Cosmetic or dermatological composition comprising a merocyanine and a
UVA-screening agent of the amino-substituted 2-hydroxybenzophenone type
and/or a hydrophilic organic UVA-screening agent
The present invention relates to a cosmetic or dermatological composition
comprising, in a physiologically acceptable support:
a) at least one oily phase
b) at least one merocyanine compound of formula ( 1 ) defined herein below and
c) at least one UVA-screening agent chosen from:
(i) an amino-substituted 2-hydroxybenzophenone compound
(ii) a hydrophilic organic UVA-screening agent , and
(iii) their mixtures ;
the said hydrophilic UVA-screening agent being present in an amount of greater
than 0.5% by weight relative to the total weight of the composition.
The present invention also relates to a non-therapeutic cosmetic process for
caring for and/or making up a keratin material, comprising the application to the
surface of the said keratin material of at least one composition according to the
invention as defined above.
The invention also relates to a non-therapeutic cosmetic process for limiting the
darkening of the skin and/or the improving the colour and/or the uniformity of the
complexion, comprising the application to the surface of the keratin material of at
least one composition as defined previously.
The invention also relates to a non-therapeutic cosmetic process for preventing
and/or treating the signs of ageing of a keratin material, comprising the application
to the surface of the keratin material of at least one composition as defined
previously.
It is known that UV-A rays with wavelengths of between 320 and 400 nm penetrate
more deeply into the skin than UV-B rays. UV-A rays cause immediate and
persistent browning of the skin. Daily exposure to UVA rays, even of short
duration, under normal conditions can result in damage to the collagen fibres and
the elastin, which is reflected by a modification in the microrelief of the skin, the
appearance of wrinkles and uneven pigmentation (liver spots, lack of uniformity of
the complexion).
Protection against UVA rays is thus necessary.
Many photoprotective compositions have been proposed to date to overcome the
effects induced by UVA rays. They generally contain organic or mineral UVscreening
agents, which function according to their own chemical nature and
according to their own properties by absorption, reflection or scattering of the UV
rays. They generally comprise mixtures of liposoluble organic screening agents
and/or water-soluble UV-screening agents in combination with metal oxide
pigments, such as titanium dioxide or zinc oxide.
It is also known that radiation with wavelengths of between 280 nm and 400 nm
permits tanning of the human epidermis and that radiation with wavelengths of
between 280 and 320 nm, known as UV-B rays, harms the development of a
natural tan. Exposure is also liable to bring about a detrimental change in the
biomechanical properties of the epidermis, which is reflected by the appearance of
wrinkles, leading to premature ageing of the skin.
Protection against UVA and UVB rays is thus necessary. An efficient
photoprotective product should protect against both UVA and UVB rays.
Combinations of UV-screening agents which absorb UVA radiation and screening
agents which absorb UVB radiation are generally used in antisun formulations, so
as to obtain the broadest possible protection.
Many cosmetic compositions for limiting the darkening of the skin and improving
the colour and the uniformity of the complexion have been proposed to date. It is
well known in the field of antisun products that such compositions may be obtained
by using UV-screening agents, and in particular UVB-screening agents. Certain
compositions may also contain UVA-screening agents. This screening system
should cover UVB protection for the purpose of limiting and controlling the
neosynthesis of melanin, which promotes the overall pigmentation, but should also
cover UVA protection so as to limit and control the oxidation of the already existing
melanin leading to darkening of the skin colour.
However, it is extremely difficult to find a composition which contains a particular
combination of UV-screening agents that would be especially suited to improving
the quality of the skin as regards both the colour and its mechanical elasticity
properties. This improvement is particularly sought on already pigmented skin so
as not to increase the melanin pigmentary load or the structure of the melanin
already present in the skin.
In point of fact, the majority of the organic UV-screening agents consist of aromatic
compounds which absorb in the wavelength range between 280 and 370 nm. In
addition to their power for screening out sunlight, the desired photoprotective
compounds should also have good cosmetic properties, good solubility in the
usual solvents and in particular in fatty substances such as oils, and also good
chemical stability and good photostability alone or in combination with other UVscreening
agents. They should also be colourless or at least have a colour that is
cosmetically acceptable to the consumer.
One of the main drawbacks known to date is that these organic systems for
screening out UVA radiation are insufficiently effective against UVA rays and
particularly against long UVA rays with wavelengths beyond 370 nm.
In this respect, a particularly advantageous family of UVA-screening agents is
currently composed of amino-substituted 2-hydroxybenzophenone derivatives and
especially n-hexyl 2-(4-diethylamino-2-hydroxybenzoyl)benzoate, which in fact
show high intrinsic absorbing power. These amino-substituted 2-
hydroxybenzophenone derivatives are known per se and their structures and
syntheses are described in patent applications EP-A-1 046 391 , EP 1 133 980, DE
100 12 408 and WO 2007/071 584.
n-Hexyl 2-(4-diethylamino-2-hydroxybenzoyl)benzoate is more particularly known,
which is sold under the trade name Uvinul A Plus® by the company BASF.
However, these compounds do not afford broad UV protection over the range from
320 to 400 nm. Specifically, they afford protection from 320 nm to 370 nm, and at
best to 380 nm in large amounts, but do not in particular make it possible to obtain
observable absorbance up to a wavelength of 400 nm inclusive.
Among the UVA-screening agents, hydrophilic aromatic organic molecules which
absorb in the wavelength range between 320 and 370 nm are particularly
advantageous. Specifically, their solubility in the aqueous phase reduces the
amounts of oil needed in the formulations and thus limits the cosmetic drawbacks
often caused by the presence of lipophilic UV-screening agents, such as the
greasy aspect on application. They may be used especially in oil-in-water
emulsions (i.e. a cosmetically and/or dermatologically acceptable support
consisting of an aqueous dispersing continuous phase and of a fatty dispersed
discontinuous phase) or water-in-oil emulsions (aqueous phase dispersed in a
continuous fatty phase).
Among the hydrophilic organic UVA-screening agents, benzene-1 ,4-bis(3-
methylidene-1 0-camphorsulfonic acid) and the various salts thereof are especially
known, which are described especially in patent applications FR-A-2 528 420 and
FR-A-2 639 347, which are screening agents that are already known per se
("broad-band" screening agents) with absorption maxima of between 320 and
370 nm, in particular at about 345 nm.
Among the hydrophilic organic UVA-screening agents, compounds comprising at
least two benzazolyl groups bearing sulfonic groups are also known in patent
application EP-A-0 669 323. They are described and prepared according to the
syntheses indicated in patent US 2 463 264 and in patent application
EP-A-0 669 323.
Among the hydrophilic organic UVA-screening agents, benzophenone derivatives
comprising at least one sulfonic radical are also known, for instance
Benzophenone-4, sold by the company BASF under the name Uvinul MS 40:
Benzophenone-5 of structu
and Benzophenone-9, sold by the company BASF under the name Uvinul DS 49:
However, these compounds do not afford broad protection against UV radiation
over the range from 320 to 400 nm. Specifically, they afford protection from
320 nm to 370 nm, and at best to 380 nm in large amounts, but do not in particular
make it possible to obtain observable absorbance up to a wavelength of 400 nm
inclusive.
Merocyanine compounds are known in patent US 4 195 999, patent application
WO 2004/006 878, patent applications WO2008/090066, WO201 / 13718,
WO2009/027258, WO201 3/01 0590, WO201 3/01 1094, WO201 30/1 1480 and the
documents IP COM JOURNAL N°0001 79675D published on February 23, 2009,
IP COM JOURNAL N°0001 82396D published on April 29, IP COM JOURNAL N°
0001 89542D published on November 12, 2009, IP COM Journal
N°IPCOM00001 1179D published on 03/04/2004.
Some of these compounds may show the following drawbacks :
- relatively unsatisfactory solubility in the usual solvents and in particular in fatty
substances such as oils which may require a laborious formulation process and/or
may result in cosmetic drawbacks such as a greasy effect on application ;
- an unsatisfactory chemical stability and/or unsatisfactory photostability
- produce a color liable to discourage the consumer from using a cosmetic or
dermatological composition containing them.
The UVA and UVB screening systems consisting of some of these merocyanine
screening agents as the compound Octyl-5-N,N-diethylamino-2-phenysulfonyl-2,4-
pentadienoate corresponding to the compound MC172 of structure
and an amino-substituted 2-
hydroxybenzophenone compound or a hydrophilic UVA-screening agent do not
always make it possible to afford broad UV protection over the range 280 to 400
nm and especially to obtain an observable absorbance up to a wavelength of 400
nm inclusive.
There thus remains a need to find a novel UVA-screening system based on a
merocyanine compound and an amino-substituted 2-hydroxybenzophenone
compound and/or a hydrophilic UVA-screening agent, which is photostable and
which ensures overall protection against UVA rays from 320 to 400 nm especially
having notable absorbance ranging up to a wavelength of 400 nm inclusive, in a
manner that is stable over time and at high temperatures, without the drawbacks
as previously defined.
The Applicant has found, surprisingly, that this objective can be achieved by
combining at least one UVA-screening agent chosen from: (i) an amino-substituted
2-hydroxybenzophenone compound , (ii) a hydrophilic UVA-screening agent and
(iii) their mixtures, with at least one particular merocyanine compound of formula
( 1) which will be defined in detail herein below.
Furthermore, the merocyanine compounds of formula ( 1 ) herein below, present
surprinsingly the advantage to be significantly less colored than the merocyanine
compounds as disclosed in the application WO2008/090066 as the compound
MC1 1 also called MC03 in the application WO2009/027258.
Those discoveries form the basis of the present invention.
Thus, in accordance with one of the objects of the present invention, a cosmetic or
dermatological composition is now proposed, comprising, in a physiologically
acceptable support:
a) at least one oily phase
b) at least one merocyanine compound of formula ( 1 ) defined herein below and
c) at least one UVA-screening agent chosen from :
(i) an amino-substituted 2-hydroxybenzophenone compound ;
(ii) a hydrophilic organic UVA-screening agent and
(iii) their mixtures ;
the said hydrophilic UVA-screening agent being present in an amount of greater
than 0.5% by weight relative to the total weight of the composition.
The present invention also relates to a non-therapeutic cosmetic process for
caring for and/or making up a keratin material, comprising the application to the
surface of the said keratin material of at least one composition according to the
invention as defined above.
The invention also relates to a non-therapeutic cosmetic process for limiting the
darkening of the skin and/or improving the colour and/or the uniformity of the
complexion, comprising the application to the surface of the keratin material of at
least one composition as defined previously.
