U.S. patent application number 17/715355 was filed with the patent office on 2022-07-21 for photoprotective compositions comprising a dibenzoylmethane derivative, a merocyanine compound and a compound capable of accepting the triplet excited level energy of the dibenzoylmethane compound.
This patent application is currently assigned to L'Oreal. The applicant listed for this patent is L'Oreal. Invention is credited to Alexandra Batista, Didier Candau, Julie Grumelard, Angelina Roudot, Mahassine Safouane.
Application Number | 20220226215 17/715355 |
Document ID | / |
Family ID | |
Filed Date | 2022-07-21 |
United States Patent
Application |
20220226215 |
Kind Code |
A1 |
Batista; Alexandra ; et
al. |
July 21, 2022 |
PHOTOPROTECTIVE COMPOSITIONS COMPRISING A DIBENZOYLMETHANE
DERIVATIVE, A MEROCYANINE COMPOUND AND A COMPOUND CAPABLE OF
ACCEPTING THE TRIPLET EXCITED LEVEL ENERGY OF THE DIBENZOYLMETHANE
COMPOUND
Abstract
Photoprotective compositions comprising a dibenzoylmethane
derivative, a merocyanine compound and a compound capable of
accepting the triplet excited level energy of the dibenzoylmethane
compound The present invention relates to a photoprotective
composition for topical use comprising, in a cosmetically
acceptable medium, at least one dibenzoylmethane derivative
compound, at least one merocyanine compound and at least one
compound capable of accepting the triplet excited level energy of
said dibenzoylmethane derivative compound(s). The invention also
relates to the use of at least one compound capable of accepting
the triplet excited level energy of said dibenzoylmethane
derivative compound(s), for photostabilizing with respect to UV
radiation a composition comprising at least one dibenzoylmethane
derivative compound and at least one merocyanine compound.
Inventors: |
Batista; Alexandra;
(CHEVILLY-LARUE, FR) ; Candau; Didier;
(CHEVILLY-LARUE, FR) ; Roudot; Angelina;
(CHEVILLY-LARUE, FR) ; Safouane; Mahassine;
(CHEVILLY-LARUE, FR) ; Grumelard; Julie;
(VILLAGE-NEUF, FR) |
|
Applicant: |
Name |
City |
State |
Country |
Type |
L'Oreal |
Paris |
|
FR |
|
|
Assignee: |
L'Oreal
Paris
FR
|
Appl. No.: |
17/715355 |
Filed: |
April 7, 2022 |
Related U.S. Patent Documents
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Application
Number |
Filing Date |
Patent Number |
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16627177 |
Dec 27, 2019 |
11344487 |
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PCT/EP2018/067472 |
Jun 28, 2018 |
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17715355 |
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International
Class: |
A61K 8/35 20060101
A61K008/35; A61K 8/06 20060101 A61K008/06; A61K 8/44 20060101
A61K008/44; A61K 8/49 20060101 A61K008/49; A61Q 17/04 20060101
A61Q017/04 |
Foreign Application Data
Date |
Code |
Application Number |
Jun 29, 2017 |
FR |
1756014 |
Claims
1. Photoprotective composition for topical use, characterized in
that it comprises, in a cosmetically acceptable medium: (i) one or
more dibenzoylmethane derivative compounds chosen from those of
formula (I) below, and/or mixtures thereof: ##STR00029## in which
formula (I): R.sub.1, R.sub.4, R.sub.5 and R.sub.6 represent,
independently of one another, a hydrogen atom, a hydroxyl radical,
a linear or branched C.sub.1-C.sub.4 alkyl radical or a linear or
branched C.sub.1-C.sub.4 alkoxy radical, and R.sub.2 and R.sub.3
represent, independently of one another, a hydrogen atom, a
hydroxyl radical, a linear or branched C.sub.1-C.sub.4 alkyl
radical or a linear or branched C.sub.1-C.sub.4 alkoxy radical, or
form, with the 2 carbon atoms of the covalent bonds C--R.sub.2 and
C--R.sub.3, a 5- or 6-membered heterocycle optionally substituted
with a linear or branched C.sub.1-C.sub.4 hydrocarbon-based chain;
(ii) one or more merocyanine compounds chosen from those of formula
(II) below, the tautomeric forms thereof, the geometric isomers E/E
or E/Z thereof; and/or mixtures thereof: ##STR00030## in which
formula (II), R represents a linear or branched C.sub.1-C.sub.22
alkyl, C.sub.2-C.sub.22 alkenyl or C.sub.2-C.sub.22 alkynyl
radical, a C.sub.3-C.sub.22 cycloalkyl radical or a
C.sub.3-C.sub.22 cycloalkenyl radical, said radicals possibly being
interrupted with one or more oxygen atoms; and (iii) one or more
compounds capable of accepting the triplet excited level energy of
said dibenzoylmethane derivative compound(s) (i).
2. Composition according to claim 1, characterized in that the
dibenzoylmethane derivative compound(s) are chosen, alone or as a
mixture, from 2-methyldibenzoylmethane, 4-methyldibenzoylmethane,
4-isopropyldibenzoylmethane, 4-tert-butyldibenzoylmethane,
2,4-dimethyldibenzoylmethane, 2,5-dimethyldibenzoylmethane,
4,4'-diisopropyldibenzoylmethane, 4,4'-dimethoxydibenzoylmethane,
4-tert-butyl-4'-methoxydibenzoylmethane,
2-methyl-5-isopropyl-4'-methoxydibenzoylmethane,
2-methyl-5-tert-butyl-4'-methoxydibenzoylmethane,
2,4-dimethyl-4'-methoxydibenzoylmethane,
2,6-dimethyl-4-tert-butyl-4'-methoxydibenzoylmethane,
1-(4-tert-butylphenyl)-3-(2-hydroxyphenyl)propane-1,3-dione,
1-(4-methoxy-1-benzofuran-5-yl)-3-phenylpropane-1,3-dione;
preferably chosen, alone or as a mixture, from
4-tert-butyl-4'-methoxydibenzoylmethane and/or
4-isopropyldibenzoylmethane; preferentially chosen from
4-tert-butyl-4'-methoxydibenzoylmethane.
3. Composition according to claim 1, characterized in that the
total content of the dibenzoylmethane derivative compound(s) (i) is
between 0.1% and 15% by weight, preferably between 0.2% and 10% by
weight, more preferentially between 0.3% and 5% by weight, relative
to the total weight of the composition.
4. Composition according to claim 1, characterized in that it
comprises at least one merocyanine compound (ii) of formula (II) in
which R represents a linear or branched C.sub.1-C.sub.22 alkyl
radical which may be interrupted with one or more oxygen atoms.
5. Composition according to claim 1, characterized in that it
comprises at least one merocyanine compound (ii) chosen from the
compounds (1') to (6') below, and also the tautomeric forms
thereof, the geometric isomers E/E or E/Z thereof; and/or mixtures
thereof: ##STR00031## ##STR00032##
6. Composition according to claim 5, characterized in that it
comprises at least one merocyanine compound (ii) chosen from
2-ethoxyethyl
2-cyano{3-[(3-methoxypropyl)amino]cyclohex-2-en-1-ylidene}ethanoate
(2') in its geometric configuration E/Z having the structure below:
##STR00033## and/or in its geometric configuration E/E having the
structure below: ##STR00034## and also the tantomeric forms
thereof; and mixtures thereof.
7. Composition according to claim 1, characterized in that the
total content of the merocyanine compound(s) (ii) is between 0.1%
and 10% by weight, preferably between 0.2% and 10% by weight, more
preferentially between 0.3% and 5% by weight, relative to the total
weight of the composition.
8. Composition according to claim 1, characterized in that the
compound(s) (iii) capable of accepting the triplet excited level
energy of said dibenzoylmethane derivative compound(s) have a
triplet excited level energy ranging from 40 kcal/mol to 70
kcal/mol.
9. Composition according to claim 1, characterized in that the
compound(s) (iii) capable of accepting the triplet excited level
energy of said dibenzoylmethane derivative compound(s) are chosen,
alone or as a mixture, from: (A) the compounds of formula (III)
and/or (IIIbis) below, and also the tautomeric forms thereof, the
optical isomers thereof, the geometric isomers thereof; and/or
mixtures thereof, ##STR00035## in which: A represents a chromophore
group which absorbs UV radiation, comprising two monovalent groups
having a carbonyl function; R.sub.14 represents a hydrogen atom, a
linear or branched C.sub.1-C.sub.8 alkyl radical, or a linear or
branched C.sub.1-C.sub.8 alkoxy radical; and R.sub.15 denotes a
linear or branched C.sub.1-C.sub.8 alkyl radical; (B) piperidinol
salts of formula (V) below, and also the optical isomers thereof,
the geometric isomers thereof, and/or mixtures thereof,
##STR00036## in whichw: R and R.sup.1, which may be identical or
different, denote a hydrogen atom or a methyl group, y is 1, 2 or
4; z is 1, 2, 3 or 4; x is 1 or 2; 1) when x is equal to 1: R.sup.2
denotes a hydrogen atom; a C.sub.1-C.sub.18 alkyl radical; a
C.sub.2-C.sub.18 alkenyl radical; a propargyl radical; a glycidyl
group; a C.sub.2-C.sub.50 alkyl radical interrupted with 1 to 20
oxygen atoms and substituted with 1 to 10 hydroxyl groups; a
C.sub.1-C.sub.4 alkyl radical substituted with a carboxy group or a
group --COOZ where Z represents a hydrogen atom, a C.sub.1-C.sub.4
alkyl, a phenyl, a C.sub.1-C.sub.4 alkyl substituted with a group
(COO.sup.-).sub.p M.sup.p+ where p is an integer from 1 to 3 and M
is a metal ion of groups 1, 2 and 3 of the periodic table, or Zn,
Cu, Ni or Co or else M is a group N.sup.p+(R'').sub.4 where R'' is
a C.sub.1-C.sub.8 alkyl or a benzyl; 2) when X is 2: R.sup.2 is a
C.sub.1-C.sub.12 alkylene radical; a C.sub.4-C.sub.12 alkenylene
radical; a xylylene group; a C.sub.1-C.sub.50 alkylene radical
interrupted with 1 to 20 oxygen atoms and substituted with 1 to 10
hydroxyl groups; Y denotes an organic or inorganic anion; the total
charge of cations y being equal to the total charge of anions z;
(D) the compounds of formula (X) below, and also the optical
isomers thereof, the geometric isomers thereof, and/or mixtures
thereof, ##STR00037## in which: R.sub.1 represents a hydrogen atom
or a linear or branched C.sub.1-C.sub.8 alkyl radical, R.sub.2
represents a linear or branched C.sub.1-C.sub.20, preferably
C.sub.1-C.sub.8, alkyl radical.
10. Composition according to claim 1, characterized in that the
compound(s) (iii) capable of accepting the triplet excited level
energy of said dibenzoylmethane derivative compound(s) are chosen,
alone or as a mixture, from the diethylhexyl syringylidenemalonate
of formula (IV) below and also the tautomeric forms thereof, the
optical isomers thereof, and/or mixtures thereof, the
bisethylhexylhydroxydimethoxy benzylmalonate of formula (IVbis)
below and also the tautomeric forms thereof, the optical isomers
thereof, and/or mixtures thereof; the
tris(tetramethylhydroxypiperidinol) citrate of formula (VI) below
and also the optical isomers thereof, and/or mixtures thereof;
diethylhexyl 2,6-naphthalate and also the optical isomers thereof,
and the ethylhexyl methoxycrylene of formula (Xbis) below and also
the tautomeric forms thereof, the optical ##STR00038##
11. Composition according to claim 1, characterized in that the
total content of the compound(s) (iii) capable of accepting the
triplet excited level energy of said dibenzoylmethane derivative
compound(s) is between 0.001% and 15% by weight, preferably between
0.003% and 10% by weight, and more preferentially between 0.005%
and 5% by weight, relative to the total weight of the
composition.
12. Composition according to claim 1, characterized in that the
ratio of the weight content of the compound(s) (iii) capable of
accepting the triplet excited level energy of said dibenzoylmethane
derivative compound(s) to the sum of the weight contents of the
dibenzoylmethane derivative compound(s) (i) and of the merocyanine
compound(s) (ii), is between 0.01 and 20, preferably between 0.1
and 15, and more preferentially between 0.5 and 10.
13. Composition according to claim 1, characterized in that it also
comprises one or more additional UV-screening agents chosen from
hydrophilic, lipophilic or insoluble organic UV-screening agents
and/or one or more mineral pigments; preferably chosen, alone or as
a mixture, from anthranilates; salicylic derivatives;
benzylidenecamphor derivatives; benzophenone derivatives;
.beta.,.beta.-diphenylacrylate compounds different from ethylhexyl
methoxycrylene derivatives; triazine derivatives such as
derivatives of bisresorcinyl triazine type; benzotriazole
derivatives; benzalmalonate derivatives; benzimidazole derivatives;
imidazolines; bisbenzoazolyl derivatives; p-aminobenzoic acid
(PABA) derivatives; methylenebis(hydroxyphenyl benzotriazole)
derivatives; benzoxazole derivatives; screening polymers and
screening silicones; .alpha.-alkylstyrene-based dimers;
4,4-diarylbutadienes; and/or treated or untreated metal oxide
pigments or nanopigments, such as titanium oxides, zinc oxides,
iron oxides, zirconium oxides, cerium oxides and mixtures thereof,
preferably chosen, alone or as a mixture, from titanium oxides.
14. Composition according to claim 13, in which the additional
UV-screening agents are chosen, alone or as a mixture, from the
following UV-screening agents: ethylhexyl salicylate, octocrylene,
phenylbenzimidazole sulfonic acid, benzophenone-3, benzophenone-4,
benzophenone-5, n-hexyl
2-(4-diethylamino-2-hydroxybenzoyl)benzoate,
4-methylbenzylidenecamphor, terephthalylidenedicamphorsulfonic
acid, disodium phenyldibenzimidazole tetrasulfonate,
methylenebisbenzotriazolyl tetramethylbutylphenol, ethylhexyl
triazone, diethylhexyl butamido triazone, drometrizole trisiloxane,
polysilicone-15,
1,1-dicarboxy(2,2'-dimethylpropyl)-4,4-diphenylbutadiene,
2,4-bis[5-1-(dimethylpropyl)benzoxazol-2-yl(4-phenyl)imino]-6-(2-ethylhex-
yl)imino-1,3,5-triazine, and mixtures thereof.
15. Composition according to claim 1, characterized in that it
comprises at least one oil, preferably chosen from
hydrocarbon-based oils, silicone oils, fluoro oils, and/or mixtures
thereof.
16. Composition according to claim 1, characterized in that it is
in the form of an oil-in-water or water-in-oil emulsion.
17. Cosmetic method for treating the skin, in particular human
skin, against UV radiation, comprising at least one step of
applying to the skin a composition as defined in claim 1.
18. Use of at least one compound capable of accepting the triplet
excited level energy of said dibenzoylmethane derivative
compound(s) as defined in claim 1, for photostabilizing, with
respect to UV radiation, a composition comprising at least one
dibenzoylmethane derivative compound (i), and at least one
merocyanine compound (ii).
Description
[0001] This application is a continuation of U.S. Ser. No.
16/627,177 filed Dec. 27, 2019, which claims the benefit of
International Patent Application No. PCT/EP2018/067472 filed Jun.
28, 2018 and French Patent Application No. 1756014 filed Jun. 29,
2017, the contents of which are incorporated herein by reference in
their entirety.
[0002] The present invention relates to a photoprotective
composition for topical use comprising, in a cosmetically
acceptable medium, at least one dibenzoylmethane derivative
compound, at least one merocyanine compound and at least one
compound capable of accepting the triplet excited level energy of
said dibenzoylmethane derivative compound(s).
