U.S. patent application number 10/304861 was filed with the patent office on 2003-07-03 for use of a composition containing at least one oxidation-sensitive hydrophilic active principle and at least one n-vinylimidazole polymer or copolymer.
This patent application is currently assigned to L'OREAL. Invention is credited to Biatry, Bruno, Lheureux, Eric.
Application Number | 20030124075 10/304861 |
Document ID | / |
Family ID | 8869872 |
Filed Date | 2003-07-03 |
United States Patent
Application |
20030124075 |
Kind Code |
A1 |
Biatry, Bruno ; et
al. |
July 3, 2003 |
Use of a composition containing at least one oxidation-sensitive
hydrophilic active principle and at least one N-vinylimidazole
polymer or copolymer
Abstract
The invention relates to the use of a composition contains at
least one oxidation-sensitive hydrophilic active principle selected
from the group consisting of ascorbic acid and its derivatives and
at least one non-crosslinked N-vinylimidazole polymer or copolymer,
the active principle and the said polymer or copolymer both being
in the aqueous phase, for lightening and/or depigmenting the skin
and/or hair, including body hair.
Inventors: |
Biatry, Bruno; (Vincennes,
FR) ; Lheureux, Eric; (Montgeron, FR) |
Correspondence
Address: |
OBLON, SPIVAK, MCCLELLAND, MAIER & NEUSTADT, P.C.
1940 DUKE STREET
ALEXANDRIA
VA
22314
US
|
Assignee: |
L'OREAL
Paris
FR
|
Family ID: |
8869872 |
Appl. No.: |
10/304861 |
Filed: |
November 27, 2002 |
Current U.S.
Class: |
424/62 |
Current CPC
Class: |
A61P 17/00 20180101;
A61P 43/00 20180101; A61K 8/817 20130101; A61K 2800/522 20130101;
A61K 8/676 20130101; A61Q 19/08 20130101; A61P 17/16 20180101; A61Q
5/08 20130101; A61Q 19/02 20130101 |
Class at
Publication: |
424/62 |
International
Class: |
A61K 007/135 |
Foreign Application Data
Date |
Code |
Application Number |
Nov 28, 2001 |
FR |
0115375 |
Claims
1. A method for lightening the skin and/or hair, comprising
applying to hair and/or skin to be lightened a composition
comprising: a physiologically acceptable medium comprising an
aqueous phase; at least one lightening oxidation-sensitive
hydrophilic active principle selected from the group consisting of
ascorbic acid and its derivatives present in an amount sufficient
to lighten the skin and/or hair, and: at least one non-crosslinked
N-vinylimidazole polymer or copolymer, the at least one active
principle and the at least one polymer or copolymer both being
present in the aqueous phase.
2. The method according to claim 1, wherein the hydrophilic active
principle is selected from the group consisting of ascorbic acid
esters and salts.
3. The method according to claim 1, wherein the hydrophilic active
principle is selected from the group consisting of
5,6-di-O-dimethylsilylascorbate, dl-.alpha.-tocopheryl dl-ascorbyl
phosphate potassium salt, magnesium ascorbyl phosphate and sodium
ascorbyl phosphate.
4. The method according to claim 1, wherein the oxidation-sensitive
hydrophilic active principle is ascorbic acid.
5. The method according to claim 1, wherein said composition
comprises a non-crosslinked copolymer that is a combination of the
N-vinylimidazole with N-vinylpyrrolidone and/or N-vinylcaprolactam
subunits.
6. The method according to claim 1, wjerein said composition
comprises a non-crosslinked N-vinylimidazole/N-vinylpyrrolidone
copolymer.
7. The method according to claim 1, wherein the composition
comprises a non-crosslinked copolymer selected from the group
consisting of a vinylpyrrolidone/vinylimidazole (50/50) copolymer
having a weight-average molar mass of 1 200 000 and a
vinylpyrrolidone/vinylimidazole (50/50) copolymer having a
weight-average molar mass of 10 000.
8. The method according to claim 1, wherein the molar ratio of
N-vinylimidazole unit equivalent in said polymer or copolymer to
the oxidation-sensitive hydrophilic active principle varies between
0.004 and 16.
9. The method according to claim 8, wherein the molar ratio of the
N-vinylimidazole unit equivalent to the oxidation-sensitive
hydrophilic active principle varies between 0.01 and 1.
10. The method according to claim 1, wherein the polymer or
copolymer is present in said composition in a concentration of from
0.1 to 5% by weight of the aqueous phase.
11. The method according to claim 10, wherein the polymer or
copolymer is present at a concentration of between 0.1 and 2% by
weight of the aqueous phase.
12. The method according to claim 1, wherein the polymer or
copolymer has a molar fraction of N-vinylimidazole units of between
0.1 and 1.
13. The method according to claim 12, wherein the polymer or
copolymer has a molar fraction of N-vinylimidazole units of between
0.4 and 0.9.
14. The method according to claim 1, wherein the composition
further comprises a depigmenting or anti-pigmentation agent which
is different from the oxidation-sensitive hydrophilic active
principle.
15. The method according to claim 14, wherein the depigmenting or
anti-pigmentation agent is selected from the group consisting of
kojic acid; ellagic acid; arbutin and its derivatives;
hydroquinone; aminophenols; iminophenols;
L-2-oxothiazolidine-4-carboxylic acid or procysteine, and its salts
and esters; 4-butylresorcinol or lucinol; thioureas; calcium
D-pantetheinesulphonate; ascorbyl glucoside, magnesium ascorbyl
phosphate; and plant extracts.
Description
BACKGROUND OF THE INVENTION
[0001] 1. Field of the Invention
[0002] The present invention relates to the use of a composition
comprising at least one oxidation-sensitive hydrophilic active
principle and at least one N-vinylimidazole polymer or copolymer,
preferably in a physiologically acceptable medium comprising an
aqueous phase. Preferably the use is a cosmetic and/or
dermatological use related to lightening or depigmenting the skin
and/or the hair, and is thus preferably targeted to skin and/or
hair to be lightened.