The invention also relates to a non-therapeutic cosmetic process for preventing
and/or treating the signs of ageing of a keratin material, comprising the application
to the surface of the keratin material of at least one composition as defined
previously.
Other characteristics, aspects and advantages of the invention will emerge on
reading the detailed description that follows.
The term "hydrophilic organic UVA-screening agent" means any cosmetic or
dermatological organic compound for screening out UVA rays in the wavelength
range from 320 to 400 nm, 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. The said hydrophilic organic UVAscreening
agent is different from an amino-substituted 2-hydroxybenzophenone
compound.
The expression "human keratin materials" means the skin (body, face, area
around the eyes), hair, eyelashes, eyebrows, body hair, nails, lips or mucous
membranes.
The term "physiologically acceptable" means 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.
The term "between X and Y" means the range of values also including the limits X
and Y.
According to the invention, the term "preventing" or "prevention" means reducing
the risk of occurrence or slowing down the occurrence of a given phenomenon,
namely, according to the present invention, the signs of ageing of a keratin
material.
MEROCYANINES
According to the present invention, the merocyanine compounds in accordance
with the invention correspond to formula ( 1 ) below, and also the E/E- or E/Zgeometrical
isomer forms thereof:
in which:
R is a C1-C22 alkyl group, a C2-C22 alkenyl group, a C2-C22 alkynyl group, a C3-C22
cycloalkyl group or a C3-C22 cycloalkenyl group, the said groups possibly being
interrupted with one or more O.
The merocyanine compounds of the invention may be in their E/E- or E/Zgeometrical
isomer forms.
The preferential compounds of formula ( 1 ) are those in which:
R is a C1-C22 alkyl, which may be interrupted with one or more O.
Among the compounds of formula ( 1 ) , use will be made more particularly of those
chosen from the following compounds, and also the E/E- or E/Z- geometrical
isomer forms thereof:
ylidene}ethanoate
2-methylpropyl (2Z)-cyano{3-[(3- 3-ethoxypropyl (2Z)-cyano{3-[(3-
methoxypropyl)amino]cyclohex-2-en-1- methoxypropyl)amino]cyclohex-2-en-1-
ylidene}ethanoate ylidene}ethanoate
According to a more particularly preferred mode of the invention, use will be made
of the compound 2-ethoxyethyl (2Z)-cyano{3-[(3-methoxypropyl)amino]cyclohex-2-
en-1 -ylidene}ethanoate (2) in its E/Z geometrical configuration having the following
structure:
and/or in its E/E geometrical configuration having the following structure:
The merocyanines of formula ( 1 ) according to the invention are preferably present
in the compositions according to the invention in a concentration ranging from
0.1 % to 10% by weight and preferentially from 0.2% to 5% by weight relative to the
total weight of the composition.
The compounds of formula ( 1 ) may be prepared according to the protocols
described in Pat. Appl. WO 2007/071 582, 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 US-A-4 749 643 on column 13, line 66 - column 14,
line 57 and the references cited in this regard.
AMINO-SUBSTITUTED 2-HYDROXYBENZOPHENONE COMPOUND
The amino-substituted 2-hydroxybenzophenone compounds according to the
invention are preferably chosen from the compounds corresponding to formula (I)
below:
in which:
R1 and R2, which may be identical or different, denote a C1-C20 alkyl radical, a C2-
C20 alkenyl radical, a C3-C 10 cycloalkyl radical or a C3-C 10 cycloalkenyl radical or
form, with the nitrogen atom to which they are attached, a 5- or 6-membered ring;
n is a number ranging from 1 to 4;
when n = 1, R3 denotes a C1-C20 alkyl radical, a C1-C20 alkenyl radical, a C1-C5
hydroxyalkyl radical, a C 6-C12 cyclohexyl radical, a phenyl which may be
substituted with O, N or S, an aminocarbonyl radical or a C1-C5 alkylcarbonyl
radical;
when n = 2, R3 denotes an alkyl diradical, a cycloalkyl diradical, an alkenyl
diradical or an aryl diradical or R3 with E form a diradical of formula (II):
with m being a number ranging from
when n = 3, R3 is an alkyl triradical;
when n = 4, R3 is an alkyl tetraradical;
E is -O- or -N(R 4)- or N;
R4 is hydrogen or a C1-C5 alkyl or C1-C5 hydroxyalkyl radical.
Examples of C1-C20 alkyl radicals that may be mentioned include: methyl, ethyl, npropyl,
1-methylethyl, n-butyl, 1-methylpropyl, 2-methyl propyl, 1,1-dimethylethyl, npentyl,
1-methylbutyl, 2-methylbutyl, 3-methylbutyl, 2,2-dimethylpropyl, 1-
ethylpropyl, n-hexyl, 1, 1 -dimethylpropyl, 1,2-dimethylpropyl, 1-methylpentyl, 2-
methylpentyl, 3-methylpentyl, 4-methylpentyl, 1, 1 -dimethylbutyl, 1,2-dimethylbutyl,
1,3-dimethylbutyl, 2,2-dimethylbutyl, 2,3-dimethylbutyl, 3,3-dimethylbutyl, 1-
ethylbutyl, 2-ethylbutyl, 1,2,2-trimethylpropyl, 1-ethyl-1-methylpropyl, 1-ethyl-2-
methylpropyl, n-heptyl, n-octyl, n-nonyl, n-decyl, n-undecyl, n-dodecyl, n-tridecyl,
n-tetradecyl, n-pentadecyl, n-hexadecyl, n-heptadecyl, n-octadecyl, n-nonadecyl or
n-eicosyl.
Examples of C3-C10 cycloalkyl radicals that may be mentioned include:
cyclopropyl, cyclobutyl, cyclopentyl, cyclohexyl, cycloheptyl, 1-methylcyclopropyl,
1-ethylcyclopropyl, 1-propylcyclopropyl, 1-butylcyclopropyl, 1-pentylcyclopropyl, 1-
methyl-1 -butylcyclopropyl, 1,2-dimethylcyclopropyl, 1-methyl-2-ethylcyclopropyl,
cyclooctyl, cyclononyl or cyclodecyl.
As C3-C10 cycloalkenyl radicals bearing one or more double bonds, mention may
be made of: cyclopropenyl, cyclobutenyl, cyclopentenyl, cyclopentadienyl,
cyclohexenyl, 1,3-cyclohexadienyl, 1,4-cyclohexadienyl, cycloheptenyl,
cycloheptatrienyl, cyclooctenyl, 1,5-cyclooctadienyl, cyclooctatetraenyl,
cyclononenyl or cyclodecenyl.
As examples of 5- or 6-membered rings formed by the radicals R 1 and R2 with the
nitrogen atom, mention may be made in particular of pyrrolidine or piperidine.
A compound of formula (I) with n = 1 that is most particularly preferred is n-hexyl
2-(4-diethylamino-2-hydroxybenzoyl)benzoate of formula (a):
such as the product sold under the trade name Uvinul A Plus® by the company
BASF.
A compound of formula (I) with n = 2 that is most particularly preferred is the
derivative (2-{4-[2-(4-diethylamino-2-hydroxybenzoyl)benzoyl]piperazine-1-
carbonyl}phenyl)(4-diethylamino-2-hydroxyphenyl)methanone (CAS 9 19803-06-8)
of formula (b):
which is described in patent application WO 2007/071 584. This compound is
advantageously used in micronized form (mean size of 0.02 to 2 miti ) , 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 more particularly in
the form of an aqueous dispersion.
The compounds of formula (I) as defined above are known per se and their
structures and syntheses are described in patent applications EP-A-1 046 391 , EP
1 133 980, DE 100 12 408 and WO 2007/071 584.
The amino-substituted 2-hydroxybenzophenone compound(s) are preferably
present in the compositions in accordance with the invention in contents preferably
ranging from 0.01 % to 10% by weight and more preferentially from 0.1 % to 6% by
weight relative to the total weight of the composition.
HYDROPHILIC ORGANIC UVA-SCREENING AGENTS
Among the hydrophilic organic UVA-screening agents that may be used according
to the present invention, mention may be made of:
benzene-1 ,4-bis(3-methylidene-10-camphorsulfonic acid) (INCI name:
Terephthalylidenedicamphorsulfonic acid) and the various salts thereof, described
especially in patent applications FR-A-2 528 420 and FR-A-2 639 347.
These screening agents correspond to the general formula (I) below:
in which F denotes a hydrogen atom, an alkali metal or a radical NH(Ri) 3
+ in which
the radicals Ri, which may be identical or different, denote a hydrogen atom, a Ci-
C4 alkyl or hydroxyalkyl radical or a group Mn+ n, Mn+ denoting a multivalent metal
cation in which n is equal to 2 or 3 or 4, Mn+ preferably denoting a metal cation
chosen from Ca2+, Zn2+, Mg2+, Ba2+, Al3+ and Zr4+. It is clearly understood that the
compounds of formula (I) above may give rise to the "cis-trans" isomer about one
or more double bonds and that all the isomers are included in the context of the
present invention.
Among the hydrophilic organic UVA-screening agents that may be used according
to the present invention, mention may also be made of compounds comprising at
least two benzazolyl groups bearing sulfonic groups, such as those described in
patent application EP-A-0 669 323. They are described and prepared according to
the syntheses indicated in patent US 2 463 264 and in patent application EP-A-0
669 323.
The compounds comprising at least two benzazolyl groups in accordance with the
invention correspond to the general formula (II) below:
in which:
- Z represents an organic residue of valency ( I + n) comprising one or more double
bonds placed such that it completes the double bond system of at least two
benzazolyl groups as defined within the brackets to form a fully conjugated
assembly;
- X' denotes S, O or NR6
- R1 denotes hydrogen, C1-C18 alkyl, Ci-C 4 alkoxy, a C5-C1 5 aryl, a C2-C18 acyloxy,
, R3, R4 and R5, which may be identical or different, denote a nitro
group or a radical R1;
- R6 denotes hydrogen, a Ci-C 4 alkyl or a Ci-C 4 hydroxyalkyl;
- Y denotes hydrogen, Li, Na, K, NH , 1/2Ca, 1/2Mg, 1/3AI or a cation resulting
from the neutralization of a free acid group with a nitrogenous organic base;
- m is 0 or 1;
- n is a number from 2 to 6;
- 1is a number from 1 to 4;
- with the proviso that I + n does not exceed the value 6 .