[0003] The invention also relates to the use of at least one
compound capable of accepting the triplet excited level energy of
said dibenzoylmethane derivative compound(s), for photostabilizing
with respect to UV radiation a composition comprising at least one
dibenzoylmethane derivative compound and at least one merocyanine
compound.
[0004] It is known that light radiation with wavelengths of between
280 nm and 400 nm makes possible browning of the human epidermis
and that rays with wavelengths more particularly of between 280 and
320 nm, known under the name of UV-B, cause erythemas and skin
burns which may be harmful to the development of natural
tanning.
[0005] For these reasons, as well as for aesthetic reasons, there
is a constant demand for means for controlling this natural tanning
in order thus to control the colour of the skin; this UV-B
radiation should thus be screened out.
[0006] It is also known that UV-A rays, with wavelengths between
320 and 400 nm, which cause tanning of the skin, are liable to
induce adverse changes therein, in particular in the case of
sensitive skin or skin that is continually exposed to solar
radiation. UV-A rays cause in particular a loss in the elasticity
of the skin and the appearance of wrinkles, resulting in premature
skin ageing. Thus, for aesthetic and cosmetic reasons, such as the
preservation of the natural elasticity of the skin, for example,
more and more people wish to control the effect of UV-A rays on
their skin. It is therefore desirable also to screen out UV-A
radiation.
[0007] With the aim of providing protection of the skin and keratin
materials against UV radiation, use is generally made of antisun
compositions comprising organic screening agents which are active
in the UV-A region and which are active in the UV-B region. The
majority of these screening agents are fat-soluble.
[0008] In this respect, a particularly efficient family of UV-A
screening agents is constituted of dibenzoylmethane derivatives and
in particular 4-tert-butyl-4'-methoxydibenzoylmethane, this being
because these exhibit a high intrinsic absorption power. These
dibenzoylmethane derivatives, which are products that are now well
known per se as screening agents that are active in the UV-A range,
are described in particular in French patent applications FR-A-2
326 405 and FR-A-2 440 933, and also in European patent application
EP-A-0 114 607; 4-tert-butyl-4'-methoxydibenzoylmethane is moreover
currently sold under the trade name Parsol 1789.RTM. by the company
DSM Nutritional Products.
[0009] Another family, which is also particularly advantageous, is
constituted of lipophilic merocyanine derivatives. These
derivatives are known to screen out long-wave UV-A radiation with
wavelengths above 370 nm, and are particularly described in patent
U.S. Pat. No. 4,195,999, application WO 2004/006878, document IP
COM Journal 4 (4), 16 N.sup.o IPCOM000011179D published on Apr. 3,
2004.
[0010] However, the applicant has been able to note that
combinations of merocyanine derivatives with dibenzoylmethane
derivatives have the drawback of being particularly photo-unstable
with regard to ultraviolet radiation (especially UV-A radiation).
These particular combinations of UV-screening agents degrade more
or less rapidly under the action of UV radiation; this degradation
being particularly significant for merocyanine derivatives. Thus,
this substantial lack of photochemical stability of the combination
of merocyanine derivatives with dibenzoylmethane derivatives in the
face of the ultraviolet radiation to which this combination is by
nature intended to be subjected does not make it possible to
guarantee continuous protection during prolonged exposure to the
sun, so that repeated applications at regular and close intervals
of time have to be carried out by the user in order to obtain
effective and long-lasting protection of the skin against UV
rays.
[0011] There is therefore a real need to photostabilize the
combination of merocyanine derivatives with dibenzoylmethane
derivatives with respect to UV radiation, in order to guarantee
constant protection during prolonged exposure to the sun with
respect to UV-A radiation.
[0012] However, not all stabilizers of dibenzoylmethane derivatives
such as 4-tert-butyl-4'-methoxydibenzoylmethane make it possible to
stabilize combinations thereof with merocyanine compounds.
[0013] As it happens, the applicant has just recently discovered,
surprisingly, that the use of at least one particular compound
capable of accepting the triplet excited level energy of said
dibenzoylmethane derivative compound(s) makes it possible to
substantially improve the photochemical stability (or
photostability) of combinations of merocyanine compounds and
dibenzoylmethane derivatives, and thus to improve the
photoprotective performance levels of compositions containing these
two types of sunscreens.
[0014] A subject of the present invention is therefore a
photoprotective composition for topical use, characterized in that
it comprises, in a cosmetically acceptable medium: [0015] (i) one
or more dibenzoylmethane derivative compounds chosen from those of
formula (I) below, and/or mixtures thereof:
##STR00001##
[0015] in which formula (I): [0016] R.sub.1, R.sub.4, R.sub.5 and
R.sub.6 represent, independently of one another, a hydrogen atom, a
hydroxyl radical, a linear or branched C.sub.1-C.sub.4 alkyl
radical or a linear or branched C.sub.1-C.sub.4 alkoxy radical, and
[0017] R.sub.2 and R.sub.3 represent, independently of one another,
a hydrogen atom, a hydroxyl radical, a linear or branched
C.sub.1-C.sub.4 alkyl radical or a linear or branched
C.sub.1-C.sub.4 alkoxy radical, or form, with the 2 carbon atoms of
the covalent bonds C--R.sub.2 and C--R.sub.3, a 5- or 6-membered
heterocycle optionally substituted with a linear or branched
C.sub.1-C.sub.4 hydrocarbon-based chain; [0018] (ii) one or more
merocyanine compounds chosen from those of formula (II) below, the
tautomeric forms thereof, the geometric isomers E/E or E/Z thereof;
and/or mixture thereof.
##STR00002##
[0018] in which formula (II), R represents a linear or branched
C.sub.1-C.sub.22 alkyl, C.sub.2-C.sub.22 alkenyl or
C.sub.2-C.sub.22 alkynyl radical, a C.sub.3-C.sub.22 cycloalkyl
radical or a C.sub.3-C.sub.22 cycloalkenyl radical, said radicals
possibly being interrupted with one or more oxygen atoms; and
[0019] (iii) one or more compounds capable of accepting triplet
excited level energy of said dibenzoylmethane derivative
compound(s) (i).
[0020] These compositions make it possible to screen out solar
radiation efficiently, they are broad-spectrum, in particular for
UV-A radiation (including long-wave UV-A radiation), while the same
time being particularly stable over time under UV exposure.
[0021] These compositions may also in certain cases exhibit an
improved sun protection factor or "SPF".
[0022] Other subjects, characteristics, aspects and advantages of
the invention will emerge even more clearly on reading the
description and the examples that follow.
[0023] In the text hereinbelow, and unless otherwise indicated, the
limits of a range of values are included in that range, in
particular in the expressions "between . . . and . . . " and
"ranging from . . . to . . . ".
[0024] Moreover, the expressions "one or more" and "greater than or
equal to" used in the present description are equivalent to the
expressions "at least one" and "at least", respectively.
[0025] The term "cosmetically acceptable medium" is intended to
mean compatible with the skin and/or its integuments, having a
pleasant colour, odour and feel and not causing any unacceptable
discomfort (stinging, tautness or redness) liable to discourage the
consumer from using this composition.
[0026] The expressions "optionally substituted" and "substituted or
unsubstituted" are intended to mean that the radical or group may
be optionally substituted with one or more hydroxyls; amino groups
--NR.sub.1R.sub.2, such that R.sub.1 and R.sub.2 represent,
independently of one another, hydrogen atoms or C.sub.1-C.sub.3
alkyl radicals; carboxylic --COOH, carbonyl or C.sub.1-C.sub.4
alkyl groups.
[0027] The Dibenzoylmethane Derivative Compounds
[0028] The composition according to the present invention comprises
one or more dibenzoylmethane derivatives chosen from those of
formula (I) below and/or mixtures thereof:
##STR00003##
in which formula (I): [0029] R.sub.1, R.sub.4, R.sub.5 and R.sub.6
represent, independently of one another, a hydrogen atom, a
hydroxyl radical, a linear or branched C.sub.1-C.sub.4 alkyl
radical or a linear or branched C.sub.1-C.sub.4 alkoxy radical, and
[0030] R.sub.2 and R.sub.3 represent, independently of one another,
a hydrogen atom, a hydroxyl radical, a linear or branched
C.sub.1-C.sub.4 alkyl radical or a linear or branched
C.sub.1-C.sub.4 alkoxy radical, or form, with the 2 carbon atoms of
the covalent bonds C--R.sub.2 and C--R.sub.3, a 5- or 6-membered
heterocycle optionally substituted with a linear or branched
C.sub.1-C.sub.4 hydrocarbon-based chain.
[0031] When R.sub.2 and R.sub.3 form a heterocycle with the 2
carbon atoms of the covalent bonds C--R.sub.2 and C--R.sub.3, they
preferably form a 5-membered aromatic heterocycle, more
preferentially a furan ring.
[0032] Preferably, R.sub.2 and R.sub.3 represent, independently of
one another, a hydrogen atom, a hydroxyl radical, a linear or
branched C.sub.1-C.sub.4 alkyl radical or a linear or branched
C.sub.1-C.sub.4 alkoxy radical.
[0033] According to one preferred embodiment of the invention, the
dibenzoylmethane derivative compound(s) included in the composition
according to the invention are chosen, alone or as a mixture, from
2-methyldibenzoylmethane, 4-methyldibenzoylmethane,
4-isopropyldibenzoylmethane, 4-tert-butyldibenzoylmethane,
2,4-dimethyldibenzoylmethane, 2,5-dimethyldibenzoylmethane,
4,4'-diisopropyldibenzoylmethane, 4,4'-dimethoxydibenzoylmethane,
4-tert-butyl-4'-methoxydibenzoylmethane,
2-methyl-5-isopropyl-4'-methoxydibenzoylmethane,
2-methyl-5-tert-butyl-4'-methoxydibenzoylmethane,
2,4-dimethyl-4'-methoxydibenzoylmethane,
2,6-dimethyl-4-tert-butyl-4'-methoxydibenzoylmethane,
1-(4-tert-butylphenyl)-3-(2-hydroxyphenyl)propane-1,3-dione,
1-(4-methoxy-1-benzofuran-5-yl)-3-phenylpropane-1,3-dione;
preferably chosen, alone or as a mixture, from
4-tert-butyl-4'-methoxydibenzoylmethane and/or
4-isopropyldibenzoylmethane; preferentially chosen from
4-tert-butyl-4'-methoxydibenzoylmethane.
[0034] By way of example, 4-isopropyldibenzoylmethane is sold under
the name Eusolex 8020 by the company Merck, and
4-tert-butyl-4'-methoxydibenzoylmethane or
butylmethoxydibenzoylmethane is sold under the name Parsol 1789 by
the company Roche Vitamins.
[0035] By way of example, likewise,
1-(4-methoxy-1-benzofuran-5-yl)-3-phenylpropane-1,3-dione is sold
under the name Pongamol by the company Quest, of formula:
##STR00004##
[0036] Preferably, the total content of the dibenzoylmethane
derivative compound(s) (I) present in the composition is between
0.1% and 15% by weight, preferably between 0.2% and 10% by weight,
more preferentially between 0.3% and 5% by weight, relative to the
total weight of the composition.
[0037] The Merocyanine Compounds
[0038] The composition according to the present invention comprises
one or more merocyanine compounds chosen from those of formula (II)
below, the tautomeric forms thereof, the geometric isomers E/E or
E/Z thereof; and/or mixtures thereof:
##STR00005##
in which formula (II), R represents a linear or branched
C.sub.1-C.sub.22 alkyl, C.sub.2-C.sub.22 alkenyl or
C.sub.2-C.sub.22 alkynyl radical, a C.sub.3-C.sub.22 cycloalkyl
radical or a C.sub.3-C.sub.22 cycloalkenyl radical, said radicals
possibly being interrupted with one or more oxygen atoms.
[0039] As indicated above, the merocyanine compounds of the
invention may be present in their geometric isomer forms E/E, E/Z,
and/or mixtures of these two types of forms:
##STR00006##
[0040] Preferably, the merocyanine compounds of formula (II) have a
radical R denoting a linear or branched C.sub.1-C.sub.22 alkyl
radical which may be interrupted with one or more oxygen atoms.
[0041] According to one preferred embodiment of the invention, the
merocyanine compound(s) are chosen from the following compounds
(1') to (6'), and also the tautomeric forms thereof, the geometric
isomers E/E or E/Z thereof, and/or mixtures thereof:
##STR00007##
[0042] According to a more particularly preferred embodiment of the
invention, at least one merocyanine compound is chosen from
2-ethoxyethyl
2-cyano{3-[(3-methoxypropyl)amino]cyclohex-2-en-1-ylidene}ethanoate
(2') (INCI name: methoxypropylamino cyclohexenylidene
ethoxyethylcyanoacetate) in its geometric configuration E/Z having
the structure below:
##STR00008##
and/or in its geometric configuration E/E having the structure
below:
##STR00009##
and also the tautomeric forms thereof, and mixtures thereof.
[0043] The composition according to the invention preferably
comprises said merocyanine compound(s) (ii) in a content of between
0.10% and 10% by weight, preferably between 0.2% and 10% by weight
and even more preferentially between 0.3% and 5% by weight,
relative to the total weight of the composition.
[0044] The compounds of formula (II) may be prepared according to
the protocols described in patent application WO 2007/071582, in
IP.com Journal (2009), 9(5A), 29-30 IPCOM000182396D under the title
"Process for producing 3-amino-2-cyclohexan-1-ylidene compounds"
and in U.S. Pat. No. 4,749,643 in col, 13, line 66-col. 14, line 57
and the references cited in this regard.
[0045] The compounds capable of accepting the triplet excited level
energy of said dibenzoylmethane derivative compound(s)
[0046] The composition according to the present invention comprises
one or more compounds capable of accepting the triplet excited
level energy of said dibenzoylmethane derivative compound(s) in
such a way as to deactivate the excited states of the
dibenzoylmethane molecule excited under the influence of UV
radiation and to allow that molecule to return to its fundamental
state.
[0047] The compounds capable of accepting the triplet excited level
energy of said dibenzoylmethane derivative compound(s) may be
chosen from: [0048] (a) 4-hydroxybenzylidene malonate derivatives
or 4-hydroxycinnamate derivatives such as those described in patent
application WO 03/007906, and/or 4-hydroxybenzyl malonate
derivatives; [0049] (b) piperidinol salts such as those described
in patent application WO 03/103622; [0050] (c) naphthalene
derivatives such as those described in patents U.S. Pat. Nos.
5,993,789, 6,113,931, 6,126,925 and 6,284,916; [0051] (d)
ethylhexyl methoxycrylene derivatives; and/or [0052] (e) mixtures
thereof.
[0053] According to one preferred embodiment of the invention, the
compounds capable of accepting the triplet excited level energy of
said dibenzoylmethane derivative compound(s) have a triplet excited
level energy ranging from 40 kcal/mol to 70 kcal/mol.
[0054] The triplet excited level energies can be determined using
the techniques of oxygen perturbation or phosphorescence, as
described in the article by J. Gonzenbach, T. J. Hill, T. G
Truscott The Triplet Energy Levels in UVA and UVB Sunscreens, J.
Photochem. Photobiol. B: Biol, vol 16, pages 337-379 (1992). The
technique of oxygen perturbation consists in measuring the UV
absorption spectrum of a compound when the latter is placed in an
environment under a high oxygen pressure: i.e. 2000 psi. Under
these conditions, the spin selection rules are perturbed and the
exposure of the compound to the UV leads to the lowest triplet
excited level by direct excitation of the ground state. The
wavelength .lamda. (in .mu.m) at which the transition takes place
is used to calculate the energy of the triplet level in kcal/mol
via the formula E=28.635/k which is derived from the equation E=hv
where E is the energy, h is Planck's constant and v is the
frequency of the electromagnetic wave.