[0003] 2. Background of the Invention
[0004] It is known to introduce, into cosmetic compositions,
various active principles intended to contribute specific
treatments to the skin and/or hair. However, some of these active
principles exhibit the disadvantage of being unstable in an aqueous
medium and of easily decomposing on contact with water, in
particular because of oxidation phenomena. They thus rapidly lose
their activity over time and this instability conflicts with the
desired effectiveness.
[0005] Attempts have thus been made for a long time to formulate
ascorbic acid or vitamin C because of its numerous beneficial
properties. In particular, ascorbic acid stimulates the synthesis
of the connective tissue and in particular of collagen, strengthens
the defences of the cutaneous tissue against external attacks, such
as ultraviolet radiation and pollution, compensates for vitamin E
deficiency of the skin, depigments the skin and has a role in
combatting free radicals. These last two properties make it an
excellent candidate as cosmetic or dermatological active principle
for combatting ageing of the skin or for preventing ageing of the
skin. Unfortunately, because of its chemical structure (of
.alpha.-ketolactone), ascorbic acid is highly sensitive to certain
environmental parameters and in particular to oxidation phenomena.
There thus ensues rapid decomposition of formulated ascorbic acid
in the presence of these parameters and in particular in the
presence of oxygen, light or metal ions, as a function of the
temperature or under certain pH conditions (Pharm. Acta. Helv.,
1969, 44, 611-667; STP Pharma, 1985, 4, 281-286).
[0006] Several solutions have thus been envisaged in the prior art
for reducing and/or slowing down the decomposition of ascorbic
acid.
[0007] Provision has thus been made to use ascorbic acid in the
form of a chemical derivative (magnesium ascorbyl phosphate or
esters of fatty acids and ascorbic acid), but the bioavailability
of these derivatives is very low (J. Am. Acad. Dermatol., 1996, 34,
29-33).
[0008] The instability of ascorbic acid with respect to oxygen can
be improved by using specific packagings, such as twin compartments
under an inert atmosphere, as disclosed in U.S. Pat. No. 5,935,584,
or alternatively by the use of two-phase emulsions, one phase of
which is composed of a dry powder comprising ascorbic acid and the
second phase of which is a liquid phase. The mixing of the two
phases has to be carried out at the time of use (WO 98/43598).
These solutions have disadvantages with regard to the cost and the
complexity of the manufacturing operations and significant
restrictions with regard to use.
[0009] Another solution provided in the prior art consists in using
a high concentration of glycols or polyols in order to reduce the
solubility of oxygen in the formulation, thus protecting the
ascorbic acid (WO 96/24325, EP 0 755 674, U.S. Pat. No. 5,981,578).
The polyols can optionally be incorporated in liposomes, as
disclosed in U.S. Pat No. 6,020,367. However, these solutions
exhibit the disadvantage of resulting in sticky formulations, the
cosmetic quality of which is difficult to improve. Furthermore, the
presence of a high concentration of these compounds can lead to
phenomena of irritation.
[0010] Ascorbic acid can also be formulated in anhydrous media,
such as silicones (U.S. Pat. No. 6,194,452), which are capable of
creating an anhydrous barrier around ascorbic acid. A major
disadvantage of such solutions results from the lack of freshness
on application.
[0011] The need thus remains for a composition employable in
particular in the cosmetics field, in which a hydrophilic active
principle which is unstable in an oxidizing medium is stabilized,
which is comfortable on application, which does not lead to any
skin irritation after application and which is compatible with the
constraints of an industrial implementation of its manufacturing
process.
[0012] The activity of ascorbic acid or of its derivatives on
pigmentation has been known for many years. Various mechanisms have
been described to explain their effect on the reduction of
melanogenesis. The inhibiting effect on tyrosinase has been
demonstrated for ascorbic acid (J. Soc. Cosmet. Chem., 42, 1991, p.
361-368). Some of its esters have been used for some years in
depigmenting treatments, that is to say, magnesium ascorbyl
phosphate and ascorbyl glucoside. More recently, a study has shown
that magnesium ascorbyl phosphate can reduce the dendricity of
melanocytes (Pigment. Cell. Res., 13, 2000, p. 89-98 and p.
190-192).
OBJECTS OF THE INVENTION
[0013] One object of the present invention is to provide a
composition comprising an oxidation-sensitive active principle
selected from the group consisting of ascorbic acid and its
derivatives, which exhibits good cosmetic properties, both with
regard to touch and with regard to tolerance, the preservation of
which over time does not require specific precautions, and which
retains the depigmenting and/or lightening ability of the active
principle.
DETAILED DESCRIPTION OF THE INVENTION
[0014] The Inventors have discovered that the use of
non-crosslinked N-vinylimidazole polymers or copolymers in
compositions in which the aqueous phase includes an
oxidation-sensitive active principle, such as ascorbic acid, makes
it possible to achieve the abovementioned object.
[0015] In the prior art, some compounds having an imidazole
structure have been disclosed for their stabilizing properties.
Thus, in Patent Application EP 0 586 106, several imidazole-based
molecules are used to stabilize certain retinoids against chemical
decomposition. Furthermore, polymeric emulsifiers composed of
N-vinylimidazole, of alkyl acrylates and of vinyl acetates are
disclosed in U.S. Pat. No. 4,057,622. They are used for the purpose
of replacing known emulsifiers in order to overcome their
disadvantages, in particular with regard to smell, and to stabilize
water-in-oil emulsions. Finally,
N-vinylimidazole/N-vinylcaprolactam/N-vi- nylpyrrolidone copolymers
are disclosed in U.S. Pat. No. 6,191,188. They are used in the
manufacture of hair-strengthening compositions.
