U.S. patent application number 10/528699 was filed with the patent office on 2006-06-22 for nail varnish composition comprising a sequenced polymer.
Invention is credited to Philippe Ilekti, Bertrand Lion.
Application Number | 20060134032 10/528699 |
Document ID | / |
Family ID | 32045662 |
Filed Date | 2006-06-22 |
United States Patent
Application |
20060134032 |
Kind Code |
A1 |
Ilekti; Philippe ; et
al. |
June 22, 2006 |
Nail varnish composition comprising a sequenced polymer
Abstract
The present invention relates to a nail varnish composition
comprising, in a cosmetically acceptable medium, at least one
particular block polymer, the said composition being free of
nitrocellulose and having a mean gloss greater than 50 out of 100.
A subject of the invention is also the use of such a composition to
obtain a film, deposited on the nails, which is glossy and which
shows good staying power and wear resistance.
Inventors: |
Ilekti; Philippe; (Paris,
FR) ; Lion; Bertrand; (Luzarches, FR) |
Correspondence
Address: |
FINNEGAN, HENDERSON, FARABOW, GARRETT & DUNNER;LLP
901 NEW YORK AVENUE, NW
WASHINGTON
DC
20001-4413
US
|
Family ID: |
32045662 |
Appl. No.: |
10/528699 |
Filed: |
September 26, 2003 |
PCT Filed: |
September 26, 2003 |
PCT NO: |
PCT/FR03/02846 |
371 Date: |
November 21, 2005 |
Current U.S.
Class: |
424/61 |
Current CPC
Class: |
A61K 8/8182 20130101;
A61K 8/8152 20130101; A61Q 3/02 20130101; Y10S 514/937 20130101;
A61K 8/26 20130101; A61Q 1/10 20130101; C08F 265/04 20130101; C08F
265/06 20130101; A61K 2800/594 20130101; C08L 51/003 20130101; C08L
53/00 20130101; C08L 53/00 20130101; A61K 8/922 20130101; A61K
8/927 20130101; Y10S 514/845 20130101; A61K 8/90 20130101; C08L
51/003 20130101; A61K 8/8111 20130101; Y10S 514/844 20130101; C08F
291/00 20130101; A61K 8/891 20130101; A61Q 1/04 20130101; A61Q 1/06
20130101; C08F 293/005 20130101; C08L 2666/02 20130101; C08L
2666/02 20130101 |
Class at
Publication: |
424/061 |
International
Class: |
A61K 8/81 20060101
A61K008/81 |
Foreign Application Data
Date |
Code |
Application Number |
Sep 26, 2002 |
FR |
0211949 |
Dec 20, 2002 |
FR |
0216437 |
May 21, 2003 |
FR |
0306121 |
Claims
1. Nitrocellulose-free nail varnish composition, characterized in
that it comprises, in a cosmetically acceptable organic solvent
medium, at least one film-forming linear ethylenic block polymer,
the said block polymer being such that, when it is present 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 50 out of 100.
2. Composition according to claim 1, characterized in that the
block polymer is non-elastomeric.
3. Composition according to claim 1 or 2, characterized in that the
block polymer is free of styrene units.
4. Composition according to one 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 --CON-- group.
5. 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.).
6. Composition according to one of the preceding claims,
characterized in that the block polymer contains first and second
blocks that are 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.
7. Composition according to one of the preceding claims,
characterized in that the block polymer contains first and second
blocks that have different glass transition temperatures (Tg).
8. Composition according to the preceding claim, characterized in
that the first and second blocks are linked together via an
intermediate segment with a glass transition temperature between
the glass transition temperatures of the first and second
blocks.
9. 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 block polymer has a polydispersity index
I of greater than 2.
11. Composition according to claim 7, 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) that is different from the first block.
12. Composition according to claim 11, characterized in that the
block with a Tg of greater than or equal to 40.degree. C. is
totally or partially derived from one or more monomers which are
such that the homopolymer prepared from these monomers has a glass
transition temperature of greater than or equal to 40.degree.
C.
13. 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 with 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.
14. Composition according to claim 12 or 13, 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.
15. Composition according to claim 11, 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.
16. Composition according to claim 15, characterized in that the
monomers whose corresponding homopolymer has a glass transition
temperature of less than or equal to 20.degree. C. are chosen from
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.
17. Composition according to claim 15 or 16, 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.
18. Composition according to claim 11, 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.
19. Composition according to claim 11, 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.
20. Composition according to claim 18 or 19, 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, isobornyl methacrylate, butyl acrylate and
2-ethylhexyl acrylate, and mixtures thereof.
21. Composition according to one of claims 11 to 20, characterized
in that it comprises a block polymer comprising at least a first
block and at least a 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.
22. 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.
23. Composition according to claim 22, 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.
24. Composition according to claim 22 or 23, characterized in that
the monomers whose corresponding homopolymer has a glass transition
temperature of greater than or equal to 40.degree. C. are chosen
from 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 with 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 one of claims 22 to 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 methacrylate and
isobornyl (meth)acrylate, and mixtures thereof.
26. Composition according to one of claims 22 to 25, characterized
in that the proportion of the first block ranges from 20% to 90%,
better still from 30% to 80% and even better still from 50% to 70%,
by weight of the polymer.
27. Composition according to one of claims 21 to 26, 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.
28. Composition according to one of claims 21 to 27, 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.
29. Composition according to one of claims 27 or 28, characterized
in that the monomers whose corresponding homopolymer has a glass
transition temperature of less than or equal to 20.degree. C. are
chosen from 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.
30. Composition according to one of claims 27 to 29, 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.
31. Composition according to one of claims 21 to 30, 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 still from 25% to 45%, by weight of the
polymer.
32. Composition according to one of claims 11 to 20, characterized
in that it comprises a block polymer comprising at least a first
block and at least a 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.
33. 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.