[0055] The phosphorescence technique is based on the fact that many
compounds emit phosphorescence during the deactivation of their
triplet excited level. By measuring the wavelength at which the
phosphorescence intervenes, the triplet excited level energies can
be calculated as previously. The triplet excited level energies can
be determined by measuring the phosphorescence spectra of samples
with a spectrophotometer equipped with a phosphorescence accessory.
Such triplet excited levels have been widely reported for example
in the article by A. J. Gordon, R. A. Ford, The Chemist Companion,
John Wiley & Sons, pages 351-355 (1992).
[0056] Among the 4-hydroxybenzylidene malonate derivatives or the
4-hydroxycinnamate derivatives, use will preferentially be made of
those of formula below (III) below, and also the tautomeric forms
thereof, the optical isomers thereof, the geometric isomers
thereof; and/or mixtures thereof:
##STR00010##
in which: [0057] A is a chromophore group which absorbs UV
radiation, comprising two monovalent groups having a carbonyl
function; [0058] R.sub.14 represents a hydrogen atom; a linear or
branched C.sub.1-C.sub.8 alkyl radical; a linear or branched
C.sub.1-C.sub.8 alkoxy radical; [0059] R.sub.15 denotes a linear or
branched C.sub.1-C.sub.8 alkyl radical.
[0060] Among these compounds, use will more preferentially be made
of those of formula (IIIa) below, and also the tautomeric forms
thereof, the optical isomers thereof, the geometric isomers
thereof; and/or mixtures thereof:
##STR00011##
in which [0061] R.sub.14 represents a hydrogen atom, a linear or
branched C.sub.1-C.sub.8 alkyl radical, or a linear or branched
C.sub.1-C.sub.8 alkoxy radical; [0062] R.sub.15 represents a
hydrogen atom or a linear or branched C.sub.1-C.sub.8 alkyl
radical; R.sub.16 is chosen from --C(O)CH.sub.3,
--CO.sub.2R.sub.18, --C(O)NH.sub.2 and --C(O)N(R.sub.19).sub.2;
[0063] X denotes O or NH; [0064] R.sub.17 represents a linear or
branched C.sub.1-C.sub.30 alkyl radical; [0065] R.sub.18 represents
a linear or branched C.sub.1-C.sub.20 alkyl radical; [0066] each
R.sub.19 represents, independently of one another, a linear or
branched C.sub.1-C.sub.8 alkyl radical.
[0067] Among these compounds, use will more preferentially be made
of those of formula (IIIb) or (IIIc) below, and also the tautomeric
forms thereof, the optical isomers thereof, the geometric isomers
thereof; and/or mixtures thereof:
##STR00012##
in which: [0068] R.sub.16 denotes --CO.sub.2R.sub.18; [0069]
R.sub.17 denotes a linear or branched C.sub.1-C.sub.8 alkyl; [0070]
R.sub.18 denotes a linear or branched C.sub.1-C.sub.8 alkyl; [0071]
X denotes O.
[0072] The diethylhexyl syringylidenemalonate compound (INCI name:
diethylhexyl syringylidenemalonate) of formula (IV) below will in
particular be used:
##STR00013##
such as the commercial product sold under the trade name Oxynex ST
by the company Merck, and also tautomeric forms thereof, the
optical isomers thereof, and/or mixtures thereof.
[0073] Among the 4-hydroxybenzyl malonate derivatives, use will
preferentially be made of those of formula (IIIbis) below, and also
the tautomeric forms thereof, the optical isomers thereof, the
geometric isomers thereof; and/or mixtures thereof:
##STR00014##
in which: [0074] A is a chromophore group which absorbs UV
radiation, comprising two monovalent groups having a carbonyl
function; [0075] R.sub.14 represents a hydrogen atom; a linear or
branched C.sub.1-C.sub.8 alkyl radical; a linear or branched
C.sub.1-C.sub.8 alkoxy radical; [0076] R.sub.15 denotes a linear or
branched C.sub.1-C.sub.8 alkyl radical.
[0077] Among these compounds, use will more preferentially be made
of those of formula (IIIbis a) below, and also the tautomeric forms
thereof, the optical isomers thereof, the geometric isomers
thereof, and/or mixtures thereof:
##STR00015##
in which [0078] R.sub.14 represents a hydrogen atom, a linear or
branched C.sub.1-C.sub.8 alkyl radical, or a linear or branched
C.sub.1-C.sub.8 alkoxy radical; [0079] R.sub.15 denotes a hydrogen
atom or a linear or branched C.sub.1-C.sub.8 alkyl radical; [0080]
R.sub.16 is chosen from --C(O)CH.sub.3, --CO.sub.2R.sub.18,
--C(O)NH.sub.2 and --C(O)N(R.sub.19).sub.2; [0081] X denotes 0 or
NH; [0082] R.sub.17 represents a linear or branched
C.sub.1-C.sub.30 alkyl radical; [0083] R.sub.18 represents a linear
or branched C.sub.1-C.sub.20 alkyl radical; [0084] each R.sub.19
represents, independently of one another, a linear or branched
C.sub.1-C.sub.8 alkyl radical.
[0085] Among these compounds, use will more preferentially be made
of those of formula (IIIbis b) or (IIIbis c) below, and also the
tautomeric forms thereof, the optical isomers thereof, the
geometric isomers thereof; and/or mixtures thereof:
##STR00016##
in which: [0086] R.sub.16 denotes --CO.sub.2R.sub.18; [0087]
R.sub.17 denotes a linear or branched C.sub.1-C.sub.8 alkyl; [0088]
R.sub.18 denotes a linear or branched C.sub.1-C.sub.8 alkyl; [0089]
X denotes O.
[0090] Use will in particular be made of the compound
bis(2-ethylhexyl)
2-[(4-hydroxy-3,5-dimethoxyphenyl)methyl]propanedioate (INCI name:
Bis-ethylhexyl hydroxydimethoxy benzylmalonate) of formula (IVbis)
below:
##STR00017##
such as the commercial product sold under the trade name Ronacare
AP by the company Merck, and also tautomeric forms thereof, the
optical isomers thereof, and/or mixtures thereof.
[0091] Among the piperidinol salts in accordance with the
invention, use will preferably be made of those of formula (V)
below, and also the optical isomers thereof, the geometric isomers
thereof; and/or mixtures thereof:
##STR00018##
in which: [0092] R and R.sup.1, which may be identical or
different, denote a hydrogen atom or a methyl group; [0093] y is 1,
2, 3 or 4; [0094] z is 1, 2, 3 or 4; [0095] x is 1 or 2; [0096] 1)
when x is equal to 1: [0097] R.sup.2 denotes a hydrogen atom; a
C.sub.1-C.sub.18 alkyl radical; a C.sub.2-C.sub.18 alkenyl radical;
a propargyl radical; a glycidyl group; a C.sub.2-C.sub.50 alkyl
radical interrupted with 1 to 20 oxygen atoms and substituted with
1 to 10 hydroxyl groups; a C.sub.1-C.sub.4 alkyl radical
substituted with a carboxy group or a group --COOZ where Z
represents a hydrogen atom, a C.sub.1-C.sub.4 alkyl, a phenyl, a
C.sub.1-C.sub.4 alkyl substituted with a group (COO.sup.-).sub.p
M.sup.p+ where p is an integer from 1 to 3 and M is a metal ion of
groups 1, 2 and 3 of the periodic table, or Zn, Cu, Ni or Co or
else M is a group N.sup.p+ (R'').sub.4 where R'' is a
C.sub.1-C.sub.8 alkyl or a benzyl; [0098] 2) when X is 2: [0099]
R.sup.2 is a C.sub.1-C.sub.12 alkylene radical; a C.sub.4-C.sub.12
alkenylene radical; a xylylene group; a C.sub.1-C.sub.50 alkylene
radical interrupted with 1 to 20 oxygen atoms and substituted with
1 to 10 hydroxyl groups; [0100] Y denotes an organic or inorganic
anion; [0101] the total charge of cations y being equal to the
total charge of anions z.
[0102] Among the anions Y, mention may be made of a phosphate,
phosphonate, carbonate, bicarbonate, nitrate, chloride, bromide,
bisulfite, sulfite, bisulfate, sulfate, borate, formate, acetate,
benzoate, citrate, oxalate, tartrate, acrylate, polyacrylate,
fumarate, maleate, itaconate, glycolate, gluconate, malate,
mandelate, tiglate, ascorbate, polymethacrylate, nitrilotriacetic
acid carboxylate, hydroxyethylenediaminetriacetic acid carboxylate,
ethylenediaminetetraacetic acid carboxylate,
diethylenediaminepentaacetic acid carboxylate,
diethylenetriaminepentamethylenephosphonate, alkylsulfonate or an
arylsulfonate.
[0103] Use will in particular be made of the compounds for which R,
R.sup.1 and R.sup.2 denote a hydrogen atom, x=1 and Y denotes the
citrate anion citrate and even more particularly the compound
tris(tetramethylhydroxypiperidinol) citrate of formula (VI):
##STR00019##
with y=3, such as the commercial product sold under the name
Tinoguard Q or Tinoguard S--FX by the company Ciba-Geigy, and also
tautomeric forms thereof, the optical isomers thereof, and/or
mixtures thereof.
[0104] Among the naphthalene derivatives in accordance with the
invention, use will more particularly be made of the
naphthalenedicarboxylic acid diesters and polyesters chosen from
[0105] (i) the diesters of formula (VII) below:
[0105] ##STR00020## [0106] (ii) the diesters or the polyesters of
formula (VIII) below:
[0106] ##STR00021## [0107] (iii) the diesters or the polyesters
blocked with an alcohol of formula (IX) below:
[0107] ##STR00022## [0108] (iv) mixtures thereof; [0109] in which:
[0110] the radicals R.sup.1, which may be identical or different,
denote a linear or branched C.sub.1-C.sub.22 alkyl radical; [0111]
the radicals R.sup.2 and R.sup.3, which may be identical or
different, denote a linear or branched C.sub.1-C.sub.6 alkylene
radical; [0112] k and 1 are numbers from 1 to 100, preferably from
1 to 10 and more preferentially from 2 to 7.
[0113] Among these naphthalenedicarboxylic acid diesters and
polyesters of formula (VII), (VIII) or (IX), use will preferably be
made of the 2,6-naphthalenedicarboxylic acid diesters and
polyesters.
[0114] Among the polyesters corresponding to formula (IX), those
resulting from the reaction of 2,6-naphthalenedicarboxylic acid and
of tripropylene glycol and blocked with 2-butyloctanol, and also
the polyesters resulting from the reaction of 2,6-naphthalene
dicarboxylic acid, of tripropylene glycol and of diethylene glycol
and blocked with 2-ethylhexanol, will preferably be chosen.
[0115] Among the naphthalene derivatives in accordance with the
invention, use will preferably be made of diethylhexyl
2,6-naphthalate (INCI name) and also the optical isomers thereof,
such as the product sold under the trade name Coropan TQ by the
company C.P. HALL.
[0116] Among the ethylhexyl methoxycrylene derivatives, use will
preferentially be made of those of formula (X) below, and also the
optical isomers thereof, the geometric isomers thereof; and/or
mixtures thereof:
##STR00023##
in which: [0117] R.sub.1 represents a hydrogen atom or a linear or
branched C.sub.1-C.sub.8 alkyl radical, R.sub.2 represents a linear
or branched C.sub.1-C.sub.20, preferably C.sub.1-C.sub.8, alkyl
radical.
[0118] Use will in particular be made of the compound
2-ethylhexyl-2-cyano-3-(4-methoxyphenyl)-3-phenylprop-2-enoate
(INCI name: Ethylhexyl Methoxycrylene) of formula (Xbis) below:
##STR00024##
such as the commercial product sold under the trade name Solastay
S1 by the company Hallstar, and also tautomeric forms thereof, the
optical isomers thereof, and/or mixtures thereof.
[0119] Preferably, the total content of the compound(s) (iii)
capable of accepting the triplet excited level energy of said
dibenzoylmethane derivative compound(s) present in the composition
is between 0.001% and 15% by weight, preferably between 0.003% and
10% by weight, and more preferentially between 0.005% and 5% by
weight, relative to the total weight of the composition.
[0120] According to one preferred embodiment of the invention, the
compound(s) (iii) capable of accepting the triplet excited level
energy of said dibenzoylmethane derivative compound(s) are chosen,
alone or as a mixture, from the diethylhexyl syringylidenemalonate
of formula (IV) and also the tautomeric forms thereof, the optical
isomers thereof, and/or mixtures thereof, the
bisethylhexylhydroxydimethoxy benzylmalonate of formula (IVbis) and
also the tautomeric forms thereof, the optical isomers thereof,
and/or mixtures thereof, the tris(tetramethylhydroxypiperidinol)
citrate of formula (VI) and also the optical isomers thereof,
and/or mixtures thereof, diethylhexyl 2,6-naphthalate and also the
optical isomers thereof, and the ethylhexyl methoxycrylene of
formula (Xbis) and also the tautomeric forms thereof, the optical
isomers thereof, and/or mixtures thereof.
[0121] According to another preferred embodiment of the invention,
the ratio of the weight content of the compound(s) (iii) capable of
accepting the triplet excited level energy of said dibenzoylmethane
derivative compound(s) to the sum of the weight contents of the
dibenzoylmethane derivative compound(s) (i) and of the merocyanine
compound(s) (ii), is between 0.01 and 20, preferably between 0.1
and 15, more preferentially between 0.5 and 10.
[0122] Additional UV-Screening Agents
[0123] The composition according to the present invention may
optionally comprise one or more additional UV-screening agents
chosen from hydrophilic, lipophilic or insoluble organic
UV-screening agents and/or one or more mineral pigments. It will
preferentially be constituted of at least one hydrophilic,
lipophilic or insoluble organic UV-screening agent.
[0124] The term "hydrophilic UV-screening agent" is intended to
mean any cosmetic or dermatological organic or inorganic compound
for screening out UV radiation, which can be fully dissolved in
molecular form in a liquid aqueous phase or which can be dissolved
in colloidal form (for example in micellar form) in a liquid
aqueous phase.
[0125] The term "lipophilic screening agent" is intended to mean
any cosmetic or dermatological organic or inorganic compound for
screening out UV radiation, which can be fully dissolved in
molecular form in a liquid fatty phase or which can be dissolved in
colloidal form (for example in micellar form) in a liquid fatty
phase.
[0126] The term "insoluble UV-screening agent" is intended to mean
any cosmetic or dermatological organic or inorganic compound for
screening out UV radiation which has a solubility in water of less
than 0.5% by weight and a solubility of less than 0.5% by weight in
the majority of organic solvents such as liquid paraffin, fatty
alcohol benzoates and fatty acid triglycerides, for example Miglyol
812.RTM. sold by the company Dynamit Nobel. This solubility,
determined at 70.degree. C., is defined as the amount of product in
solution in the solvent at equilibrium with an excess of solid in
suspension after returning to ambient temperature. It may be
readily evaluated in the laboratory.