[0016] To the knowledge of the inventors, polymers or copolymers
comprising N-vinylimidazole units have never been used in
combination with hydrophilic active principles sensitive to
decomposition by oxidation for the purpose of improving their
stability in an aqueous medium. This is true in particular in the
case of ascorbic acid.
[0017] One embodiment of the present invention is therefore the
preferably cosmetic and/or dermatological use of a composition for
depigmenting and/or lightening the skin and/or hair, including body
hair, the composition comprising, preferably in a physiologically
acceptable medium comprising an aqueous phase, at least one
oxidation-sensitive hydrophilic active principle selected from the
group consisting of ascorbic acid and its derivatives and at least
one non-crosslinked N-vinylimidazole polymer or copolymer, the
active principle and the polymer or copolymer both being present in
the aqueous phase. The copolymer is preferably present in an amount
sufficient to stabilize the said oxidation-sensitive hydrophilic
active principle.
[0018] The use of such a composition furthermore exhibits the
advantage of acting both by inhibiting tyrosinase, thus reducing
melanogenesis, and also by inhibiting the dendricity of
melanocytes. The depigmenting effect thus obtained is much greater
than that obtained, for example, with ascorbic acid alone, which
acts solely on melanogenesis.
[0019] Another embodiment of the present invention is the use of a
combination composed of at least one oxidation-sensitive
hydrophilic active principle selected from the group consisting of
ascorbic acid and its derivatives and of at least one
non-crosslinked N-vinylimidazole polymer or copolymer, the active
principle and the polymer or copolymer both being in the aqueous
phase, in a cosmetic composition, as depigmenting agent.
[0020] According to the invention, the term "hydrophilic active
principle" is understood to mean a compound having a solubility in
water of at least 0.25% at ambient temperature (25.degree. C.).
[0021] According to the invention, the term "oxidation-sensitive
hydrophilic active principle" is understood to mean any active
principle of natural or synthetic origin capable of undergoing
decomposition by an oxidation mechanism. This oxidation phenomenon
can have several causes, in particular the presence of oxygen, of
light or of metal ions, a high temperature or certain pH
conditions.
[0022] Mention may be made, by way of example and without implied
limitation, of: ascorbic acid and its derivatives, such as salts
and esters thereof, particularly the
5,6-di-O-dimethylsilylascorbate (sold by Exsymol under the
reference PRO-AA), the potassium salt of dl-.alpha.-tocopheryl
dl-ascorbyl phosphate (sold by Senju Pharmaceutical under the
reference SEPIVITAL EPC), magnesium ascorbyl phosphate or sodium
ascorbyl phosphate (sold by Roche under the reference Stay-C
50).
[0023] In a particularly advantageous aspect, the
oxidation-sensitive hydrophilic active principle is ascorbic acid.
Other preferred principles meet the above requirements and possess
the ability to lighten the skin and/or the hair.
[0024] The oxidation sensitive hydrophilic active principle is
preferably present in an amount sufficient to lighten the hair
and/or skin, which amount is determinable by one of ordinary skill
without undue effort. Example amounts include 1-10% based on total
weight.
[0025] According to the invention, the term "non-crosslinked
N-vinylimidazole polymer or copolymer" is understood to mean any
polymer comprising N-vinylimidazole units and not comprising a
crosslinking agent. Copolymers suitable for the implementation of
the invention are copolymers combining N-vinylimidazole with
N-vinylpyrrolidone and/or N-vinylcaprolactam subunits.
[0026] In an advantageous aspect of the invention, the copolymer
has a molar fraction of N-vinylimidazole units of between 0.1 and
1, more preferably between 0.4 and 0.9.
[0027] According to an advantageous aspect of the invention, the
molar ratio of the N-vinylimidazole unit equivalent to the
oxidation-sensitive hydrophilic active principle varies between
0.004 and 16 and preferably between 0.01 and 1.
[0028] Use is preferably made of an
N-vinylimidazole/N-vinylpyrrolidone copolymer.
[0029] The weight-average molar mass of the N-vinylimidazole
polymers is preferably between 1 000 and 1.times.10.sup.7 and more
preferably between 5 000 and 5.times.10.sup.6.
[0030] Use may be made, to this end, of the
vinylpyrrolidone/vinylimidazol- e (50/50) copolymer having a
weight-average molar mass of 1 200 000 sold under the reference
LUVITEC VPI 55K72W by BASF or the vinylpyrrolidone/vinylimidazole
(50/50) copolymer having a weight-average molar mass of 10 000 sold
under the reference LUVITEC VPI 55K18P by BASF. The polymers or
copolymers according to the invention can, for example, be prepared
according to the method disclosed in Patent Application
WO-97/45517.
[0031] The at least one polymer or copolymer is preferably present
in the composition according to the invention in an amount
sufficient to produce the desired effect, that is to say in an
amount sufficient to stabilize the oxidation-sensitive hydrophilic
active principle. Preferably, the polymer or copolymer is present
at a concentration of between 0.1 and 5% by weight with respect to
the total weight of the aqueous phase and more particularly at a
concentration of between 0.1 and 2% by weight with respect to the
total weight of the aqueous phase.
[0032] The compositions used according to the invention are
preferably intended for topical application to the skin and/or its
superficial body growths and therefore comprise a physiologically
acceptable medium, that is to say a medium compatible with
cutaneous tissues, such as the skin, scalp, eyelashes, eyebrows,
hair, nails and mucous membranes. This physiologically acceptable
medium comprises at least one aqueous phase and optionally a
physiologically acceptable organic solvent chosen, for example,
from lower alcohols comprising from 1 to 8 carbon atoms and in
particular from 1 to 6 carbon atoms, such as ethanol, isopropanol,
propanol or butanol; polyethylene glycols having from 6 to 80
ethylene oxide units; or polyols, such as propylene glycol,
isoprene glycol, butylene glycol, glycerol or sorbitol.