34. Composition according to claim 32 or 33, 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.
35. Composition according to one of claims 32 to 34, 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, isobornyl methacrylate, butyl acrylate and 2-ethylhexyl
acrylate, and mixtures thereof.
36. Composition according to one of claims 32 to 35, 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 still from 50% to 70% by weight of the
polymer.
37. Composition according to any one of claims 32 to 35,
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.
38. Composition according to any one of claims 32 to 37,
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.
39. Composition according to either of claims 37 and 38,
characterized in that the monomers whose corresponding polymer 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 with
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.
40. Composition according to one of claims 36 to 39, 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.
41. Composition according to one of claims 37 to 40, 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.
42. Composition according to one of claims 32 to 41, 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.
43. Composition according to one of claims 32 to 41, 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.
44. Composition according to claim 42 or 43, 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.
45. Composition according to one of claims 42 to 44, 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.
46. Composition according to one of claims 42 to 45, 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 still from
50% to 70%, by weight of the polymer.
47. Composition according to one of claims 5 to 8 or any one of
their preceding dependant claims, characterized in that the first
block and/or the second block comprises at least one additional
monomer.
48. 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.
49. Composition according to claim 47 or 48, characterized in that
the additional monomer is chosen from: a) hydrophilic monomers such
as: ethylenically unsaturated monomers comprising at least one
carboxylic or sulfonic acid function, for instance: acrylic acid,
methacrylic acid, crotonic acid, maleic anhydride, itaconic acid,
fumaric acid, maleic acid, acrylamidopropanesulfonic acid,
vinylbenzoic acid, vinylphosphoric acid, and salts thereof,
ethylenically unsaturated monomers comprising at least one tertiary
amine function, for instance 2-vinylpyridine, 4-vinylpyridine,
dimethylaminoethyl methacrylate, diethylaminoethyl methacrylate and
dimethylaminopropylmethacrylamide, and salts thereof, methacrylates
of formula CH.sub.2.dbd.C(CH.sub.3)--COOR.sub.6 in which R.sub.6
represents a linear or branched alkyl group containing from 1 to 4
carbon atoms, such as a methyl, ethyl, propyl or isobutyl group,
the said alkyl group being substituted with one or more
substituents chosen from hydroxyl groups (for instance
2-hydroxypropyl methacrylate and 2-hydroxyethyl methacrylate) and
halogen atoms (Cl, Br, I or F), such as trifluoroethyl
methacrylate, methacrylates of formula
CH.sub.2.dbd.C(CH.sub.3)--COOR.sub.9, R.sub.9 representing a linear
or branched C.sub.6 to C.sub.12 alkyl group in which one or more
hetero atoms chosen from O, N and S is (are) optionally
intercalated, the said alkyl group being substituted with one or
more substituents chosen from hydroxyl groups and halogen atoms
(Cl, Br, I or F); acrylates of formula CH.sub.2.dbd.CHCOOR.sub.10,
R.sub.10 representing a linear or branched C.sub.1 to C.sub.12
alkyl group substituted with one or more substituents chosen from
hydroxyl groups and halogen atoms (Cl, Br, I or F), such as
2-hydroxypropyl acrylate and 2-hydroxyethyl acrylate, or R.sub.10
represents a (C.sub.1 to C.sub.12) alkyl-O-POE (polyoxyethylene)
with repetition of the oxyethylene unit 5 to 30 times, for example
methoxy-POE, or R.sub.10 represents a polyoxyethylenated group
comprising from 5 to 30 ethylene oxide units, and b) ethylenically
unsaturated monomers comprising one or more silicon atoms, such as
methacryloxypropyltrimethoxysilane and
methacryloxypropyltris(trimethylsiloxy)silane, and mixtures
thereof.
50. Composition according to either of claims 47 and 48,
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.
51. Composition according to either of claims 47 and 48,
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.
52. Composition according to either of claims 47 and 48,
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.
53. Composition according to one of claims 47 to 52, 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.
54. Composition according to claim 7 or any one of its preceding
dependant claims, 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.
55. Composition according to claim 10, characterized in that the
block polymer has a polydispersity index of greater than or equal
to 2.5 and preferably greater than or equal to 2.8.
56. Composition according to claim 55, characterized in that has a
polydispersity index of between 2.8 and 6.
57. Composition according to one of the preceding claims,
characterized in that the block polymer has a weight-average mass
(Mw) which is less than or equal to 300 000.
58. Composition according to claim 57, characterized in that the
weight-average mass (Mw) ranges from 35 000 to 200 000 and better
still from 45 000 to 150 000.
59. Composition according to claim 58, characterized in that the
wight-average mass (Mn) is less than or equal to 70 000.
60. Composition according to one of claims 57 to 59, whose
weight-average mass (Mn) ranges from 10 000 to 60 000 and better
still from 12 000 to 50 000.
61. Composition according to any one of the preceding claims,
characterized in that it comprises from 0.1% to 60% by weight of
polymer active material, preferably from 5% to 50% by weight and
more preferably from 10% to 40% by weight.
62. Composition according to one of the preceding claims,
characterized in that the organic solvent medium comprises an
organic solvent chosen from: ketones that are liquid at room
temperature, such as methyl ethyl ketone, methyl isobutyl ketone,
diisobutyl ketone, isophorone, cyclohexanone or acetone; alcohols
that are liquid at room temperature, such as ethanol, isopropanol,
diacetone alcohol, 2-butoxy-ethanol or cyclohexanol; glycols that
are liquid at room temperature, such as ethylene glycol, propylene
glycol, pentylene glycol or glycerol; propylene glycol ethers that
are liquid at room temperature such as propylene glycol monomethyl
ether, propylene glycol monomethyl ether acetate or dipropylene
glycol mono-n-butyl ether; cyclic ethers such as
.gamma.-butyrolactone; short-chain esters (containing from 3 to 8
carbon atoms in total) such as ethyl acetate, methyl acetate,
propyl acetate, isopropyl acetate, n-butyl acetate, isopentyl
acetate, methoxypropyl acetate or butyl lactate; ethers that are
liquid at room temperature, such as diethyl ether, dimethyl ether
or dichlorodiethyl ether; alkanes that are liquid at room
temperature, such as decane, heptane, dodecane or cyclohexane;
alkyl sulphoxides, such as dimethyl sulphoxide; aldehydes that are
liquid at room temperature, such as benzaldehyde or acetaldehyde;
heterocyclic compounds such as tetrahydrofuran; propylene carbonate
or ethyl 3-ethoxypropionate; mixtures thereof.