[0127] The additional organic UV-screening agents are chosen in
particular from cinnamic compounds; anthranilate compounds;
salicylic compounds; benzylidenecamphor compounds; benzophenone
compounds; 0,0-diphenylacrylate compounds different from the
ethylhexyl methoxycrylene derivatives; triazine compounds;
benzotriazole compounds; benzalmalonate compounds, in particular
those cited in patent U.S. Pat. No. 5,624,663; benzimidazole
derivatives; imidazoline compounds; bis-benzazolyl compounds, as
described in patents EP 669 323 and U.S. Pat. No. 2,463,264;
p-aminobenzoic acid (PABA) compounds;
methylenebis(hydroxyphenylbenzotriazole) compounds, as described in
patent applications U.S. Pat. Nos. 5,237,071, 5,166,355, GB 2 303
549, DE 197 26 184 and EP 893 119; benzoxazole compounds, as
described in patent applications EP 0 832 642, EP 1 027 883, EP 1
300 137 and DE 101 62 844; screening polymers and screening
silicones, such as those described in particular in patent
application WO 93/04665; .alpha.-alkylstyrene-based dimers, such as
those described in patent application DE 198 55 649;
4,4-diarylbutadiene compounds, such as those described in patent
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 mixtures thereof.
[0128] As examples of organic photoprotective agents, mention may
be made of those denoted hereinbelow under their INCI name:
[0129] Cinnamic Compounds:
[0130] Ethylhexyl methoxycinnamate sold in particular under the
trade name Parsol MCX.RTM. by DSM Nutritional Products, [0131]
Isopropyl methoxycinnamate, [0132] Isoamyl p-methoxycinnamate sold
under the trade name Neo Heliopan E 1000.RTM. by Symrise, [0133]
DEA methoxycinnamate, [0134] Diisopropyl methylcinnamate, [0135]
Glyceryl Ethylhexanoate Dimethoxycinnamate.
[0136] Para-Aminobenzoic Compounds: [0137] PABA, [0138] Ethyl PABA,
[0139] Ethyl dihydroxypropyl PABA, [0140] Ethylhexyl dimethyl PABA,
sold in particular under the name Escalol 507.RTM. by ISP, [0141]
Glyceryl PABA, [0142] PEG-25 PABA, sold under the name Uvinul P
25.RTM. by BASF.
[0143] Salicylic Compounds: [0144] Homosalate, sold under the name
Eusolex HMS.RTM. by Rona/EM Industries, [0145] Ethylhexyl
salicylate, sold under the name Neo Heliopan OS.RTM. by Symrise,
[0146] Dipropylene glycol salicylate, sold under the name
Dipsal.RTM. by Scher, [0147] TEA salicylate, sold under the name
Neo Heliopan TS.RTM. by Symrise.
[0148] .beta.,.beta.-Diphenylacrylate Compounds: [0149]
Octocrylene, sold in particular under the trade name Uvinul N
539.RTM. by BASF, [0150] Etocrylene, sold in particular under the
trade name Uvinul N 35.RTM. by BASF.
[0151] Benzophenone Compounds: [0152] Benzophenone-1 sold under the
trade name Uvinul 400.RTM. by BASF, [0153] Benzophenone-2, sold
under the trade name Uvinul D 50.RTM. by BASF, [0154]
Benzophenone-3 or Oxybenzone, sold under the trade name Uvinul M
40.RTM. by BASF, [0155] Benzophenone-4, sold under the trade name
Uvinul MS 40.RTM. by BASF, [0156] Benzophenone-5, [0157]
Benzophenone-6, sold under the trade name Helisorb 11.RTM. by
Norquay, [0158] Benzophenone-8, sold under the trade name
Spectra-Sorb UV-24.RTM. by American Cyanamid, [0159]
Benzophenone-9, sold under the trade name Uvinul DS 49.RTM. by
BASF, [0160] Benzophenone-12, [0161] n-Hexyl
2-(4-diethylamino-2-hydroxybenzoyl)benzoate, sold under the trade
name Uvinul A Plus.RTM. or, as a mixture with octyl
methoxycinnamate, under the trade name Uvinul A Plus B.RTM. by the
company BASF, [0162]
1,1'-(1,4-Piperazinediyl)bis[1-[2-[4-(diethylamino)-2-hydroxybenzoyl]phen-
yl]methanone] (CAS 919803-06-8), as described in patent application
WO 2007/071 584; this compound advantageously being used in
micronized form (mean size of 0.02 to 2 .mu.m), which may be
obtained, for example, according to the micronization process
described in patent applications GB-A-2 303 549 and EP-A-893 119,
and in particular in the form of an aqueous dispersion.
[0163] Benzylidenecamphor Compounds: [0164] 3-Benzylidenecamphor,
manufactured under the name Mexoryl SD.RTM. by Chimex, [0165]
4-Methylbenzylidenecamphor, sold under the name Eusolex 6300.RTM.
by Merck, [0166] Benzylidenecamphorsulfonic acid, manufactured
under the name Mexoryl SL.RTM. by Chimex, [0167] Camphor
benzalkonium methosulfate, manufactured under the name Mexoryl
SO.RTM. by Chimex, [0168] Terephthalylidenedicamphorsulfonic acid,
manufactured under the name Mexoryl SX.RTM. by Chimex, [0169]
Polyacrylamidomethylbenzylidenecamphor, manufactured under the name
Mexoryl SW.RTM. by Chimex.
[0170] Phenylbenzimidazole Compounds: [0171]
Phenylbenzimidazolesulfonic acid, sold in particular under the
trade name Eusolex 232.RTM. by Merck.
[0172] Bisbenzoazolyl Compounds: [0173] Disodium phenyl
dibenzimidazole tetrasulfonate sold under the trade name Neo
Heliopan AP.RTM. by Haarmann and Reimer.
[0174] Phenylbenzotriazole Compounds: [0175] Drometrizole
trisiloxane, sold under the name Silatrizole.RTM. by Rhodia
Chimie.
[0176] Methylenebis(Hydroxyphenylbenzotriazole) Compounds:
[0177] Methylene bis-benzotriazolyl tetramethylbutylphenol in
particular in solid form, such as the product sold under the trade
name MIXXIM BB/100.RTM. by Fairmount Chemical or in the form of an
aqueous dispersion of micronized particles having a mean particle
size which ranges from 0.01 to 5 .mu.m and more preferentially from
0.01 to 2 .mu.m and more particularly from 0.020 to 2 .mu.m, with
at least one alkylpolyglycoside surfactant of structure:
C.sub.nH.sub.2n+1O(C.sub.6H.sub.10O.sub.5).sub.xH in which n is an
integer from 8 to 16 and x is the average degree of polymerization
of the (C.sub.6H.sub.10O.sub.5) unit and ranges from 1.4 to 1.6, as
described in patent GB-A-2 303 549, in particular sold under the
trade name Tinosorb M.RTM. by BASF or in the form of an aqueous
dispersion of micronized particles having a mean particle size
which ranges from 0.02 to 2 .mu.m and more preferentially from 0.01
to 1.5 .mu.m and more particularly from 0.02 to 1 .mu.m in the
presence of at least one mono-(C.sub.5-C.sub.20)alkyl ester of
polyglycerol having a degree of glycerol polymerization of at least
5, such as the aqueous dispersions described in application WO
2009/063392.
[0178] Triazine Compounds: [0179] Bis-ethylhexyloxyphenol
methoxyphenyl triazine, sold under the trade name Tinosorb S.RTM.
by BASF, [0180] Ethylhexyltriazone sold in particular under the
trade name Uvinul T 150.RTM. by BASF, [0181] Diethylhexyl butamido
triazone, sold under the trade name Uvasorb HEB.RTM. by Sigma 3V,
[0182] 2,4,6-tris(dineopentyl 4'-aminobenzalmalonate)-s-triazine,
[0183] 2,4,6-tris(diisobutyl 4'-aminobenzalmalonate)-s-triazine,
[0184] 2,4-bis(n-butyl
4'-aminobenzoate)-6-(aminopropyltrisiloxane)-s-triazine, [0185]
2,4-bis(dineopentyl 4'-aminobenzalmalonate)-6-(n-butyl
4'-aminobenzoate)-s-triazine, [0186] symmetrical triazine screening
agents substituted with naphthalenyl groups or polyphenyl groups
described in patent U.S. Pat. No. 6,225,467, patent application WO
2004/085 412 (see compounds 6 and 9) or the document "Symmetrical
Triazine Derivatives", IP.COM IPCOM000031257 Journal, INC West
Henrietta, NY, US (20 Sep. 2004), in particular
2,4,6-tris(diphenyl)triazine and 2,4,6-tris(terphenyl)triazine,
which is also mentioned in patent applications WO 06/035 000, WO
06/034 982, WO 06/034 991, WO 06/035 007, WO 2006/034 992 and WO
2006/034 985, these compounds advantageously being used in
micronized form (mean particle size of 0.02 to 3 .mu.m), which may
be obtained, for example, according to the micronization process
described in patent applications GB-A-2 303 549 and EP-A-893 119,
and in particular in aqueous dispersion form, [0187] Silicone
triazines substituted with two aminobenzoate groups, as described
in patent EP 0 841 341, in particular 2,4-bis(n-butyl
4'-aminobenzalmalonate)-6-[(3-{1,3,3,3-tetramethyl-1-[(trimethylsilyl)oxy-
]disiloxanyl}propyl)amino]-s-triazine.
[0188] Anthranilic Compounds:
[0189] Menthyl anthranilate sold under the trade name Neo Heliopan
MA.RTM. by Symrise.
[0190] Imidazoline Compounds:
[0191] Ethylhexyl dimethoxybenzylidene dioxoimidazoline
propionate.
[0192] Benzalmalonate Compounds:
[0193] Polyorganosiloxane comprising benzalmalonate functions, such
as Polysilicone-15, sold under the trade name Parsol SLX.RTM. by
Hoffmann-LaRoche.
[0194] 4,4-Diarylbutadiene Compounds:
[0195]
1,1-Dicarboxy(2,2'-dimethylpropyl)-4,4-diphenylbutadiene.
[0196] Benzoxazole Compounds:
[0197]
2,4-Bis[5-(1,1-dimethylpropyl)benzoxazol-2-yl(4-phenyl)imino]-6-(2--
ethylhexyl)imino-1,3,5-triazine, sold under the name Uvasorb
K2A.RTM. by Sigma 3V.
[0198] The preferential organic screening agents are chosen from:
[0199] Ethylhexyl methoxycinnamate [0200] Ethylhexyl salicylate,
[0201] Homosalate, [0202] Octocrylene, [0203]
Phenylbenzimidazolesulfonic acid, [0204] Benzophenone-3, [0205]
Benzophenone-4, [0206] Benzophenone-5, [0207] n-Hexyl
2-(4-diethylamino-2-hydroxybenzoyl)benzoate, [0208]
4-Methylbenzylidene camphor, [0209]
Terephthalylidenedicamphorsulfonic acid, [0210] Disodium phenyl
dibenzimidazole tetrasulfonate, [0211]
Methylenebis(benzotriazolyl)tetramethylbutylphenol, [0212]
Bis-ethylhexyloxyphenol methoxyphenyl triazine, [0213] Ethylhexyl
triazone [0214] Diethylhexyl butamido triazone, [0215]
2,4,6-Tris(dineopentyl 4'-aminobenzalmalonate)-s-triazine, [0216]
2,4,6-Tris(diisobutyl 4'-aminobenzalmalonate)-s-triazine, [0217]
2,4-Bis(n-butyl
4'-aminobenzoate)-6-(aminopropyltrisiloxane)-s-triazine, [0218]
2,4-Bis(dineopentyl 4'-aminobenzalmalonate)-6-(n-butyl
4'-aminobenzoate)-s-triazine, [0219] 2,4-Bis(n-butyl
4'-aminobenzalmalonate)-6-[(3-{1,3,3,3-tetramethyl-1-[(trimethylsilyl)oxy-
]disiloxanyl}propyl)amino]-s-triazine, [0220]
2,4,6-Tris(diphenyl)triazine, [0221] 2,4,6-Tris(terphenyl)triazine,
[0222] Drometrizole trisiloxane, [0223] Polysilicone-15, [0224]
1,1-Dicarboxy(2,2'-dimethylpropyl)-4,4-diphenylbutadiene; [0225]
2,4-Bis[5-(1-dimethylpropyl)benzoxazol-2-yl-(4-phenyl)imino]-6-(2-ethylhe-
xyl)imino-1,3,5-triazine, [0226] and mixtures thereof.
[0227] The particularly preferred organic screening agents are
chosen from: [0228] Ethylhexyl salicylate, [0229] Homosalate,
[0230] Octocrylene, [0231] n-Hexyl
2-(4-diethylamino-2-hydroxybenzoyl)benzoate, [0232]
Terephthalylidenedicamphorsulfonic acid, [0233]
Bis-ethylhexyloxyphenol methoxyphenyl triazine, [0234] Ethylhexyl
triazone [0235] Diethylhexyl butamido triazone, [0236]
2,4-Bis(n-butyl
4'-aminobenzalmalonate)-6-[(3-{1,3,3,3-tetramethyl-1-[(trimethylsilyl)oxy-
]disiloxanyl}propyl)amino]-s-triazine, [0237] Drometrizole
trisiloxane, [0238] and mixtures thereof.
[0239] The inorganic UV-screening agents used in accordance with
the present invention are metal oxide pigments. More
preferentially, the inorganic UV-screening agents of the invention
are metal oxide particles with a mean elementary particle size of
less than or equal to 0.5 .mu.m, more preferentially between 0.005
and 0.5 .mu.m, even more preferentially between 0.01 and 0.2 .mu.m,
better still between 0.01 and 0.1 .mu.m and more particularly
between 0.015 and 0.05 .mu.m.
[0240] They may be chosen in particular from titanium oxide, zinc
oxide, iron oxide, zirconium oxide and cerium oxide, or mixtures
thereof.
[0241] Such coated or uncoated metal oxide pigments are described
in particular in patent application EP-A-0 518 773. Commercial
pigments that may be mentioned include the products sold by the
companies Sachtleben Pigments, Tayca, Merck and Degussa.
[0242] The metal oxide pigments may be coated or uncoated.
[0243] The coated pigments are pigments that have undergone one or
more surface treatments of chemical, electronic, mechanochemical
and/or mechanical nature with compounds such as amino acids,
beeswax, fatty acids, fatty alcohols, anionic surfactants,
lecithins, sodium, potassium, zinc, iron or aluminium salts of
fatty acids, metal alkoxides (of titanium or aluminium),
polyethylene, silicones, proteins (collagen, elastin),
alkanolamines, silicon oxides, metal oxides or sodium
hexametaphosphate.
