Cosmetic or dermatological composition comprising a merocyanine and
an insoluble organic UV-screening agent and/or an insoluble inorganic UVscreening
agent
The present invention relates to a cosmetic or dermatological composition
comprising, in a physiologically acceptable support:
a) at least one oily phase and
b) at least one merocyanine compound of formula ( 1 ) defined herein below
and
c) at least one insoluble organic UV-screening agent and/or one insoluble
inorganic UV-screening agent.
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 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 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.
It is also 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 UV-A 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 (brown spots, lack of uniformity
of the complexion).
Protection against UVA and UVB rays is thus necessary. An efficient
photoprotective product should protect against both UVA and UVB radiation.
Many photoprotective compositions have been proposed to date to overcome the
effects induced by UVA and/or UVB radiation. They generally contain organic
and/or inorganic UV-screening agents, which function according to their own
chemical nature and according to their own properties by absorption, reflection or
scattering of the UV radiation. They generally contain 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.
Many cosmetic compositions for limiting the darkening of the skin and improving
the colour and 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 of these antisun compositions is that
their systems for screening out UVA and UVB radiation are insufficiently effective
against UV rays and in particular against long UVA rays with wavelengths beyond
370 nm, for the purpose of controlling photo-induced pigmentation and its
evolution by a UV-screening system on the entire UV spectrum.
In this respect, a particularly advantageous family of UV-A screening agents is
currently composed of dibenzoylmethane derivatives and in particular 4-tert-butyl-
4'-methoxydibenzoyl methane, this being because they have high intrinsic
absorbing 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 FRA-
2 440 933, and also in European patent application EP-A-0 114 607; 4-tertbutyl-
4'-methoxydibenzoylmethane is moreover currently sold under the trade
name Parsol 1789® by the company DSM Nutritional Products. However, these
compounds are photo-unstable and cannot be combined with UVB-screening
agents to afford broad UV protection over the range 280 to 400 nm. In point of
fact, these UVA and UVB screening systems thus constituted make it possible to
protect from 280 nm to 370 nm, and at best to 380 nm in large amounts.
Furthermore, they have the drawback of needing to be dissolved in substantial
amounts of oil, which often leads to formulation difficulties and also to formulation
sensory drawbacks, such as a greasy effect on application.
Insoluble organic screening agents thus appear to be particularly advantageous
since they can be dispersed in water and introduced directly into the aqueous
phase. The ones mentioned in patent US 5 869 030 are especially known. Among
these screening agents, mention may be made most particularly of
methylenebis(benzotriazolyl)tetramethylbutylphenol sold in solid form under the
trade name Mixxim BB/100® by Fairmount Chemical, or in micronized form as an
aqueous dispersion under the trade name Tinosorb M® by the company BASF.
This UV-screening agent absorbs both UVA radiation and UVB radiation.
The UVA and UVB screening systems described in the said patent US 5 869 030
especially with the UVB and UVA screening agent
methylenebis(benzotriazolyl)tetramethylbutylphenol do not, however, make it
possible to afford broad UV protection over the range 280 to 400 nm especially
having an observable absorbance up to a wavelength of 400 nm inclusive.
The insoluble inorganic UV-screening agents are generally metal oxide pigments
with a mean elemental 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 0.01 5 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. The agent most commonly used is titanium dioxide. Such metal
oxide pigments have in particular been described in patent application EP-A-0 5 18
773.
These insoluble inorganic screening agents are particularly advantageous since
they do not need to be dissolved. They may be dispersed and thus introduced
directly into the aqueous or oily phase of the antisun formulations, especially oil-inwater
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).
However, UVA and UVB screening systems containing these inorganic screening
agents do not make it possible to afford broad UV protection over the range 280 to
400 nm especially having an 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 1/1 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 insoluble organic filters and/or insoluble
inorganic filters 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 and UVB screening system based
on a merocyanine compound and an insoluble organic UV-screening agent and/or
an insoluble inorganic UV-screening agent which is photostable and which
ensures overall protection against UV rays from 280 to 400 nm especially having
notable absorbance ranging up to a wavelength of 400 nm inclusive, without the
drawbacks as previously defined.