63. Composition according to claim 62, characterized in that the
organic solvent medium has a polarity P ranging from 0.422 to
0.725.
64. Composition according to claim 62 or 63, characterized in that
the organic solvent medium represents from 10% to 95% by weight,
preferably from 15% to 80% by weight and better still from 20% to
60% by weight, relative to the total weight of the composition.
65. Composition according to any one of the preceding claims,
characterized in that it comprises a dyestuff.
66. Composition according to the preceding claim, characterized in
that the dyestuff is present in a content ranging from 0.01% to 50%
by weight and preferably from 0.01% to 30% by weight, relative to
the total weight of the composition.
67. Composition according to the preceding claim, characterized in
that it contains a plasticizer, which is present in an amount of
less than 20%, preferably less than 15%, better still less than 10%
and even better still less than 5% by weight, relative to the total
weight of the composition.
68. Composition according to the preceding claim, characterized in
that the mean gloss of the composition measured at 20.degree. is
greater than or equal to 50 out of 100, better still greater than
or equal to 55, even better still greater than or equal to 60, even
better still greater than or equal to 65, even better still greater
than or equal to 70 or even better still greater than or equal to
75 out of 100, or even greater than or equal to 80 out of 100.
69. Composition according to the preceding claim, 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.
70. 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.
71. Cosmetic assembly according to claim 70, characterized in that
the container is at least partly made of glass.
72. Cosmetic assembly according to claim 70, characterized in that
the container is at least partly made of at least one material
other than glass.
73. Assembly according to any one of claims 70 to 72, characterized
in that, in the closed position of the container, the closing
member is screwed onto the container.
74. Assembly according to any one of claims 70 to 72, 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.
75. Assembly according to any one of claims 70 to 74, characterized
in that it comprises an applicator in the form of a fine brush
comprising at least one tuft of hairs.
76. Assembly according to any one claims 70 to 74, characterized in
that it comprises an applicator other than a fine brush.
77. Non-therapeutic cosmetic makeup or care process for the nails,
comprising the application to the nails of at least one coat of a
nail varnish composition according to one of claims 1 to 69.
Description
[0001] The present invention relates to a nail varnish free from
nitrocellulose comprising a block polymer. The invention also
relates to a makeup or care process for the nails. These
compositions may be applied to human nails or to false nails.
[0002] The compositions to be applied to the nails, of the type
such as solvent-based nail varnishes or nailcare bases, usually
comprise at least one film-forming polymer, optionally plasticizer,
pigments, rheological agents and solvents.
[0003] Nitrocellulose is a film-forming agent commonly used in
solvent-based nail varnishes to obtain glossy compositions with
good strength.
[0004] Nitrocellulose is a polymer consisting of an assembly of
partially nitrated anhydroglucose rings obtained by esterification
of some of the free hydroxyl functions of a cellulose with nitric
acid in the presence of sulfuric acid.
[0005] At the present time, nitrocellulose is still the main
film-forming agent the most widely used in solvent-based nail
varnishes in formulations with optimized gloss and strength.
[0006] However, formulations comprising nitrocelluloses have the
following drawbacks: [0007] they make it possible to obtain films
with satisfactory levels of hardness and gloss, but with
unsatisfactory strength over time, especially due to the poor chip
strength of the film; [0008] they give hard films that lack
adhesion to the nail. This drawback may be overcome by adding
plasticizers, but, in this case, very large amounts of plasticizers
and of co-resins, of the order of that of nitrocellulose, need to
be used. Furthermore, the presence of plasticizers in these
formulations is reflected, after film formation and drying,
especially by a change in the properties of the film over time, due
both to slow evaporation of the residual solvents contained in the
film after drying, and to a potential loss of some of the
plasticizers, especially by evaporation, resulting in hardening of
the film over time and poor chip strength.
[0009] Certain known formulations comprising nitrocellulose have
the drawback of yellowing on the nail over time. In addition, the
manufacture of nitrocellulose, its transportation and its
incorporation into formulations pose safety problems which are such
that it is sought to replace it with other film-forming agents.
[0010] The studies conducted with regard to the replacement of
nitrocellulose with other film-forming agents such as polyacrylics
and polyurethanes in nail varnishes, for instance the aqueous
polyurethane dispersions described in document EP 0 648 485, have
not given satisfactory results, especially in terms of strength and
resistance to external factors such as water or detergents.
[0011] Patent application US 2002/18759 describes an acrylic
acid/butyl methacrylate copolymer as film-forming polymer for
partially replacing nitrocellulose. Nail varnishes containing this
polymer do not show sufficient strength and in particular
sufficient gloss strength, and require the addition of
plasticizers.
[0012] The Applicant has discovered a novel route for formulating a
nitrocellulose-free nail varnish that has good gloss and strength
properties.
[0013] This nail varnish also makes it possible to obtain
plasticization of films without the need to add large amounts of
external plasticizers, while at the same time maintaining a good
level of hardness of the films and good impact strength and/or chip
strength of the varnishes on the nail, and thus an improvement in
the strength over time of the varnishes on the nail and/or in their
wear resistance.
[0014] One subject of the invention is, more specifically, a nail
varnish composition comprising, in a cosmetically acceptable
organic solvent, at least one linear ethylenic film-forming block
polymer, the said composition being free of nitrocellulose, the
block polymer being such that, when it is present 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 50 out of 100.