[0033] When the physiologically acceptable medium is an aqueous
medium, it generally has a pH which is compatible with the skin,
preferably ranging from 3 to 9 and better still from 3.5 to
7.5.
[0034] The compositions according to the invention can be provided
in any form, including any pharmaceutical dosage form used for
topical application and in particular in the form of aqueous or
aqueous/alcoholic solutions, of oil-in-water (O/W) or water-in-oil
(W/O) or multiple (triple: W/O/W or O/W/O) emulsions, of aqueous
gels or of dispersions of a fatty phase in an aqueous phase using
spherules, it being possible for these spherules to be polymeric
nanoparticles, such as nanospheres and nanocapsules, or lipid
vesicles of ionic and/or nonionic type (liposomes, niosomes or
oleosomes). These compositions are prepared according to the usual
methods.
[0035] In addition, the compositions used according to the
invention can be more or less fluid and can have the appearance of
a white or coloured cream, of an ointment, of a milk, of a lotion,
of a serum, of a paste or of a foam. They can optionally be applied
to the skin in the form of an aerosol. They can also be provided in
a solid form, for example in the form of a stick.
[0036] When the composition used according to the invention
comprises an oily phase, the latter preferably comprises at least
one oil. It can additionally comprise other fatty substances.
[0037] Mention may be made, as oils which can be used in the
composition of the invention, of, for example:
[0038] hydrocarbonaceous oils of animal origin, such as
perhydrosqualene;
[0039] hydrocarbonaceous oils of vegetable origin, such as liquid
triglycerides of fatty acids comprising from 4 to 10 carbon atoms,
such as triglycerides of heptanoic acid or octanoic acid, or
alternatively, for example, sunflower, maize, soybean, gourd, grape
seed, sesame, hazelnut, apricot, macadamia, arara, castor or
avocado oils, triglycerides of caprylic/capric acids, such as those
sold by Starineries Dubois or those sold under the names Miglyol
810, 812 and 818 by Dynamit Nobel, jojoba oil, or karite butter
oil;
[0040] synthetic esters and ethers, in particular of fatty acids,
such as the oils of formulae R.sup.1COOR.sup.2 and R.sup.1OR.sup.2
in which R.sup.1 represents the residue of a fatty acid comprising
from 8 to 29 carbon atoms and R.sup.2 represents a branched or
unbranched hydrocarbonaceous chain comprising from 3 to 30 carbon
atoms, such as, for example, purcellin oil, isononyl isononanoate,
isopropyl myristate, 2-ethylhexyl palmitate, 2-octyldodecyl
stearate, 2-octyldodecyl erucate or isostearyl isostearate;
hydroxylated esters, such as isostearyl lactate, octyl
hydroxystearate, octyldodecyl hydroxystearate, diisostearyl malate,
triisocetyl citrate or heptanoates, octanoates or decanoates of
fatty alcohols; polyol esters, such as propylene glycol
dioctanoate, neopentyl glycol diheptanoate and diethylene glycol
diisononanoate; and pentaerythritol esters, such as pentaerythrityl
tetraisostearate;
[0041] linear or branched hydrocarbons of mineral or synthetic
origin, such as volatile or nonvolatile liquid paraffins and their
derivatives, liquid petrolatum, polydecenes or hydrogenated
polyisobutene, such as parleam oil;
[0042] fatty alcohols having from 8 to 26 carbon atoms, such as
cetyl alcohol, stearyl alcohol and their mixture (cetearyl
alcohol), octyldodecanol, 2-butyloctanol, 2-hexyldecanol,
2-undecylpentadecanol, oleyl alcohol or linoleyl alcohol;
[0043] partially hydrocarbon-comprising and/or silicone-comprising
fluorinated oils, such as those disclosed in the document
JP-A-2-295912;
[0044] silicone oils, such as volatile or nonvolatile
polymethylsiloxanes (PDMS) comprising a linear or cyclic silicone
chain which are liquid or pasty at ambient temperature, in
particular cyclopolydimethylsiloxanes (cyclomethicones), such as
cyclohexasiloxane; polydimethylsiloxanes comprising pendent alkyl,
alkoxy or phenyl groups or alkyl, alkoxy or phenyl groups at the
end of the silicone chain, which groups have from 2 to 24 carbon
atoms; or phenylated silicones, such as phenyl trimethicones,
phenyl dimethicones, phenyltrimethylsiloxydiphenylsiloxane- s,
diphenyl dimethicones, diphenylmethyldiphenyltrisiloxanes,
(2-phenylethyl)trimethylsiloxysilicates and
polymethylphenylsiloxanes;
[0045] their mixtures.
[0046] The term "hydrocarbonaceous oil" is understood to mean, in
the list of the oils mentioned above, any oil predominantly
comprising carbon and hydrogen atoms and optionally ester, ether,
fluorinated, carboxylic acid and/or alcohol groups.
[0047] The other fatty substances which can be present in the oily
phase are, for example, fatty acids comprising from 8 to 30 carbon
atoms, such as stearic acid, lauric acid, palmitic acid and oleic
acid; waxes, such as lanolin, beeswax, carnauba or candelilla wax,
paraffin or lignite waxes or microcrystalline waxes, ceresin or
ozokerite, or synthetic waxes, such as polyethylene waxes or
Fischer-Tropsch waxes; silicone resins, such as trifluoromethyl
C.sub.1-4 alkyl dimethicone and trifluoropropyl dimethicone; and
silicone elastomers, such as the products sold under the names
"KSG" by Shin-Etsu, under the names "Trefil", "BY29" or "EPSX" by
Dow Corning or under the names "Gransil" by Grant Industries.
[0048] These fatty substances can be chosen in a way varied by a
person skilled in the art in order to prepare a composition having
the desired properties, for example of consistency or of texture,
in view of this disclosure.
