U.S. patent application number 13/146242 was filed with the patent office on 2012-03-15 for aqueous copolymer dispersion of polysiloxane/polyurea, cosmetic composition comprising the same, method for cosmetic treatment and method for preparation.
This patent application is currently assigned to L'Oreal. Invention is credited to Jocelyne Dorkel, Gregory Plos, Xavier Schultze.
Application Number | 20120064018 13/146242 |
Document ID | / |
Family ID | 41165452 |
Filed Date | 2012-03-15 |
United States Patent
Application |
20120064018 |
Kind Code |
A1 |
Schultze; Xavier ; et
al. |
March 15, 2012 |
AQUEOUS COPOLYMER DISPERSION OF POLYSILOXANE/POLYUREA, COSMETIC
COMPOSITION COMPRISING THE SAME, METHOD FOR COSMETIC TREATMENT AND
METHOD FOR PREPARATION
Abstract
The invention relates to an aqueous dispersion of
polysiloxane/polyurea copolymer and a method for preparation
thereof comprising the steps: solubilisation of the copolymer and
silane in an organic phase, preparation of an aqueous phase
comprising one or more surfactants, mixing the organic and aqueous
phase followed by emulsification. The invention further relates to
a cosmetic composition comprising said dispersion and a cosmetic
treatment using said composition.
Inventors: |
Schultze; Xavier; (Les
Pavillons Sous Bois, FR) ; Plos; Gregory; (Paris,
FR) ; Dorkel; Jocelyne; (Le Plessis Bouchard,
FR) |
Assignee: |
L'Oreal
Paris
FR
|
Family ID: |
41165452 |
Appl. No.: |
13/146242 |
Filed: |
January 29, 2010 |
PCT Filed: |
January 29, 2010 |
PCT NO: |
PCT/FR2010/050148 |
371 Date: |
November 15, 2011 |
Related U.S. Patent Documents
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Application
Number |
Filing Date |
Patent Number |
|
|
61151200 |
Feb 10, 2009 |
|
|
|
Current U.S.
Class: |
424/59 ;
424/70.122; 424/70.6; 424/78.03 |
Current CPC
Class: |
A61K 8/898 20130101;
C08K 5/5419 20130101; C08J 2383/08 20130101; C08G 18/0866 20130101;
C08J 3/07 20130101; A61Q 19/00 20130101; C08G 77/458 20130101; C08J
2375/02 20130101; C08L 83/10 20130101; A61Q 5/06 20130101; C08G
18/61 20130101; C08K 5/5419 20130101; C08L 83/10 20130101 |
Class at
Publication: |
424/59 ;
424/70.6; 424/70.122; 424/78.03 |
International
Class: |
A61K 8/898 20060101
A61K008/898; A61Q 17/04 20060101 A61Q017/04; A61Q 5/02 20060101
A61Q005/02; A61Q 5/06 20060101 A61Q005/06; A61K 8/04 20060101
A61K008/04; A61Q 1/00 20060101 A61Q001/00 |
Foreign Application Data
Date |
Code |
Application Number |
Jan 30, 2009 |
FR |
0950602 |
Claims
1. An aqueous dispersion of polysiloxane/polyurea copolymer
obtained from a reaction between: a) at least one polymer of
formula (I) bearing at its ends at least one reactive function
containing labile hydrogen: ##STR00012## wherein: the radicals R1,
identical or different, are selected from the group consisting of
(i) linear or branched monovalent C1-C20 hydrocarbon-based
radicals, which are optionally unsubstituted or substituted with
heteroatoms and (ii) C6-C30 aromatic radicals; Y, which is
optionally identical or different, represents a C1-C20 aliphatic,
cycloaliphatic or aromatic hydrocarbon-based radical, comprising at
least one reactive function containing labile hydrogen; and n is an
integer wherein an average molecular weight of the polysiloxane
segment is between 300 and 10 000 g/mol; and b) at least one
diisocyanate derivative; wherein the said dispersion comprises at
least one silane of structure: ##STR00013## wherein: X represents a
C1-C6 alkoxy group; Y is a C1-C6 alkoxy or C1-C6 alkyl group; Z is
a linear or branched, saturated or unsaturated C1-C22
hydrocarbon-based chain, which is optionally substituted with an
amine group NH.sub.2 or NHR (R.dbd.C1-C20 alkyl, C3-C40 cycloalkyl
or C6-C30 aromatic); or with a hydroxyl group, a thiol group, or a
substituted or unsubstituted aryl group; Z optionally being
interrupted with a heteroatom or a carbonyl group (CO); n
represents an integer equal to 1 or 2.
2. The dispersion according to claim 1, wherein the copolymer
further comprises at least one additional nonionic unit bearing at
least two reactive functions containing labile hydrogen.
3. The dispersion according to claim 1, wherein the copolymer is a
block copolymer.
4. The dispersion according to claim 1, wherein the polymer is of
general formula (IV): ##STR00014## wherein: R represents a
monovalent hydrocarbon-based radical, where appropriate substituted
with fluorine or chlorine, containing 1 to 20 carbon atoms, X
represents an alkylene radical containing 1 to 20 carbon atoms,
wherein non-neighbouring methylene units are optionally replaced
with --O-- radicals, A represents an oxygen atom or an amino
radical --NR'--, Z represents an oxygen atom or an amino radical
--NR'--, R' represents hydrogen or an alkyl radical containing 1 to
10 carbon atoms, Y represents a divalent hydrocarbon-based radical,
where appropriate substituted with fluorine or chlorine, containing
1 to 20 carbon atoms, D represents an alkylene radical, where
appropriate substituted with fluorine, chlorine, C1-C6 alkyl or
C1-C6 alkyl ester, containing from 1 to 700 carbon atoms, wherein
non-neighbouring methylene units are optionally replaced with
--O--, --C(O)O--, --OC(O)-- or --OC(O)O-- radicals, n is a number
ranging from 1 to 2000, a is a number at least equal to 1, b is a
number ranging from 0 to 40, c is a number ranging from 0 to 30,
and d is a number greater than 0, wherein A represents in at least
one of the units (a) an NH radical.
5. The dispersion according to claim 1, wherein the silane is,
alone or as a mixture, selected from the group consisting of
N-(3-acryloxy-2-hydroxypropyl)-3-aminopropyltriethoxysilane,
4-aminobutyltriethoxysilane, 3-aminopropylmethyldiethoxysilane,
3-aminopropyltriethoxysilane,
3-aminopropyltris(methoxyethoxyethoxy)silane,
bis(methyldiethoxysilylpropyl)amine,
bis[3-(triethoxysilyl)propyl]urea,
3-(2,4-dinitrophenylamino)propyltriethoxysilane,
hydromethyltriethoxysilane, mercaptomethylmethyldiethoxysilane,
3-mercaptopropyltriethoxysilane,
o-(methacryloxyethyl)-N-(triethoxysilylpropyl)urethane,
N-(3-methacryloxy-2-hydroxypropyI)-3-aminopropyltriethoxysilane,
o-(propargyloxy)-N-(triethoxysilylpropyl)urethane,
(3-triethoxysilylpropyl)-t-butylcarbamate,
triethoxysilylpropylethylcarbamate,
N-(3-triethoxysilylpropyl)gluconamide,
N-(3-triethoxysilylpropyl)-4-hydroxybutyramide,
3-(triethoxysilylpropyl)-p-nitrobenzamide,
N-(triethoxysilylpropyl)-O-polyethylene oxide urethane,
ureidopropyltriethoxysilane and o-(vinyloxyethyl)-N-(triethoxysi
lylpropyl)urethane.
6. The dispersion according to claim 1, wherein the silane, alone
or as a mixture, is present in a proportion of from 0.5% to 30% by
weight, relative to the weight of the dispersion.
7. The dispersion according to claim 1, which is optionally
obtained via a dispersion process comprising: dissolving the
copolymer and the silane in an organic phase, preparing an aqueous
phase comprising one or more surfactants, mixing together the
organic and aqueous phases, and then emulsifying.