[0015] A subject of the invention is also a nail varnish
composition comprising, in a cosmetically acceptable medium, at
least one linear block ethylenic film-forming polymer as described
below, the said composition being free of nitrocellulose.
[0016] The term "nitrocellulose" means any nitrated cellulose
derivative, in particular nitrocellulose.
[0017] 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, and especially to keratin
materials.
[0018] The term "nitrocellulose-free composition" means a
composition containing less than 5%, preferably less than 3%,
preferably less than 2%, preferably less than 1%, preferably less
than 0.5%, preferably less than 0.1% and preferably less than 0.05%
of nitrocellulose.
[0019] A subject of the invention is also a non-therapeutic
cosmetic process for making up or caring for the nails, comprising
the application to the nails of at least one coat of the nail
varnish composition as defined above.
[0020] A subject of the invention is also a nail varnish
composition comprising at least one film-forming linear ethylenic
block polymer, the said composition being free of nitrocellulose,
to obtain a film, once spread onto a support, which has a gloss at
200 of greater than 50 out of 100, and which incidentally has good
strength.
Mean Gloss of the Composition
[0021] The term "mean gloss" means the gloss as may be
conventionally measured using a glossmeter by the following
method.
[0022] 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.
[0023] 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.
[0024] The mean gloss of the composition measured at 20.degree. is
advantageously greater than or equal to 50 out of 100, better still
greater than or equal to 55, even better still greater than or
equal to 60, even better still greater than or equal to 65, even
better still greater than or equal to 70 or even better still
greater than or equal to 75 out of 100, or even greater than or
equal to 80 out of 100.
[0025] 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.
[0026] The mean gloss at 60.degree. is measured as follows. The
gloss may be conventially measured using a glossmeter by the
following method.
[0027] 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.
[0028] 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.
[0029] According to one embodiment, the gloss of the composition
measured at 20.degree. is preferably greater than or equal to 60,
preferably 65, 70 or 75 out of 100, and/or the gloss of the
composition measured at 60.degree. is preferably greater than or
equal to 80, 85 or 90 out of 100.
Block Polymer:
[0030] 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.
[0031] 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 polymerization
of ethylenically unsaturated monomers.
[0032] 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.
[0033] According to one embodiment, the block polymer of the
composition according to the invention is a film-forming polymer.
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 and especially
to keratin materials.
[0034] According to one embodiment, the block polymer of the
composition according to the invention is a non-elastomeric
polymer.
[0035] The term "non-elastomeric polymer" means a polymer which,
when subjected to a stress 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 stress is
removed.
[0036] More specifically, the expression "non-elastomeric polymer"
means a polymer with an instantaneous recovery R.sub.i<50% and a
delayed recovery R.sub.2h<70% after having undergone a 30%
elongation. Preferably, R.sub.i is <30%, and
R.sub.2h<50%.
[0037] More specifically, the non-elastomeric nature of the polymer
is determined according to the following protocol:
[0038] A polymer film is prepared by pouring a solution of the
polymer into a Teflon-coated mould followed by drying for 7 days
under ambient conditions regulated to 23.+-.5.degree. C. and
50.+-.10% relative humidity.
[0039] 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.
[0040] 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 operation.
[0041] The specimens are drawn at a speed of 50 mm/minute and the
distance between the jaws is 50 mm, which corresponds to the
initial length (l.sub.0) of the specimen.
[0042] The instantaneous recovery R.sub.i is determined in the
following manner: [0043] the specimen is stretched by 30%
(.epsilon..sub.max), i.e. about 0.3 times its initial length
(l.sub.0) [0044] the stress is released by applying a return speed
equal to the tensile speed, i.e. 50 mm/minute, and the residual
percentage elongation of the specimen, after returning to zero load
(.epsilon..sub.i), is measured.
[0045] The percentage instantaneous recovery (R.sub.i) is given by
the formula below:
R.sub.i=((.epsilon..sub.max-.epsilon..sub.i)/.epsilon..sub.max).times.100
[0046] To determine the delayed recovery, the residual elongation
of the sample is measured as a percentage (.epsilon..sub.2h), 2
hours after returning to zero stress.
[0047] The percentage delayed recovery (R.sub.2h) is given by the
formula below:
R.sub.2h=((.epsilon..sub.max-.epsilon..sub.2h)/.epsilon..sub.max)-
.times.100
[0048] Purely by way of indication, a polymer according to an
embodiment of the invention has an instantaneous recovery R.sub.i
of 10% and a delayed recovery R.sub.2h of 30%.
[0049] 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.
[0050] 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.
[0051] 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.
[0052] According to one embodiment, the block polymer comprises at
least one first block and at least one second block.
[0053] The term "at least one block" means one or more blocks.
[0054] It is pointed out that, in the text hereinabove and
hereinbelow, the terms "first" and "second" blocks do not in any
way condition the order of the said blocks in the polymer
structure.
[0055] 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).
[0056] 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.
[0057] 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.
[0058] Preferably, the intermediate block is derived essentially
from constituent monomers of the first block and of the second
block.
[0059] The term "essentially" means at least 85%, preferably at
least 90%, better still 95% and even better still 100%.
[0060] 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.
[0061] 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.
[0062] 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 organic 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:
[0063] 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
[0064] 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%.
[0065] 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.
[0066] When the organic liquid medium comprises only one organic
liquid, this liquid obviously constitutes the liquid that is in
major amount by weight.
[0067] 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.
[0068] 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.
[0069] 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.
[0070] 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.
[0071] 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.
[0072] 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.).
[0073] According to one embodiment, the block polymer has a
polydispersity index I of greater than 2.
[0074] Advantageously, the block polymer used in the. compoisitions
according to the invention has a polydispersity index 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.
[0075] The polydispersity index I of the polymer is equal to the
ratio of the weight-average mass Mw to the number-average mass
Mn.
[0076] 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).
[0077] 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.
[0078] 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.