[0244] The coated pigments are more particularly titanium oxides
that have been coated: [0245] with silica, such as the product
Sunveil.RTM. from the company Ikeda, [0246] with silica and iron
oxide, such as the product Sunveil F.RTM. from the company Ikeda,
[0247] with silica and alumina, such as the products Microtitanium
Dioxide MT 500 SA.RTM. and Microtitanium Dioxide MT 100 SA from the
company Tayca and Tioveil from the company Tioxide, [0248] with
alumina, such as the products Tipaque TTO-55 (B).RTM. and Tipaque
TTO-55 (A).RTM. from the company Ishihara and UVT 14/4 from the
company Sachtleben Pigments, [0249] with alumina and aluminium
stearate, such as the products Microtitanium Dioxide MT 100 T.RTM.,
MT 100 TX.RTM., MT 100 Z.RTM. and MT-01.RTM. from the company
Tayca, the products Solaveil CT-10 W.RTM. and Solaveil CT 100.RTM.
from the company Croda and the product Eusolex T-AVO.RTM. from the
company Merck, [0250] with silica, alumina and alginic acid, such
as the product MT-100 AQ.RTM. from the company Tayca, [0251] with
alumina and aluminium laurate, such as the product Microtitanium
Dioxide MT 100 S.RTM. from the company Tayca, [0252] with iron
oxide and iron stearate, such as the product Microtitanium Dioxide
MT 100 F.RTM. from the company Tayca, [0253] with zinc oxide and
zinc stearate, such as the product BR 351.RTM. from the company
Tayca, [0254] with silica and alumina and treated with a silicone,
such as the products Microtitanium Dioxide MT 600 SAS.RTM.,
Microtitanium Dioxide MT 500 SAS.RTM. or Microtitanium Dioxide MT
100 SAS.RTM. from the company Tayca, [0255] with silica, alumina
and aluminium stearate and treated with a silicone, such as the
product STT-30-DS.RTM. from the company Titan Kogyo, [0256] with
silica and treated with a silicone, such as the product UV-Titan X
195.RTM. from the company Sachtleben Pigments, [0257] with alumina
and treated with a silicone, such as the products Tipaque TTO-55
(S).RTM. from the company Ishihara or UV Titan M 262.RTM. from the
company Sachtleben Pigments, [0258] with triethanolamine, such as
the product STT-65-S from the company Titan Kogyo, [0259] with
stearic acid, such as the product Tipaque TTO-55 (C).RTM. from the
company Ishihara, [0260] with sodium hexametaphosphate, such as the
product Microtitanium Dioxide MT 150 W.RTM. from the company Tayca,
[0261] TiO.sub.2 treated with octyltrimethylsilane, sold under the
trade name T 805.RTM. by the company Degussa Silices, [0262]
TiO.sub.2 treated with a polydimethylsiloxane, sold under the trade
name 70250 Cardre UF TiO.sub.2SI3.RTM. by the company Cardre,
[0263] anatase/rutile TiO.sub.2 treated with a
polydimethylhydrogenosiloxane, sold under the trade name Micro
Titanium Dioxide USP Grade Hydrophobic.RTM. by the company Color
Techniques. [0264] TiO.sub.2 coated with triethylhexanoin, with
aluminium stearate and with alumina sold under the trade name
Solaveil CT-200-LQ-(WD) by Croda, [0265] TiO.sub.2 coated with
aluminium stearate, with alumina and with silicone sold under the
trade name Solaveil CT-12W-LQ-(WD) by Croda, [0266] TiO.sub.2
coated with lauroyl lysine sold by Daito Kasei Kogyo under the name
LL 5 Titanium Dioxyde CR 50, [0267] TiO.sub.2 coated with
C.sub.9-C.sub.15 fluoroalcohol phosphate and with aluminium
hydroxide sold by Daito Kasei Kogyo under the name PFX-5 TiO.sub.2
CR-50.
[0268] Mention may also be made of TiO.sub.2 pigments doped with at
least one transition metal such as iron, zinc or manganese and more
particularly manganese. Preferably, said doped pigments are in the
form of an oily dispersion. The oil present in the oily dispersion
is preferably chosen from triglycerides including those of
capric/caprylic acids. The oily dispersion of titanium oxide
particles may also comprise one or more dispersants, for instance a
sorbitan ester, for instance sorbitan isostearate, or a
polyoxyalkylenated fatty acid ester of glycerol, for instance
TRI-PPG-3 myristyl ether citrate and polyglyceryl-3
polyricinoleate. Preferably, the oily dispersion of titanium oxide
particles comprises at least one dispersant chosen from
polyoxyalkylenated fatty acid esters of glycerol. Mention may be
made more particularly of the oily dispersion of TiO.sub.2
particles doped with manganese in capric/caprylic acid triglyceride
in the presence of TRI-PPG-3 myristyl ether citrate and
polyglyceryl-3 polyricinoleate and sorbitan isostearate having the
INCI name: titanium dioxide (and) TRI-PPG-3 myristyl ether citrate
(and) polyglyceryl-3 ricinoleate (and) sorbitan isostearate, for
instance the product sold under the trade name Optisol TD50.RTM. by
the company Croda.
[0269] The uncoated titanium oxide pigments are sold, for example,
by the company Tayca under the trade names Microtitanium Dioxide MT
500 B or Microtitanium Dioxide MT 600 B.RTM., by the company
Degussa under the name P 25, by the company Wackher under the name
Transparent titanium oxide PW.RTM., by the company Miyoshi Kasei
under the name UFTR.RTM., by the company Tomen under the name
ITS.RTM. and by the company Tioxide under the name Tioveil AQ.
[0270] The uncoated zinc oxide pigments are, for example: [0271]
those sold under the name Z-Cote by Sunsmart; [0272] those sold
under the name Nanox.RTM. by the company Elementis; [0273] those
sold under the name Nanogard WCD 2025.RTM. by the company Nanophase
Technologies.
[0274] The coated zinc oxide pigments are, for example: [0275]
those sold under the name Zinc Oxide CS-5.RTM. by the company
Toshibi (ZnO coated with polymethylhydrogenosiloxane); [0276] those
sold under the name Nanogard Zinc Oxide FN.RTM. by the company
Nanophase Technologies (as a 40% dispersion in Finsolv TN.RTM.,
C.sub.12-C.sub.15 alkyl benzoate); [0277] those sold under the name
Daitopersion Zn-30.RTM. and Daitopersion Zn-50.RTM. by the company
Daito (dispersions in cyclopolymethylsiloxane/oxyethylenated
polydimethylsiloxane, containing 30% or 50% of zinc oxides coated
with silica and polymethylhydrogenosiloxane); [0278] those sold
under the name NFD Ultrafine ZnO.RTM. by the company Daikin (ZnO
coated with perfluoroalkyl phosphate and copolymer based on
perfluoroalkylethyl as a dispersion in cyclopentasiloxane); [0279]
those sold under the name SPD-Z1.RTM. by the company Shin-Etsu (ZnO
coated with silicone-grafted acrylic polymer, dispersed in
cyclodimethylsiloxane); [0280] those sold under the name Escalol
Z100.RTM. by the company ISP (alumina-treated ZnO dispersed in the
ethylhexyl methoxycinnamate/PVP-hexadecene copolymer/methicone
mixture); [0281] those sold under the name Fuji ZnO-SMS-10.RTM. by
the company Fuji Pigment (ZnO coated with silica and
polymethylsilsesquioxane); [0282] those sold under the name Nanox
Gel TN.RTM. by the company Elementis (ZnO dispersed at a
concentration of 55% in C.sub.12-C.sub.15 alkyl benzoate with
hydroxystearic acid polycondensate).
[0283] The uncoated cerium oxide pigments may be, for example,
those sold under the name Colloidal Cerium Oxide.RTM. by the
company Rhone-Poulenc.
[0284] The uncoated iron oxide pigments are sold, for example, by
the company Arnaud under the names Nanogard WCD 2002.RTM. (FE
45B.RTM.), Nanogard Iron FE 45 BL AQ, Nanogard FE 45R AQ.RTM. and
Nanogard WCD 2006.RTM. (FE 45R.RTM.) or by the company Mitsubishi
under the name TY-220.RTM..
[0285] The coated iron oxide pigments are sold, for example, by the
company Arnaud under the names Nanogard WCD 2008 (FE 45B FN).RTM.,
Nanogard WCD 2009.RTM. (FE 45B 556.RTM.), Nanogard FE 45 BL
345.RTM. and Nanogard FE 45 BL.RTM. or by the company BASF under
the name Transparent Iron Oxide.RTM..
[0286] Mention may also be made of mixtures of metal oxides,
especially of titanium dioxide and of cerium dioxide, including the
equal-weight mixture of titanium dioxide and cerium dioxide coated
with silica, sold by the company Ikeda under the name Sunveil
A.RTM., and also the mixture of titanium dioxide and zinc dioxide
coated with alumina, silica and silicone, such as the product M
261.RTM. sold by the company Sachtleben Pigments, or coated with
alumina, silica and glycerol, such as the product M 211.RTM. sold
by the company Sachtleben Pigments.
[0287] According to the invention, coated or uncoated titanium
oxide pigments are particularly preferred.
[0288] According to one preferred embodiment of the invention, the
composition also comprises one or more additional UV-screening
agents chosen from hydrophilic, lipophilic or insoluble organic
UV-screening agents and/or one or more mineral pigments; more
preferentially chosen, alone or as a mixture, from anthranilates;
salicylic derivatives; benzylidenecamphor derivatives; benzophenone
derivatives; .beta.,.beta.-diphenylacrylate compounds different
from ethylhexyl methoxycrylene derivatives; triazine derivatives
such as derivatives of bisresorcinyl triazine type; benzotriazole
derivatives; benzalmalonate derivatives; benzimidazole derivatives;
imidazolines; bisbenzoazolyl derivatives; p-aminobenzoic acid
(PABA) derivatives; methylenebis(hydroxyphenyl benzotriazole)
derivatives; benzoxazole derivatives; screening polymers and
screening silicones; .alpha.-alkylstyrene-based dimers;
4,4-diarylbutadienes; and/or treated or untreated metal oxide
pigments or nanopigments, such as titanium oxides, zinc oxides,
iron oxides, zirconium oxides, cerium oxides and mixtures thereof,
preferably chosen, alone or as a mixture, from titanium oxides.
[0289] According to a very preferred embodiment of the invention,
the composition according to the present invention also comprises
one or more additional UV-screening agents chosen, alone or as a
mixture, from the following UV-screening agents: ethylhexyl
salicylate, octocrylene, phenylbenzimidazole sulfonic acid,
benzophenone-3, benzophenone-4, benzophenone-5, n-hexyl
2-(4-diethylamino-2-hydroxybenzoyl)benzoate,
4-methylbenzylidenecamphor, terephthalylidenedicamphorsulfonic
acid, disodium phenyldibenzimidazole tetrasulfonate,
methylenebisbenzotriazolyl tetramethylbutylphenol, ethylhexyl
triazone, diethylhexyl butamido triazone, drometrizole trisiloxane,
polysilicone-15,
1,1-dicarboxy(2,2'-dimethylpropyl)-4,4-diphenylbutadiene,
2,4-bis[5,1(dimethylpropyl)benzoxazol-2-yl(4-phenyl)imino]-6-(2-ethylhexy-
l)imino-1,3,5-triazine, and mixtures thereof.
[0290] The amount of additional UV-screening agent(s) present in
the composition according to the invention may range from 0.10% to
50% by weight, relative to the total weight of the composition. It
preferably ranges from 0.2% to 30% by weight, more preferentially
from 0.5% to 25% by weight and better still ranges from 1% to 15%
by weight, relative to the total weight of the composition.
[0291] Surfactants
[0292] The composition according to the present invention may
optionally also comprise one or more surfactants.
[0293] The surfactants according to the invention are preferably
selected from anionic surfactants, non-ionic surfactants and/or
gemini surfactants, and mixtures thereof.
[0294] The anionic surfactants that may be present in the
composition according to the invention may be chosen especially
from anionic derivatives of proteins of plant origin or of silk
proteins, phosphates and alkyl phosphates, carboxylic acids and
carboxylates, sulfosuccinates, amino acid derivatives, alkyl
sulfates, alkyl ether sulfates, sulfonates, isethionates, taurates,
alkyl sulfoacetates, polypeptides, anionic derivatives of alkyl
polyglucoside, soaps (fatty acid salts), and mixtures thereof
[0295] a) Anionic derivatives of proteins of plant origin are
protein hydrolysates bearing a hydrophobic group, it being possible
for said hydrophobic group to be naturally present in the protein
or to be added by reaction of the protein and/or of the protein
hydrolysate with a hydrophobic compound. The proteins are of plant
origin or are derived from silk, and the hydrophobic group may in
particular be a fatty chain, for example an alkyl chain comprising
from 10 to 22 carbon atoms. As anionic derivatives of proteins of
plant origin, mention may more particularly be made of apple,
wheat, soybean or oat protein hydrolysates comprising an alkyl
chain having from 10 to 22 carbon atoms, and salts thereof. The
alkyl chain may especially be a lauryl chain and the salt may be a
sodium, potassium and/or ammonium salt.
[0296] Thus, as protein hydrolysates bearing a hydrophobic group,
mention may be made, for example, of salts of protein hydrolysates
where the protein is a silk protein modified with lauric acid, such
as the product sold under the name Kawa Silk by Kawaken; salts of
protein hydrolysates where the protein is a wheat protein modified
with lauric acid, such as the potassium salt sold under the name
Aminofoam W OR by Croda (CTFA name: potassium lauroyl wheat amino
acids) and the sodium salt sold under the name Proteol LW 30 by the
company SEPPIC (CTFA name: sodium lauroyl wheat amino acids); salts
of protein hydrolysates where the protein is an oat protein
comprising an alkyl chain containing from 10 to 22 carbon atoms and
more especially salts of protein hydrolysates where the protein is
an oat protein modified with lauric acid, such as the sodium salt
sold under the name Proteol OAT (30% aqueous solution) by the
company SEPPIC (CTFA name: sodium lauroyl oat amino acids); or
salts of apple protein hydrolysates comprising an alkyl chain
containing from 10 to 22 carbon atoms, such as the sodium salt sold
under the name Proteol APL (30% aqueous glycol solution) by the
company SEPPIC (CTFA name: Sodium Cocoyl Apple amino acids).