8. The dispersion according to claim 7, wherein the organic phase
comprises a liquid compound (at 20-25.degree. C., 1 atm.) that is
insoluble in water and is solubilizing for the copolymer, wherein
the compound is selected from the group consisting of: linear or
branched, saturated or unsaturated, optionally cyclic or aromatic
C5-C30 alcohols or polyols, which optionally contain heteroatoms;
esters of monoalcohols or polyols and of monoacids or polyacids,
and triglycerides and esters of general formula R3-O--CO--R4, in
which R3 and R4, which are optionally identical or different, are
linear or branched, or even cyclic, saturated or unsaturated,
C3-C30 hydrocarbon-based radicals; ketones of the type R3-CO-R4 in
which R3 and R4, which are optionally identical or different, are
linear or branched, or even cyclic, saturated or unsaturated,
C3-C30 hydrocarbon-based radicals; aromatic hydrocarbons; linear,
cyclic or branched C5-C30 alkanes; and volatile or non-volatile
silicone oils.
9. The dispersion according to claim 7, wherein the surfactant is a
cationic surfactant.
10. A cosmetic composition comprising at least one aqueous
dispersion of polysiloxane/polyurea copolymer according to claim
1.
11. The cosmetic composition according to claim 10, wherein the
amount of copolymer is between 0.01% and 30% by weight of polymer
solids relative to the weight of the cosmetic composition.
12. The cosmetic composition according to claim 10, which is in the
form of a product for caring for, cleansing and/or making up bodily
or facial skin, the lips, the eyebrows, the eyelashes, the nails
and the hair, an antisun or self-tanning product, a body hygiene
product, or a haircare product.
13. A cosmetic treatment process, comprising applying a cosmetic
composition according to claim 10 to making up, caring for,
cleansing, colouring or shaping keratin materials.
14. A kit in two or more parts, comprising at least one cosmetic
composition according Claim 10.
15. A process for preparing an aqueous dispersion of
polysiloxane/polyurea copolymer according to claim 1, comprising:
dissolving the copolymer and the silane in an organic phase,
preparing an aqueous phase comprising one or more surfactants,
mixing together the organic and aqueous phases, and then
emulsifying.
Description
[0001] The present invention relates to aqueous dispersions of
silicone copolymers, which are especially nonionic and
hydrogen-bond donors, to cosmetic compositions comprising them, and
to their use in particular for cosmetically treating the hair.
[0002] The shaping of hair is generally achieved by depositing a
film-forming polymer on the surface of the fibre, via the use of a
styling product. It is important for this polymer to have good
affinity for the fibre and good styling properties, while at the
same time maintaining a pleasant cosmetic feel, especially good
softness and absence of tack. However, this shaping mode presents a
few problems, especially in terms of resistance over time:
specifically, the polymer may become brittle under the styling
stresses; problems of water resistance: the shaping may be
eliminated by washing with water or in the presence of surfactants;
or alternatively problems in terms of a laden feel or a coarse
and/or unnatural feel.
[0003] Moreover, compositions with a low content of volatile
organic compounds (VOC) are most particularly sought.
[0004] The shaping of hair may also be performed via a chemical
treatment of the fibre, such as permanent waving. In this case, the
shaping of the hair has improved durability when compared with
shaping by means of a styling product. However, this gain in
durability is achieved by means of a chemical treatment that
generally intimately modifies the hair proteins and is liable to
lead to more or less substantial degradation of the physicochemical
properties of the fibre, especially its intrinsic softness,
hydrophilicity and/or mechanical strength.
[0005] One of the aims of the present invention is thus to propose
a means for achieving long-lasting and non-degrading shaping of the
fibre, especially by virtue of the presence of a polymer
dispersion, while otherwise affording, especially by virtue of the
presence of the silane, good resistance of the latex deposit
(aqueous polymer dispersion), in particular shampoo resistance,
which will be reflected by better resistance of the shaping of the
hair.
[0006] It is also desired to obtain a natural appearance for the
shaped hairstyle, and to improve the resistance of the deposit to
mechanical abrasion, which will be reflected especially by the
better resistance to combing (absence of appearance of
particles).
[0007] The Applicants have discovered, surprisingly, that the use
of an aqueous dispersion of nonionic silicone copolymer furthermore
comprising a silane can provide such long-lasting shaping that is
non-degrading to the fibre and resistant.
[0008] It is known that the introduction of water into compositions
comprising nonionic silicone polymers can be difficult.
Specifically, if the silicone polymer does not bear any hydrophilic
grafts and/or if high concentrations of surfactants are not
introduced into the formulation, precipitation of the silicone
occurs, making its formulation impossible.
[0009] The addition of high concentrations of surfactants is not
always desirable either. In particular, in leave-in applications,
the surfactant not removed may give rise to a change in the
mechanical properties of the deposits, especially plasticization,
or the appearance of a laden feel (greasy, transferring onto the
fingers) in particular in the field of haircare.
[0010] It is known practice, in the prior art, to prepare aqueous
dispersions of silicone polymers.
[0011] Thus, document US 2005/137 327 describes the synthesis of
aqueous dispersions of polyorgano-siloxane/polyurea via a process
that consists in dispersing an organopolysiloxane ending with amine
groups in an acidic aqueous solution preferably comprising a
surfactant, in adding a diisocyanate and then in adding a base so
as to regain a neutral pH and bring about polycondensation of the
amino organopolysiloxane with the diisocyanate, in order finally to
obtain a polyorganosiloxane/polyurea copolymer in dispersion.
[0012] However, this approach requires the handling of
diisocyanates, which may pose toxicity problems. Furthermore, the
diisocyanates may react on contact with water and form a more or
less large amount of diamines that are liable to intervene in the
polymerization: this phenomenon may have an influence on the
polymerization, or even may harm its control and also the nature of
the final dispersion obtained. Finally, the addition of acid in a
first stage, and then of a base in a second stage, may be
problematic for compounds that are sensitive in alkaline and acidic
medium. Furthermore, this process gives rise to the formation of
salts, which may harm the compositions subsequently comprising the
dispersions thus prepared.
[0013] Patent FR 2 708 199 describes the synthesis of aqueous
dispersions of anionic or cationic polyurethanes/polyureas.
According to the described process, it is necessary to introduce a
sufficiently large quantity of ionic groups to enable dispersion of
the polymer in water.
[0014] Now, it has been found that an excessive content of ionic
units can result in reduced water resistance of the polymer.
Furthermore, there are only a limited number of anionic or cationic
units that can be introduced during the synthesis, which limits the
chemical diversity of the polyurethane or polyurea. Furthermore,
the stability of the polymers prepared according to this process is
dependent on the formulation pH, which may limit their formulation
range.
[0015] In these documents, it is found that the polymer dispersion
is generally prepared using monomers, which are synthesized either
directly in the required solvent, or in another solvent, the
synthesis then being followed in the latter case by a step of
changing the solvent.
[0016] The aim of the present invention is, in particular, to
propose a novel process for preparing aqueous dispersions of
silicone copolymers, the said dispersion being prepared from the
already-formed polymer.
[0017] Moreover, the process according to the invention allows the
introduction, into the dispersion, of silane, this being a compound
that is difficult to incorporate into an aqueous polymer
dispersion. Specifically, its introduction generally brings about
virtually instantaneous precipitation of the polymer in aqueous
medium.
[0018] It has thus been discovered that it is possible to formulate
high concentrations of nonionic silicone copolymers that are
hydrogen-bond donors in the presence of a high proportion of water,
this being possible without the mandatory addition of large amounts
of surfactants or the presence of ionic units in the copolymer.
[0019] It has also been discovered that it is possible to introduce
the silane during the phase of constitution/preparation of the
dispersion.
[0020] One subject of the present invention is thus an aqueous
dispersion of polysiloxane/polyurea copolymer derived from the
reaction between: [0021] a) at least one polymer of formula (I) as
defined below and [0022] b) at least one diisocyanate-based unit;
characterized in that the said dispersion also comprises at least
one silane of structure:
##STR00001##
[0023] as defined below.
[0024] Another subject of the invention is a cosmetic composition
comprising the said dispersion.
[0025] Another subject of the invention is a cosmetic treatment
process, especially for making up, caring for, cleansing, colouring
or shaping keratin materials, especially bodily or facial skin, the
lips, the nails, the hair and/or the eyelashes, comprising the
application to the said materials of a cosmetic composition as
defined above.
[0026] Another subject of the invention is a kit in two or more
parts, comprising at least one such cosmetic composition.
[0027] It has been found that the silicone copolymer dispersions
according to the invention can contain a large amount of water,
which allows the easy introduction of hydrophilic compounds into
the compositions. These hydrophilic compounds may prove to be
advantageous in terms of affording novel cosmetic properties.
[0028] Moreover, the properties obtained with the compositions
comprising these dispersions, in terms of deposition, are entirely
different from those of the prior art. In particular, in the field
of haircare, these compositions make it possible to obtain
individualized hairs, whose coating is resistant to external
mechanical stresses, such as being handled, massaged or combed.