[0079] Each block of the block polymer is derived from one type of
monomer or from several different types of monomer.
[0080] 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.
[0081] The glass transition temperatures indicated for the first
and second blocks may be theoretical Tg values determined from the
theoretical Tg values of the constituent monomers of each of the
blocks, which may be found in a reference manual such as the
Polymer Handbook, 3rd Edition, 1989, John Wiley, according to the
following relationship, known as Fox's law: 1 / Tg = i .times. (
.PI. i / Tg i ) , ##EQU1## {overscore (.omega.)} 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.
[0082] Unless otherwise indicated, the Tg values indicated for the
first and second blocks in the present patent application are
theoretical Tg values.
[0083] 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.
[0084] 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:
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 may be chosen from a category a), b) or c) that is
different from the first block.
[0085] 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.
[0086] 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.
[0087] The block with a Tg of greater than or equal to 40.degree.
C. may be a homopolymer or a copolymer.
[0088] 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.
[0089] 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.).
[0090] 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: [0091] 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
[0092] 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.
[0093] The monomers whose homopolymers have a glass transition
temperature of greater than or equal to 40.degree. C. are chosen,
for example, from the following monomers, also known as the main
monomers: [0094] 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, [0095]
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, [0096] (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, [0097] and mixtures thereof.
[0098] 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.
[0099] 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.
[0100] The block with a Tg of less than or equal to 20.degree. C.
may be a homopolymer or a copolymer.
[0101] 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.
[0102] 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.).
[0103] 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.
[0104] It may comprise, for example [0105] 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 [0106] 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.
[0107] Preferably, the block with a Tg of less than or equal to
20.degree. C. is a homopolymer.
[0108] 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: [0109] 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,
[0110] 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, [0111] 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, [0112] C.sub.4
to C.sub.12 alkyl vinyl ethers, [0113] N-(C.sub.4 to C.sub.12)alkyl
acrylamides; such as N-octylacrylamide, [0114] and mixtures
thereof.
[0115] The main monomers that are particularly preferred for the
block with a Tg of less than or equal to 20.degree. C. are alkyl
acrylates whose alkyl chain contains from 1 to 10 carbon atoms,
with the exception of the tert-butyl group, such as methyl
acrylate, isobutyl acrylate and 2-ethylhexyl acrylate, and mixtures
thereof.
c) Block With a Tg of Between 20 and 40.degree. C.
[0116] The block with a Tg of between 20 and 40.degree. C. may be a
homopolymer or a copolymer.
[0117] 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.
[0118] 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.
[0119] 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.).
[0120] 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.
[0121] 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.
[0122] Advantageously, the block with a Tg of between 20 and
40.degree. C. is a copolymer totally or partially derived from:
[0123] 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 [0124] 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.
[0125] Such main monomers are chosen, for example, from methyl
methacrylate, isobornyl acrylate and methacrylate, butyl acrylate
and 2-ethylhexyl acrylate, and mixtures thereof.
[0126] 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.
[0127] 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.
[0128] 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.
[0129] However, each of the blocks may contain in small proportion
at least one constituent monomer of the other block.
[0130] Thus, the first block may contain at least one constituent
monomer of the second block, and vice versa.
[0131] 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.
[0132] 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.
[0133] This additional monomer is chosen, for example, from:
[0134] hydrophilic monomers such as: [0135] ethylenically
unsaturated monomers comprising at least one carboxylic or
sulphonic acid function, for instance:
[0136] acrylic acid, methacrylic acid, crotonic acid, maleic
anhydride, itaconic acid, fumaric acid, maleic acid,
acrylamidopropanesulphonic acid, vinylbenzoic acid, vinylphosphoric
acid, and salts thereof, [0137] 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, [0138]
methacrylates of formula CH.sub.2.dbd.C(CH.sub.3)--COOR.sub.6
[0139] 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, [0140] methacrylates of formula
CH.sub.2.dbd.C(CH.sub.3)--COOR.sub.9,
[0141] 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); [0142]
acrylates of formula CH.sub.2.dbd.CHCOOR.sub.10,
[0143] 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 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-C.sub.12) alkyl-O-POE (polyoxyethylene) with
repetition of the oxyethylene unit 5 to 30 times, for example
methoxy-POE, or R.sub.10 represents a polyoxyethylenated group
comprising from 5 to 30 ethylene oxide units
[0144] b) ethylenically unsaturated monomers comprising one or more
silicon atoms, such as methacryloxypropyltrimethoxysilane and
methacryloxypropyltris(trimethylsiloxy)silane, [0145] and mixtures
thereof.
[0146] Additional monomers that are particularly preferred are
acrylic acid, methacrylic acid and trifluoroethyl methacrylate, and
mixtures thereof.
[0147] 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.
[0148] 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
from at least one additional monomer such as (meth)acrylic acid,
and mixtures thereof.
[0149] According to one preferred embodiment, the block polymer is
a non-silicone polymer, i.e. a polymer free of silicon atoms.
[0150] 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.
[0151] The block polymer may be obtained by free-radical solution
polymerization according to the following preparation process:
[0152] 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.), [0153] once this temperature is reached, the constituent
monomers of the first block are introduced in the presence of some
of the polymerization initiator, 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,
[0154] the mixture is left to react for a time {dot over (T)}'
(ranging from 3 to 6 hours), after which the mixture is cooled to
room temperature, [0155] the polymer dissolved in the
polymerization solvent is obtained.
FIRST EMBODIMENT
[0156] 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).
[0157] 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.
[0158] 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.
[0159] 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.
[0160] Thus, according to a first variant, the polymer according to
the invention may comprise: [0161] 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, [0162] 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
[0163] an intermediate block which is a methyl methacrylate/acrylic
acid/methyl acrylate copolymer.
[0164] According to a second variant, the polymer according to the
invention may comprise: [0165] 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, [0166] 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 [0167] an intermediate block which is a methyl
methacrylate/acrylic acid/methyl acrylate/trifluoroethyl
methacrylate random copolymer.