Mention may also be made of the mixture of lauroyl amino acids
(aspartic acid, glutamic acid, glycine, alanine) neutralized with
sodium N-methylglycinate sold under the name Proteol SAV 50 S by
the company SEPPIC (CTFA name: Sodium Cocoyl amino acids). [0297]
b) Examples of phosphates and alkyl phosphates that may be
mentioned include monoalkyl phosphates and dialkyl phosphates, such
as the lauryl monophosphate sold under the name MAP 20.RTM. by the
company Kao Chemicals, the potassium salt of dodecylphosphoric
acid, mixture of monoester and diester (predominantly diester) sold
under the name Crafol AP-31.RTM. by the company Cognis, the mixture
of octylphosphoric acid monoester and diester sold under the name
Crafol AP-20.RTM. by the company Cognis, the mixture of ethoxylated
(7 mol of EO) phosphoric acid monoester and diester of
2-butyloctanol, sold under the name Isofol 12 7 EO-Phosphate
Ester.RTM. by the company Condea, the potassium or triethanolamine
salt of mono(C12-C13)alkyl phosphate sold under the references
Arlatone MAP 230K-40.RTM. and Arlatone MAP 230T-60.RTM. by the
company Uniqema, the potassium lauryl phosphate sold under the name
Dermalcare MAP XC-99/09.RTM. by the company Rhodia Chimie, and the
potassium cetyl phosphate sold under the name Arlatone MAP 160K by
the company Uniqema. [0298] c) As carboxylic acids and
carboxylates, mention may for example be made of amide ether
carboxylates (AECs), such as sodium laurylamide ether carboxylate
(3 EO), sold under the name Akpyo Foam 30.RTM. by the company Kao
Chemicals, polyoxyethylenated carboxylic acid salts, such as
oxyethylenated (6 EO) sodium lauryl ether carboxylate (C12-14-16
65/25/10) sold under the name Akpyo Soft 45 NV.RTM. by the company
Kao Chemicals, polyoxyethylenated and carboxymethylated fatty acids
of olive oil origin, sold under the name Olivem 400.RTM. by the
company Biologia E Tecnologia, oxyethylenated (6 EO) sodium
tridecyl ether carboxylate sold under the name Nikkol
ECTD-6NEX.RTM. by the company Nikkol, fatty acids having a C.sub.6
to C.sub.22 alkyl chain, such as stearic acid, and fatty acid salts
(soaps) having a C.sub.6 to C.sub.22 alkyl chain, neutralized with
an organic or mineral base such as potassium hydroxide, sodium
hydroxide, triethanolamine, N-methyl glucamine, lysine and
arginine. [0299] d) Amino acid derivatives that may especially be
mentioned include alkaline salts of amino acids, such as: [0300]
sarcosinates, for instance sodium cocoyl sarcosinate, the sodium
lauroyl sarcosinate sold under the name Sarkosyl NL 97.RTM. by the
company Ciba or sold under the name Oramix L 30.RTM. by the company
SEPPIC, sodium myristoyl sarcosinate sold under the name Nikkol
Sarcosinate MN.RTM. by the company Nikkol, and sodium palmitoyl
sarcosinate sold under the name Nikkol Sarcosinate PN.RTM. by the
company Nikkol; [0301] alaninates, for instance sodium N-lauroyl
N-methyl amidopropionate sold under the name Sodium Nikkol
Alaninate LN 30.RTM. by the company Nikkol, or sold under the name
Alanone ALE.RTM. by the company Kawaken, and triethanolamine
N-lauroyl N-methyl alanine sold under the name Alanone Alta.RTM. by
the company Kawaken; [0302] glutamates, for instance
triethanolamine monococoyl glutamate sold under the name
Acylglutamate CT-12.RTM. by the company Ajinomoto, triethanolamine
lauroyl glutamate sold under the name Acylglutamate LT-12.RTM. by
the company Ajinomoto, aspartates, for instance the mixture of
triethanolamine N-lauroyl aspartate/triethanolamine N-myristoyl
aspartate sold under the name Asparack.RTM. by the company
Mitsubishi; [0303] glycine derivatives (glycinates), for instance
the sodium N-cocoyl glycinate sold under the names Amilite
GCS-12.RTM. and Amilite GCK 12 by the company Ajinomoto; [0304]
citrates, such as the oxyethylenated (9 mol) citric monoester of
cocoyl alcohols sold under the name Witconol EC 1129 by the company
Goldschmidt, and galacturonates such as sodium dodecyl
D-galactoside uronate sold by the company Soliance. [0305] e)
Examples of sulfosuccinates that may be mentioned include the
oxyethylenated (3 EO) lauryl alcohol monosulfosuccinate (70/30
C12/C14) sold under the names Setacin 103 Special.RTM. and Rewopol
SB-FA 30 K 4.RTM. by the company Witco, the disodium salt of a
hemisulfosuccinate of C12-C14 alcohols, sold under the name Setacin
F Special Paste.RTM. by the company Zschimmer Schwarz, the
oxyethylenated (2 EO) disodium oleamidosulfosuccinate sold under
the name Standapol SH 135.RTM. by the company Cognis, the
oxyethylenated (5 EO) laurylamide monosulfosuccinate sold under the
name Lebon A-5000.RTM. by the company Sanyo, the oxyethylenated (10
EO) disodium salt of lauryl citrate monosulfosuccinate sold under
the name Rewopol SB CS 50.RTM. by the company Witco, and the
ricinoleic monoethanolamide monosulfosuccinate sold under the name
Rewoderm S 1333.RTM. by the company Witco. Polydimethylsiloxane
sulfosuccinates may also be used, such as the disodium PEG-12
dimethicone sulfosuccinate sold under the name Mackanate-DC30 by
the company MacIntyre. [0306] f) Examples of alkyl sulfates that
may be mentioned include triethanolamine lauryl sulfate (CTFA name:
TEA lauryl sulfate), such as the product sold by Huntsman under the
name Empicol TL40 FL or the product sold by Cognis under the name
Texapon T42, which products are at 40% in aqueous solution. Mention
may also be made of ammonium lauryl sulfate (CTFA name: ammonium
lauryl sulfate), such as the product sold by Huntsman under the
name Empicol AL 30FL, which is at 30% in aqueous solution. [0307]
g) Examples of alkyl ether sulfates that may be mentioned include
sodium lauryl ether sulfate (CTFA name: sodium laureth sulfate),
such as the product sold under the names Texapon N40 and Texapon
AOS 225 UP by the company Cognis, or ammonium lauryl ether sulfate
(CTFA name: ammonium laureth sulfate), such as the product sold
under the name Standapol EA-2 by the company Cognis. [0308] h)
Examples of sulfonates that may be mentioned include
.alpha.-olefinsulfonates, such as the sodium
.alpha.-olefinsulfonate (C14-C16), sold under the name Bio-Terge
AS-40.RTM. by the company Stepan, sold under the names Witconate
AOS Protege.RTM. and Sulframine AOS PH 12.RTM. by the company Witco
or sold under the name Bio-Terge AS-40 CG.RTM. by the company
Stepan, secondary sodium olefinsulfonate, sold under the name
Hostapur SAS 30.RTM. by the company Clariant; or linear
alkylarylsulfonates, such as sodium xylenesulfonate, sold under the
names Manrosol SXS30.RTM., Manrosol SXS40.RTM. and Manrosol SXS93@
by the company Manro. [0309] i) Isethionates that may be mentioned
include (C.sub.8-C.sub.18)acylisethionates, for instance sodium
cocoyl isethionate, such as the product sold under the name
Jordapon CI P.RTM. by the company Jordan. [0310] j) Taurates that
may be mentioned include the salts (in particular sodium salt) of
palm kernel oil methyltaurate sold under the name Hostapon CT
Pate.RTM. by the company Clariant; N--(C.sub.8-C.sub.18)acyl
N-methyltaurates, for instance the sodium N-cocoyl N-methyltaurate
sold under the name Hostapon LT-SF.RTM. by the company Clariant or
sold under the name Nikkol CMT-30-T.RTM. by the company Nikkol, and
the sodium palmitoyl methyltaurate sold under the name Nikkol
PMT.RTM. by the company Nikkol. [0311] k) The anionic derivatives
of (C.sub.8-C.sub.18)alkyl polyglucosides may especially be
citrates, tartrates, sulfosuccinates, carbonates and ethers of
glycerol obtained from alkyl polyglucosides. Mention may be made,
for example, of the sodium salt of cocoylpolyglucoside (1,4)
tartaric ester, sold under the name Eucarol AGE-ET.RTM. by
Cesalpinia, the disodium salt of cocoylpolyglucoside (1,4)
sulfosuccinic ester, sold under the name Essai 512 MP.RTM. by
Seppic, or the sodium salt of cocoylpolyglucoside (1,4) citric
ester, sold under the name Eucarol AGE-EC.RTM. by Cesalpinia.
[0312] l) The soaps are obtained from a fatty acid which is
partially or completely saponified (neutralized) with a basic
agent. These are alkali metal or alkaline-earth metal soaps or
soaps of organic bases. Use may be made, as fatty acids, of
saturated, linear or branched fatty acids comprising from 8 to 30
carbon atoms and preferably comprising from 8 to 22 carbon atoms.
This fatty acid may be chosen in particular from palmitic acid,
stearic acid, myristic acid and lauric acid, and mixtures
thereof.
[0313] Examples of basic agents that may be used include alkali
metal hydroxides (sodium hydroxide and potassium hydroxide),
alkaline-earth metal hydroxides (for example magnesium hydroxide),
ammonium hydroxide or else organic bases, such as triethanolamine,
N-methylglucamine, lysine and arginine.
[0314] The soaps may especially be fatty acid alkali metal salts,
the basic agent being an alkali metal hydroxide and preferably
potassium hydroxide (KOH).
[0315] The amount of basic agent must be sufficient for the fatty
acid to be at least partially neutralized.
[0316] Preferably, the anionic surfactant(s) are chosen from alkyl
sulfates, alkyl ether sulfates such as sodium lauryl ether sulfate,
phosphates, alkylphosphates such as potassium cetylphosphate, amino
acid derivatives, in particular sarcosine derivatives
(sarcosinates), such as sodium cocoyl sarcosinate, soaps such as
sodium stearate, carboxylic acids such as stearic acid, and
mixtures thereof.
[0317] Preferentially, the anionic surfactant(s) are chosen from
phosphates, alkylphosphates such as potassium cetylphosphate,
sarcosine derivatives (sarcosinates), such as sodium cocoyl
sarcosinate, soaps such as sodium stearate, carboxylic acids such
as stearic acid, and mixtures thereof.
[0318] The non-ionic surfactants that may be present in the
composition of the invention can be chosen in particular from alkyl
polyglucosides (APGs), oxyalkylenated glycerol esters,
oxyalkylenated fatty acid esters of sorbitan, polyoxyalkylenated
(in particular polyoxyethylenated and/or polyoxypropylenated) fatty
acid esters optionally in combination with a fatty acid ester of
glycerol, such as the PEG-100 stearate/glyceryl stearate mixture
sold for example by the company ICI under the name Arlacel 165,
oxyalkylenated sugar esters, and mixtures thereof.
[0319] Use is preferably made, as alkyl polyglucosides, of those
containing an alkyl group comprising from 6 to 30 carbon atoms and
preferably from 8 to 16 carbon atoms and containing a glucoside
group preferably comprising from 1.2 to 3 glucoside units. The
alkylpolyglucosides may be chosen, for example, from decylglucoside
(alkyl-C9/C11-polyglucoside (1.4)), for instance the product sold
under the name Mydol 10.RTM. by the company Kao Chemicals or the
product sold under the name Plantacare 2000 UP.RTM. by the company
Cognis; caprylyl/capryl glucoside, for instance the product sold
under the name Plantacare KE 3711.RTM. by the company Cognis;
laurylglucoside, for instance the product sold under the name
Plantacare 1200 UP.RTM. by the company Cognis; cocoyl glucoside,
for instance the product sold under the name Plantacare 818 UP.RTM.
by the company Cognis; caprylylglucoside, for instance the product
sold under the name Plantacare 810 UP.RTM. by the company Cognis;
and mixtures thereof.
[0320] The oxyalkylenated glycerol esters are especially
polyoxyethylenated derivatives of esters of glycerol and of a fatty
acid and of their hydrogenated derivatives. These oxyalkylenated
glycerol esters can be chosen, for example, from glyceryl esters of
fatty acids which are hydrogenated and oxyethylenated, such as
PEG-200 hydrogenated glyceryl palmate, sold under the name Rewoderm
LI-S 80 by the company Goldschmidt; oxyethylenated glyceryl
cocoates, such as PEG-7 glyceryl cocoate, sold under the name
Tegosoft GC by the company Goldschmidt, and PEG-30 glyceryl
cocoate, sold under the name Rewoderm LI-63 by the company
Goldschmidt; oxyethylenated glyceryl stearates; and mixtures
thereof.
[0321] The oxyalkylenated sugar esters are especially polyethylene
glycol ethers of fatty acid and sugar esters. These oxyalkylenated
sugar esters may be chosen, for example, from oxyethylenated
glucose esters, such as PEG-120 methyl glucose dioleate, sold under
the name Glucamate DOE 120 by the company Amerchol.
[0322] Preferably, the non-ionic surfactant(s) are chosen, alone or
as a mixture, from oxyalkylenated glycerol esters and
polyoxyalkylenated fatty acid esters optionally in combination with
a fatty acid ester of glycerol.
[0323] Preferentially, the non-ionic surfactant(s) are chosen from
PEG-200 hydrogenated glyceryl palmate, PEG-7 glyceryl cocoate and
PEG-30 glyceryl cocoate, the PEG-100 stearate/glyceryl stearate
mixture; and mixtures thereof.
[0324] In the context of the present invention, the term "gemini
surfactant" is intended to mean a dimer surfactant comprising two
surfactant units, each constituted of a hydrophilic head and a
hydrophobic tail and linked to one another, at the hydrophilic
heads, by a spacer group.
[0325] The gemini surfactants that can be used in the present
invention are in particular assembled in German patent application
DE 199 43 681, namely the compounds of formula (XI), described in
WO 96/14926:
##STR00025##
in which: [0326] R.sub.1 and R.sub.3 denote, independently of each
other, an alkyl radical containing from 1 to 25 carbon atoms;
[0327] R.sub.2 denotes a spacer group constituted of a linear or
branched alkylene chain containing from 1 to 12 carbon atoms;
[0328] X denotes a
--(C.sub.2H.sub.4O).sub.a--(C.sub.3H.sub.6O).sub.bZ group [0329] Y
denotes a --(C.sub.2H.sub.4O).sub.c--(C.sub.3H.sub.6O).sub.aZ group
[0330] Z denotes a hydrogen atom or a radical --CH.sub.2--COOM,
--SO.sub.3M, --P(O)(OM).sub.2, --C.sub.2H.sub.4--SO.sub.3M,
--C.sub.3H.sub.6--SO.sub.3M or --CH.sub.2(CHOH).sub.4CH.sub.2OH,
where M and M' represent a hydrogen atom or an alkali metal or
alkaline-earth metal ion or ammonium or alkanolammonium ion, [0331]
a and c, independently of one another, range from 0 to 15, [0332] b
and d, independently of one another, range from 0 to 10, and [0333]
the sum of a+b+c+d ranges from 1 to 25; and [0334] n ranges from 1
to 10.
[0335] Preferably, b and d are equal to 0.
[0336] R.sub.1 and R.sub.3 denote, independently of each other,
preferably an alkyl radical containing from 5 to 21 and more
particularly from 7 to 19 carbon atoms.
[0337] The gemini surfactant(s) are preferably such that each of
the groups R.sub.1--CO-- and R.sub.3--CO-- comprises from 8 to 20
carbon atoms, and preferably denotes a coconut fatty acid residue
(mainly comprising lauric acid and myristic acid).
[0338] In addition, the gemini surfactant(s) are preferably such
that the sum of a, b, c and d has an average value ranging from 10
to 20 and is preferably from 12 to 18 and more particularly equal
to 15.
[0339] A preferred group for Z is the group --SO.sub.3M, where M is
preferably an alkali metal ion, such as a sodium ion.
[0340] The spacer group R.sub.2 is advantageously constituted of a
linear C.sub.1-C.sub.3 alkylene chain, and preferably an ethylene
(--CH.sub.2CH.sub.2--) chain.
[0341] Finally, n is advantageously equal to 1.
[0342] A gemini surfactant is in particular the one identified by
the INCI name: Disodium Ethylene Dicocamide PEG-15 Disulfate,
having the following structure:
##STR00026##
in which R represents a coconut oil fatty acid and m+n has an
average value of 15.
[0343] Preferably, the gemini surfactant(s) according to the
invention are used as a mixture with other surfactants, and in
particular as a mixture with (a) a glyceryl ester of a
C.sub.6-C.sub.22 fatty acid (preferably C.sub.14-C.sub.20 such as a
stearate), (b) a diester of a C.sub.6-C.sub.22 fatty acid
(preferably C.sub.14-C.sub.20 such as a stearate) and of citric
acid and of glycerol (in particular a diester of a C.sub.6-C.sub.22
fatty acid and of glyceryl monocitrate), and (c) a
C.sub.10-C.sub.30 fatty alcohol (preferably behenyl alcohol).
[0344] The gemini surfactant(s) may be used, for example, as a
mixture with other surfactants in the form of the products sold by
the company Sasol under the name Ceralution.RTM., and in particular
the following products: [0345] Ceralution.RTM. H: Behenyl Alcohol,
Glyceryl Stearate, Glyceryl Stearate Citrate and disodium ethylene
dicocoamide PEG-15 disulfate, [0346] Ceralution.RTM. F: Sodium
Lauroyl Lactylate and disodium ethylene dicocamide PEG-15
disulfate. [0347] Ceralution.RTM. C: Capric/Caprylic triglyceride,
Ceteareth-25, disodium ethylene dicocamide PEG-15 disulfate, Sodium
Lauroyl Lactylate, Behenyl Alcohol, Glyceryl Stearate, Glyceryl
Stearate Citrate, (INCI names).
[0348] The gemini surfactant represents from 3 to 50% of the weight
of these mixtures.
[0349] The gemini surfactant can be present in the composition
according to the invention in a content of active material ranging
from 0.05 to 10% by weight, preferably ranging from 0.1 to 5% by
weight and better still ranging from 0.2 to 2% by weight, relative
to the total weight of the composition.