[0029] Furthermore, the compositions according to the invention do
not require the use of large amounts of solvents of VOC type, for
example ethanol, or of the type such as alkanes or isododecane, for
example, or alternatively of silicone type, for example D5 or D6;
this allows greater latitude of formulation.
[0030] The silicone copolymers used in the context of the invention
are nonionic silicones, which are hydrogen-bond donors; they are
especially described in patent application US 2005/137 327.
[0031] They may especially be derived from the reaction between:
[0032] at least one polymer of formula (I) bearing at its ends at
least one reactive function containing labile hydrogen (in
particular OH, SH, NH.sub.2 or NHR with R=C1-C20 alkyl, C3-C40
cycloalkyl or C6-C30 aromatic); and [0033] at least one
diisocyanate-based unit.
[0034] Optionally, it is also possible to react at least one
additional nonionic unit, bearing at least two reactive functions
containing labile hydrogen.
[0035] The polymer of formula (I), bearing at its ends reactive
units containing labile hydrogen, is of the formula:
##STR00002##
[0036] in which: [0037] the radicals R1, which may be identical or
different, are chosen from (i) linear or branched monovalent C1-C20
hydrocarbon-based radicals, which may be unsubstituted or
substituted with heteroatoms (in particular O, N, S or P) and (ii)
C6-C30 aromatic radicals; [0038] Y, which may be identical or
different, represents a C1-C20 aliphatic, cycloaliphatic or
aromatic hydrocarbon-based radical, comprising at least one
reactive function containing labile hydrogen (OH, SH, NH.sub.2 or
NHR with R=C1-C20 alkyl, C3-C40 cycloalkyl or C6-C30 aromatic); and
[0039] n is an integer such that the average molecular weight of
the polysiloxane segment is between 300 and 10 000 g/mol and
preferably from 500 to 8000 g/mol.
[0040] As radicals R1 that are suitable for use in the context of
the invention, mention may be made more particularly of C1-C20
alkyl radicals, and especially methyl, ethyl, propyl, isopropyl,
butyl, pentyl, hexyl, octyl, decyl, dodecyl and octadecyl radicals;
C3-C7 cycloalkyl radicals, in particular the cyclohexyl radical;
aryl radicals, especially phenyl and naphthyl; arylalkyl radicals,
especially benzyl and phenylethyl, and also tolyl and xylyl
radicals.
[0041] Preferably, Y is chosen from the alkylene radicals of
formula --(CH.sub.2).sub.a,-- in which a represents an integer
between 1 and 10; it being understood that these radicals are
substituted with at least one reactive function containing labile
hydrogen, especially located at the end of the chain.
[0042] The silicones that will preferentially be chosen are those
of formula:
##STR00003##
[0043] with n such that the average molecular weight (Mw) is
between 300 and 10 000 g/mol.
[0044] Optionally, it is also possible to react one or more other
polymers bearing reactive end groups containing labile hydrogen,
chosen especially from polyethers, polyesters, polyolefins,
polycarbonates, polyamides, polyimides and polypeptides.
[0045] Obviously, a mixture of different polymers of formula (I)
may be reacted.
[0046] The diisocyanate may be represented by the general formula
(II):
[0047] OCN--R--NCO (II)
[0048] in which R is a linear, branched and/or cyclic, saturated or
unsaturated, or even aromatic, C1-20 divalent alkylene group, which
may be unsubstituted or substituted with one or more heteroatoms
(in particular O, N, S or P).
[0049] In particular, R may be chosen from the radicals of
formulae:
##STR00004##
[0050] in which b is an integer between 0 and 3, and c is an
integer between 1 and 20.
[0051] The diisocyanate will preferentially be chosen from
1,6-hexamethylene diisocyanate, 1,4-tetramethylene diisocyanate,
4,4'-methylenedicyclohexyl diisocyanate, 4,4'-methylenediphenyl
diisocyanate, 2,4-toluene diisocyanate, 2,5-toluene diisocyanate,
2,6-toluene diisocyanate, m-phenylene diisocyanate, p-phenylene
diisocyanate, m-xylylene diisocyanate, tetramethyl-m-xylylene
diisocyanate, naphthalene diisocyanate, butane diisocyanate, hexyl
diisocyanate and isophorone diisocyanate. Needless to say, these
diisocyanates may be used alone or in the form of a mixture of two
or more diisocyanates.
[0052] The additional nonionic unit may be represented by formula
(III):
X--R'--X (III)
[0053] in which: [0054] X, which may be identical or different, is
a reactive function containing labile hydrogen (in particular OH,
SH, NH.sub.2 or NHR with R=C1-C20 alkyl, C3-C40 cycloalkyl or
C6-C30 aromatic); and [0055] R' is a linear, branched and/or
cyclic, saturated or unsaturated C1-20 divalent alkylene group,
which may be unsubstituted or substituted with one or more
heteroatoms (in particular O, N, S or P).
[0056] Mention may be made especially of propanediol (1,2- or
1,3-), butanediol, neopentyl glycol and cyclohexanediol.
[0057] According to the invention, the copolymer is a nonionic
polysiloxane/polyurea copolymer, i.e. it does not contain any
ionized or ionizable groups.
[0058] Preferably, it is a block copolymer. In the context of the
invention, the term "block copolymer" means a copolymer formed from
at least two blocks that are different from each of the polymers
constituting the copolymer in the backbone of the copolymer. For
example, the copolymer of the invention contains at least one
siloxane block and at least one polyurea block in the copolymer
backbone.
[0059] As indicated previously, the copolymer of the invention may
comprise, in addition to the polysiloxane/polyurea, other blocks of
different units. Mention will be made in particular of
polysiloxane/polyurea/polyurethane block terpolymers.
[0060] According to one particular embodiment, the copolymer
contains a weight amount of polysiloxane of greater than 5%.
[0061] According to one particular embodiment, the amount of
polysiloxane is predominant in the copolymer, preferably greater
than 90% by weight relative to the total weight of the
copolymer.
[0062] According to one variant, the copolymer contains solely one
or more siloxane blocks and one or more polyurea blocks.
[0063] According to the invention, the copolymer may correspond to
the general formula (IV):
##STR00005##
[0064] in which: [0065] R represents a monovalent hydrocarbon-based
radical, where appropriate substituted with fluorine or chlorine,
containing 1 to 20 carbon atoms, [0066] X represents an alkylene
radical containing 1 to 20 carbon atoms, in which non-neighbouring
methylene units may be replaced with --O-- radicals, [0067] A
represents an oxygen atom or an amino radical
[0068] 13 NR'--, [0069] Z represents an oxygen atom or an amino
radical
[0070] 13 NR'--, [0071] R' represents hydrogen or an alkyl radical
containing 1 to 10 carbon atoms, [0072] Y represents a divalent
hydrocarbon-based radical, where appropriate substituted with
fluorine or chlorine, containing 1 to 20 carbon atoms, [0073] D
represents an alkylene radical, where appropriate substituted with
fluorine, chlorine, C1-C6 alkyl or C1-C6 alkyl ester, containing
from 1 to 700 carbon atoms, in which non-neighbouring methylene
units may be replaced with --O--, --C(O)O--, --OC(O)-- or
--OC(O)O-- radicals, [0074] n is a number ranging from 1 to 2000,
[0075] a is a number at least equal to 1, [0076] b is a number
ranging from 0 to 40, [0077] c is a number ranging from 0 to 30,
and [0078] d is a number greater than 0,
[0079] on condition that A represents in at least one of the units
(a) an NH radical.
[0080] Preferably, R represents a monovalent C1-C16
hydrocarbon-based radical, for example methyl, ethyl, vinyl and
phenyl. According to one particular embodiment, R is an
unsubstituted alkyl radical.
[0081] Preferably, X represents a C2-C10 alkylene radical.
Preferably, the alkylene radical X is not interrupted.
[0082] According to one particular embodiment, the group A in all
the units (b) and (c), when they are present, represents NH.
[0083] According to one particularly preferred embodiment, all the
groups A represent an NH radical.
[0084] Preferably, Z represents an oxygen atom or an NH
radical.
[0085] Preferably, Y represents a C3-C13 hydrocarbon-based radical,
which is preferably unsubstituted.
[0086] Preferably, Y represents a linear or cyclic aralkylene or
alkylene radical.
[0087] Preferably, D represents an alkylene radical containing at
least 2 and in particular at least 4 carbon atoms, and not more
than 12 carbon atoms.