[0168] According to a third variant, the polymer according to the
invention may comprise: [0169] 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, [0170] 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
[0171] an intermediate block, which is an isobornyl
acrylate/isobutyl methacrylate/2-ethylhexyl acrylate random
copolymer.
[0172] According to a fourth variant, the polymer according to the
invention may comprise: [0173] 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, [0174] 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 [0175] an
intermediate block which is an isobornyl acrylate/methyl
methacrylate/2-ethylhexyl acrylate. random copolymer.
[0176] According to a fifth variant, the polymer according to the
invention may comprise: [0177] 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, [0178] 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
[0179] an intermediate block which is an isobornyl
acrylate/isobornyl methacrylate/2-ethylhexyl acrylate random
copolymer.
[0180] According to a sixth variant, the polymer according to the
invention may comprise: [0181] 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, [0182] 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
[0183] an intermediate block which is an isobornyl
methacrylate/isobutyl methacrylate/isobutyl acrylate random
copolymer.
[0184] According to a seventh variant, the polymer according to the
invention may comprise: [0185] 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, [0186] 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
[0187] an intermediate block which is an isobornyl
acrylate/isobornyl methacrylate/isobutyl acrylate random
copolymer.
[0188] According to an eighth variant, the polymer according to the
invention may comprise: [0189] a first block with a Tg of greater
than or equal to 40.degree. C., for example ranging from 60 to
90.degree. C., which is an isobornyl acrylate/isobutyl methacrylate
copolymer, [0190] 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 [0191] an intermediate
block which is an isobornyl acrylate/isobutyl methacrylate/isobutyl
acrylate random copolymer.
[0192] The examples that follow illustrate, in a non-limiting
manner, polymers corresponding to this first embodiment.
[0193] The amounts are expressed in grams.
EXAMPLE 1
Preparation of a poly(methyl methacrylate)/acrylic acid/methyl
acrylate) polymer
[0194] 100 g of butyl acetate are introduced into a 1 litre reactor
and the temperature is then raised so as to pass from room
temperature (25.degree. C.) to 90.degree. C. in 1 hour. 180 g of
methyl methacrylate, 30 g of acrylic acid, 40 g of butyl acetate,
70 g of isopropanol and 1.8 g of
2,5-bis(2-ethylhexanoylperoxy)-2,5-dimethyl-hexane (Trigonox.RTM.
141 from Akzo Nobel) are then added, at 90.degree. C. and over 1
hour.
[0195] The mixture is maintained at 90.degree. C. for 1 hour.
[0196] 90 g of methyl acrylate, 70 g of butyl acetate, 20 g of
isopropanol and 1.2 g of
2,5-bis(2-ethylhexanoylperoxy)-2,5-dimethylhexane are then
introduced into the above mixture, still at 90.degree. C. and over
1 hour.
[0197] The mixture is maintained at 90.degree. C. for 3 hours and
then diluted with 105 g of butyl acetate and 45 g of isopropanol,
and the mixture is then cooled.
[0198] A solution containing 40% polymer-active material in a butyl
acetate/isopropanol mixture is obtained.
[0199] A polymer comprising a poly(methyl methacrylate/acrylic
acid) first block with a Tg of 100.degree. C., a polymethyl
acrylate second block with a Tg of 10.degree. C. and an
intermediate block which is a methyl methacrylate/acrylic
acid/polymethyl acrylate random polymer is obtained.
[0200] This polymer has a weight-average mass of 52 000 and a
number-average mass of 18 000, i.e. a polydispersity index I of
2.89.
SECOND EMBODIMENT
[0201] 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.
[0202] Preferably, the proportion of the first block with a Tg of
between 20 and 40.degree. C. ranges from 10% to 85% by weight of
the polymer, better still from 30% to 80% and even better still
from 50% to 70%.
[0203] 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.
[0204] 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.
[0205] 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.
[0206] 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.
[0207] Thus, according to a first variant of this second
embodiment, the block polymer may comprise: [0208] 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, [0209] 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 [0210] an intermediate block
comprising at least one methyl acrylate, methyl methacrylate
monomer, and [0211] an intermediate block comprising methyl
methacrylate, at least one acrylic acid monomer and at least one
methyl acrylate monomer.
[0212] According to a second variant of this second embodiment, the
block polymer may comprise: [0213] 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, [0214] 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 [0215] an intermediate block which is
an isobornyl acrylate/isobutyl methacrylate/2-ethylhexyl acrylate
random copolymer.
[0216] According to a third variant of this second embodiment, the
block polymer may comprise: [0217] 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, [0218] 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
[0219] an intermediate block which is an isobornyl acrylate/methyl
acrylate/acrylic acid random copolymer.
[0220] By way of non-limiting illustration, the polymers
corresponding to this second embodiment may be produced as
follows.
EXAMPLE 2
Preparation of a poly(methyl methacrylate)/methyl acrylate/acrylic
acid) polymer
[0221] 100 g of butyl acetate are introduced into a 1 litre reactor
and the temperature is then raised so as to pass from room
temperature (25.degree. C.) to 90.degree. C. in 1 hour. 50.4 g of
methyl methacrylate, 21 g of acrylic acid, 138.6 g of methyl
acrylate, 40 g of butyl acetate, 70 g of isopropanol and 1.8 g of
2,5-bis(2-ethylhexanoylperoxy)-2,5-dimethylhexane (Trigonox.RTM.
141 from Akzo Nobel) are then added, at 90.degree. C. and over 1
hour.
[0222] The mixture is maintained at 90.degree. C. for 1 hour.
[0223] 90 g of methyl methacrylate, 70 g of butyl acetate, 20 g of
isopropanol and 1.2 g of
2,5-bis(2-ethylhexanoylperoxy)-2,5-dimethylhexane are then
introduced into the above mixture, still at 90.degree. C. and over
1 hour.