Among these compounds, the ones that are preferred are those for which the
group Z is chosen from the group consisting of:
(a) an olefinic linear aliphatic C2-C6 hydrocarbon-based radical which may be
interrupted with a C 5-C12 aryl group or a C4-Cio heteroaryl group, chosen in
particular from the following groups:
-CH=CH-, -CH=CH-CH=CH- or
(b) a C5-C15 aryl group which may be interrupted with an olefinic linear aliphatic C2-
C 6 hydrocarbon-based radical chosen in particular from the following groups:
(c) a C3-C10 heteroaryl residue chosen in particular from the following groups:
in which R6 has the same meaning indicated above; the said radicals Z as defined
in paragraphs (a), (b) and (c) possibly being substituted with C 1-C6 alkyl, C 1-C6
alkoxy, phenoxy, hydroxyl, methylenedioxy or amino radicals optionally substituted
with one or two C 1-C5 alkyl radicals.
Preferably, the compounds of formula (II) comprise, per molecule, 1, 3 or 4 groups
As examples of compounds of formula (II) that may be used, mention may be
made of the compounds of formulae (a) to (j) and having the following structure,
and also the salts thereof:
Among all these compounds, preference will be given most particularly to 1,4-
bis(benzimidazolyl)phenylene-3,3',5,5'-tetrasulfonic acid (INCI name: Disodium
Phenyl Dibenzimidazole Tetrasulfonate) (compound (d)) or one of the salts thereof
having the following structure, sold under the name Neo Heliopan AP® by the
company Symrise:
Among the hydrophilic organic UVA-screening agents that may be used according
to the present invention, mention may also be made of benzophenone compounds
comprising at least one sulfonic acid function, for instance the following
compounds:
Benzophenone-4, sold by the company BASF under the name Uvinul MS40®:
Benzophenone-5 of structu
Benzophenone-9, sold by the company BASF under the name Uvinul DS49®:
Among the hydrophilic organic UVA-screening agents, use will be made more
particularly of benzene-1 ,4-bis(3-methylidene-1 0-camphorsulfonic acid) and the
various salts thereof (INCI name: terephthalylidenedicamphorsulfonic acid)
manufactured by the company Chimex under the trade name Mexoryl SX®.
The hydrophilic organic UVA-screening agent(s) in accordance with the invention
are preferably present in the compositions according to the invention in an active
material concentration ranging from 0.6% to 15% and preferably from 1% to 10%
by weight relative to the total weight of the composition.
OILY PHASE
The compositions in accordance with the invention comprise at least one oily
phase.
For the purposes of the invention, the term "oily phase" means 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.
The term "oil" means any fatty substance which is in liquid form at room
temperature (20 - 25°C) and at atmospheric pressure (760 mmHg).
An oil that is suitable for use in the invention may be volatile or non-volatile.
An oil that is suitable for use in the invention may be chosen from hydrocarbonbased
oils, silicone oils and fluoro oils, and mixtures thereof.
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 hydrocarbonbased
oil or a synthetic hydrocarbon-based oil.
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.
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.
The term "hydrocarbon-based oil" means an oil comprising mainly hydrogen and
carbon atoms.
The term "fluoro oil" means an oil comprising at least one fluorine atom.
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.
The oily phase generally comprises, in addition to the lipophilic UV-screening
agent(s), at least one volatile or non-volatile hydrocarbon-based oil and/or one
volatile and/or non-volatile silicone oil.
For the purposes of the invention, the term "volatile oil" means an oil that is
capable of evaporating on contact with the skin or the keratin fibre in less than one
hour, at room temperature and atmospheric pressure. The volatile oil(s) of the
invention are volatile cosmetic oils which are liquid at room temperature and which
have a non-zero vapour pressure, at room temperature and atmospheric pressure,
ranging in particular from 0.1 3 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).
The term "non-volatile oil" means an oil which remains on the skin or the keratin
fibre, at room temperature and atmospheric pressure, for at least several hours
and which in particular has a vapour pressure of less than 10 3 mmHg (0.13 Pa).
Hydrocarbon-based oils
As non-volatile hydrocarbon-based oils that may be used according to the
invention, mention may be made especially of:
(i) hydrocarbon-based oils of plant origin, such as glyceride triesters, which are
generally triesters of fatty acids and of glycerol, the fatty acids of which can have
varied chain lengths from C4 to C24 , it being possible for these chains to be
saturated or unsaturated and linear or branched; these oils are in particular
wheatgerm oil, sunflower oil, grape seed oil, sesame oil, corn oil, apricot oil, castor
oil, shea oil, avocado oil, olive oil, soybean oil, sweet almond oil, palm oil,
rapeseed oil, cottonseed oil, hazelnut oil, macadamia oil, jojoba oil, alfalfa oil,
poppy oil, pumpkin oil, marrow oil, blackcurrant oil, evening primrose oil, millet oil,
barley oil, quinoa oil, rye oil, safflower oil, candlenut oil, passionflower oil and
musk rose oil; or also caprylic/capric acid triglycerides, such as those sold by
Stearineries Dubois or those sold under the names Miglyol 8 10®, 8 12® and 818®
by Dynamit Nobel,
(ii) synthetic ethers containing from 10 to 40 carbon atoms;
(iii) linear or branched hydrocarbons of mineral or synthetic origin, such as
petroleum jelly, polydecenes, hydrogenated polyisobutene such as Parleam, and
squalane, and mixtures thereof;
(iv) synthetic esters, for instance oils of formula RCOOR' in which R represents a
linear or branched fatty acid residue containing from 1 to 40 carbon atoms and R'
represents a hydrocarbon-based chain that is especially branched, containing from
1 to 40 carbon atoms, on condition that
R + R' is > 10, for instance purcellin oil (cetostearyl octanoate), isopropyl myristate,
isopropyl palmitate, C12-C15 alkyl benzoate, such as the product sold under the
trade name Finsolv TN® or Witconol TN® by Witco or Tegosoft TN® by Evonik
Goldschmidt, 2-ethylphenyl benzoate, such as the commercial product sold under
the name X-Tend 226® by ISP, isopropyl lanolate, hexyl laurate, diisopropyl
adipate, isononyl isononanoate, oleyl erucate, 2-ethylhexyl palmitate, isostearyl
isostearate, diisopropyl sebacate, such as the product sold under the name of
"Dub Dis" by Stearinerie Dubois, octanoates, decanoates or ricinoleates of
alcohols or polyalcohols, such as propylene glycol dioctanoate; hydroxylated
esters, such as isostearyl lactate or diisostearyl malate; and pentaerythritol esters;
citrates or tartrates, such as di(linear C12-C1 3 alkyl) tartrates, such as those sold
under the name Cosmacol ETI® by Enichem Augusta Industriale, and also
di(linear C14-C15 alkyl) tartrates, such as those sold under the name Cosmacol
ETL® by the same company; or acetates;
(v) fatty alcohols that are liquid at room temperature, containing a branched and/or
unsaturated carbon-based chain containing from 12 to 26 carbon atoms, for
instance octyldodecanol, isostearyl alcohol, oleyl alcohol, 2-hexyldecanol, 2-
butyloctanol or 2-undecylpentadecanol;
(vi) higher fatty acids, such as oleic acid, linoleic acid or linolenic acid;
(vii) carbonates such as dicaprylyl carbonate, for instance the product sold under
the name Cetiol CC® by the company Cognis;
(viii) fatty amides, such as isopropyl N-lauroyl sarcosinate, such as the product
sold under the trade name Eldew SL205® from Ajinomoto;
and mixtures thereof.
Among the non-volatile hydrocarbon-based oils that may be used according to the
invention, preference will be given more particularly to glyceride triesters and in
particular to caprylic/capric acid triglycerides, synthetic esters and in particular
isononyl isononanoate, oleyl erucate, C12-C15 alkyl benzoate, 2-ethylphenyl
benzoate and fatty alcohols, in particular octyldodecanol.
As volatile hydrocarbon-based oils that may be used according to the invention,
mention may be made especially of hydrocarbon-based oils containing from 8 to
16 carbon atoms and in particular of branched Cs-Ci6 alkanes, such as Cs-Ci6
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 Cs-Ci6 esters,
isohexyl neopentanoate, and mixtures thereof.
Mention may also be made of the alkanes described in the Cognis patent
applications WO 2007/068 371 or WO 2008/1 55 059 (mixtures of distinct alkanes
differing by at least one carbon). These alkanes are obtained from fatty alcohols,
which are themselves obtained from coconut or palm oil. Mention may be made of
the mixtures of n-undecane (Cn) and n-tridecane (C1 3) obtained in Examples 1
and 2 of patent application WO 2008/1 55 059 from the company Cognis. Mention
may also be made of n-dodecane (C12) and n-tetradecane (CM), sold by Sasol
under the respective references Parafol 12-97® and Parafol 14-97®, and also
mixtures thereof.
Other volatile hydrocarbon-based oils, for instance petroleum distillates, especially
those sold under the name Shell Solt® by the company Shell, may also be used.
According to one embodiment, the volatile solvent is chosen from volatile
hydrocarbon-based oils containing from 8 to 16 carbon atoms, and mixtures
thereof.
b) Silicone oils
The non-volatile silicone oils may be chosen in particular from 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.
Examples of volatile silicone oils that may be mentioned include volatile linear or
cyclic silicone oils, especially those with a viscosity < 8 centistokes (8 10 6 m2/s)
and especially 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.
Mention may also be made of the volatile linear alkyltrisiloxane oils of general
formula (I):
in which R represents an alkyl group comprising from 2 to 4 carbon atoms, one or
more hydrogen atoms of which may be replaced with a fluorine or chlorine atom.
Among the oils of general formula (I) that may be mentioned are:
3-butyl-1 , 1 , 1 ,3,5,5,5-heptamethyltrisiloxane,
3-propyl-1 , 1 , 1 ,3,5,5,5-heptamethyltrisiloxane, and
3-ethyl-1 , 1 , 1 ,3,5,5,5-heptamethyltrisiloxane,
corresponding to the oils of formula (I) for which R is, respectively, a butyl group, a
propyl group or an ethyl group.
Fluoro oils
Use may also be made of volatile fluoro oils, such as nonafluoromethoxybutane,
decafluoropentane, tetradecafluorohexane, dodecafluoropentane, and mixtures
thereof.
An oily phase according to the invention may also comprise other fatty
substances, mixed with or dissolved in the oil.