[0088] Also preferably, D represents a polyoxyalkylene radical, in
particular a polyoxyethylene or polyoxypropylene radical containing
at least 20 and in particular at least 100 carbon atoms, and not
more than 600 and in particular not more than 200 carbon atoms.
[0089] Preferably, the radical D is unsubstituted. Preferably, n
represents a number equal to at least 3 and in particular at least
25, and preferably not more than 800, in particular not more than
400 and particularly preferably not more than 250.
[0090] Preferably, a represents a number greater than 50.
[0091] When b is other than 0, b preferably represents a number not
greater than 50 and in particular not greater than 25.
[0092] Preferably, c represents a number not greater than 10 and in
particular not greater than 5.
[0093] The copolymers of the invention may be obtained according to
the polymerization processes described in patent application US
2004/0 254 325 or patent application WO 03/014 194.
[0094] The copolymer may thus be obtained via a two-step process,
such that: [0095] in the first step, a silazane of formula (2) or
(2'):
##STR00006##
[0096] W representing a hydrogen atom, a substituted or
unsubstituted hydrocarbon-based radical, preferably containing from
1 to 20 carbon atoms, or a radical R.sub.2Si--X--NH.sub.2;
[0097] is reacted with an organosilicon compound of general formula
(3):
(HO) (R.sub.2SiO).sub.n-1[H] (3)
[0098] to obtain an aminoalkylpolydiorganosiloxane of general
formula (4):
H.sub.2N--X--[SiR.sub.2O].sub.nSiR.sub.2--X--NH.sub.2 (4) [0099] in
a second step, the aminoalkylpolydiorgano-siloxane of general
formula (4) is polymerized with a diisocyanate of general formula
(5):
[0099] OCN--Y--NCO (5)
[0100] In general, in the first step, silazanes of general formula
(2) or (2') and reagents containing silanol groups in liquid molar
proportions are used.
[0101] For the preparation of very pure silicones containing
bisaminoalkyl end groups, of general formula (4), a small excess of
the silazane compound of general formula (2) or (2'), which may
then be removed, in an additional simple process step, for instance
the addition of small amounts of water, is preferably used.
[0102] If b is at least 1, up to 95% by weight, on the basis of all
of the components used, of chain extenders, which are chosen from
diamines, hydroxy compounds blocked with an isocyanate, dihydroxy
compounds or mixtures thereof, may be used during the second
step.
[0103] Preferably, the chain extenders have the general formula
(6):
HZ-D-ZH (6)
[0104] in which D and Z have the preceding meanings. If Z has the
meaning O, the chain extender of general formula (6) may also be
reacted before the reaction in the second step, with the
diisocyanate of general formula (5). Where appropriate, water may
be used as chain extender.
[0105] Examples of diisocyanates of general formula (5) to be used
are aliphatic compounds such as isophorone diisocyanate,
1,6-hexamethylene diisocyanate, 1,4-tetramethylene diisocyanate and
4,4'-methylene-dicyclohexyl diisocyanate or aromatic compounds, for
instance 4,4'-methylenediphenyl diisocyanate, 2,4-toluene
diisocyanate, 2,5-toluene diisocyanate, 2,6-toluene diisocyanate,
m-phenylene diisocyanate, p-phenylene diisocyanate, m-xylylene
diisocyanate, tetramethyl-m-xylylene diisocyanate, or mixtures of
these isocyanates. An example of a commercially available compound
is a diisocyanate of the Desmodur.RTM. series (H, I, M, T or W)
from Bayer AG, Germany. Aliphatic diisocyanates, in which Y is an
alkylene radical, are preferred since they lead to materials that
have improved UV stabilities.
[0106] The alkylenes containing .alpha., .omega.-OH end groups of
general formula (6) are preferably polyalkylenes or
polyoxyalkylenes. They are preferably essentially free of
contaminations of mono- or trifunctional polyoxyalkylenes or
polyoxyalkylenes of higher functionality. Polyetherpolyols,
polytetramethylene-diols, polyesterpolyols or
polycaprolactonediols, but also polyalkylenes containing .alpha.,
.omega.-OH end groups based on poly(vinyl acetate), poly(vinyl
acetate)-ethylene copolymers, poly(vinyl chloride) copolymers or
polyisobutyldiols may be used here. Preferably, polyoxyalkyls and
particularly preferably polypropylene glycols are used. Such
compounds are commercially available as base materials, inter alia,
for polyurethane foams and for uses as coating, with molecular
masses Mn of up to 10 000. Examples are the polyetherpolyols and
polyesterpolyols Baycoll.RTM. from Bayer AG, Germany or the
polyetherpolyols Acclaim.RTM. from Lyondell Inc., USA. .alpha.,
.omega.-Alkylenediol monomers, for instance ethylene glycol,
propanediol, butanediol or hexanediol, may also be used. Moreover,
for the purposes of the invention, the term "dihydroxylated
compounds" also means bishydroxyalkyl silicones, such as those
sold, for example, by the company Goldschmidt under the names
Tegomer H--Si 2111, 2311 and 2711.
[0107] The preparation of the copolymers described above of general
formula (I) may be performed in solution, but also in solid form,
in continuous or batch mode.
[0108] If the amount of urethane or urea segments is large, a
solvent having a high solubility parameter is chosen, for instance
dimethylacetamide. THF may also be used. According to one
particular embodiment, the synthesis of the copolymer is performed
without solvent.
[0109] The synthesis is preferably performed in the absence of
moisture and under a protective gas, usually nitrogen or argon.
[0110] The reaction is preferably performed in the presence of a
catalyst. The catalysts that are suitable for the preparation are
dialkyltin compounds, for instance dibutyltin dilaurate or
dibutyltin diacetate, or tertiary amines, for instance
N,N-dimethylcyclo-hexanamine, 2-dimethylaminoethanol or
4-dimethylaminopyridine.
[0111] According to one particular embodiment, the copolymer that
is useful in the present invention does not contain any
polyurethane.
[0112] Examples of copolymers that may be mentioned include the
dimethylpolysiloxane/urea copolymer, of INCI name
polyureadimethicone.
[0113] Mention may be made especially of commercial polymers such
as Belsil UD-60 (Wacker SLM TPSE 60 or Geniomer 60), Belsil UD-80
(Wacker SLM TPSE 80 or Geniomer 80), Wacker Belsil UD-140 (Wacker
SLM TPSE 180 or Geniomer 180, and Wacker Belsil UD-200 (Wacker SLM
TPSE 200 or Geniomer 200) sold by the company Wacker.
[0114] Preferably, the copolymers according to the invention have a
number-average molecular mass (Mn) of between 1000 and 5 000 000,
especially between 2000 and 1 000 000 and more preferentially
between 2000 and 100 000 g/mol.
[0115] The use of these copolymers as an aqueous dispersion, in the
presence of silane, requires a dispersion process, or a process of
preparing the dispersion, that preferably comprises the following
steps: [0116] dissolution of the copolymer and the silane in an
organic phase composed of one or more cosmetic oils and/or
solvents; [0117] addition of the said organic phase comprising the
polymer to an aqueous phase comprising one or more surfactants,
followed by emulsification with rapid stirring.
[0118] Optionally, all or some of the cosmetic oils or solvents
used to dissolve the polymer may be evaporated off via any
technique considered appropriate by a person skilled in the art,
such as evaporation under vacuum.
[0119] An aqueous dispersion of silicone copolymer that is stable
over time (absence of macroscopic phase separation after 5 days at
room temperature) may thus be obtained, the said dispersion also
comprising a silane.
[0120] As cosmetic oil or solvent that may be used in the context
of the invention, mention may be made of any liquid compound (at
20-25.degree. C., 1 atm.) that is insoluble in water and
solubilizing for the copolymer.
[0121] The term "insoluble in water" refers to a compound whose
solubility in water (at 25.degree. C., 1 atm.) is less than 1% by
weight.
[0122] The term "solubilizing for the copolymer" refers to a
compound that enables the dissolution of at least 1% by weight of
polymer (at 25.degree. C., 1 atm.).
[0123] Preferably, at least one solvent compound with a boiling
point of less than 150.degree. C., at 1 atm., and/or a solvent
compound that can form an azeotrope with water, is used.