[0224] The mixture is maintained at 90.degree. C. for 3 hours and
then diluted with 105 g of butyl acetate and 45 g of isopropanol,
and the mixture is then cooled.
[0225] A solution containing 40% polymer active material in a butyl
acetate/isopropanol mixture is obtained.
[0226] The polymer obtained comprises a first poly(methyl
acrylate/methyl methacrylate/acrylic acid) block with a Tg of
35.degree. C., a second poly(methyl methacrylate) block with a Tg
of 100.degree. C. and an intermediate block that is a methyl
methacrylate/acrylic acid/polymethyl acrylate random polymer.
[0227] Generally, the compositions of the invention contain from
0.1% to 60% by weight, preferably from 0.5% to 50% by weight and
more preferably from 1% to 40% by weight of the block polymer
according to the invention.
Solvent Medium
[0228] The cosmetic composition may comprise an organic solvent
medium or a mixture of organic solvents.
[0229] The organic solvent may be chosen from: [0230] ketones that
are liquid at room temperature, such as methyl ethyl ketone, methyl
isobutyl ketone, diisobutyl ketone, isophorone, cyclohexanone or
acetone; [0231] alcohols that are liquid at room temperature, such
as ethanol, isopropanol, diacetone alcohol, 2-butoxy-ethanol or
cyclohexanol; [0232] glycols that are liquid at room temperature,
such as ethylene glycol, propylene glycol, pentylene glycol or
glycerol; [0233] propylene glycol ethers that are liquid at room
temperature such as propylene glycol monomethyl ether, propylene
glycol monomethyl ether acetate or dipropylene glycol mono-n-butyl
ether; cyclic ethers such as .gamma.-butyrolactone; [0234]
short-chain esters (containing from 3 to 8 carbon atoms in total)
such as ethyl acetate, methyl acetate, propyl acetate, isopropyl
acetate, n-butyl acetate, isopentyl acetate, methoxypropyl acetate
or butyl lactate; [0235] ethers that are liquid at room
temperature, such as diethyl ether, dimethyl ether or
dichlorodiethyl ether; [0236] alkanes that are liquid at room
temperature, such as decane, heptane, dodecane or cyclohexane;
alkyl sulphoxides, such as dimethyl sulphoxide; aldehydes that are
liquid at room temperature, such as benzaldehyde or acetaldehyde;
heterocyclic compounds such as tetrahydrofuran; propylene carbonate
or ethyl 3-ethoxypropionate; [0237] mixtures thereof.
[0238] The organic solvent medium preferably has a polarity P
ranging from 0.422 to 0.725.
[0239] The polarity is defined as a function of the solubility
parameters according to the Hansen solubility space, according to
the following relationship: P=
(.delta.p.sup.2+.delta.h.sup.2)/.delta.t [0240] .delta.h
characterizing the specific forces of interaction (such as hydrogen
bonding, acid/base bonding, donor/acceptor bonding, etc.); [0241]
.delta.p characterizing the Debye interaction forces between
permanent dipoles and also the Keesom interaction forces between
induced dipoles and permanent dipoles; and [0242] .delta.t=
(.delta.p.sup.2+.delta.h.sup.2+.delta.d.sup.2), .delta.d
characterizing the London dispersion forces derived from the
formation of induced dipoles during molecular impacts.
[0243] The definition and calculation of the solubility parameters
in the Hansen three-dimensional solubility space are described in
the article by C. M. Hansen: "The three dimensional solubility
parameters" J. Paint Technol. 39, 105 (1967).
[0244] When the solvent medium comprises a mixture of solvents, the
polarity is determined from the solubility parameters of the
mixture, which are themselves determined from those of the
compounds taken separately, according to the following
relationships: .delta. .times. .times. dmixt = i .times. xi .times.
.times. .delta. .times. .times. di ; .delta. .times. .times. pmixt
= i .times. xi .times. .times. .delta. .times. .times. pl .times.
.times. and .times. .times. .delta. .times. .times. hmixt = i
.times. xi .times. .times. .delta. .times. .times. hi ##EQU2## in
which xi represents the volume fraction of the compound i in the
mixture.
[0245] As organic solvents with a polarity ranging from 0.422 to
0.725, mention may be made in particular of methyl acetate,
isopropyl acetate, methoxypropyl acetate, butyl lactate, acetone,
methyl ethyl ketone, diacetone alcohol, .gamma.-butyrolactone,
tetrahydrofuran, propylene carbonate, ethyl 3-ethoxypropionate and
dimethyl sulphoxide, and mixtures thereof.
[0246] The organic solvent medium may represent from 10% to 95% by
weight, preferably from 15% to 80% by weight and better still from
20% to 60% by weight, relative to the total weight of the
composition.
Additional Film-forming Polymer
[0247] The composition may comprise, besides the block polymer of
the composition according to the invention, an additional polymer
such as a film-forming polymer.
[0248] 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,
and polymers of natural origin, and mixtures thereof.
[0249] The film-forming polymer may be chosen in particular from
cellulose-based polymers such as cellulose acetate, cellulose
acetobutyrate, cellulose acetopropionate or ethylcellulose, or
alternatively polyurethanes, acrylic polymers, vinyl polymers,
polyvinylbutyrals, alkyd resins, resins derived from aldehyde
condensation products such as arylsulphonamide-formaldehyde resins,
for instance toluenesulphonamide-formaldehyde resin, and
arylsulphonamide-epoxy resins.
[0250] Film-forming polymers that may especially be used include
the toluenesulphonamide-formaldehyde resins "Ketjentflex MS80" from
the company Akzo or "Santolite MHP" or "Santolite MS 80" from the
company Faconnier or "Resimpol 80" from the company Pan Americana,
the alkyd resin "Beckosol ODE 230-70-E" from the company Dainippon,
the acrylic resin "Acryloid B66" from the company Rohm & Haas,
and the polyurethane resin "Trixene PR 4127" from the company
Baxenden.