[0350] According to one preferred embodiment of the invention, the
composition according to the present invention also comprises one
or more surfactants chosen from PEG-200 hydrogenated glyceryl
palmate, PEG-7 glyceryl cocoate, PEG-30 glyceryl cocoate, the
PEG-100 stearate/glyceryl stearate mixture, stearic acid, disodium
ethylene dicocamide PEG-15 disulfate; and mixtures thereof.
[0351] The surfactant(s) can also be chosen from silicone
surfactants, for instance dimethicone copolyols, such as the
mixture of cyclomethicone and of dimethicone copolyol, sold under
the name DC 5225 C.RTM. by the company Dow Corning, and
alkyldimethicone copolyols such as laurylmethicone copolyol sold
under the name Dow Corning 5200 Formulation Aid by the company Dow
Corning; cetyldimethicone copolyol, such as the product sold under
the name Abil EM 90R.RTM. by the company Goldschmidt, and the
mixture of cetyldimethicone copolyol, of polyglyceryl isostearate
(4 mol) and of hexyl laurate, sold under the name Abil WE 09.RTM.
by the company Goldschmidt. One or more coemulsifiers, which may be
chosen advantageously from the group comprising polyol alkyl
esters, may also be added thereto.
[0352] Mention may also be made of non-silicone emulsifying
surfactants, in particular alkyl esters or ethers of a polyol. As
alkyl esters of a polyol, mention may in particular be made of
polyethylene glycol esters, for instance PEG-30
dipolyhydroxystearate, such as the product sold under the name
Arlacel P135.RTM. by the company ICI.
[0353] Amphiphilic Polymers
[0354] The composition according to the present invention may
optionally also comprise one or more amphiphilic polymers.
[0355] The amphiphilic polymer(s) used in the composition according
to the invention can be polymers derived from
2-acrylamido-2-methylpropanesulfonic acid (AMPS) comprenant: [0356]
(a) from 80 mol % to 99 mol % of
2-acrylamido-2-methylpropanesulfonic acid (AMPS) units of formula
(XII) below:
##STR00027##
[0356] in which X is a proton, an alkali metal cation, an
alkaline-earth metal cation or the ammonium ion; it being
understood that when X represents an alkaline-earth metal cation,
it shares two positive charges with two SO.sub.3-- groups; and
[0357] (b) from 1 mol % to 20 mol % and preferably from 1 mol % to
15 mol % of units of formula (XIIbis) below:
##STR00028##
[0357] in which n and p, independently of each other, denote a
number of moles and ranges from 0 to 30 and preferably from 1 to
20, with the proviso that n+p is less than or equal to 30,
preferably less than 25 and better still less than 20; R.sub.1
denotes a hydrogen atom or a linear or branched C.sub.1-C.sub.6
alkyl radical (preferably methyl) and R.sub.3 denotes a linear or
branched alkyl group comprising m carbon atoms, ranging from 6 to
30 and preferably from 10 to 25 carbon atoms.
[0358] The term "amphiphilic polymer" is intended to mean a polymer
which comprises at least one hydrophilic portion (or block) and at
least one hydrophobic portion (or block). This polymer is
water-soluble or water-dispersible.
[0359] The amphiphilic polymers used in the composition of the
invention are water-soluble or water-dispersible. The term
"water-soluble or water-dispersible polymer" is intended to mean a
polymer which, when introduced into water at a concentration equal
to 1% by weight, gives a macroscopically homogeneous solution of
which the light transmittance, at a wavelength equal to 500 nm,
through a sample 1 cm thick, is at least 10%, which corresponds to
an absorbance [abs=-log(transmittance)] of less than 1.5.
[0360] The amphiphilic polymers in accordance with the invention
generally have a weight-average molar mass ranging from 50 000 to
10 000 000, more preferentially from 100 000 to 8 000 000 and even
more preferentially from 200 000 to 3 000 000.
[0361] The polymers in accordance with the invention are
preferentially partially or totally neutralized with a mineral
base, for instance sodium hydroxide, potassium hydroxide or aqueous
ammonia, or with an organic base such as monoethanolamine,
diethanolamine, triethanolamine, aminomethylpropanediol,
N-methylglucamine, or basic amino acids, for instance arginine and
lysine, and mixtures thereof.
[0362] The polymers used according to the invention may be obtained
according to the standard free-radical polymerization processes in
the presence of one or more initiators such as, for example,
azobisisobutyronitrile (AIBN), azobisdimethylvaleronitrile,
2,2-azobis[2-amidinopropane] hydrochloride (ABAH), organic
peroxides such as dilauryl peroxide, benzoyl peroxide, tert-butyl
hydroperoxide, etc., mineral peroxide compounds such as potassium
persulfate or ammonium persulfate, or H.sub.2O.sub.2 optionally in
the presence of reducing agents.
[0363] The polymers are obtained especially by free-radical
polymerization in tert-butanol medium in which they precipitate.
Using polymerization in tert-butanol, it is possible to obtain a
size distribution of the polymer particles that is particularly
favourable for its uses.
[0364] The polymerization reaction may be performed at a
temperature of between 0 and 150.degree. C., preferably between 20
and 100.degree. C., either at atmospheric pressure or under reduced
pressure. It may also be performed under inert atmosphere and
preferably under nitrogen.
[0365] The amphiphilic polymers of AMPS used in the composition
according to the invention are non-crosslinked.
[0366] As AMPS-based polymers that may be used in the composition
according to the invention, mention may be made of the polymers
prepared from 2-acrylamido-2-methylpropanesulfonic acid (AMPS) or a
sodium or ammonium salt thereof, with an ester of (meth)acrylic
acid and of an oxyethylenated C.sub.10 to C.sub.20 alcohol
comprising from 6 to 25 oxyethylene groups.
[0367] Mention may be made in particular of the polymers prepared
from 2-acrylamido-2-methylpropanesulfonic acid (AMPS), or a sodium
or ammonium salt thereof, with an ester of (meth)acrylic acid and:
[0368] of a C.sub.10-C.sub.18 alcohol oxyethylenated with 8 mol of
ethylene oxide (Genapol C-080 from Clariant), [0369] of a C.sub.11
oxo alcohol oxyethylenated with 8 mol of ethylene oxide (Genapol
UD-080 from Clariant), [0370] of a C.sub.11 oxo alcohol
oxyethylenated with 7 mol of ethylene oxide (Genapol UD-070 from
Clariant), [0371] of a C.sub.12-C.sub.14 alcohol oxyethylenated
with 7 mol of ethylene oxide (Genapol LA-070 from Clariant), [0372]
of a C.sub.12-C.sub.14 alcohol oxyethylenated with 9 mol of
ethylene oxide (Genapol LA-090 from Clariant), [0373] of a
C.sub.12-C.sub.14 alcohol oxyethylenated with 11 mol of ethylene
oxide (Genapol LA-110 from Clariant), [0374] of a C.sub.16-C.sub.18
alcohol oxyethylenated with 8 mol of ethylene oxide (Genapol T-080
from Clariant), [0375] of a C.sub.16-C.sub.18 alcohol
oxyethylenated with 11 mol of ethylene oxide (Genapol T-110 from
Clariant), [0376] of a C.sub.16-C.sub.18 alcohol oxyethylenated
with 15 mol of ethylene oxide (Genapol T-150 from Clariant), [0377]
of a C.sub.16-C.sub.18 alcohol oxyethylenated with 20 mol of
ethylene oxide (Genapol T-200 from Clariant), [0378] of a
C.sub.16-C.sub.18 alcohol oxyethylenated with 25 mol of ethylene
oxide (Genapol T-250 from Clariant), [0379] of a C.sub.18-C.sub.22
alcohol oxyethylenated with 25 mol of ethylene oxide, [0380] of a
C.sub.16-C.sub.18 isoalcohol oxyethylenated with 25 mol of ethylene
oxide.
[0381] According to one preferred embodiment, the amphiphilic
polymer is a copolymer of AMPS and of a C.sub.16-C.sub.18 alkyl
methacrylate comprising from 6 to 25 mol of oxyethylene groups,
obtained from methacrylic acid or a methacrylic acid salt and from
a C.sub.16-C.sub.18 alcohol oxyethylenated with 6 to 25 mol of
ethylene oxide. The amphiphilic polymer may also be a copolymer of
AMPS and of a C.sub.12-C.sub.14 alkyl methacrylate comprising from
6 to 25 oxyethylene groups, obtained from methacrylic acid or a
methacrylic acid salt and from a C.sub.12-C.sub.14 alcohol
oxyethylenated with 6 to 25 mol of ethylene oxide.
[0382] As amphiphilic polymers that are preferred according to the
present invention, mention may be made of: [0383] the
non-crosslinked copolymer obtained from 92.65 mol % of AMPS and
7.35 mol % of a C.sub.16-C.sub.18 alkyl methacrylate comprising 8
oxyethylene groups (Genapol T-080), such as the product sold by the
company Clariant under the name Aristoflex SNC; [0384] the
non-crosslinked copolymer obtained from 91.5 mol % of AMPS and 8.5
mol % of a C.sub.12-C.sub.14 alkyl methacrylate comprising 7
oxyethylene groups (Genapol LA-070), such as the product sold by
the company Clariant under the name Aristoflex LNC; [0385] and
mixtures thereof.
[0386] The amphiphilic polymer(s) as described above are optionally
present in the composition according to the invention in a content
of between 0.01% and 10% by weight, preferably between 0.05% and 5%
by weight, more preferentially between 0.1% and 3% by weight,
relative to the total weight of the composition.
[0387] Salts of an Ester of Phosphoric Acid and of a Fatty
Alcohol
[0388] The composition according to the present invention can
optionally additionally comprise one or more salts of an ester of
phosphoric acid and of a fatty alcohol.
[0389] The alkali metal salts of an ester of phosphoric acid and of
a fatty alcohol in accordance with the invention correspond to
formula (XIII) below:
(R'O)--P(O)--(O.sup.-M).sub.2 (XIII)
in which R' represents a linear or branched, saturated
C.sub.8-C.sub.22 alkyl group and M represents an alkali metal such
as sodium or potassium, and even more preferentially potassium;
[0390] R' can denote for example lauryl, cetyl, stearyl and more
preferentially cetyl. The salts of an ester of phosphoric acid and
of a fatty alcohol can be in the form of a salt of a mixture of
esters of phosphoric acid and of a fatty alcohol.
[0391] According to one preferred mode of the invention, use will
be made of a potassium salt of a mixture of esters of phosphoric
acid and of cetyl alcohol, having the INCI name Potassium Cetyl
Phosphate, for example the product sold under the trade name
Amphisol K.RTM. by the company DSM Nutritional Products Inc, or the
product sold under the trade name Evermap 160K.RTM. by the company
Sino Lion (USA) Ltd., or the product sold under the trade name
Hostaphat CK 100 .RTM. by the company Clariant International
Ltd.
[0392] The salt(s) of an ester of phosphoric acid and of a fatty
alcohol as described above are optionally present in the
composition according to the invention in a content of between 0.1%
and 5% by weight, and more preferentially from 0.10% to 3% by
weight, relative to the total weight of the composition.
[0393] Additives
[0394] The composition according to the present invention can
optionally also comprise one or more additives, different from the
compounds of the invention and normally used in cosmetics, and
particularly in the field of anti-sun, care and makeup products,
such as alcohols such as ethanol; glycols, such as dipropylene
glycol and butylene glycol; glycerol; active agents; salts; organic
particles; amphiphilic polymers, such as the Pemulens TR1 or TR2 or
Carbopol ETD2020, sold by the company Lubrizol; hydrophilic
polymers, such as poly(N-vinylpyrrolidone); polysaccharides, for
instance guar gums, xanthan gums and cellulose-based derivatives;
water-soluble or water-dispersible silicone derivatives, for
instance acrylic silicones, polyether silicones and cationic
silicones; and mixtures thereof.
[0395] As active agents, mention may in particular be made of
vitamins (A, C, E, K, PP, etc), alone or as a mixture, and also
derivatives thereof, keratolytic and/or desquamating agents
(salicylic acid and derivatives thereof, alpha-hydroxy acids,
ascorbic acid and derivatives thereof); depigmenting agents;
tensioning agents such as synthetic polymers; plant proteins;
polysaccharides of plant origin optionally in the form of
microgels; wax dispersions; mixed silicates and colloidal particles
of inorganic fillers; matting agents; agents for preventing hair
loss and/or hair restorers; or anti-wrinkle agents; and mixtures
thereof.
[0396] Of course, those skilled in the art will take care to select
this or these optional additional compound(s) such that the
advantageous properties intrinsically associated with the
composition in accordance with the invention are not, or are not
substantially, adversely affected by the envisaged addition(s).
[0397] The above additives may generally be present in an amount,
for each of them, of between 0 and 20% by weight relative to the
total weight of the composition.
[0398] Forms of the Composition
[0399] The compositions according to the invention may be prepared
according to the techniques that are well known to those skilled in
the art. They may in particular be in the form of a simple or
complex emulsion (oil-in-water, or abbreviated to O/W, water-in-oil
or W/O, oil-in-water-in-oil or O/W/O, or water-in-oil-in-water or
W/O/W), such as a cream, a milk or a cream gel.
[0400] When the composition according to the invention is in the
form of an oil-in-water emulsion, the composition according to the
invention comprises a continuous aqueous phase and at least one
oily phase dispersed in the aqueous phase.
[0401] When the composition according to the invention is in the
form of a water-in-oil emulsion, the composition according to the
invention comprises a continuous oily phase and at least one
aqueous phase dispersed in the oily phase.
[0402] According to the invention, the aqueous phase contains water
and optionally other water-soluble or water-miscible organic
solvents.
[0403] An aqueous phase that is suitable for use in the invention
may comprise, for example, a water chosen from a natural spring
water, such as water from La Roche-Posay, water from Vittel or
waters from Vichy, or a floral water.
[0404] The water-soluble or water-miscible solvents that are
suitable for use in the invention comprise short-chain
monoalcohols, for example C.sub.2-C.sub.4 monoalcohols, such as
ethanol or isopropanol; diols or polyols, such as ethylene glycol,
propylene glycol, 1,3-butylene glycol, hexylene glycol, diethylene
glycol, dipropylene glycol, propane-1,3-diol, pentylene glycol,
caprylyl glycol, 2-ethoxyethanol, diethylene glycol monomethyl
ether, triethylene glycol monomethyl ether, glycerol and sorbitol,
and mixtures thereof.
[0405] According to one preferred embodiment of the invention, use
may more particularly be made of ethanol, propylene glycol,
glycerol, propane-1,3-diol, and mixtures thereof.
[0406] In particular, the water may be present in a total quantity
ranging from 30 to 99% by weight, preferably from 50 to 99% by
weight, and better still from 60 to 98% by weight, relative to the
total weight of the aqueous phase.
[0407] The water may be present in a total quantity greater than or
equal to 30% by weight, preferably greater than or equal to 45% by
weight, and preferentially ranges from 45% to 65% by weight,
relative to the total weight of composition.
[0408] According to the invention, the term "oily phase" is
intended to mean a phase comprising at least one oil and all of the
liposoluble and lipophilic ingredients and the fatty substances
used for the formulation of the compositions of the invention.
[0409] The term "oil" is intended to mean any fatty substance that
is in liquid form at ambient temperature (25.degree. C.) and at
atmospheric pressure (1.013.times.10.sup.5 Pa).