[0124] Mention may be made especially of the following compounds,
it being understood that they are liquid at 20-25.degree. C., 1
atm.: [0125] linear or branched, saturated or unsaturated,
optionally cyclic or aromatic C5-C30 alcohols or polyols, which may
contain heteroatoms (O, N, P or S); and more particularly
saturated, linear or branched C5-C30 alcohols or polyols; or even
saturated, linear or branched C5-C20 alcohols or polyols;
preferentially monoalcohols; [0126] esters of monoalcohols or
polyols and of monoacids or polyacids, and in particular
triglycerides such as plant oils and esters of general formula
R3-O-- CO-R4, in which R3 and R4, which may be identical or
different, are linear or branched, or even cyclic, saturated or
unsaturated, preferably C3-C30 or even C4-C20 alkyl
hydrocarbon-based radicals; in particular, R3 is preferably a C1-C6
or even C2-C4 alkyl; in particular, R4 is preferably a C1-C18 or
even C1-C15 alkyl; [0127] ketones of the type R3-CO-R4 in which R3
and R4, which may be identical or different, are linear or
branched, or even cyclic, saturated or unsaturated, preferably
C3-C30 alkyl hydrocarbon-based radicals; preferentially, R3 and R4
are linear or branched C4-C8 alkyls; [0128] aromatic hydrocarbons,
such as toluene; [0129] linear, cyclic or branched C5-C30 alkanes;
preferably C6-C20, better still C10-C16, or even C11-C13; [0130]
volatile or non-volatile silicone oils; mention may be made
especially of polydimethylsiloxanes (PDMS), phenylated
polyorganosiloxanes such as phenyl trimethicones,
phenyltrimethylsiloxydiphenylsiloxanes,
diphenylmethyldimethyltrisiloxanes, diphenyl dimethicones, phenyl
dimethicones and polymethylphenyl-siloxanes, which are optionally
fluorinated; polysiloxanes modified with fatty acids, fatty
alcohols or polyoxyalkylenes, fluoro silicones and perfluoro
silicone oils.
[0131] Among the preferred silicone oils, mention may be made of
polydimethylsiloxanes, polymethylphenyl-siloxanes, silicones
comprising polyoxyalkylene blocks or grafts, in particular
polyoxyalkylene or copoly(oxyethylene/oxypropylene) such as
dimethicone copolyols, silicones bearing both hydrocarbon-based
hydrophobic groups (for example C.sub.2-C.sub.30 alkyl groups) and
polyoxyethylene or copoly(oxyethylene/oxypropylene) blocks or
grafts such as alkyldimethicone copolyols, silicones bearing fluoro
or perfluoro groups, such as perfluoroalkyl polydimethylsiloxanes
and perfluoroalkyl polymethylphenylsiloxanes, and mixtures thereof.
These silicone oils may optionally comprise alkyl or alkoxy groups
at the end of the silicone chain or pendent thereon.
[0132] Mention may also be made of linear or cyclic silicones, in
particular comprising from 2 to 7 silicon atoms. Mention may be
made especially of octamethylcyclotetrasiloxane,
decamethylcyclopenta-siloxane, hexadecamethylcyclopentasiloxane,
hepta-methylhexyltrisiloxane and heptamethyloctyltrisiloxane, and
mixtures thereof.
[0133] Among these solvents, ethyl acetate, butyl acetate, propyl
acetate, isopropyl acetate, isopropyl palmitate, pentanol, hexanol,
heptanol, heptane, decane, dodecane, isododecane, undecane,
tridecane, cyclotetramethylsiloxane (D4), cyclopentamethylsiloxane
(D5), cyclohexamethylsiloxane (D6), methyl ethyl ketone and
toluene; and also mixtures thereof, will preferentially be
chosen.
[0134] Needless to say, a mixture of solvents may be employed.
[0135] In one particular embodiment, a solvent of linear or
branched C5-C20 alcohol type is used, alone or as a mixture with a
C5-C20 alkane, a cyclic volatile silicone oil and/or a C4-C20
ester, which are themselves alone or as a mixture.
[0136] The surfactants that may be used may be anionic, cationic,
amphoteric or nonionic; a mixture of surfactants may be used.
[0137] Preferably, the surfactants are cationic or anionic,
preferentially cationic.
[0138] Mention may thus be made of the following anionic
surfactants, which may be used alone or as mixtures: salts, in
particular alkali metal salts such as sodium salts, ammonium salts,
amine salts, amino alcohol salts or alkaline-earth metal salts, for
example magnesium salts, of the following compounds: alkyl
sulfates, alkyl ether sulfates, alkylamido ether sulfates,
alkylaryl polyether sulfates, monoglyceride sulfates, alkyl
sulfonates, alkyl phosphates, alkylamide sulfonates, alkylaryl
sulfonates, .alpha.-olefin sulfonates, paraffin sulfonates, alkyl
sulfosuccinates, alkyl ether sulfosuccinates, alkylamide
sulfosuccinates, alkyl sulfoacetates, acyl sarcosinates and acyl
glutamates, the alkyl and acyl groups of all these compounds
containing from 6 to 24 carbon atoms, and the aryl group preferably
denoting a phenyl or benzyl group. It is also possible to use
esters of C.sub.6-C.sub.24 alkyl and of polyglycoside-carboxylic
acids, such as alkyl glucoside citrates, polyalkyl glycoside
tartrates and polyalkyl glycoside sulfosuccinates; alkyl
sulfosuccinamates, acyl isethionates and N-acyltaurates, the alkyl
or acyl group of all these compounds containing from 12 to 20
carbon atoms. Among the anionic surfactants that may also be used,
mention may also be made of acyl lactylates in which the acyl group
contains from 8 to 20 carbon atoms. In addition, mention may also
be made of alkyl-D-galactosideuronic acids and salts thereof, and
also polyoxyalkylenated (C.sub.6-C.sub.24 alkyl)ethercarboxylic
acids, polyoxyalkylenated (C.sub.6-C.sub.24 alkyl)
(C.sub.6-C.sub.24 aryl)ethercarboxylic acids and polyoxyalkylenated
(C.sub.6-C.sub.24 alkyl)amidoethercarboxylic acids and salts
thereof, in particular those comprising from 2 to 50 ethylene oxide
groups, and mixtures thereof.
[0139] Among the preferred anionic surfactants, mention may be made
of the salts, in particular of sodium, of magnesium or of ammonium,
of alkyl sulfates; of alkyl ether sulfates, for instance sodium
lauryl ether sulfate, preferably containing 2 or 3 mol of ethylene
oxide; of alkyl ether carboxylates; and mixtures thereof, the alkyl
groups generally containing from 6 to 24 carbon atoms and
preferably from 8 to 16 carbon atoms.
[0140] As nonionic surfactants that may be used in the composition
according to the invention, mention may be made of polyethoxylated,
polypropoxylated or polyglycerolated fatty acids,
(C.sub.1-C.sub.20)alkylphenols, .alpha.-diols or alcohols, having a
fatty chain containing, for example, 8 to 18 carbon atoms, it being
possible for the number of ethylene oxide or propylene oxide groups
to range in particular from 2 to 50 and for the number of glycerol
groups to range in particular from 2 to 30. Mention may also be
made of copolymers of ethylene oxide and of propylene oxide,
condensates of ethylene oxide and of propylene oxide with fatty
alcohols; polyethoxylated fatty amides preferably having from 2 to
30 mol of ethylene oxide, polyglycerolated fatty amides containing
on average 1 to 5, and in particular 1.5 to 4, glycerol groups;
polyethoxylated fatty amines preferably having 2 to 30 mol of
ethylene oxide; oxyethylenated fatty acid esters of sorbitan having
from 2 to 30 mol of ethylene oxide; fatty acid esters of sucrose,
fatty acid esters of polyethylene glycol,
(C.sub.6-C.sub.24)alkylpolyglycosides,
N-(C.sub.6-C.sub.24)alkylglucamine derivatives, amine oxides such
as (C.sub.10-C.sub.14) alkylamine oxides or
N-(C.sub.10-C.sub.14)acylaminopropylmorpholine oxides; and mixtures
thereof.
