solution containing 50% polymer active material in
isododecane is obtained.
[0237] 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 that is an isobornyl acrylate/isobornyl
methacrylate/2-ethylhexyl acrylate random polymer is obtained.
[0238] 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 3
Preparation of a poly(isobornyl acrylate/isobutyl
methacrylate/isobutyl acrylate) polymer
[0239] 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.
[0240] 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.
[0241] The mixture is maintained at 90.degree. C. for 1 hour 30
minutes.
[0242] 90 g of isobutyl acrylate, 90 g of isododecane and 1.2 g of
2,5-bis(2-ethylhexanoyl-peroxy)-2,5-dimethylhexane are then
introduced into the above mixture, still at 90.degree. C. and over
30 minutes.
[0243] The mixture is maintained at 90.degree. C. for 3 hours and
is then cooled.
[0244] A solution containing 50% polymer active material in
isododecane is obtained.
[0245] 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 that is an isobornyl acrylate/isobutyl
methacrylate/isobutyl acrylate random polymer is obtained.
[0246] This polymer has a weight-average mass of 144 200 and a
number-average mass of 49 300, i.e. a polydispersity index I of
2.93.
SECOND EMBODIMENT
[0247] 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.
[0248] 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.
[0249] 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% by weight, better still from 20% to 70% and
even better still from 30% to 70% by weight of the polymer.
[0250] 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% by weight, better still from 20% to 70% and
even better still from 20% to 50% by weight of the polymer.
[0251] 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.
[0252] 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.
[0253] Thus, according to a first variant of this second
embodiment, the block polymer may comprise:
[0254] 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,
[0255] 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
[0256] an intermediate block comprising at least one methyl
acrylate, methyl methacrylate monomer, and
[0257] an intermediate block comprising methyl methacrylate, at
least one acrylic acid monomer and at least one methyl acrylate
monomer.
[0258] According to a second variant of this second embodiment, the
block polymer may comprise:
[0259] 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,
[0260] 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
[0261] an intermediate block which is an isobornyl
acrylate/isobutyl methacrylate/2-ethylhexyl acrylate random
copolymer.
[0262] According to a third variant of this second embodiment, the
block polymer may comprise:
[0263] 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,
[0264] 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
[0265] an intermediate block which is an isobornyl acrylate/methyl
acrylate/acrylic acid random copolymer.
[0266] The composition according to the invention preferably
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 the polymer.
[0267] 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.
[0268] 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.
[0269] The composition according to the invention comprises a
cosmetically acceptable organic liquid medium (acceptable
tolerance, toxicology and feel).
[0270] 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.
[0271] According to one embodiment, the organic liquid medium
comprises fatty substances that are liquid at room temperature (in
general 25.degree. C.). These liquid fatty substances may be of
animal, plant, mineral or synthetic origin.
[0272] 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 polyisobutylene 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, phenyltrimethylsiloxy-diphenylsiloxanes,
diphenylmethyl dimethyl trisiloxanes, diphenyl dimethicones, phenyl
dimethicones and polymethyl phenylsiloxanes; mixtures thereof.
[0273] 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.
[0274] 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).
[0275] 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.
[0276] 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.
[0277] 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.
[0278] 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.
[0279] 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.
[0280] 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.
[0281] 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.
[0282] 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.
[0283] As waxes that may be used in the composition of the
invention, mention may be made of beeswax, carnauba wax or
candelilla wax, paraffin, microcrystal-line 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.
[0284] 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.
[0285] 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.
[0286] 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.
[0287] The term "nacres" should be understood as meaning iridescent
particles of any shape, produced especially by certain molluscs in
their shell, or alternatively synthesized.
[0288] 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.
[0289] 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.
[0290] 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.
[0291] 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.
[0292] The water-soluble dyes are, for example, beetroot juice or
methylene blue.
[0293] The composition according to the invention may also 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.
[0294] 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 Expancel.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.
[0295] The composition according to the invention may especially be
in the form of a stick, 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 an anhydrous paste.
[0296] 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.
[0297] The composition according to the invention may be a makeup
composition, for instance products for the complexion
(foundations), makeup rouges, eyeshadows, lipsticks, concealer
products, blushers, mascaras, eyeliners, eyebrow makeup products,
lip or eye pencils, nail products, such as nail varnishes, body
makeup products or hair makeup products (hair mascara or hair
lacquer).
[0298] 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).
[0299] The composition according to the invention may also be a
haircare product, especially for holding or styling the hair or for
shaping the hair. The haircare compositions are preferably
shampoos, hairsetting gels or lotions, blow-drying lotions, or
fixing and styling compositions such as lacquers or sprays.