[0410] The term "fatty substance" is intended to mean an organic
compound that is insoluble in water at ambient temperature
(25.degree. C.) and at atmospheric pressure (1.013.times.10.sup.5
Pa) (solubility of less than 5% by weight, preferably less than 1%
by weight and even more preferably less than 0.1% by weight). The
fatty substances have in their structure at least one
hydrocarbon-based chain comprising at least six carbon atoms and/or
a sequence of at least two siloxane groups. In addition, the fatty
substances are generally soluble in organic solvents under the same
temperature and pressure conditions, for instance chloroform,
dichloromethane, carbon tetrachloride, ethanol, benzene, toluene,
tetrahydrofuran (THF), liquid petroleum jelly or
decamethylcyclopentasiloxane.
[0411] The oils suitable for the invention may be volatile or
non-volatile.
[0412] The oils suitable for the invention may be chosen from
hydrocarbon-based oils, silicone oils and fluoro oils, and mixtures
thereof.
[0413] A hydrocarbon-based oil that is suitable for use in the
invention may be an animal hydrocarbon-based oil, a plant
hydrocarbon-based oil, a mineral hydrocarbon-based oil or a
synthetic hydrocarbon-based oil.
[0414] An oil that is suitable for use in the invention may be
advantageously chosen from mineral hydrocarbon-based oils, plant
hydrocarbon-based oils, synthetic hydrocarbon-based oils and
silicone oils, and mixtures thereof.
[0415] For the purposes of the present invention, the term
"silicone oil" means an oil comprising at least one silicon atom,
and especially at least one Si--O group.
[0416] The term "hydrocarbon-based oil" means an oil mainly
containing hydrogen and carbon atoms.
[0417] The term "fluoro oil" refers to an oil comprising at least
one fluorine atom.
[0418] A hydrocarbon-based oil that is suitable for use in the
invention may also optionally comprise oxygen, nitrogen, sulfur
and/or phosphorus atoms, for example in the form of hydroxyl,
amine, amide, ester, ether or acid groups, and in particular in the
form of hydroxyl, ester, ether or acid groups.
[0419] The oily phase may comprise one or more volatile or
non-volatile hydrocarbon-based oils and/or one or more volatile
and/or non-volatile silicone oils.
[0420] For the purposes of the invention, the term "volatile oil"
is intended to mean an oil that is capable of evaporating on
contact with the skin or the keratin fibre in less than one hour,
at ambient temperature and atmospheric pressure. The volatile
oil(s) of the invention are volatile cosmetic oils that are liquid
at ambient temperature with a non-zero vapour pressure, at ambient
temperature and atmospheric pressure ranging in particular from
0.13 Pa to 40 000 Pa (10-3 to 300 mmHg), in particular ranging from
1.3 Pa to 13 000 Pa (0.01 to 100 mmHg) and more particularly
ranging from 1.3 Pa to 1300 Pa (0.01 to 10 mmHg).
[0421] The term "non-volatile oil" is intended to mean an oil that
remains on the skin or the keratin fibre at ambient temperature and
atmospheric pressure for at least several hours, and that in
particular has a vapour pressure of less than 10-3 mmHg (0.13
Pa).
[0422] Among the non-volatile hydrocarbon-based oils that can be
used according to the invention, mention may be made of glyceride
triesters and in particular caprylic/capric acid triglycerides such
as those sold by the company Stearineries Dubois or those sold
under the names Miglyol 810.RTM., 812.RTM. and 818.RTM. by the
company Dynamit Nobel, fatty amides such as isopropyl N-lauroyl
sarcosinate, such as the product sold under the trade name Eldew SL
205.RTM. from Ajinomoto, synthetic esters, and in particular
isononyl isononanoate, diisopropyl sebacate, C.sub.12-C.sub.15
alkyl benzoate, such as the product sold under the trade name
Finsolv TN.RTM. or Witconol TN.RTM. by the company Witco or
Tegosoft TN.RTM. by the company Evonik Goldschmidt,
2-ethylphenylbenzoate, such as the commercial product sold under
the name X-Tend 226.RTM. by the company ISP, and fatty alcohols, in
particular octyldodecanol.
[0423] As volatile hydrocarbon-based oils that may be used
according to the invention, mention may be made in particular of
hydrocarbon-based oils having from 8 to 16 carbon atoms and in
particular of branched C.sub.8-C.sub.16 alkanes, such as
C.sub.8-C.sub.16 isoalkanes of petroleum origin (also known as
isoparaffins), such as isododecane (also known as
2,2,4,4,6-pentamethylheptane), isodecane or isohexadecane, the oils
sold under the Isopar or Permethyl trade names, branched
C.sub.8-C.sub.16 esters, isohexyl neopentanoate, and mixtures
thereof.
[0424] Among the non-volatile silicone oils, mention may be made of
non-volatile polydimethylsiloxanes (PDMSs), polydimethylsiloxanes
comprising alkyl or alkoxy groups which are pendent and/or at the
end of the silicone chain, which groups each contain from 2 to 24
carbon atoms, or phenyl silicones, such as phenyl trimethicones,
phenyl dimethicones, phenyl(trimethylsiloxy)diphenylsiloxanes,
diphenyl dimethicones, diphenyl(methyldiphenyl)trisiloxanes or
(2-phenylethyl)trimethylsiloxysilicates.
[0425] Among the volatile silicone oils, mention may for example be
made of volatile linear or cyclic silicone oils, in particular
those with a viscosity at 25.degree. C. of less than or equal to 8
centistokes (8.times.10.sup.-6 m.sup.2/s) and in particular
containing from 2 to 7 silicon atoms, these silicones optionally
comprising alkyl or alkoxy groups containing from 1 to 10 carbon
atoms. As volatile silicone oils that may be used in the invention,
mention may be made especially of octamethylcyclotetrasiloxane,
decamethylcyclopentasiloxane, dodecamethylcyclohexasiloxane,
heptamethylhexyltrisiloxane, heptamethyloctyltrisiloxane,
hexamethyldisiloxane, octamethyltrisiloxane,
decamethyltetrasiloxane and dodecamethylpentasiloxane, and mixtures
thereof.
[0426] Among the volatile fluoro oils, mention may be made of
nonafluoromethoxybutane, decafluoropentane, tetradecafluorohexane
and dodecafluoropentane, and mixtures thereof.
[0427] An oily phase according to the invention may also comprise
other fatty substances, mixed with or dissolved in the oil.
[0428] Another fatty substance that may be present in the oily
phase may be, for example: [0429] a fatty acid, for example chosen
from fatty acids comprising from 8 to 30 carbon atoms, such as
lauric acid, palmitic acid, oleic acid and stearic acid; [0430] a
wax chosen from waxes such as lanolin, beeswax, camauba or
candelilla wax, paraffin waxes, lignite waxes, microcrystalline
waxes, ceresin or ozokerite, or synthetic waxes, such as
polyethylene waxes or Fischer-Tropsch waxes; [0431] a gum chosen
from silicone gums (dimethiconol); [0432] a pasty compound, such as
polymeric or non-polymeric silicone compounds, esters of a glycerol
oligomer, arachidyl propionate, fatty acid triglycerides and
derivatives thereof; [0433] and mixtures thereof.
[0434] When the composition according to the invention is in the
form of an oil-in-water emulsion, the amount of aqueous phase
preferably ranges from 50% to 95% by weight, more preferentially
from 50% to 90% by weight, even better still from 50% to 80% by
weight, and even more preferentially from 55% to 75% by weight,
relative to the total weight of the composition.
[0435] The amount of oily phase preferably ranges from 5% to 50% by
weight and more preferentially from 10% to 45% by weight, relative
to the total weight of the composition.
[0436] The numerical mean size of the droplets of oil, present in
the composition of the invention, preferably ranges from 0.4 to 40
microns and more preferentially from 1 to 20 microns.
[0437] This numerical mean size can be measured using a particle
size analyser.
[0438] When the composition according to the invention is in the
form of a water-in-oil emulsion, the amount of oily phase
preferably ranges from 50% to 95% by weight, more preferentially
from 50% to 90% by weight, even better still from 50% to 80% by
weight, and even more preferentially from 55% to 75% by weight,
relative to the total weight of the composition.
[0439] The amount of aqueous phase preferably ranges from 5% to 50%
by weight and more preferentially from 10% to 45% by weight,
relative to the total weight of the composition.
[0440] The numerical mean size of the droplets of water, present in
the composition of the invention, preferably ranges from 0.4 to 40
microns and more preferentially from 1 to 20 microns.
[0441] This numerical mean size can be measured using a particle
size analyser.
[0442] In the case of compositions in the form of oil-in-water or
water-in-oil emulsions, the emulsification processes that may be
used are of the paddle or impeller, rotor-stator and HHP (high
hydrostatic pressure) type.
[0443] In order to obtain stable emulsions with a low content of
polymer (oil/polymer ratio >25), it is possible to prepare the
dispersion in concentrated phase and then to dilute the dispersion
with the remainder of the aqueous phase.
[0444] The emulsions generally contain at least one emulsifier
chosen from amphoteric, anionic, cationic or non-ionic surfactants
as described above, used alone or as a mixture. The emulsifiers are
chosen in an appropriate manner according to the emulsion to be
obtained (W/O or O/W emulsion).
[0445] When it is an emulsion, the aqueous phase of this emulsion
may comprise a non-ionic vesicular dispersion prepared according to
known processes (Bangham, Standish and Watkins, J. Mol. Biol. 13,
238 (1965), FR 2 315 991 and FR 2 416 008).
[0446] The compositions according to the invention may also be in
the form of an anhydrous composition, for instance in the form of
an oil. The term "anhydrous composition" is intended to mean a
composition containing less than 2% by weight of water, preferably
less than 1% by weight of water, and even more preferentially less
than 0.5% by weight of water relative to the total weight of the
composition, or even a composition that is free of water. In
compositions of this type, the water possibly present is not added
during the preparation of the composition, but corresponds to the
residual water provided by the mixed ingredients. They may
optionally be packaged in aerosol form and may be in the form of a
mousse or a spray.
[0447] The anhydrous compositions according to the invention
comprise at least one oil, preferably chosen from those described
above, and more preferentially chosen from hydrocarbon-based oils,
silicone oils, fluoro oils, and/or mixtures thereof.
[0448] According to one preferred embodiment of the invention, the
composition according to the invention comprises at least one oil
chosen from hydrocarbon-based oils, silicone oils, fluoro oils,
and/or mixtures thereof.
[0449] According to a first variant of this preferred embodiment,
the composition according to the invention is in the form of an
oil-in-water or water-in-oil emulsion, preferentially in the form
of an oil-in-water emulsion.
[0450] According to a second variant of this preferred embodiment,
the composition according to the invention is in the form of an
anhydrous composition.
[0451] The cosmetic compositions according to the invention may
have a liquid to semi-liquid consistency, such as milks, more or
less smooth creams, cream gels, or pastes. They may optionally be
packaged in aerosol form and may be in the form of a mousse or a
spray.
[0452] The compositions according to the invention in the form of
vapourizable fluid lotions in accordance with the invention are
applied to the skin or hair in the form of fine particles by means
of pressurizing devices. The devices in accordance with the
invention are well known to those skilled in the art and comprise
non-aerosol pumps or "atomizers", aerosol containers comprising a
propellant and aerosol pumps using compressed air as propellant.
These devices are described in patents U.S. Pat. Nos. 4,077,441 and
4,850,517.
[0453] The compositions packaged in aerosol form in accordance with
the invention generally contain conventional propellants, for
instance hydrofluoro compounds, dichlorodifluoromethane,
difluoroethane, dimethyl ether, isobutane, n-butane, propane or
trichlorofluoromethane. They are preferably present in amounts
ranging from 15% to 50% by weight relative to the total weight of
the composition.
[0454] The cosmetic compositions according to the invention may be
used as care products and/or anti-sun protection products for the
face and/or the body.
[0455] A subject of the present invention is also a cosmetic method
for treating the skin, in particular human skin, against UV
radiation, comprising at least one step of applying to the skin a
composition as defined previously.
[0456] A subject of the present invention is also the use of at
least one compound capable of accepting the triplet excited level
energy of said dibenzoylmethane derivative compound(s) as defined
previously, for photostabilizing with respect to UV radiation, a
composition comprising at least one dibenzoylmethane derivative
compound (i) as defined previously and at least one merocyanine
compound (ii) as defined previously; preferably, the UV radiation
corresponds to solar radiation.
[0457] A subject of the present invention is also a composition as
defined previously, for use in a method for protecting the skin
against UV radiation, in particular against solar radiation.
[0458] The examples that follow serve to illustrate the invention
without, however, being limiting in nature.
EXAMPLES
[0459] The compositions 1, 2 and 3 are prepared from the
ingredients shown in the table below, the amounts of which are
expressed as weight percentages of active material (AM).
TABLE-US-00001 Composition Composition Composition 1 2 3 Phases
Ingredients (Comparative) (Invention) (Invention) A Water qs qs qs
Glycerol 5 5 5 Triethanolamine 0.45 0.45 0.45 Disodium EDTA 0.1 0.1
0.1 Preservative qs qs qs Ammonium acryloyldimethyltaurate/ 0.5 0.5
0.5 Steareth-8 Methacrylate Copolymer (ARISTOFLEX SNC .RTM.) B
Isopropyl Lauroyl Sarcosinate 30 30 30
4-tert-butyl-4'-methoxydibenzoylmethane 2 2 2 2-ethoxyethyl
2-cyano{3-[(3- 1 1 1 methoxypropyl)amino]cyclohex-2-en-1-
ylidene}ethanoate Diethylhexyl syringylidenemalonate + -- 2 --
90/10 Caprylic/Capric Triglyceride (OXYNEX ST LIQUID)
Tris(Tetramethylhydroxypiperidinol) -- -- 0.01 Citrate (TINOGARD
QS) Stearyl Alcohol 1 1 1 Glyceryl Isostearate 0.5 0.5 0.5 C
Isohexadecane 1 1 1 Xanthan gum 0.2 0.2 0.2 Ammonium
Polyacryloyldimethyl 0.4 0.4 0.4 Taurate (HOSTACERIN AMPS
.RTM.)
[0460] Composition Preparation Method:
[0461] The aqueous phase A and the oily phase B were prepared by
mixing the starting materials with mechanical stirring at
80.degree. C. Once the aqueous phase A and the oily phase B are
macroscopically homogeneous, the emulsion is prepared by
introducing the phase B into the phase A with stirring by means of
a rotor-stator homogenizer at a stirring speed of 4500 revolutions
per minute for 20 minutes. The phase C is then added, and the
composition is called to ambient temperature (25.degree. C.).
[0462] Results:
[0463] Once the compositions 1 to 3 have been prepared, these are
then irradiated under a UV-A sun lamp at 21.6 J/cm.sup.2, for one
hour.
[0464] After irradiation, the residual contents of the compounds
4-tert-butyl-4'-methoxydibenzoylmethane and 2-ethoxyethyl
2-cyano{3-[(3-methoxypropyl)amino]-cyclohex-2-en-1-ylidene}ethanoate
in each of the compositions were measured by conventional HPLC
chromatography methods.
[0465] The residual content of the ingredient corresponds to the
weight ratio of the content of the ingredient after UV irradiation
to the content of the ingredient before UV irradiation. The
residual contents are expressed as percentages.
[0466] The results obtained are collated in the table below:
TABLE-US-00002 Composition 1 Composition 2 Composition 3 Residual
contents after irradiation (Comparative) (Invention) (Invention)
4-tert-butyl-4'- 72% 86% 87% methoxydibenzoylmethane 2-ethoxyethyl
2-cyano{3-[(3- 46% 72% 71% methoxypropyl)amino]cyclohex-
2-en-1-ylidene}ethanoate
[0467] These results show that the compositions 2 and 3 according
to the invention exhibit residual contents of the dibenzoylmethane
derivative and of the merocyanine compound that are substantially
higher compared with the comparative composition 1, and thus
exhibit better photostability with respect to UV radiation.
* * * * *