[0251] The additional film-forming polymer may be present in the
composition according to the invention in a content ranging from
0.1% to 60% by weight, preferably ranging from 2% to 40% by weight
and better still from 5% to 25% by weight, relative to the total
weight of the composition.
Plasticizer
[0252] The composition may also comprise at least one plasticizer.
In particular, mention may be made, alone or as a mixture, of the
usual plasticizers, such as: [0253] glycols and derivatives thereof
such as diethylene glycol ethyl ether, diethylene glycol methyl
ether, diethylene glycol butyl ether or diethylene glycol hexyl
ether, ethylene glycol ethyl ether, ethylene glycol butyl ether or
ethylene glycol hexyl ether; [0254] glycerol esters, [0255]
propylene glycol derivatives and in particular propylene glycol
phenyl ether, propylene glycol diacetate, dipropylene glycol butyl
ether, tripropylene glycol butyl ether, propylene glycol methyl
ether, dipropylene glycol ethyl ether, tripropylene glycol methyl
ether, diethylene glycol methyl ether and propylene glycol butyl
ether, [0256] acid esters, especially carboxylic acid esters, such
as citrates, phthalates, adipates, carbonates, tartrates,
phosphates or sebacates, [0257] oxyethylenated derivatives such as
oxyethylenated oils, especially plant oils such as castor oil;
mixtures thereof.
[0258] The amount of plasticizer may be chosen by a person skilled
in the art on the basis of his general knowledge, so as to obtain a
composition with cosmetically acceptable properties. The
plasticizer is preferably present in an amount of less than 20%,
preferably less than 15%, better still less than 10% and even
better still less than 5% by weight, relative to the total weight
of the composition. The composition according to the invention is
preferably free of plasticizer.
Dyestuff
[0259] 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.
[0260] 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.
[0261] The term "nacres" should be understood as meaning iridescent
particles of any shape, produced especially by certain molluscs in
their shell, or alternatively synthesized.
[0262] 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. 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.
[0263] 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.
[0264] The water-soluble dyes are, for example, beetroot juice or
methylene blue.
[0265] 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.
[0266] 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
polytetrafluoroethylene polymers (Teflon.RTM.), lauroyllysine,
starch, boron nitride, hollow polymer microspheres such as those of
polyvinylidene chloride/acrylonitrile, for instance Exapancel.RTM.
(Nobel Industrie) or acrylic acid copolymers (Polytrap.RTM. from
the company Dow Corning) and silicone resin microbeads (for example
Tospearls.RTM. from Toshiba), elastomeric polyorganosiloxane
particles, precipitated calcium carbonate, magnesium carbonate,
magnesium hydrocarbonate, hydroxyapatite, hollow silica
microspheres (Silica Beads.RTM. from Maprecos), glass or ceramic
microcapsules, and metal soaps derived from organic carboxylic
acids containing from 8 to 22 carbon atoms and preferably from 12
to 18 carbon atoms, for example zinc, magnesium or lithium
stearate, zinc laurate or magnesium myristate.
Other Additives
[0267] The composition may also comprise other ingredients commonly
used in cosmetic compositions. Such ingredients may be chosen from
spreading agents, wetting agents, dispersants, antifoams,
preserving agents, UV-screening agents, active agents, surfactants,
moisturizers, fragrances, neutralizers, stabilizers and
antioxidants.
[0268] Needless to say, a person skilled in the art will take care
to select this or these optional additional compound(s), and/or the
amount thereof, such that the advantageous properties of the
composition according to the invention are not, or are not
substantially, adversely affected by the envisaged addition.
[0269] Needless to say, a person skilled in the art will take care
to select this or these optional additional compound(s) and/or the
amount thereof, such that the advantageous properties of the
composition for the use according to the invention are not, or are
not substantially, adversely affected by the envisaged
addition.
[0270] A subject of the present invention is also a cosmetic
assembly comprising: [0271] a container delimiting at least one
compartment, the said container being closed by a closing member;
and [0272] a composition placed inside the said compartment, the
composition being in accordance with the invention.
[0273] The container may be in any adequate form. It may especially
be in the form of a bottle, a case or a tube.
[0274] The closing member may be in the form of a removable
stopper.
[0275] The container is preferably equipped with an applicator to
allow the application of the product to the nails. Such an
applicator may be in the form of a fine brush consisting of at
least one tuft of hairs. The tuft of hairs may be embedded at the
end of a rod borne by the closing member. The hairs are preferably
oriented along the axis of the rod. The hairs may be embedded by
means of stapling, bonded, or obtained by moulding.
[0276] Alternatively, the applicator is in the form of a tape made
of porous material, especially of open-cell foam or of felt.
[0277] Alternatively also, the applicator may be in the form of a
spatula, especially made of elastomeric material.
[0278] 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 or by click-fastening. 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.
[0279] The container is preferably made of glass. However,
materials other than glass may be used. Examples that will be
mentioned include certain thermoplastic materials appropriately
chosen so as to be compatible with the composition. Alternatively
also, the container may be made of metal.
[0280] The examples that follow illustrate the invention in a
non-limiting manner.
EXAMPLE 3
Nail Varnish
[0281] TABLE-US-00001 Polymer of Example 1 23.8 g AM Butyl acetate
24.99 g Isopropanol 10.71 g Hexylene glycol 2.5 g DC Red 7 Lake 1 g
Hectorite modified with stearyldimethyl- 1.3 g benzylammonium
chloride (Bentone .RTM. 27V from Elementis)
EXAMPLE 4
Nail Varnish
[0282] TABLE-US-00002 Polymer of Example 2 23.8 g AM Butyl acetate
24.99 g Isopropanol 10.71 g Hexylene glycol 2.5 g DC Red 7 Lake 1 g
Hectorite modified with 1.3 g stearyldimethylbenzylammonium
chloride (Bentone .RTM. 27V from Elementis) Ethyl acetate qs 100
g
* * * * *