Another fatty substance that may be present in the oily phase may be, for
example:
- a fatty acid chosen from fatty acids comprising from 8 to 30 carbon atoms, such
as stearic acid, lauric acid, palmitic acid and oleic acid;
- a wax chosen from waxes such as lanolin, beeswax, carnauba or candelilla wax,
paraffin waxes, lignite waxes, microcrystalline waxes, ceresin or ozokerite, or
synthetic waxes, such as polyethylene waxes or Fischer-Tropsch waxes;
- a gum chosen from silicone gums (dimethiconol);
- a pasty compound, such as polymeric or non-polymeric silicone compounds,
esters of a glycerol oligomer, arachidyl propionate, fatty acid triglycerides and
derivatives thereof;
- and mixtures thereof.
Preferentially, the overall oily phase, including all the lipophilic substances of the
composition capable of being dissolved in this same phase, represents from 5% to
95% by weight and preferentially from 10% to 80% by weight, relative to the total
weight of the composition.
AQUEOUS PHASE
The compositions according to the invention may also comprise at least one
aqueous phase.
The aqueous phase comprises water and optionally other water-soluble or watermiscible
organic solvents.
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.
The water-soluble or water-miscible solvents that are suitable for use in the
invention comprise short-chain monoalcohols, for example Ci-C4 monoalcohols,
such as ethanol or isopropanol; diols or polyols, such as ethylene glycol, 1,2-
propylene glycol, 1,3-butylene glycol, hexylene glycol, diethylene glycol,
dipropylene glycol, 2-ethoxyethanol, diethylene glycol monomethyl ether,
triethylene glycol monomethyl ether, glycerol and sorbitol, and mixtures thereof.
According to a preferred embodiment, use may more particularly be made of
ethanol, propylene glycol, glycerol, and mixtures thereof.
According to a specific form of the invention, the overall aqueous phase, including
all the hydrophilic substances of the composition capable of being dissolved in this
same phase, represents from 5% to 95% by weight and preferentially from 10% to
80% by weight, with respect to the total weight of the composition.
ADDITIVES
a) Additional UV-screening agents
The compositions according to the invention may also contain 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 consist of at least one hydrophilic, lipophilic or insoluble organic UVscreening
agent.
The term "hydrophilic UV-screening agent" means any cosmetic or dermatological
organic or mineral 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.
The term "lipophilic screening agent" means any cosmetic or dermatological
organic or mineral compound for screening out UV radiation, which can be fully
dissolved in molecular state in a liquid fatty phase or which can be dissolved in
colloidal form (for example in micellar form) in a liquid fatty phase.
The term "insoluble UV-screening agent" means any cosmetic or dermatological
organic or mineral 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 sold by the company Dynamit
Nobel. This solubility, determined at 70°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 room temperature. It may be readily evaluated in the laboratory.
The compositions according to the invention may also contain one or more
additional UV-screening agents chosen from hydrophilic, lipophilic or insoluble
organic UV-screening agents other than the hydroxyaminobenzophenone
compounds and the hydrophilic UVA-screening agents and/or one or more mineral
pigments. It will preferentially consist of at least one hydrophilic, lipophilic or
insoluble organic UV-screening agent.
The additional organic UV-screening agents are chosen in particular from
cinnamic compounds; anthranilate compounds; salicylic compounds;
benzylidenecamphor compounds; benzophenone compounds; b,b-
diphenylacrylate compounds; triazine compounds; benzotriazole compounds;
benzalmalonate compounds, in particular those cited in patent US 5 624 663;
benzimidazole derivatives; imidazoline compounds; bis-benzazolyl compounds, as
described in patents EP 669 323 and US 2 463 264; p-aminobenzoic (PABA)
compounds; methylenebis(hydroxyphenylbenzotriazole) compounds, as described
in patent applications US 5 237 071 , US 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 10 1 62 844; screening polymers
and screening silicones, such as those described in particular in patent application
WO 93/04665; a-alkylstyrene-based dimers, such as those described in patent
application DE 198 55 649; 4,4-diarylbutadiene compounds, as 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.
As examples of organic photoprotective agents, mention may be made of those
denoted hereinbelow under their INCI name:
Cinnamic compounds:
Ethylhexyl Methoxycinnamate, sold in particular under the trade name Parsol
MCX® by DSM Nutritional Products,
Isopropyl Methoxycinnamate,
Isoamyl p-methoxycinnamate sold under the trade name Neo Heliopan E 1000®
by Symrise,
DEA Methoxycinnamate,
Diisopropyl Methyl Cinnamate,
Glyceryl Ethylhexanoate Dimethoxycinnamate.
para-Aminobenzoic compounds:
PABA,
Ethyl PABA,
Ethyl Dihydroxypropyl PABA,
Ethylhexyl Dimethyl PABA, sold especially under the name Escalol 507® by ISP,
Glyceryl PABA,
PEG-25 PABA, sold under the name Uvinul P 25® by BASF.
Salicylic compounds:
Homosalate, sold under the name Eusolex HMS® by Rona/EM Industries,
Ethylhexyl Salicylate, sold under the name Neo Heliopan OS® by Symrise,
Dipropylene Glycol Salicylate, sold under the name Dipsal® by Scher,
TEA Salicylate, sold under the name Neo Heliopan TS® by Symrise.
b ,b-Diphenylacrylate compounds:
Octocrylene, sold in particular under the trade name Uvinul N 539® by BASF,
Etocrylene, sold in particular under the trade name Uvinul N 35® by BASF.
Benzophenone compounds:
Benzophenone-1 , sold under the trade name Uvinul 400® by BASF,
Benzophenone-2, sold under the trade name Uvinul D50® by BASF,
Benzophenone-3 or Oxybenzone, sold under the trade name Uvinul M40® by
BASF,
Benzophenone-6, sold under the trade name Helisorb 11® by Norquay,
Benzophenone-8, sold under the trade name Spectra-Sorb UV-24® by American
Cyanamid,
Benzophenone-1 2 .
Benzylidenecamphor compounds:
3-Benzylidenecamphor, manufactured under the name Mexoryl SD® by Chimex,
4-Methylbenzylidenecamphor, sold under the name Eusolex 6300® by Merck,
Polyacrylamidomethylbenzylidenecamphor, manufactured under the name
Mexoryl SW® by Chimex.
Phenylbenzimidazole compounds:
Phenylbenzimidazolesulfonic acid, sold in particular under the trade name Eusolex
232® by Merck.
Phenylbenzotriazole compounds:
Drometrizole Trisiloxane, sold under the name Silatrizole® by Rhodia Chimie.
Methylenebis(hvdroxyphenylbenzothazole) compounds:
Methylenebis(benzotriazolyl)tetramethylbutylphenol especially in solid form, for
instance the product sold under the trade name Mixxim BB/1 00® by Fairmount
Chemical, or in the form of an aqueous dispersion of micronized particles with a
mean particle size ranging from 0.01 to 5 miti , more preferentially from 0.01 to
2 miti and more particularly from 0.020 to 2 miti , with at least one alkylpolyglycoside
surfactant having the structure CnH2n+iO(C6HioO5)xH, in which n is an integer from
8 to 16 and x is the mean degree of polymerization of the (C6H10O5) unit and
ranges from 1.4 to 1.6, as described in patent GB-A-2 303 549, sold especially
under the trade name Tinosorb M® by BASF, or in the form of an aqueous
dispersion of micronized particles with a mean particle size ranging from 0.02 to
2 miti , more preferentially from 0.01 to 1.5 miti and more particularly from 0.02 to
1 m h i, in the presence of at least one polyglyceryl mono(C8-C2o)alkyl ester with a
degree of glycerol polymerization of at least 5, such as the aqueous dispersions
described in patent application WO 2009/063 392.
Triazine compounds:
- Bis-Ethylhexyloxyphenol Methoxyphenyl Triazine, sold under the trade name
Tinosorb S® by BASF,
- Ethylhexyl Triazone, sold in particular under the trade name Uvinul T 150® by
BASF,
- Diethylhexyl Butamido Triazone, sold under the trade name Uvasorb HEB® by
Sigma 3V,
2,4,6-Tris(dineopentyl 4'-aminobenzalmalonate)-s-triazine,
2,4,6-Tris(diisobutyl 4'-aminobenzalmalonate)-s-triazine,
2,4-Bis(n-butyl 4'-aminobenzoate)-6-(aminopropyltrisiloxane)-s-triazine,
2,4-Bis(dineopentyl 4'-aminobenzalmalonate)-6-(n-butyl 4'-aminobenzoate)-striazine,
- symmetrical triazine screening agents substituted with naphthalenyl groups or
polyphenyl groups described in patent US 6 225 467, patent application WO
2004/085 4 12 (see compounds 6 and 9) or the document "Symmetrical Triazine
Derivatives", IP.COM IPCOM000031 257 Journal, INC, West Henrietta, NY, US (20
September 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 miti ) , 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;
- 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.
Anthranilic compounds:
Menthyl anthranilate, sold under the trade name Neo Heliopan MA® by Symrise.
Imidazoline compounds:
Ethylhexyl dimethoxybenzylidene dioxoimidazoline propionate.
Benzalmalonate compounds:
Polyorganosiloxane bearing benzalmalonate functions, such as Polysilicone-1 5,
sold under the trade name Parsol SLX® by Hoffmann-LaRoche.
4,4-Diarylbutadiene compounds:
1, 1 -Dicarboxy(2,2'-dimethylpropyl)-4,4-diphenylbutad
Benzoxazole compounds:
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® by Sigma 3V.
The preferred organic screening agents are chosen from:
Ethylhexyl methoxycinnamate,
Ethylhexyl salicylate,
Homosalate,
Octocrylene,
Phenylbenzimidazole sulfonic acid,
Benzophenone-3,
4-Methylbenzylidenecamphor,
Methylenebis(benzotriazolyl)tetramethylbutylphenol,
Bis(ethylhexyloxyphenol)methoxyphenyltriazine,
Ethylhexyl Triazone,
Diethylhexyl Butamido Triazone,
2,4,6-Tris(dineopentyl 4'-aminobenzalmalonate)-s-triazine,
2,4,6-Tris(diisobutyl 4'-aminobenzalmalonate)-s-triazine,
2,4-Bis(n-butyl 4'-aminobenzoate)-6-(aminopropyltrisiloxane)-s-triazine,
2,4-Bis(dineopentyl 4'-aminobenzalmalonate)-6-(n-butyl 4'-aminobenzoate)-s
triazine,
2,4-Bis(n-butyl 4'-aminobenzalmalonate)-6-[(3-{1 ,3,3,3-tetramethyl-1
[(trimethylsilyl)oxy]disiloxanyl}propyl)amino]-s-triazine,
2,4,6-Tris(diphenyl)triazine,
2,4,6-Tris(terphenyl)triazine,
Drometrizole Trisiloxane,
Polysilicone-1 5,
1, 1 -Dicarboxy(2,2'-dimethylpropyl)-4,4-diphenylbutadiene,
2,4-Bis[4-[5-(1 , 1 -dimethylpropyl)benzoxazol-2-yl]phenylimino]-6-[(2-
ethylhexyl)imino]-1 ,3,5-triazine,
and mixtures thereof.