[0049] According to a specific embodiment of the invention, the
composition according to the invention is a water-in-oil (W/O) or
oil-in-water (O/W) emulsion. The proportion of the oily phase in
the emulsion can range from 5 to 80% by weight and preferably from
5 to 50% by weight with respect to the total weight of the
composition.
[0050] The emulsions generally preferably comprise at least one
emulsifier selected from the group consisting of amphoteric,
anionic, cationic or nonionic emulsifiers, used alone or as a
mixture, and optionally a coemulsifier. The emulsifiers are
appropriately chosen according to the emulsion to be obtained (W/O
or O/W). The emulsifier and the coemulsifier are generally
preferably present in the composition in a proportion ranging from
0.3 to 30% by weight and preferably from 0.5 to 20% by weight with
respect to the total weight of the composition.
[0051] Mention may be made, for the W/O emulsions, for example, as
emulsifiers, of dimethicone copolyols, such as the mixture of
cyclomethicone and of dimethicone copolyol sold under the name "DC
5225 C" by Dow Corning, and alkyl dimethicone copolyols, such as
the laurylmethicone copolyol sold under the name "Dow Corning 5200
Formulation Aid" by Dow Coming and the cetyl dimethicone copolyol
sold under the name Abil EM 90.sup.R by Goldschmidt. Use may also
be made, as surfactant of W/O emulsions, of a crosslinked solid
organopolysiloxane elastomer comprising at least one oxyalkylenated
group, such as those obtained according to the procedure of
Examples 3, 4 and 8 of the document U.S. Pat. No. 5,412,004 and the
examples of the document U.S. Pat. No. 5,811,487, in particular the
product of Example 3 (synthetic example) of U.S. Pat. No.
5,412,004, and such as that sold under the reference KSG 21 by Shin
Etsu. Use may also be made, as emulsifier, of a polyolefin-derived
oligomer or polymer comprising a succinic ending; the latter is
preferably a polyolefin comprising an esterified or amidated
succinic ending or a salt of such a polyolefin and in particular
polyisobutylene comprising an esterified or amidated succinic
ending such as the products sold under the names L5603 and L2721
and OS131769 by Lubrizol.
[0052] Mention may be made, for the O/W emulsions, for example, as
emulsifiers, of nonionic emulsifiers, such as esters of fatty acids
and of glycerol which are oxyalkylenated (more particularly
polyoxyethylenated); esters of fatty acids and of sorbitan which
are oxyalkylenated; esters of fatty acids which are oxyalkylenated
(oxyethylenated and/or oxypropylenated); ethers of fatty alcohols
which are oxyethylenated (oxyethylenated and/or oxypropylenated);
sugar esters, such as sucrose stearate; and their mixtures, such as
the mixture of glyceryl stearate and of PEG-40 stearate.
[0053] The cosmetic or dermatological composition of the invention
can also comprise adjuvants known in the cosmetics or
dermatological field, such as hydrophilic or lipophilic gelling
agents, preservatives, solvents, fragrances, fillers, UV screening
agents, bactericides, odour absorbers, colouring materials, plant
extracts or salts. The amounts of these various adjuvants are those
generally used in the field under consideration, for example from
0.01 to 20% of the total weight of the composition. These
adjuvants, depending on their nature, can be introduced into the
fatty phase, into the aqueous phase and/or into the lipid
spherules.
[0054] Mention may be made, as fillers which can be used in the
composition of the invention, for example, of pigments, silica
powder; talc; particles of polyamide and in particular those sold
under the name Orgasol by Atochem; polyethylene powders;
microspheres based on acrylic copolymers, such as those made of
ethylene glycol dimethacrylate/lauryl methacrylate copolymer which
are sold by Dow Corning under the name Polytrap; expanded powders,
such as hollow microspheres and in particular the microspheres sold
under the name Expancel by Kemanord Plast or under the name
Micropearl F 80 ED by Matsumoto; silicone resin microbeads, such as
those sold under the name Tospearl by Toshiba Silicone; and their
mixtures. These fillers can be present in amounts ranging from 0 to
20% by weight and preferably from 1 to 10% by weight with respect
to the total weight of the composition.
[0055] According to a preferred embodiment, the compositions in
accordance with the invention can additionally comprise at least
one organic photoprotective agent and/or at least one inorganic
photoprotective agent which is active in the UV-A and/or UV-B
regions (absorbers), and which are soluble in water or in fats or
else are insoluble in the cosmetic solvents commonly used.
[0056] The organic photoprotective agents are chosen in particular
from anthranilates; cinnamic derivatives; dibenzoylmethane
derivatives; salicylic derivatives; camphor derivatives; triazine
derivatives, such as those disclosed in Patent Applications U.S.
Patent No. 4,367,390, EP 863 145, EP 517 104, EP 570 838, EP 796
851, EP 775 698, EP 878 469, EP 933 376, EP 507 691, EP 507 692, EP
790 243 and EP 944 624; benzophenone derivatives;
.beta.,.beta.-diphenylacrylate derivatives; benzotriazole
derivatives; benzalmalonate derivatives; benzimidazole derivatives;
imidazolines; bisbenzoazolyl derivatives as disclosed in Patents EP
669 323 and U.S. Pat. No. 2,463,264; p-aminobenzoic acid (PABA)
derivatives; methylenebis(hydroxyphenylbenzotriazole) derivatives
as disclosed in Applications U.S. Pat. No. 5,237,071, U.S. Pat. No.
5,166,355, GB 2 303 549, DE 197 26 184 and EP 893 119; screening
polymers and screening silicones, such as those disclosed in
particular in Application WO 93/04665; dimers derived from
.alpha.-alkylstyrene, such as those disclosed in Patent Application
DE 198 55 649; 4,4-diarylbutadienes as disclosed in Applications EP
0 967 200, DE 197 46 654, DE 197 55 649, EP-A-1 008 586, EP 1 133
980 and EP 133 981; and their mixtures.