[0300] A subject of the present invention is also a cosmetic
assembly comprising: [0301] a container delimiting at least one
compartment, the said container being closed by a closing member;
and [0302] a composition as described above placed inside the said
compartment.
[0303] 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.
[0304] 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.
[0305] 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.
[0306] 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 01/035-38.
[0307] 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.
[0308] The container may be at least partially made of
thermoplastic material. Examples of thermoplastic materials that
may be mentioned include polypropylene or polyethylene.
[0309] Alternatively, the container is made of non-thermoplastic
material, especially glass or metal (or alloy).
[0310] The container may have rigid walls or deformable walls,
especially in the form of a tube or a tubular bottle.
[0311] The container may comprise means for distributing or
facilitating the distribution of the composition. By way of
example, the container may have deformable walls so as to allow the
composition to exit in response to a positive pressure inside the
container, this positive pressure being caused by elastic (or
non-elastic) squeezing of the walls of the container.
Alternatively, especially when the product is in the form of a
stick, the product may be driven out by a piston mechanism. Still
in the case of a stick, especially of makeup product (lipstick,
foundation, etc.), the container may comprise a mechanism,
especially a rack mechanism, a threaded-rod mechanism or a helical
groove mechanism, and may be capable of moving a stick in the
direction of the said aperture. Such a mechanism is described, for
example, in patent FR 2 806 273 or in patent FR 2 775 566. Such a
mechanism for a liquid product is described in patent FR 2 727
609.
[0312] 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.
[0313] 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.
[0314] 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).
[0315] The content of the patents or patent applications mentioned
above are incorporated by reference into the present patent
application.
[0316] The examples that follow illustrate the compositions
according to the invention in a non-limiting manner.
EXAMPLE 4
Lipstick
[0317] The percentages are expressed on a weight basis.
TABLE-US-00001 Polymer of Example 3 90.7 Hydrogenated polyisobutene
2.1 Octyldodecanol 0.9 Phenyl trimethicone 2.1 (DC 556, 20 cSt, Dow
Corning) Copolymer vinylpyrrolidone/1-eicosene 1.2 (Antaron V-220,
ISP) Pigments 3
Procedure [0318] 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. [0319] 2. The ground material required for the
composition and the other ingredients are weighed out in a beaker.
[0320] 3. The mixture is stirred using a Rayneri blender for 45
minutes at room temperature. [0321] 4. The formula is cast in
isododecane-leaktight cooling boxes. Gloss Measurement [0322] 1. A
film with a wet thickness of 50 .mu.m are prepared using a
mechanical applicator. The depositions are made on a LENETA
contrast card with the reference FORM 1A PENOPAC. [0323] 2. The
film is left to dry for 24 hours at a regulated temperature of
30.degree. C. [0324] 3. The gloss measurements are performed using
a Byk Gardner micro-tri-gloss glossmeter with measuring angles of
20.degree. and 60.degree..
[0325] The in vitro gloss results obtained are given in the table
below: TABLE-US-00002 Composition whose Mean Standard Angle gloss
is measured (%) deviation 20.degree. Pigmented composition of 0.8
0.8 the product Lipfinity 20.degree. Example 4 46.2 1.9 60.degree.
Pigmented composition of 6.5 1.1 the product Lipfinity 6O.degree.
Example 4 74.5 1.5
[0326] The product Lipfinity is a lip makeup product comprising a
pigmented liquid lipstick and a transparent colourless balm in the
form of a stick. The gloss and transfer measurements were performed
on the pigmented liquid lipstick composition of the product sold
under the brand name Lipfinity.
[0327] The transfer index is measured according to the method
described above. TABLE-US-00003 Product whose transfer Transfer
value index is evaluated (in %) Pigmented composition of 1.4 .+-.
0.1 the product Lipfinity Example 4 1.3 .+-. 0.9
EXAMPLE 5
Mascara Composition
[0328] TABLE-US-00004 Beeswax 8 g Paraffin wax 3 g Carnauba wax 6 g
Hectorite modified with 5.3 g distearyldimethylbenzyl- ammonium
chloride (Bentone .RTM. 38V from Elementis) Propylene carbonate 1.7
g Filler 1 g Pigments 5 g Polymer of Example 1 12 g AM Isododecane
qs 100
EXAMPLE 6
Mascara Composition
[0329] TABLE-US-00005 Beeswax 8 g Paraffin wax 3 g Carnauba wax 6 g
Hectorite modified with 5.3 g distearyldimethylbenzyl- ammonium
chloride (Bentone .RTM. 38V from Elementis) Propylene carbonate 1.7
g Filler 1 g Pigments 5 g Polymer of Example 2 12 g AM Isododecane
qs 100
* * * * *