The particularly preferred organic screening agents are chosen from:
Ethylhexyl salicylate,
Homosalate,
Octocrylene,
Bis(ethylhexyloxyphenol)methoxyphenyltriazine,
Ethylhexyl Triazone,
Diethylhexyl Butamido Triazone,
2,4-Bis(n-butyl 4'-aminobenzalmalonate)-6-[(3-{1 ,3,3,3-tetramethyl-1
[(trimethylsilyl)oxy]disiloxanyl}propyl)amino]-s-triazine,
Drometrizole Trisiloxane,
and mixtures thereof.
The mineral UV-screening agents used in accordance with the present invention
are metal oxide pigments. More preferentially, the mineral UV-screening agents of
the invention are metal oxide particles with a mean elementary particle size of less
than or equal to 0.5 miti , more preferentially between 0.005 and 0.5 miti , even more
preferentially between 0.01 and 0.2 miti , better still between 0.01 and 0.1 miti and
more particularly preferentially between 0.015 and 0.05 miti .
They may be selected in particular from titanium oxide, zinc oxide, iron oxide,
zirconium oxide and cerium oxide, or mixtures thereof.
Such coated or uncoated metal oxide pigments are described in particular in
patent application EP-A-0 5 18 773. Commercial pigments that may be mentioned
include the products sold by the companies Sachtleben Pigments, Tayca, Merck
and Degussa.
The metal oxide pigments may be coated or uncoated.
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.
The coated pigments are more particularly titanium oxides that have been coated:
- with silica, such as the product Sunveil from the company Ikeda,
- with silica and iron oxide, such as the product Sunveil F from the company Ikeda,
- with silica and alumina, such as the products Microtitanium Dioxide MT 500 SA
and Microtitanium Dioxide MT 100 SA from the company Tayca and Tioveil from
the company Tioxide,
- with alumina, such as the products Tipaque TTO-55 (B) and Tipaque TTO-55 (A)
from the company Ishihara and UVT 14/4 from the company Sachtleben Pigments,
- with alumina and aluminium stearate, such as the products Microtitanium Dioxide
MT 100 T, MT 100 TX, MT 100 Z and MT-01 from the company Tayca, the
products Solaveil CT-10 W and Solaveil CT 100 from the company Uniqema and
the product Eusolex T-AVO from the company Merck,
- with silica, alumina and alginic acid, such as the product MT-100 AQ from the
company Tayca,
- with alumina and aluminium laurate, such as the product Microtitanium Dioxide
MT 100 S from the company Tayca,
- with iron oxide and iron stearate, such as the product Microtitanium Dioxide MT
100 F from the company Tayca,
- with zinc oxide and zinc stearate, such as the product BR 351 from the company
Tayca,
- with silica and alumina and treated with a silicone, such as the products
Microtitanium Dioxide MT 600 SAS, Microtitanium Dioxide MT 500 SAS or
Microtitanium Dioxide MT 100 SAS from the company Tayca,
- with silica, alumina and aluminium stearate and treated with a silicone, such as
the product STT-30-DS from the company Titan Kogyo,
- with silica and treated with a silicone, such as the product UV-Titan X 195 from
the company Sachtleben Pigments,
- with alumina and treated with a silicone, such as the products Tipaque TTO-55
(S) from the company Ishihara or UV Titan M 262 from the company Sachtleben
Pigments,
- with triethanolamine, such as the product STT-65-S from the company Titan
Kogyo,
- with stearic acid, such as the product Tipaque TTO-55 (C) from the company
Ishihara,
- with sodium hexametaphosphate, such as the product Microtitanium Dioxide MT
150 W from the company Tayca,
- T1O2 treated with octyltrimethylsilane, sold under the trade name T 805 by the
company Degussa Silices,
- T1O2 treated with a polydimethylsiloxane, sold under the trade name 70250
Cardre UF T1O2SI3 by the company Cardre,
- anatase/rutile T1O2 treated with a polydimethylhydrosiloxane, sold under the trade
name Microtitanium Dioxide USP Grade Hydrophobic by the company Color
Techniques.
Mention may also be made of T1O2 pigments doped with at least one transition
metal such as iron, zinc or manganese and more particularly manganese.
Preferably, the 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 T1O2 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 by the company Croda.
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, by the company Degussa under the name P 25, by the
company Wackher under the name Transparent titanium oxide PW, by the
company Miyoshi Kasei under the name UFTR, by the company Tomen under the
name ITS and by the company Tioxide under the name Tioveil AQ.
The uncoated zinc oxide pigments are, for example:
- those sold under the name Z-Cote by the company Sunsmart;
- those sold under the name Nanox by the company Elementis;
- those sold under the name Nanogard WCD 2025 by the company Nanophase
Technologies.
The coated zinc oxide pigments are for example:
- those sold under the name Zinc Oxide CS-5 by the company Toshibi (ZnO
coated with polymethylhydrogenosiloxane);
- those sold under the name Nanogard Zinc Oxide FN by the company Nanophase
Technologies (as a 40% dispersion in Finsolv TN, C12-C15 alkyl benzoate);
- those sold under the name Daitopersion Zn-30 and Daitopersion Zn-50 by the
company Daito (dispersions in cyclopolymethylsiloxane/oxyethylenated
polydimethylsiloxane, containing 30% or 50% of zinc oxides coated with silica and
polymethylhydrogenosiloxane);
- those sold under the name NFD Ultrafine ZnO by the company Daikin (ZnO
coated with perfluoroalkyl phosphate and copolymer based on perfluoroalkylethyl
as a dispersion in cyclopentasiloxane);
- those sold under the name SPD-Z1 by the company Shin-Etsu (ZnO coated with
silicone-grafted acrylic polymer, dispersed in cyclodimethylsiloxane);
- those sold under the name Escalol Z 100 by the company ISP (alumina-treated
ZnO dispersed in an ethylhexyl methoxycinnamate/PVP-hexadecene
copolymer/methicone mixture);
- those sold under the name Fuji ZnO-SMS-1 0 by the company Fuji Pigment (ZnO
coated with silica and polymethylsilsesquioxane);
- those sold under the name Nanox Gel TN by the company Elementis (ZnO
dispersed at a concentration of 55% in C12-C15 alkyl benzoate with hydroxystearic
acid polycondensate).
The uncoated cerium oxide pigments may be, for example, those sold under the
name Colloidal Cerium Oxide by the company Rhone-Poulenc.
The uncoated iron oxide pigments are, for example, sold by the company Arnaud
under the names Nanogard WCD 2002 (FE 45B), Nanogard Iron FE 45 BL AQ,
Nanogard FE 45R AQ and Nanogard WCD 2006 (FE 45R) or by the company
Mitsubishi under the name TY-220.
The coated iron oxide pigments are sold, for example, by the company Arnaud
under the names Nanogard WCD 2008 (FE 45B FN), Nanogard WCD 2009 (FE
45B 556), Nanogard FE 45 BL 345 and Nanogard FE 45 BL or by the company
BASF under the name Transparent Iron Oxide.
Mention may also be made of mixtures of metal oxides, in particular 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, and also the mixture of titanium dioxide and zinc dioxide
coated with alumina, silica and silicone, such as the product M 261 sold by the
company Sachtleben Pigments, or coated with alumina, silica and glycerol, such
as the product M 2 11 sold by the company Sachtleben Pigments.
According to the invention, coated or uncoated titanium oxide pigments are
particularly preferred.
The additional UV-screening agents according to the invention are preferably
present in the compositions according to the invention in a content ranging from
0.1 % to 45% by weight and in particular from 5% to 30% by weight relative to the
total weight of the composition.
b) Other additives:
The compositions in accordance with the present invention may also comprise
conventional cosmetic adjuvants chosen in particular from organic solvents, ionic
or nonionic thickeners, softeners, humectants, opacifiers, stabilizers, emollients,
silicones, antifoams, fragrances, preserving agents, anionic, cationic, nonionic,
zwitterionic or amphoteric surfactants, active agents, fillers, polymers, propellants,
basifying or acidifying agents or any other ingredient commonly used in the
cosmetic and/or dermatological field.
Mention may be made, among organic solvents, of alcohols other than C i -C4
monoalkanols as defined above and in particular short-chain C 2-C8 polyols, such
as glycerol or diols, such as caprylyl glycol, 1,2-pentanediol, propanediol,
butanediol, glycols and glycol ethers, such as ethylene glycol, propylene glycol,
butylene glycol, dipropylene glycol or diethylene glycol.
Mention may be made, as thickeners, of carboxyvinyl polymers, such as the
Carbopols® (Carbomers) and the Pemulens, such as Pemulen TR1® and
Pemulen TR2® (acrylate/C 10-C30 alkyl acrylate copolymer); polyacrylamides, for
instance the crosslinked copolymers sold under the names Sepigel 305® (CTFA
name: polyacrylamide/Ci3 -i 4 isoparaffin/laureth 7) or Simulgel 600 (CTFA name:
acrylamide/sodium acryloyldimethyl taurate copolymer/isohexadecane/polysorbate
80) by the company SEPPIC; 2-acrylamido-2-methylpropanesulfonic acid
polymers and copolymers, optionally crosslinked and/or neutralized, such as the
poly(2-acrylamido-2-methylpropanesulfonic acid) sold by the company Hoechst
under the trade name Hostacerin AMPS® (CTFA name: ammonium
polyacryloyldimethyl taurate) or Simulgel 800®, sold by the company SEPPIC
(CTFA name: sodium polyacryloyldimethyl taurate/polysorbate 80/sorbitan oleate);
copolymers of 2-acrylamido-2-methylpropanesulfonic acid and of hydroxyethyl
acrylate, such as Simulgel NS® and Sepinov EMT 10®, sold by the company
SEPPIC; cellulose derivatives, such as hydroxyethylcellulose; polysaccharides
and in particular gums, such as xanthan gum; water-soluble or water-dispersible
silicone derivatives, such as acrylic silicones, polyether silicones and cationic
silicones, and mixtures thereof.