[0057] By way of illustration, mention may be made, as
photoprotective agents which are active in the UV-A and/or UV-B
regions, denoted below under their INCI names, of:
[0058] p-aminobenzoic acid (PABA) derivatives, in particular PABA,
ethyl PABA, ethyl dihydroxypropyl PABA, ethylhexyl dimethyl PABA
(sold in particular under the name "Escalol 507" by ISP), glyceryl
PABA or PEG-25 PABA (sold under the name "Uvinul P25" by BASF),
[0059] salicylic derivatives, in particular homosalate (sold under
the name "Eusolex HMS" by Rona/EM Industries), ethylhexyl
salicylate (sold under the name "Neo Heliopan OS" by Haarmann and
Reimer), dipropylene glycol salicylate (sold under the name
"Dipsal" by Scher), or TEA salicylate (sold under the name "Neo
Heliopan TS" by Haarmann and Reimer),
[0060] dibenzoylmethane derivatives, in particular butyl
methoxydibenzoylmethane (sold in particular under the trade name
"Parsol 1789" by Hoffmann-LaRoche), or isopropyl
dibenzoylmethane,
[0061] cinnamic derivatives, in particular ethylhexyl
methoxycinnamate (sold in particular under the trade name "Parsol
MCX" by Hoffmann-LaRoche), isopropyl methoxycinnamate, isoamyl
methoxycinnamate (sold under the trade name "Neo Heliopan E 1000"
by Haarmann and Reimer), cinoxate, DEA methoxycinnamate,
diisopropyl methyl cinnamate, or glyceryl ethylhexanoate
dimethoxycinnamate,
[0062] .beta.,.beta.-diphenylacrylate derivatives, in particular
octocrylene (sold in particular under the trade name "Uvinul N539"
by BASF) or etocrylene (sold in particular under the trade name
"Uvinul N35" by BASF),
[0063] benzophenone, in particular benzophenone-1 (sold under the
trade name "Uvinul 400" by BASF), benzophenone-2 (sold under the
trade name "Uvinul D50" by BASF), benzophenone-3 or oxybenzone
(sold under the trade name "Uvinul M40" by BASF), benzophenone-4
(sold under the trade name "Uvinul MS40" by BASF), benzophenone-5,
benzophenone-6 (sold under the trade name "Helisorb 11" by
Norquay), benzophenone-8 (sold under the trade name "Spectra-Sorb
UV-24" by American Cyanamid), benzophenone-9 (sold under the trade
name "Uvinul DS-49" by BASF), benzophenone-12, or n-hexyl
2-(4-diethylamino-2-hydroxybenzoyl)benzoate,
[0064] benzylidene camphor derivatives, in particular 3-benzylidene
camphor (manufactured under the name "Mexoryl SD" by Chimex),
4-methylbenzylidene camphor (sold under the name "Eusolex 6300" by
Merck), benzylidene camphor sulphonic acid (manufactured under the
name "Mexoryl SL" by Chimex), camphor benzalkonium methosulphate
(manufactured under the name "Mexoryl SO" by Chimex),
terephthalylidene dicamphor sulphonic acid (manufactured under the
name "Mexoryl SX" by Chimex), or polyacrylamidomethyl benzylidene
camphor (manufactured under the name "Mesoryl SW" by Chimex),
[0065] benzimidazole derivatives, in particular phenylbenzimidazole
sulphonic acid (sold in particular under the trade name "Eusolex
232" by Merck), or disodium phenyl dibenzimidazole tetrasulphonate
(sold under the trade name "Neo Heliopan AP" by Haarmann and
Reimer),
[0066] triazine derivatives, in particular anisotriazine (sold
under the trade name "Tinosorb S" by Ciba Specialty Chemicals),
ethylhexyl triazone (sold in particular under the trade name
"Uvinul T150" by BASF), diethylhexyl butamido triazone (sold under
the trade name "Uvasorb HEB" by Sigma 3V) or 2,4,6-tris(diisobutyl
4'-amino-benzalmalonate)-s-triazine- ,
[0067] benzotriazole derivatives, in particular drometrizole
trisiloxane (sold under the name "Silatrizole" by Rhodia Chimie) or
methylene bisbenzotriazolyl tetramethylbutylphenol (sold in the
solid form under the trade name "Mixxim BB/100" by Fairmount
Chemical or in the micronized form in aqueous dispersion under the
trade name "Tinosorb M" by Ciba Specialty Chemicals),
[0068] anthranilic derivatives, in particular menthyl anthranilate
(sold under the trade name "Neo Heliopan MA" by Haarmann and
Reimer),
[0069] imidazoline derivatives, in particular ethylhexyl
dimethoxybenzylidene dioxoimidazoline propionate,
[0070] benzalmalonate derivatives, in particular polyorganosiloxane
comprising benzalmalonate functional groups (sold under the trade
name "Parsol SLX" by Hoffmann-LaRoche),
[0071] 4,4-diarylbutadiene derivatives, in particular
1,1'-dicarboxy (2,2'-dimethyl-propyl)-4,4-diphenylbutadiene,
[0072] and their mixtures.
[0073] The organic photoprotective agents which are more
particularly preferred are selected from the group consisting of
ethylhexyl salicylate, ethylhexyl methoxycinnamate, octocrylene,
phenylbenzimidazole sulphonic acid, benzophenone-3, benzophenone-4,
benzophenone-5, 4-methylbenzylidene camphor, terephthalylidene
dicamphor sulphonic acid, disodium phenyl dibenzimidazole
tetrasulphonate, 2,4,6-tris(diisobutyl
4'-aminobenzalmalonate)-s-triazine, anisotriazine, ethylhexyl
triazone, diethylhexyl butamido triazone, methylene
bisbenzotriazolyl tetramethylbutylphenol, drometrizole trisiloxane,
1,1'-dicarboxy (2,2'-dimethylpropyl)-4,4-diphenylbutadiene, and
their mixtures.