[0141] Among the amphoteric surfactants, mention may be made of
aliphatic secondary or tertiary amine derivatives, in which the
aliphatic group is a linear or branched chain containing 8 to 22
carbon atoms and containing at least one water-soluble anionic
group, such as, for example, a carboxylate, sulfonate, sulfate,
phosphate or phosphonate group; mention may also be made of
(C.sub.8-C.sub.20)alkylbetaines, sulfobetaines, (C.sub.8-C.sub.20)
alkylamido (C.sub.6-C.sub.8) alkylbetaines or (C.sub.8-C.sub.20)
alkyl-amido(C.sub.6-C.sub.8)alkylsulfobetaines; and mixtures
thereof. Among the amine derivatives that may be mentioned are the
products sold under the name Miranol.RTM., as described in patents
U.S. Pat. No. 2,528,378 and U.S. Pat. No. 2,781,354 and classified
in the CTFA dictionary, 3rd edition, 1982, under the names
Amphocarboxyglycinate and amphocarboxypropionate, having the
respective structures (2) and (3):
R.sub.2--CONHCH.sub.2CH.sub.2--N.sup.+(R.sub.3)(R.sub.4)(CH.sub.2COO.sup-
.-) (2)
[0142] in which:
[0143] R.sub.2 represents an alkyl group derived from an acid
R.sub.2--COOH present in hydrolysed coconut oil, or a heptyl, nonyl
or undecyl group,
[0144] R.sub.3 represents a .beta.-hydroxyethyl group, and
[0145] R.sub.4 represents a carboxymethyl group; and
R.sub.2'--CONHCH.sub.2CH.sub.2--N(B)(C) (3)
[0146] in which:
[0147] B represents --CH.sub.2CH.sub.2OX',
[0148] C represents --(CH.sub.2).sub.z-Y', with z=1 or 2,
[0149] X' represents the --CH.sub.2CH.sub.2--COOH group or a
hydrogen atom,
[0150] Y' represents --COOH or the --CH.sub.2--CHOH--SO.sub.3H
group,
[0151] R.sub.2, represents the alkyl group of an acid R.sub.9--COOH
present in coconut oil or in hydrolysed linseed oil, an alkyl
group, especially a C.sub.17 group and its iso form, or an
unsaturated C.sub.17 group.
[0152] These compounds are classified in the CTFA dictionary, 5th
edition, 1993, under the names disodium cocoamphodiacetate,
disodium lauroamphodiacetate, disodium caprylamphodiacetate,
disodium capryloampho-diacetate, disodium cocoamphodipropionate,
disodium lauroamphodipropionate, disodium caprylampho-dipropionate,
disodium capryloamphodipropionate, lauroamphodipropionic acid,
cocoamphodipropionic acid.
[0153] By way of example, mention may be made of the
cocoamphodiacetate sold under the trade name Miranol.RTM. C2M
Concentrate by the company Rhodia.
[0154] Among the amphoteric surfactants that are preferably used
are (C.sub.8-C.sub.20) alkylbetaines,
(C.sub.8-C.sub.20)alkyl-amido(C.sub.6-C.sub.9)alkylbetaines and
alkylamphodiacetates, and mixtures thereof.
[0155] Among the cationic surfactants, mention may be made of:
[0156] i) alkylpyridinium salts, ammonium salts of imidazoline,
diquaternary ammonium salts, and ammonium salts containing at least
one ester function;
[0157] ii) quaternary ammonium salts having the following general
formula:
##STR00007##
[0158] in which the radicals R1 to R4, which may be identical or
different, represent a linear or branched aliphatic radical
containing from 1 to 30 carbon atoms, or an aromatic radical such
as aryl or alkylaryl; the aliphatic radicals may optionally
comprise heteroatoms (O, N, S or halogens).
[0159] The aliphatic radicals are chosen, for example, from C12-C22
alkyl, alkoxy, C2-C6 polyoxyalkylene, alkylamide,
(C12-C22)alkylamido(C2-C6)alkyl, (C12-C22)alkylacetate and
hydroxyalkyl radicals, containing from about 1 to 30 carbon
atoms.
[0160] X.sup.- is an anion chosen from the group of halides,
phosphates, acetates, lactates, C2-C6 alkyl sulfates and alkyl- or
alkylaryl-sulfonates.
[0161] iii) quaternary ammonium salts of imidazoline of formula
:
##STR00008##
[0162] in which: [0163] R5 represents an alkenyl or alkyl radical
containing from 8 to 30 carbon atoms, for example fatty acid
derivatives of tallow or of coconut, [0164] R6 represents a
hydrogen atom, a C1-C4 alkyl radical or an alkenyl or alkyl radical
containing from 8 to 30 carbon atoms, [0165] R7 represents a C1-C4
alkyl radical, [0166] R8 represents a hydrogen atom or a C1-C4
alkyl radical, [0167] X is an anion chosen from the group of
halides, phosphates, acetates, lactates, C2-C6 alkyl sulfates,
alkylsulfonates or alkylarylsulfonates.
[0168] R5 and R6 preferably denote a mixture of alkenyl or alkyl
radicals containing from 12 to 21 carbon atoms, such as, for
example, fatty acid derivatives of tallow, R7 denotes methyl and R8
denotes hydrogen. Such a product is, for example, Quaternium-27
(CTFA 1997) or Quaternium-83 (CTFA 1997), which are sold under the
names Rewoquat.RTM. W75, W90, W75PG and W75HPG by the company
Witco,
[0169] iv) diquaternary ammonium salts of formula:
##STR00009##
[0170] in which: [0171] R9 denotes an aliphatic radical containing
from about 16 to 30 carbon atoms, [0172] R10, R11, R12, R13 and
R14, which may be identical or different, are chosen from hydrogen
and an alkyl radical containing from 1 to 4 carbon atoms, and
[0173] X.sup.- is an anion chosen from the group of halides,
acetates, phosphates, nitrates and methyl sulfates. Such
diquaternary ammonium salts in particular comprise
propanetallowdiammonium dichloride;
[0174] v) quaternary ammonium salts containing at least one ester
function, such as those of formula :
##STR00010##
[0175] in which: [0176] R15 is chosen from C1-C6 alkyl radicals and
C1-C6 hydroxyalkyl or dihydroxyalkyl radicals; [0177] R16 is chosen
from the radical R19--CO--, linear or branched, saturated or
unsaturated C1-C22 hydrocarbon-based radicals R20, a hydrogen atom;
[0178] R18 is chosen from the radical R21-CO--, linear or branched,
saturated or unsaturated C1-C22 hydrocarbon-based radicals R22, a
hydrogen atom; [0179] R17, R19 and R21, which may be identical or
different, are chosen from linear or branched, saturated or
unsaturated C7-C21 hydrocarbon-based radicals; [0180] r, n and p,
which may be identical or different, are integers ranging from 2 to
6; [0181] y is an integer ranging from 1 to 10; [0182] x and z,
which may be identical or different, are integers ranging from 0 to
10; [0183] X.sup.-is a simple or complex organic or mineral
anion;
[0184] with the proviso that the sum x+y+z is from 1 to 15, that
when x is 0, then R16 denotes R20 and that when z is 0, then R18
denotes R22.
[0185] The alkyl radicals R15 may be linear or branched, and more
particularly linear. Preferably, R15 denotes a methyl, ethyl,
hydroxyethyl or dihydroxypropyl radical, and more particularly a
methyl or ethyl radical.
[0186] Advantageously, the sum x+y+z is from 1 to 10.
[0187] When R16 is a hydrocarbon-based radical R20, it may contain
from 12 to 22 carbon atoms, or contain from 1 to 3 carbon
atoms.
[0188] When R18 is a hydrocarbon-based radical R22, it preferably
contains 1 to 3 carbon atoms.
[0189] Advantageously, R17, R19 and R21, which may be identical or
different, are chosen from linear or branched, saturated or
unsaturated C11-C21 hydrocarbon-based radicals, and more
particularly from linear or branched, saturated or unsaturated
C11-C21 alkyl and alkenyl radicals.
[0190] Preferably, x and z, which may be identical or different,
are 0 or 1. Advantageously, y is equal to 1.
[0191] Preferably, r, n and p, which may be identical or different,
are equal to 2 or 3 and even more particularly equal to 2.
[0192] The anion X.sup.- is preferably a halide (chloride, bromide
or iodide) or a C1-C4 alkyl sulfate, more particularly methyl
sulfate. However, the anion X.sup.- may also represent
methanesulfonate, phosphate, nitrate, tosylate, an anion derived
from an organic acid (such as acetate or lactate), or any other
anion that is compatible with the ammonium containing an ester
function.
[0193] The surfactants may be, for example, the salts (chloride or
methyl sulfate) of diacyloxyethyl-dimethylammonium, of
diacyloxyethylhydroxyethyl-dimethylammonium, of
monoacyloxyethylhydroxyethyl-dimethylammonium, of
triacyloxyethylmethylammonium, of
monoacyloxyethylhydroxyethyldimethylammonium, and mixtures thereof.