Among the acidifying agents, examples that may be mentioned include mineral or
organic acids, for instance hydrochloric acid, orthophosphoric acid, sulfuric acid,
carboxylic acids, for instance acetic acid, tartaric acid, citric acid or lactic acid, and
sulfonic acids.
Among the basifying agents, examples that may be mentioned include aqueous
ammonia, alkali metal carbonates, alkanolamines, such as mono-, di- and
triethanolamines and derivatives thereof, sodium hydroxide or potassium
hydroxide.
Preferably, the cosmetic composition comprises one or more basifying agents
selected from alkanolamines, in particular triethanolamine, and sodium hydroxide.
In the case of a direct emulsion, the pH of the composition in accordance with the
invention is generally between 3 and 12 approximately, preferably between 5 and
11 approximately and more particularly still from 6 to 8.5.
Among the active agents for caring for keratin materials such as the skin, the lips,
the scalp, the hair, the eyelashes or the nails, examples that may be mentioned
include:
- vitamins and derivatives or precursors thereof, alone or as mixtures;
- antioxidants;
- free-radical scavengers;
- antipollution agents;
- self-tanning agents;
- antiglycation agents;
- calmatives;
- deodorants;
- essential oils;
- NO-synthase inhibitors;
- agents for stimulating the synthesis of dermal or epidermal macromolecules
and/or for preventing their degradation;
- agents for stimulating fibroblast proliferation;
- agents for stimulating keratinocyte proliferation;
- muscle relaxants,
- refreshing agents;
- tensioning agents;
- mattifying agents;
- depigmenting agents;
- propigmenting agents;
- keratolytic agents;
- desquamating agents;
- moisturizers;
- antiinflammatory agents;
- antimicrobial agents;
- slimming agents;
- agents acting on the energy metabolism of cells;
- insect repellents;
- substance P or CRGP antagonists;
- hair-loss counteractants;
- antiwrinkle agents;
- antiageing agents.
A person skilled in the art will select the said active agent(s) as a function of the
effect desired on the skin, the hair, the eyelashes, the eyebrows and the nails.
Needless to say, a person skilled in the art will take care to choose the
abovementioned optional additional compound or compounds and/or the amounts
thereof so that the advantageous properties intrinsically attached to the
compositions in accordance with the invention are not, or not substantially,
detrimentally affected by the envisaged addition(s).
GALENICAL FORMS
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 (O/W, W/O, O/W/O or W/O/W), such
as a cream, a milk or a cream gel.
They may also be in anhydrous form, for instance in the form of an oil. The term
"anhydrous composition" means a composition containing less than 1% by weight
of water, or even less than 0.5% of water, and especially free of water, the water
not being added during the preparation of the composition but corresponding 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.
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, rotorstator
and HPH type.
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.
It is also possible, by means of an HPH (between 50 and 800 bar), to obtain stable
dispersions with drop sizes that may be as low as 100 nm.
The emulsions generally comprise at least one emulsifier chosen from amphoteric,
anionic, cationic and nonionic emulsifiers, used alone or as a mixture. The
emulsifiers are appropriately chosen according to the emulsion to be obtained
(W/O or O/W).
The compositions according to the invention are preferably in the form of an oil-inwater
or water-in-oil emulsion. The emulsifying surfactants are appropriately
chosen according to the emulsion to be obtained.
Non-limiting examples of W/O emulsifying surfactants suitable for water-in-oil
emulsions are given in particular in the publication entitled McCutcheon's
Emulsifiers & Detergents, 1998, International Edition, MC Publishing Company, in
the chapter entitled HLB Index.
Examples of W/O emulsifying surfactants that may be mentioned include alkyl
esters or ethers of sorbitan, of glycerol, of polyol or of sugars; silicone surfactants,
for instance dimethicone copolyols, such as the mixture of cydomethicone and of
dimethicone copolyol, sold under the name DC 5225 C® 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® 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 O9® by the company Goldschmidt. It is also possible to add thereto one or
more coemulsifiers, which may advantageously be chosen from the group
consisting of polyol alkyl esters.
Mention may also be made of non-silicone emulsifying surfactants, in particular
alkyl esters or ethers of sorbitan, of glycerol, of polyol or of sugars.
Polyol alkyl esters that may especially be mentioned include polyethylene glycol
esters, for instance PEG-30 dipolyhydroxystearate, such as the product sold under
the name Arlacel P 135® by the company ICI.
Examples of glycerol and/or sorbitan esters that may be mentioned include
polyglyceryl isostearate, such as the product sold under the name Isolan Gl 34®
by the company Goldschmidt; sorbitan isostearate, such as the product sold under
the name Arlacel 987® by the company ICI; sorbitan glyceryl isostearate, such as
the product sold under the name Arlacel 986® by the company ICI, and mixtures
thereof.
For the O/W emulsions, examples of nonionic emulsifying surfactants that may be
mentioned include polyoxyalkylenated (more particularly polyoxyethylenated
and/or polyoxypropylenated) esters of fatty acids and of glycerol; oxyalkylenated
esters of fatty acids and of sorbitan; polyoxyalkylenated (in particular
polyoxyethylenated and/or polyoxypropylenated) esters of fatty acids, optionally in
combination with an ester of fatty acid and of glycerol, such as the PEG-1 00
Stearate/Glyceryl Stearate mixture sold, for example, by the company ICI under
the name Arlacel 165; oxyalkylenated (oxyethylenated and/or oxypropylenated)
ethers of fatty alcohols; esters of sugars, such as sucrose stearate; or ethers of
fatty alcohol and of sugar, in particular alkyl polyglucosides (APGs), such as decyl
glucoside and lauryl glucoside, sold, for example, by the company Henkel under
the respective names Plantaren 2000® and Plantaren 1200®, cetostearyl
glucoside, optionally as a mixture with cetostearyl alcohol, sold, for example,
under the name Montanov 68® by the company SEPPIC, under the name
Tegocare CG90® by the company Goldschmidt and under the name Emulgade
KE3302® by the company Henkel, and arachidyl glucoside, for example in the
form of the mixture of arachidyl and behenyl alcohols and of arachidyl glucoside
sold under the name Montanov 202® by the company SEPPIC. According to a
particular embodiment of the invention, the mixture of the alkyl polyglucoside as
defined above with the corresponding fatty alcohol may be in the form of a selfemulsifying
composition, for example as described in document WO-A-92/06778.
According to a particularly preferred form, the compositions are in the oil-in-water
form.
When it is an emulsion, the aqueous phase of this emulsion may comprise a
nonionic vesicular dispersion prepared according to known processes (Bangham,
Standish and Watkins, J. Mol. Biol., 13, 238 ( 1965), FR 2 3 15 991 and
FR 2 4 16 008).
The compositions according to the invention find their application in a large
number of treatments, especially cosmetic treatments, of the skin, the lips and the
hair, including the scalp, especially for protecting and/or caring for the skin, the lips
and/or the hair, and/or for making up the skin and/or the lips.
Another subject of the present invention consists of the use of the compositions
according to the invention as defined above for the manufacture of products for
cosmetically treating the skin, the lips, the nails, the hair, the eyelashes, the
eyebrows and/or the scalp, especially care products, antisun products and
makeup products.
The cosmetic compositions according to the invention may be used, for example,
as makeup products.
Another subject of the present invention consists of a non-therapeutic cosmetic
process for caring for and/or making up a keratin material, which consists in
applying to the surface of the said keratin material at least one composition
according to the invention as defined above.
The cosmetic compositions according to the invention may be used, for example,
as care products and/or antisun products for the face and/or the body with 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.
The compositions according to the invention in the form of vaporizable fluid lotions
in accordance with the invention are applied to the skin or the hair in the form of
fine particles by means of pressurization 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 US 4 077 441 and US 4 850 5 7 .
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.
ASSEMBLY
According to another aspect, the invention also relates to a cosmetic assembly
comprising:
i) a container delimiting one or more compartment(s), the said container being
closed by a closing member and optionally not being leaktight; and
ii) a makeup and/or care composition in accordance with the invention placed
inside the said compartment(s).
The container may be, for example, in the form of a jar or a box.
The closing member may be in the form of a lid comprising a cap mounted so as
to be able to move by translation or by pivoting relative to the container housing
the said makeup and/or care composition(s).
The examples that follow serve to illustrate the invention without, however, being
limiting in nature. In these examples, the amounts of the composition ingredients
are given as weight percentages relative to the total weight of the composition.
122.23 g of 3-[(3-methoxypropyl)amino]-2-cyclohexen-1-one were alkylated with
dimethyl sulfate or alternatively with diethyl sulfate and treated with 75.45 g of
ethyl cyanoacetate in approximately equimolar proportions in the presence of a
base and optionally of a solvent.
The following base/solvent combinations were used:
The completion of the alkylation reaction was monitored, for example, via methods
such as TLC, GC or HPLC.
162.30 g of compound (14) were obtained in the form of a brown oil.
After crystallization, the product was obtained in the form of yellowish crystals.
Melting point: 92.7°C
148.4 g of 3-[(3-methoxypropyl)amino]-2-cyclohexen-1-one were alkylated with
dimethyl sulfate or alternatively with diethyl sulfate and treated with 130.00 g of 2-
ethoxyethyl cyanoacetate in the presence of an organic base and a solvent.
The following base/solvent combinations were used:
Example A3 (outside the invention): Preparation of the compound (2Z)-2-
cvano-N-(3-methoxypropyl)-2-(3 -r(3-methoxypropyl)amino1cvclohex-2-en-1-
ylidene!ethanamide described in the unpublished patent application PCT/EP
2012/064 195
10 1.00 g of 3-[(3-methoxypropyl)amino]-2-cyclohexen-1-one were alkylated with
dimethyl sulfate or alternatively with diethyl sulfate and treated with 86.00 g of 2-
cyano-N-(3-methoxypropyl)acetamide in approximately equimolar proportions in
the presence of a base and optionally of a solvent.
The following base/solvent combinations were used:
Example Base Solvent
DBU ( 1 ,8-diazabicyclo[5.4.0]undec-7- dimethylacetamide
Example A3.1
ene)
Example A3.2 triethylamine isopropanol
Example A3.3 3-methoxypropylamine isopropanol
Example A3.4 3-methoxypropylamine tert-amyl alcohol
Example A3.5 3-methoxypropylamine toluene
Example A3.6 3-methoxypropylamine dimethylformamide
Example A3.7 3-methoxypropylamine no solvent
The crude product (2Z)-2-cyano-N-(3-methoxypropyl)-2-{3-[(3-
methoxypropyl)amino]cyclohex-2-en-1 -ylidene}ethanamide was obtained in the
form of a dark brown oil.