[0074] The inorganic photoprotective agents may be selected from
the group consisting of pigments or alternatively nanopigments
(mean size of the primary particles: generally between 5 nm and 100
nm, preferably between 10 nm and 50 nm) formed from coated or
uncoated metal oxides, such as, for example, titanium oxide
(amorphous or crystalline in the rutile and/or anatase form), iron
oxide, zinc oxide, zirconium oxide or cerium oxide nanopigments,
which are all UV photoprotective agents well known per se.
Conventional coating agents are, furthermore, alumina and/or
aluminium stearate. Such nanopigments formed from coated or
uncoated metal oxides are disclosed in particular in Patent
Applications EP 518 772 and EP 518 773.
[0075] The photoprotective agents are generally present in the
compositions according to the invention in proportions ranging from
0.1 to 20% by weight with respect to the total weight of the
composition and preferably ranging from 0.2 to 15% by weight with
respect to the total weight of the composition.
[0076] In another advantageous aspect of the invention, the
composition used can additionally comprise at least one other
depigmenting or anti-pigmentation active principle in addition to
the hydrophilic active principle mentioned above.
[0077] The depigmenting or anti-pigmentation agents capable of
being incorporated in the composition according to the present
invention include, for example, the following compounds: kojic
acid; ellagic acid; arbutin and its derivatives, such as those
disclosed in Applications EP-895 779 and EP-524 109; hydroquinone;
aminophenol derivatives, such as those disclosed in Applications WO
99/10318 and WO 99/32077, in particular
N-cholesteryloxycarbonyl-para-aminophenol and
N-ethyloxycarbonyl-para-aminophenol; iminophenol derivatives, in
particular those disclosed in Application WO 99/22707;
L-2-oxothiazolidine-4-carboxylic acid or procysteine, and its salts
and esters; ascorbic acid and its derivatives, in particular
ascorbyl glucoside and magnesium ascorbyl phosphate;
4-butylresorcinol or lucinol; thiourea and its derivatives; calcium
D-pantetheinesulphonate; and plant extracts, in particular extracts
of manzanita, of liquorice, of mulberry and of skullcap, without
this list being limiting.
[0078] The composition according to the invention can be applied
to, for example, the skin, hair, including body hair, eyelashes,
nails or lips. It can thus be used in a cosmetic treatment process
for depigmenting and/or lightening the skin and/or hair, including
body hair, comprising the application of the composition according
to the invention to the skin and/or hair, including body hair
[0079] In an alternative form, the composition according to the
invention can be used for the manufacture of a dermatological
preparation comprising an aqueous phase which is intended to
depigment the skin and/or hair, including body hair.
[0080] The examples which follow serve to illustrate the invention
without, however, exhibiting a limiting nature. The compounds are,
depending on the situation, cited according to chemical names or
according to CTFA (International Cosmetic Ingredient Dictionary and
Handbook) names.
EXAMPLES
Example 1
[0081] Accelerated Storage Test.
[0082] The aim of this test is to study the decomposition of an
oxidation-sensitive hydrophilic active principle after storing for
two months at 45.degree. C. Various solutions were prepared and
their compositions are collated in the following table:
1TABLE I Compositions (in Solution A water) (Control) Solution B
Solution C Solution D Ascorbic acid 15% 15% 15% 15% Polymer 1 -- 1%
-- -- Polymer 2 -- -- 1% -- Polymer 3 -- -- -- 1%
[0083] All the solutions are brought to pH 6 with 8.9 mol/l
KOH.
[0084] The percentages of the polymers are given as active
material.
[0085] Polymer 1: Vinylpyrrolidone/vinylimidazole (50/50) copolymer
sold under the reference Luvitec VPI 55K72W of BASF (Weight-average
molecular mass 1.2.times.10.sup.6).
[0086] Polymer 2: Vinylpyrrolidone/vinylimidazole (50/50) copolymer
sold under the reference Luvitec VPI 55K18P of BASF (Weight-average
molecular mass 10 000).
[0087] Polymer 3: Polyvinylpyrrolidone sold under the reference
Kollidon 12PF of BASF (Weight-average molecular mass 3 000).
[0088] The degree of decomposition measured is given by the
ratio:
(C.sub.0-C.sub.2 months)/C.sub.0
[0089] with C.sub.0 concentration of ascorbic acid at t=0 and
C.sub.2 months the concentration of ascorbic acid at t=2 months,
under the conditions indicated in the above table.
[0090] The concentration of ascorbic acid is determined by the HPLC
technique (LaChrom Merck system). The analytical conditions are as
follows:
[0091] Column: Lichrosphere100 RP18 (250 mm)
[0092] Eluent: 0.1 M phosphate buffer, pH 2.1
[0093] Flow rate: 1 ml/min
[0094] Detection at 257 nm
[0095] Dilution of the sample such that the concentration of
ascorbic acid is between 0.05 and 1 mg/ml.
[0096] The results obtained are collated in the following Table
II:
2 TABLE II Degree of decomposition after 2 months at 45.degree. C.
(in %) under air, amber glass bottle under nitrogen, aluminium
flask Solution A 43 19.4 Solution B 10.8 1 Solution C 23.4 4.5
Solution D 35.8 15.7
[0097] It is found, from Table II, that the stability of ascorbic
acid is improved in the presence of Polymer 1 and Polymer 2 of the
invention, even in the presence of atmospheric oxygen, in
comparison with the control. It is also found that the
N-vinylpyrrolidone homopolymer alone is not sufficient to
effectively stabilize the ascorbic acid solution. As the polymers
mentioned are hydrophilic, it will be sufficient to add them to an
aqueous ascorbic acid solution to stabilize the ascorbic acid.