The acyl radicals preferably contain 14 to 18 carbon atoms and are
more particularly derived from a plant oil, for instance palm oil
or sunflower oil. When the compound contains several acyl radicals,
these radicals may be identical or different. Such compounds are
sold, for example, under the names Dehyquart.RTM. by the company
Cognis, Stepanquat.RTM. by the company Stepan, Noxamium.RTM. by the
company Ceca, and Rewoquat.RTM. WE 18 by the company
Rewo-Goldschmidt.
[0194] vi) quaternary ammonium salts and in particular
behenyltrimethylammonium chloride, dipalmitoylethyl hydroxyethyl
methyl ammonium methosulfate, cetyltrimethylammonium chloride,
quaternium-83,
behenylamidopropyl-2,3-dihydroxypropyldimethylammonium chloride and
palmitylamidopropyltrimethylammonium chloride.
[0195] The silane present in the aqueous dispersion is of
structure:
##STR00011##
[0196] in which: [0197] X represents a C1-C6 alkoxy group, more
particularly ethoxy; [0198] Y represents a C1-C6 alkoxy group, more
particularly ethoxy; or C1-C6 alkyl, more particularly methyl;
[0199] Z is a linear or branched, saturated or unsaturated C1-C22
hydrocarbon-based chain, which may be substituted with an amine
group NH.sub.2 or NHR (R.dbd.C1-C20 and especially C1-C6 alkyl,
C3-C40 cycloalkyl or C6-C30 aromatic); or with a hydroxyl group, a
thiol group, an aryl group (more particularly benzyl), which is
substituted or unsubstituted; Z possibly being interrupted with a
heteroatom (O, S or NH) or a carbonyl group (CO); [0200] n
represents an integer equal to 1 or 2.
[0201] Examples that may be mentioned include
N-(3-acryloxy-2-hydroxypropyl)-3-aminopropyltriethoxysilane,
4-aminobutyltriethoxysilane, 3-aminopropylmethyl-diethoxysilane,
3-aminopropyltriethoxysilane,
3-aminopropyltris(methoxyethoxyethoxy)silane,
bis(methyl-diethoxysilylpropyl)amine,
bis[3-(triethoxysilyl)-propyl]urea,
3-(2,4-dinitrophenylamino)propyltriethoxy-silane,
hydroxymethyltriethoxysilane, mercapto-methylmethyldiethoxysilane,
3-mercaptopropyl-triethoxysilane,
o-(methacryloxyethyl)-N-(triethoxy-silylpropyl)urethane,
N-(3-methacryloxy-2-hydroxy-propyl)-3-aminopropyltriethoxysilane,
o-(propargyloxy)-N-(triethoxysilylpropyl)urethane,
(3-triethoxysilyl-propyl)-t-butylcarbamate,
triethoxysilylpropylethyl-carbamate,
N-(3-triethoxysilylpropyl)gluconamide,
N-(3-triethoxysilylpropyl)-4-hydroxybutyramide,
3-(triethoxysilylpropyl)-p-nitrobenzamide,
N-(triethoxy-silylpropyl)-O-polyethylene oxide urethane,
ureido-propyltriethoxysilane and
o-(vinyloxyethyl)-N-(triethoxysilylpropyl)urethane, and mixtures
thereof.
[0202] The silane may serve to promote the attachment of the
copolymer to the keratin support.
[0203] The silane, alone or as a mixture, may be present in a
proportion of from 0.5% to 30% by weight, especially 1% to 25% by
weight or even 2% to 20% by weight, relative to the weight of the
dispersion.
[0204] Other ingredients may be present in the aqueous dispersion
of silicone copolymer according to the invention; these ingredients
may be introduced into the aqueous phase or the organic phase,
during the preparation of the dispersion.
[0205] Mention may thus be made of the following, alone or as a
mixture: cationic, anionic and/or nonionic silicones bearing
hydrophilic or hydrophobic grafts; plasticizers; spreading agents
or coalescers; solid fatty substances such as fatty alcohols, fatty
acids or plant or mineral waxes; conditioning agents, especially of
cationic polymer type including polyamines; anionic (neutralized or
non-neutralized), cationic or nonionic polymers and especially
styling polymers; pH agents, bases or acids; organic or mineral
pigments or colorants; sunscreens, fragrances, peptizers,
preserving agents, amino acids or vitamins; and thickeners
[0206] As has been mentioned hereinabove, a process for preparing
the aqueous dispersions of polysiloxane/polyurea according to the
invention comprises the following steps: [0207] i) dissolving the
copolymer and the silane in an organic phase;
[0208] Preferably, the copolymer is present in a proportion of from
2% to 60% by weight, especially 5% to 40% by weight or even 8% to
25% by weight, in the organic phase. [0209] ii) preparing an
aqueous phase comprising one or more surfactants;
[0210] Preferably, the surfactant(s) are present in a proportion of
from 0.01% to 15% by weight, especially 0.05% to 10% by weight or
even 0.1% to 6% by weight, in the aqueous phase. [0211] iii) mixing
together the organic and aqueous phases, and then emulsifying,
especially with rapid stirring;
[0212] Preferably, the surfactant represents 0.01% to 15% by
weight, especially 0.05% to 10% by weight or even 0.1% to 5% by
weight relative to the weight of the organic phase comprising the
copolymer.
[0213] Preferably, 0.5 to 50 parts by weight and in particular 0.8
to 20 parts of aqueous phase comprising the surfactants are added,
especially 1 to 12 parts, or even 2 to 8 parts, per 1 part of
organic phase comprising the copolymer.
[0214] Preferably, the emulsification is performed at a temperature
from 15 to 100.degree. C., especially 18 to 50.degree. C., or even
20-30.degree. C., at a speed of between 50 and 30 000 rpm and
especially 200 to 10 000 rpm, via any means known to those skilled
in the art, especially with an homogenizer, in particular of the
Ultra-Turrax type.
[0215] Optionally, all or part of the organic phase may then be
evaporated, via any technique considered adequate by a person
skilled in the art, such as evaporation under reduced pressure
(under vacuum).
[0216] It is thus possible finally to obtain an aqueous dispersion
of polysiloxane/polyurea copolymer, whose solids content may be
between 0.1% and 50% by weight, especially 0.5% to 40% by weight,
or even 1% to 30% by weight and better still 2% to 25% by
weight.
[0217] The dispersion according to the invention may comprise
solvent compounds and/or an organic phase, which may represent
0.05% to 80% by weight and especially 1% to 70% by weight of the
said dispersion. This organic phase may also be absent (less than
0.05%, or even 0%).
[0218] The dispersion may also comprise surfactants, which may
represent 0.05% to 10% by weight, especially 0.01% to 8% by weight
or even 0.1% to 5% by weight of the said dispersion. These
surfactants may also be absent (less than 0.05%, or even 0%).
[0219] The aqueous dispersion according to the invention finds a
quite particular application in the field of cosmetics, especially
in the field of haircare.
[0220] The amount of polymer present in the compositions obviously
depends on the type of composition and on the desired properties;
it may range between 0.01% and 30% by weight, preferably between
0.1% and 20% by weight, especially between 0.5% and 10% by weight,
or even between 1% and 5% by weight of polymer solids relative to
the weight of the cosmetic composition.
[0221] The compositions according to the invention may be in any
galenical form conventionally used for topical application, and
especially in the form of an aqueous, alcoholic or
aqueous-alcoholic solution or suspension; an oily solution or
suspension; a solution or dispersion of the lotion or serum type;
an emulsion of liquid or semi-liquid consistency of the milk or
cream type, obtained by dispersing a fatty phase in an aqueous
phase (O/W) or, conversely, (W/O); an aqueous or anhydrous gel, an
ointment, a loose or compact powder to be used in this form or to
be incorporated into an excipient, or any other cosmetic form.
These compositions may be packaged, especially in pump bottles or
in aerosol containers, so as to apply the composition in vaporized
form or in the form of a mousse. Such packaging forms are
indicated, for example, when it is desired to obtain a spray or a
mousse for treating the hair. The compositions in accordance with
the invention may also be in the form of creams, gels, emulsions,
lotions or waxes. When the composition according to the invention
is packaged in the form of an aerosol in order to obtain a lacquer
or a mousse, it comprises at least one propellant.
[0222] The compositions according to the invention comprise a
cosmetically acceptable medium, i.e. a medium that is compatible
with keratin materials, especially facial or bodily skin, the lips,
the hair, the eyelashes, the eyebrows and the nails.