After chromatography on a column of silica gel (eluent: 99/1 toluene/methanol),
8 1.8 g of product were obtained in the form of yellowish crystals.
Melting point: 84.7-85.3°C.
Formulation Examples 1 to 8
The compound 2-ethoxyethyl (2Z)-cyano{3-[(3-methoxypropyl)amino]cyclohex-2-
en-1 -ylidene}ethanoate (2) of the invention was compared with:
- the compound (2Z)-2-cyano-N-(3-methoxypropyl)-2-{3-[(3-
methoxypropyl)amino]cyclohex-2-en-1 -ylidene}ethanamide according to Example
A3 (outside the invention) ;
- the compound octyl-5-N,N-diethylamino-2-phenylsulfonyl-2,4-pentadienoate
(outside the invention) ;
- the merocyanine compound MC1 1 disclosed in the application WO2008/090066
(outside the invention).
Formulations 1 to 3 below were prepared; they were constructed such that the
sum of the contents of oil and of liposoluble UV -screening agents remains
constant. The content of the screening agents was adjusted so as to ensure the
same level of UVB screening and also the same in vitro SPF, and also the same
absorbance profile between 290 and 340 nm. For each of the formulations, the
SPF, the UVAPPD index and the absorbance after 24 hours at room temperature
were measured. The amounts are expressed as weight percentages relative to the
total weight of the composition.
Formulation Formulation Formulation
1 2 3
Phase Ingredients
(outside the (outside the (invention)
invention) invention)
Water qs 100 qs 100 qs 100
Glycerin 6 6 6
Disodium EDTA 0.1 0.1 0.1
A Thethanolamine 0.45 0.45 0.45
Potassium cetyl
phosphate (Amphisol 1 1 1
K®)
2-Ethylphenyl
benzoate 24.4 23.7 23.4
(X-Tend226®)
n-Hexyl 2-(4-
diethylamino-2-
4 4 4.3
hydroxybenzoyl)benzo
ate (Uvinul A + ®)
Octyl 5-N.Ndiethylamino-
2- - -
1.6
phenylsulfonyl-2,4-
pentadienoate
(2Z)-2-cyano-N-(3-
B
methoxypropyl)-2-{3-
[(3- - 2.3 -
methoxypropyl)annino]-
cyclohex-2-en-1-
ylidene}ethanamide
Compound (2) - - 2.3
Stearic acid 1.5 1.5 1.5
Glyceryl stearate (and)
PEG-1 00 stearate 1.5 1.5 1.5
(Arlacel 165)
Dimethicone 0.5 0.5 0.5
Preservatives 1.28 1.28 1.28
Isohexadecane 2 2 2
Xanthan gum 0.1 0.1 0.1
C Acrylates/C1 0-30 alkyl
acrylate crosspolymer 0.25 0.25 0.25
(Pemulen TR1®)
D Thethanolamine 0.25 0.25 0.25
E Alcohol 2 2 2
in vitro SPF (t24h) 2.4 ± 0.2 2.4 ± 0.1 2.4 ± 0.1
in vitro UVAPPD (t24h) 11.0 ± 1.0 11.5 ± 2.0 11.6 ± 2.0
Formulations 4 to 8 below were prepared. The content of the filters was constant
in order to compare the performance of the compound (2) according to the
invention to the one of the compound (2Z)-2 -cyano-N-(3-methoxypropyl)-2-{3-[(3-
methoxypropyl)amino]cyclohex-2-en-1 -ylidene}-ethanamide according to example
A3 (outside the invention) and to the one of the compound MC1 1 disclosed in the
application WO2008/090066 (outside the invention) at the same content. For some
of these formulations, the SPF, the UVA PPD index and the absorbance 24 hours
after formulation were measured. The amounts are expressed as weight
percentages relative to the total weight of the composition.
Formulation
4 Formulation 5
Phase Ingredients
(outside the (invention)
invention)
Water qsp 100 qsp 100
Glycerin 5 5
Disodium EDTA 0.1 0.1
A
Triethanolamine 0.45 0.45
Potassium Cetyl
1 1
Phosphate(Amphisol K®)
Isopropyl Lauroyl Sarcosinate
30 30
(Eldew SL-205®)
(2Z)-2-cyano-N-(3-
methoxypropyl)-2-{3-[(3-
methoxypropyl)amino]cyclohe
x-2-en-1 -ylidene}ethanamide
Compound (2) - 2
n-hexyl 2-(4-diethylamino-2-
hydroxybenzoyl)benzoate 3 3
B (Uvinul A + ®)
Stearic Acid 1.5 1.5
Glyceryl Stearate (and) PEG-
2.5 2.5
100 Stearate (Arlacel 165®)
Dimethicone 0.5 0.5
Cetyl Alcohol 0.5 0.5
Cetearyl Alcohol (and)
Cetearyl Glucoside 2 2
(Montanov 68®)
Preservatives 1 1
C Isohexadecane 1 1
Xanthan Gum 0.2 0.2
Acrylates / C 10-C30 Alkyl
Acrylate crosspolymer 0.2 0.2
(Pemulen TR1®)
D Triethanolamine 0.2 0.2
SPF in vitro (t24h) 2.3 ± 0,1 2.3 ± 0.1
UVA PPD in vitro (t24h) 23.6 ± 7.1 22.8 ± 1.6
Formulation Formulation Formulation
Formulation
6 7 8
Phase Ingredients 5
(outside the (outside the (outside the
(invention)
invention) invention) invention)
Water qsp 100 qsp 100 qsp 100 qsp 100
Glycerin 5 5 5 5
Disodium EDTA 0,1 0,1 0,1 0,1
A
Triethanolamine 0,45 0,45 0,45 0,45
Potassium Cetyl
1 1 1 1
Phosphate(Amphisol K®)
Isopropyl Lauroyl
Sarcosinate (Eldew SL- 30 30 30 30
205®)
Compound (2) 2 - 2 -
MC1 1 of
- 2 - 2
WO2008/090066
n-hexyl 2-(4-
diethylamino-2-
3 3 - -
hydroxybenzoyl)benzoat
e (Uvinul A + ®)
B
Stearic Acid 1,5 1,5 1,5 1,5
Glyceryl Stearate (and)
PEG-1 00 Stearate 2,5 2,5 2,5 2,5
(Arlacel 165®)
Dimethicone 0,5 0,5 0,5 0,5
Cetyl Alcohol 0,5 0,5 0,5 0,5
Cetearyl Alcohol (and)
Cetearyl Glucoside 2 2 2 2
(Montanov 68®)
Preservatives 1 1 1 1
Isohexadecane 1 1 1 1
Xanthan Gum 0,2 0,2 0,2 0,2
C Acrylates / C 10-C30
Alkyl Acrylate 0,2 0,2 0,2 0,2
crosspolymer (Pemulen
TR1®)
Triethanolamine 0,2 0,2 0,2 0,2
Emulsion preparation method:
The aqueous phase A and oily phase B were prepared by mixing the starting
materials with mechanical stirring at 80°C. Once the aqueous solution A and oily
solution B were macroscopically homogeneous, the emulsion was prepared by
introducing phase B into phase A with stirring using a rotor-stator homogenizer
with a stirring speed of 4500 rpm for 20 minutes. Phases C and then D were then
successively added, with continued stirring. The emulsion was finally cooled to
room temperature before adding phase E, when it exists. The final emulsion was
characterized by drops between 1 miti and 20 miti in size.
In vitro protocol for evaluating the screening efficacy
The sun protection factor (SPF) was determined according to the in vitro method
described by B.L. Diffey in J. Soc. Cosmet. Chem. 40, 127-1 33 ( 1989). The
measurements were carried out using a UV-1 000S spectrophotometer from the
company Labsphere. The "static in vitro protection factor (SPF)" value is extracted.
Each composition is applied to a rough plate of PMMA in the form of a uniform and
even deposit in a proportion of 1 mg/cm2.
The in vitro UVAPPD index measurements were taken under the same conditions
using a UV-1 000S spectrophotometer from the company Labsphere. The "UV
APPD index (persistent pigment darkening action spectrum)" value is extracted.
Each composition was applied to a rough plate of PMMA, in the form of a
homogeneous and even deposit at a rate of 1 mg/cm2.
Protocol for evaluating the absorbance spectra of the formulations
The absorbance spectra of the formulations were extracted from the mAF data as
a function of the wavelength generated during the in vitro SPF measurement and
the in vitro UVAPPD index measurement 24 hours after the formulation. The mAF
values were then converted into absorbance values according to: Abs= log(mAF).
Absorbance of the formulations measured 24 hours after formulation at
room temperature
The absorbance values at 400 nm measured 24 hours after formulation showed
that for a same SPF in vitro, same UVA PPD index in vitro, the formulations 1 and
2 (outside the invention) are less efficient than the formulation 3 according to the
invention and that the formulation 4 ((outside the invention) is less efficient than
the formulation 5 according to the I'invention in view of the filtration of UVA
radiations.
Protocol for evaluating the color of the formulations
The color of the formulations was evaluated after preparation of thin films on
contrast map. The formulations were deposited within a circle of 2.2 cm of
diameter and planed to obtain thicknesses of reproducible deposit. The
colorimetric measures were then made by means of a spectro-colorimeter Minolta
CM2600D in two points of the film. This operation is twice reproduced, which leads
to 4 experimental values by formulation.
The results are expressed in the system (L * , has * , b * ) in which L* represents the
luminance, a* represents the red-green axis (-a* = green, +a* = red) and b*
represents the yellow-blue axis (-b* blue, +b* yellow). So, a* and b* express the
shade of the compound.
The difference of color D E * was calculated from the variations AL*, Aa* et Ab*
between the compound (2) and the compound MC1 1 with the following equation :
(D E*)2 = (AL*)2
+ (Aa*)2 + (Ab*)2
AL* = L* formulation with compound MC1 1 formulation with compound (2)
Aa* = a* formulation with compound MC1 1 formulation with compound (2)
Ab* = b* formulation with compound MC1 1 b formulation with compound (2)
We consider that the difference of color between the two compounds is significant
if D E * > 2 .