Example 2
[0098] Demonstration of the Activity With Regard to the Dendricity
of Melanocytes:
[0099] The aim of this test is to show the effect of the
combination of ascorbic acid with a polymer or copolymer according
to the invention on adjusting the melanogenesis of human
keratinocyte-melanocyte cocultures.
[0100] Method: The cells are treated from inoculation with the
ascorbic acid/vinylpyrrolidone-vinylimidazole copolymer
combinations for 7 days.
[0101] Observations:
[0102] The melanocytes are labelled using the NK1beteb antibody
(green colouring), which recognizes the melanosomes at every stage
of maturation. The nuclei of all the cells, melanocytes and
keratinocytes, are stained using propidium iodide (red
colouring).
[0103] Results:
[0104] In the absence of the ascorbic
acid/vinylpyrrolidone-vinylimidazole copolymer combinations, the
melanocytes in cocultures are highly dendritic. The pigment is
visibly transferred to the neighbouring keratinocytes.
[0105] In the presence of the ascorbic
acid/vinylpyrrolidone-vinylimidazol- e copolymer combinations, the
majority of the melanocytes show a reduced dendricity and some
melanocytes become bipolar.
[0106] For a higher concentration, the majority of the melanocytes
are bipolar and the amount of pigment transferred to the
keratinocytes is reduced.
Example 3
[0107] O/W Anti-Blemish Cream
[0108] The following composition is prepared in a way conventional
to a person skilled in the art.
3 A.sub.1 Sorbitan tristearate 0.7 g Polyethylene glycol (40 EO)
stearate 1.6 g Cetyl alcohol 3.2 g Glyceryl mono-, di-,
tripalmitate/stearate 2.4 g Myristyl myristate 2 g Liquid fraction
of karite butter 2 g Preservative 0.2 g A.sub.2
Cyclopentadimethylsiloxane 15 g B Demineralized water 60.53 g
Glycerol 3 g Ascorbic acid 5 g 50% Potassium hydroxide 3.07 g
Vinylpyrrolidone/vinylimidazole copolymer 1 g Preservative 0.2 g C
Fragrance 0.1 g
[0109] This cream which is soft on application makes it possible to
reduce pigmentary blemishes and confers good stability on ascorbic
acid.
Example 4
[0110] Depigmenting Gel
[0111] The following composition is prepared in a way conventional
to a person skilled in the art.
4 Demineralized water 78.58 g Polyacrylamide/C.sub.13-C.sub.14
isoparaffin/Laureth-7 2 g (Sepigel 305) Silicone oil 10 g Ascorbic
acid 5 g 50% Potassium hydroxide 3.07 g
Vinylpyrrolidone/vinylimidazole copolymer 1 g Preservative 0.25 g
Sequestering agent 0.1 g
[0112] A fresh gel is obtained, which gel makes it possible to
combat cutaneous blemishes and in which gel ascorbic acid has good
stability.
[0113] The above description of the invention, as illustrated by
Examples, allows one of ordinary skill in the art to lighten the
skin and/or hair, including body hair, using a composition
comprising, in a physiologically acceptable medium comprising an
aqueous phase, at least one oxidation-sensitive hydrophilic active
principle selected from the group consisting of, e.g., ascorbic
acid and its derivatives, and at least one non-crosslinked
N-vinylimidazole polymer or copolymer, the said active principle
and the said polymer or copolymer both being in the aqueous phase.
Also made available is the use of a combination composed of at
least one oxidation-sensitive hydrophilic active principle selected
from the group consisting of ascorbic acid and its derivatives and
of at least one non-crosslinked N-vinylimidazole polymer or
copolymer in the aqueous phase of a cosmetic composition as agent
for lightening the skin and/or hair, including body hair. In
addition, this invention makes available the use of at least one
oxidation-sensitive hydrophilic active principle selected from the
group consisting of ascorbic acid and its derivatives and of at
least one non-crosslinked N-vinylimidazole polymer or copolymer for
the preparation of a dermatological composition comprising an
aqueous phase which is intended to depigment the skin and/or hair,
including body hair. Similarly made available is the use of a
combination composed of at least one oxidation-sensitive
hydrophilic active principle selected from the group consisting of
ascorbic acid and its derivatives and of at least one
non-crosslinked N-vinylimidazole polymer or copolymer in the
aqueous phase of a cosmetic composition as agent for lightening the
skin and/or hair, including body hair, and the use of at least one
oxidation-sensitive hydrophilic active principle selected from the
group consisting of ascorbic acid and its derivatives and of at
least one non-crosslinked N-vinylimidazole polymer or copolymer for
the preparation of a dermatological composition comprising an
aqueous phase which is intended to depigment the skin and/or hair,
including body hair. A preferred embodiment of the invention fully
described and made available herein is a method for lightening the
skin and/or hair, comprising applying thereto a composition
comprising a physiologically acceptable medium comprising an
aqueous phase; at least one oxidation-sensitive hydrophilic active
principle selected from the group consisting of ascorbic acid and
its derivatives, and at least one non-crosslinked N-vinylimidazole
polymer or copolymer, the active principle and the polymer or
copolymer both being present in the aqueous phase.
[0114] French patent application 0115375 is hereby incorporated by
reference, as are all references, texts, documents, standards,
applications, patents, etc., mentioned above.
[0115] Also incorporated herein by reference are the following U.S.
applications, all filed Nov. 27, 2002, where the present
application is listed for information only:
5 U.S. Ser. No. . . . (Atty. Docket 230634US0) U.S. Ser. No. . . .
(Atty. Docket 230608US0) U.S. Ser. No. . . . (Atty. Docket
230616US0) U.S. Ser. No. . . . (Atty. Docket 230614US0) U.S. Ser.
No. . . . (Atty. Docket 230615US0)
* * * * *