[0223] Depending on their nature and the intended use of the
composition, the ingredients of the cosmetically acceptable medium
may be present in usual amounts, which may be readily determined by
a person skilled in the art, and which may be, for each ingredient,
between 0.01% and 80% by weight.
[0224] Mention may be made especially of the following ingredients,
alone or as a mixture: nonionic, cationic, anionic or amphoteric
surfactants; hydrophilic solvents (alcohols) or hydrophobic
solvents (alkanes); cationic, anionic or nonionic silicones bearing
hydrophilic or hydrophobic grafts, which may or may not be
phenylated; plasticizers, for example of polyol type; spreading
agents or coalescers; silanes, especially those having the
structure described above; liquid or solid fatty substances such as
fatty alcohols, fatty acids, plant or mineral oils and plant or
mineral waxes; conditioning agents such as cationic polymers
including polyamines; polymers, especially styling polymers, which
are in particular anionic (neutralized or non-neutralized),
cationic or nonionic; pH agents (bases or acids); organic or
mineral pigments or colorants; fillers such as nacres, TiO.sub.2,
resins and clays; sunscreens; fragrances; peptizers; preserving
agents; amino acids; vitamins.
[0225] The cosmetic composition according to the invention may be
in the form of a product for caring for, cleansing and/or making up
bodily or facial skin, the lips, the eyebrows, the eyelashes, the
nails and the hair, an antisun or self-tanning product, a body
hygiene product, or a haircare product, especially for caring for,
cleansing, styling, shaping or colouring the hair.
[0226] The composition especially finds a particularly advantageous
use in the field of haircare, especially for holding the hairstyle
or shaping the hair, or for the care, cosmetic treatment or
cleansing of the hair. The haircare compositions are preferably
shampoos, hair conditioners, styling or care gels, care lotions or
creams, conditioners, hairsetting lotions, blow-drying lotions,
hair styling and fixing compositions such as lacquers or sprays;
hair restructuring lotions; lotions or gels for preventing hair
loss, antiparasitic shampoos, antidandruff lotions or shampoos, and
anti-seborrhoea treating shampoos. The lotions may be packaged in
various forms, especially in vaporizers, in pump bottles or in
aerosol containers so as to apply the composition in vaporized form
or in the form of a mousse.
[0227] The composition may also be in the form of a hair colouring
product, especially an oxidation dye or direct dye, optionally in
the form of colouring shampoos; in the form of a permanent-waving,
relaxing or bleaching composition, or alternatively in the form of
a rinse-out composition, to be applied before or after dyeing,
bleaching, permanent-waving or relaxing the hair, or alternatively
between the two steps of a permanent-waving or relaxing
operation.
[0228] The composition according to the invention may also be in
the form of a care composition, especially a moisturizer, for
bodily or facial skin, the lips and/or the integuments, especially
a care product for cosmetically treating the skin and especially
for moisturizing it, making it smooth, depigmenting it, nourishing
it, protecting it against sunlight, or giving it a specific
cosmetic treatment. Thus, it may be a lipcare base, a fixing base
for lipsticks, an antisun or artificial tanning composition, a
facial care composition (a day, night, anti-ageing or moisturizing
composition); a matting composition; a skin cleansing composition,
for example a makeup-removing product or a bath or shower gel, or a
cleansing bar or soap; a body hygiene composition, especially a
deodorant or antiperspirant product, or alternatively a
hair-removing composition or an aftershave gel or lotion. It may
also be in the form of a makeup product for bodily or facial skin,
the lips, the eyelashes, the nails or the hair; in particular a
foundation, a blusher, a makeup rouge, an eyeshadow, a concealer
product, an eyeliner, a mascara, a lipstick, a lip gloss, a lip
pencil; a nail varnish, a nailcare product; a temporary tattoo
product for bodily skin.
[0229] Even more particularly, the composition according to the
invention finds an advantageous application in holding the
hairstyle or shaping the hair, or alternatively in caring for,
cosmetically treating or cleansing the hair.
[0230] One subject of the invention is thus a cosmetic treatment
process, especially for making up, caring for, cleansing, colouring
or shaping keratin materials, especially bodily or facial skin, the
lips, the nails, the hair and/or the eyelashes, comprising the
application to the said materials of a cosmetic composition
comprising at least one compound according to the invention.
[0231] Preferably, it is a cosmetic treatment process for
conditioning the hair, in particular to give it or improve its
suppleness, disentangling, smoothing, combability and
manageability.
[0232] The application of the composition may optionally be
followed by a heat treatment step.
[0233] The composition may also be in the form of a kit in two or
more parts.
[0234] These parts may be intended for mixing together at the time
of use or alternatively for application successively to the keratin
substrate to be treated, in particular the hair. These successive
application steps may or may not be interrupted by a step of manual
drying, for example with a towel, or by means of an appliance, for
instance a hairdryer.
[0235] In one preferred case of the invention, the composition
comprising the dispersion according to the invention is used in
leave-in mode.
[0236] In one preferred case of the invention, the composition
comprising the dispersion according to the invention is used in
combination with a heating appliance for shaping the hair, such as
a curling iron, a waving iron, a crimping iron, a straightening
iron or heated curlers. The temperature of the heating appliance
used is preferably between 60.degree. C. and 200.degree. C.
[0237] In one preferred embodiment, the composition according to
the invention may be applied to wet or dry hair, a step optionally
followed by partial or total drying of the hair, optionally
followed by the application of a heating tool, which may be a
hairdryer or a tool for simultaneously applying a mechanical
constraint and heating (straightening iron, waving iron, crimping
iron or curling iron, using or not using steam). The temperature of
the tool is preferably between 60.degree. C. and 200.degree. C.
[0238] The invention is illustrated in greater detail in the
examples that follow.
EXAMPLE 1
[0239] A polysiloxane/polyurea copolymer (Belsil UD80) and
aminopropyltriethoxysilane (APTES) are dissolved in hexanol. This
solution is added to an aqueous solution of cationic surfactant
(cetyltrimethylammonium chloride) diluted in water and stirred with
an Ultra-Turrax blender at 13 000 rpm. The mixture is homogenized
for 30 minutes and the hexanol is then removed on a rotary
evaporator. An opaque white aqueous dispersion is thus obtained,
the composition of which is given below.
TABLE-US-00001 Copoly- Organic Surfac- mer APTES phase tant Water
Disper- Before 20 g 22 g 140 g 4.8 g 1964 g sion (1) evaporation
Hexanol After 7.8% 8.6% 0% 1.9% 81.7% evaporation Disper- Before 20
g 53.3 g 140 g 4.8 g 1964 g sion (2) evaporation Hexanol After 7.1%
18.8% 0% 1.7% 72.4% evaporation Disper- Before 20 g 53.3 g 140 g
4.8 g 1964 g sion (3) evaporation Hexanol After 7.2% 19.1% 0% 1.7%
72.0% evaporation Disper- Before 20 g 106.6 g 140 g 4.8 g 1964 g
sion (4) evaporation Hexanol After 4.9% 26.1% 0% 1.2% 67.8%
evaporation
EXAMPLE 2
[0240] The following compositions are prepared (weight %):
TABLE-US-00002 compo- composition 1 composition 2 composition 3
sition 4 Dispersion 48% -- -- -- (1) Dispersion -- 53% -- -- (2)
Dispersion -- -- 52% -- (3) Dispersion -- -- -- 76.5% (4) lactic qs
pH 10 qs pH 10 qs pH 10 qs pH 10 acid deionized qs 100% qs 100% qs
100% qs 100% water
[0241] 1 g of composition is deposited on a lock of 2.7 g of
natural hair. After drying, shaping is performed using a heating
tool such as a curling iron, applied for 30 seconds, with the
thermostat set for a temperature of between 140 and 180.degree. C.
After cooling, the lock is suspended in ambient medium. The shape
setting and its hold over time are evaluated, at T0 and after 6
shampoo washes.
[0242] The resistance of the coating to shampooing is evaluated in
the following manner: 1 g of Ultra Doux shampoo from Garnier is
deposited on the prewetted lock; the lock is massaged from the root
to the end in passes; the lock is then rinsed in water for 10
seconds. The operation is repeated six times in a row. After
drying, the iron is reapplied and the lock is again suspended for
evaluation of the shape.
[0243] The comparative composition only contains water.
[0244] A tighter shape, which holds well over time, is obtained
with the compositions according to the invention; this effect is
also resistant after 6 shampoo washes.
* * * * *