Colorimetric measures on the formulations 5 to 8
The colorimetry results on the examples 5 to 8 show that the formulation 5 with the
compound (2) is significantly less yellow than the equivalent formulations 6,7 and
8 with the compound MC1 1 of the application WO2008/ 090066 .
Formulation examples 9 to 11
The compound 2-ethoxyethyl (2Z )-cyano{3-[(3-methoxypropyl)amino]cyclohex-2-
en-1 -ylidene}ethanoate (2) of the invention was compared with:
- the compound (2Z)-2 -cyano-N-(3-methoxypropyl)-2-{3-[(3-
methoxypropyl)amino]cyclohex-2-en-1 -ylidene}etnanamide according to
Example A 3 (outside the invention)
- the compound octyl-5-N,N-diethylamino-2-phenylsulfonyl-2,4-pentadienoate
(outside the invention)
Formulations 9 to 11 below were prepared; they were constructed such that the
sum of the contents of oil and of liposoluble UV-screening agents remains
constant. The content of the screening agents was adjusted so as to ensure the
same level of UVB screening and also the same in vitro SPF, and also the same
absorbance profile between 290 and 340 nm. For each of the formulations, the
SPF, the UVAPPD index and the absorbance after 24 hours at room temperature
were measured. The amounts are expressed as weight percentages relative to the
total weight of the composition.

Emulsions 9 to 11 were prepared according to the same preparation mode as for
Examples 1 to 8 .
The in vitro SPF and UVAPpD index values were measured under the same
conditions indicated previously.
Protocol for evaluating the absorbance spectra of the formulations
The absorbance spectra of the formulations were extracted from the mAF data as
a function of the wavelength generated during the in vitro SPF measurement and
the in vitro PPD measurement. The mAF values were then converted into
absorbance values according to: Abs= log(mAF).
Absorbance of the formulations measured after 24 hours
Absorbance of the formulations measured after 10 days at 60°C
Conclusions
The absorbance values at 400 nm measured 24 hours after formulation show that
for the same in vitro SPF value and the same in vitro UVA PpD index, formulation 9
(outside the invention) is less efficient than formulation 11 of the invention in terms
of screening out UVA. The absorbance values at 400 nm measured after 10 days
of storage at 60°C show that for the same in vitro SPF value and the same
UVAPPD index, formulation 10 (outside the invention) is less efficient than
formulation 11 of the invention in terms of screening out UVA.

CLAIMS
1. Cosmetic or dermatological composition comprising, in a physiologically
acceptable support:
a) at least one oily phase and
b) at least one merocyanine compound corresponding to formula ( 1 ) below, and
also the E/E- or E/Z- geometrical isomer forms thereof:
in which:
R is a C1-C22 alkyl group, a C2-C22 alkenyl group, a C2-C22 alkynyl group, a C3-C22
cydoalkyi group or a C3-C22 cydoalkenyl group, the said groups possibly being
interrupted with one or more O, and
c) at least one UVA-screening agent chosen from:
(i) an amino-substituted 2-hydroxybenzophenone compound and/or
(ii) a hydrophilic organic UVA-screening agent, and
(iii) their mixtures ;
the said hydrophilic organic UVA-screening agent being present in an amount of
greater than 0.5% by weight relative to the total weight of the composition.
2. Composition according to Claim 1, in which the merocyanine compound(s) of
formula ( 1 ) are chosen from those in which:
R is a C1-C22 alkyl, which may be interrupted with one or more O.
3. Composition according to Claim 1 or 2, in which the merocyanine compound(s)
of formula ( 1 ) are chosen from the following compounds, and also the E/E- or E/Zgeometrical
isomer forms thereof:
ethyl (2Z)-cyano{3-[(3- 2-butoxyethyl (2Z)-cyano{3-[(3-
methoxypropyl)amino]cyclohex-2-en-1- methoxypropyl)amino]cyclohex-2-en-1-
ylidene}ethanoate ylidene}ethanoate
4 . Connposition according to Claim 3, in which the merocyanine compound is 2-
ethoxyethyl (2Z)-cyano{3-[(3-methoxypropyl)amino]cyclohex-2-en-1-
ylidene}ethanoate (2) in its E/Z geometrical configuration having the following
structure:
and/or in its E/E geometrical configuration having the following structure:
5 . Composition according to any one of Claims 1 to 4, in which the merocyanine
compound(s) of formula ( 1 ) are present in a concentration ranging from 0.1 % to
10% by weight and preferentially from 0.2% to 5% by weight relative to the total
weight of the composition.
6 . Composition according to any one of Claims 1 to 5, in which the aminosubstituted
2-hydroxybenzophenone compound(s) correspond to formula (I)
below:
in which:
R1 and R2, which may be identical or different, denote a C 1-C20 alkyl radical, a C2-
C20 alkenyl radical, a C3-C10 cycloalkyl radical or a C3-C10 cycloalkenyl radical or
form, with the nitrogen atom to which they are attached, a 5- or 6-membered ring;
n is a number ranging from 1 to 4;
when n = 1, R3 denotes a C 1-C20 alkyl radical, a C 1-C20 alkenyl radical, a C 1-C5
hydroxyalkyl radical, a C 6-C12 cyclohexyl radical, a phenyl which may be
substituted with O, N or S, an aminocarbonyl radical or a C 1-C5 alkylcarbonyl
radical;
when n = 2, R3 denotes an alkyl diradical, a cycloalkyl diradical, an alkenyl
diradical or an aryl diradical or R3 with E form a diradical of formula (II):
with m being a number ranging from 1 to 3;
when n = 3, R3 is an alkyl triradical;
when n = 4, R3 is an alkyl tetraradical;
E is -O- or -N(R 4)- or N;
R4 is hydrogen or a C 1-C5 alkyl or C 1-C5 hydroxyalkyl radical.
7. Composition according to Claim 6, in which the compound of formula (I) is nhexyl
2-(4-diethylamino-2-hydroxybenzoyl)benzoate of formula (a):
8. Composition according to Claim 6, in which the compound of formula (I) is (2-{4-
[2-(4-diethylamino-2-hydroxybenzoyl)benzoyl]piperazine-1 -carbonyl}phenyl)(4-
diethylamino-2-hydroxyphenyl)methanone of formula (b):
9. Connposition according to any one of Clainns 1 to 5, in which the hydrophilic
organic UVA-screening agent is benzene-1 ,4-bis(3-methylidene-1 0-
camphorsulfonic acid) or one of the salts thereof, and also the geometrical isomers
thereof, corresponding to the general formula (I) below:
(I)
in which F denotes a hydrogen atom, an alkali metal or a radical NH(Ri) 3
+ in which
the radicals Ri, which may be identical or different, denote a hydrogen atom, a Ci-
C4 alkyl or hydroxyalkyl radical or a group Mn+ n, Mn+ denoting a multivalent metal
cation in which n is equal to 2 or 3 or 4, Mn+ preferably denoting a metal cation
chosen from Ca2+, Zn2+, Mg2+, Ba2+, Al3+ and Zr +.
10. Composition according to any one of Claims 1 to 5, in which the hydrophilic
organic UVA-screening agent is a compound comprising at least two benzazolyl
groups corresponding to the general formula (II) below:
in which:
- Z represents an organic residue of valency ( I + n) comprising one or more double
bonds placed such that it completes the double bond system of at least two
benzazolyl groups as defined within the brackets to form a fully conjugated
assembly;
- X' denotes S, O or NR6
- R1 denotes hydrogen, C1-C18 alkyl, Ci-C 4 alkoxy, a C5-C1 5 aryl, a C2-C18 acyloxy,
SO3Y or COOY;
- the radicals R2, R3, R4 and R5, which may be identical or different, denote a nitro
group or a radical R1;
- R6 denotes hydrogen, a C i-C4 alkyl or a C i-C4 hydroxyalkyl;
- Y denotes hydrogen, Li, Na, K, NH , 1/2Ca, 1/2Mg, 1/3AI or a cation resulting
from the neutralization of a free acid group with a nitrogenous organic base;
- m is 0 or 1;
- n is a number from 2 to 6;
- 1is a number from 1 to 4;
- with the proviso that I + n does not exceed the value 6 .
11. Composition according to Claim 10, in which the compound of formula (II) is
chosen from those for which the group Z is chosen from the group consisting of:
(a) an olefinic linear aliphatic C2-C6 hydrocarbon-based radical which may be
interrupted with a C 5-C12 aryl group or a C4-Cio heteroaryl group, chosen in
particular from:
-C or
(b) a C5-C15 aryl group which may be interrupted with an olefinic linear aliphatic C2-
C 6 hydrocarbon-based radical chosen in particular from the following groups:
(c) a C 3-C10 heteroaryl residue chosen in particular from the following groups:
in which R6 has the same meaning indicated above; the said radicals Z as defined
in paragraphs (a), (b) and (c) possibly being substituted with C 1-C6 alkyl, C 1-C6
alkoxy, phenoxy, hydroxyl, methylenedioxy or amino radicals optionally substituted
with one or two C 1-C5 alkyl radicals.
12. Composition according to Claim 10 or 11, in which the compound of formula
(II) comprises, per molecule, 1, 3 or 4 groups SO3Y.
13. Composition according to any one of Claims 10 to 12, in which the compound
of formula (II) is 1,4-bis(benzimidazolyl)phenylene-3,3',5,5'-tetrasulfonic acid
having the following structure, or one of the salts thereof:
14. Composition according to any one of Claims 1 to 5, in which the hydrophilic
organic UVA-screening agent is chosen from benzophenone compounds
comprising at least one sulfonic acid function, and especially chosen from the
following compounds:
Benzophenone-4,
Benzophenone-5,
Benzophenone-9, or mixtures thereof.
15. Composition according to any one of Claims 1 to 5, 9 to 14 in which the
hydrophilic organic UVA-screening agent(s) are present in an active material
concentration ranging from 0.6% to 15% and preferably from 1% to 10% by weight
relative to the total weight of the composition.
16. Non-therapeutic cosmetic process for caring for and/or making up a keratin
material, comprising the application to the surface of the said keratin material of at
least one composition as defined in any one of the preceding claims.
17. Non-therapeutic cosmetic process for limiting the darkening of the skin and/or
improving the colour and/or the uniformity of the complexion, comprising the
application to the surface of the skin of at least one composition as defined in any
one of the preceding claims.
18. Non-therapeutic cosmetic process for preventing and/or treating the signs of
ageing of a keratin material, comprising the application to the surface of the keratin
material of at least one composition as defined in any one of the preceding claims.