The Applicant has discovered, surprisingly, that this objective can be achieved by
using at least one insoluble organic and/or at least one insoluble inorganic UVscreening
agent and at least one particular merocyanine of formula ( 1 ) which will
be defined in greater detail hereinbelow.
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 and
b) at least one merocyanine compound of formula ( 1 ) defined herein below
and
c) at least one insoluble organic UV-screening agent and/or one insoluble
inorganic UV-screening agent.
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 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 "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 term "organic UV-screening agent" means any organic chemical molecule that
is capable of absorbing and/or of physically blocking (especially by reflection or
scattering) UV radiation in the wavelength range between 280 and 400 nm.
The term "mineral UV-screening agent" means any non-organic chemical molecule
that is capable of absorbing and/or of physically blocking (especially by reflection
or scattering) UV radiation in the wavelength range between 280 and 400 nm.
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
substituted 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 C 1-C22 alkyl, which may be substituted 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:
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.
INSOLUBLE ORGANIC UV-SCREENING AGENT
The insoluble organic UV-screening agents according to the invention preferably
have a mean particle size which ranges from 0.01 to 5 miti , more preferentially
from 0.01 to 2 miti and more particularly from 0.020 to 2 miti .
The mean particle diameter is measured with a particle size distribution analyser
such as the Coulter N4 Plus machine manufactured by Beckman Coulter Inc.
The insoluble organic screening agents according to the invention may be brought
to the desired particulate form by any suitable means, especially such as dry
milling or milling in a solvent medium, screening, atomization, micronization or
spraying.
The insoluble organic screening agents according to the invention in micronized
form may in particular be obtained by means of a process for milling an insoluble
organic UV-screening agent in the form of coarse-sized particles in the presence
of a suitable surfactant for improving the dispersion of the particles thus obtained
in the cosmetic formulations.
An example of a process for the micronization of insoluble organic screening
agents is described in applications GB-A-2 303 549 and EP-A-8931 19 . The milling
apparatus used according to those documents may be an air-jet mill, a ball mill, a
vibration mill or a hammer mill, and preferably a mill with high stirring speed or an
impact mill and more particularly a rotary ball mill, a vibration mill, a tube mill or a
rod mill.
According to this particular process, use is made, as surfactants for milling the
said screening agents, of alkylpolyglucosides of structure CnH2n+iO(C6HioO5)xH in
which n is an integer from 8 to 16 and x is the average degree of polymerisation of
the (C6H10O5) unit and ranges from 1.4 to 1.6. They may be chosen from C1-C12
esters of a compound of structure CnH2n+iO(C6HioO 5)xH and more particularly an
ester obtained by reacting a C1-C12 carboxylic acid, such as formic acid, acetic
acid, propionic acid, butyric acid, sulfosuccinic acid, citric acid or tartaric acid, with
one or more free OH functions on the glucoside (C6H10O5) unit. As
alkylpolyglucoside, mention may be made in particular of decylglucoside.
The said surfactants are generally used at a concentration ranging from 1% to
50% by weight and more preferentially from 5% to 40% by weight relative to the
insoluble screening agent in its micronized form.
The insoluble organic UV-screening agents in accordance with the invention may
be chosen especially from organic UV-screening agents of the oxalanilide type, of
the triazine type, of the benzotriazole type, of the vinylamide type, of the
cinnamide type, of the type comprising one or more benzazole and/or benzofuran,
benzothiophenene groups or of the indole type; of the aryl vinylene ketone type; of
the phenylene bis-benzoxazinone derivative type, or of the amide, sulfonamide or
acrylonitrile carbamate derivative type, or mixtures thereof.
In the sense in which it is used in the present invention, the term "benzazole"
encompasses benzothiazoles, benzoxazoles and benzimidazoles.
A/ Oxalanides
Among the UV-screening agents of the oxalanilide type in accordance with the
invention, mention may be made of those corresponding to the structure:
(I)
in which Ti, Ti', T2 and T2 which may be identical or different, denote a Ci-Cs
alkyl radical or a Ci-Cs alkoxy radical. These compounds are described in patent
application WO 95/22959.
Examples that may be mentioned include the commercial products Tinuvin® 3 15
and Tinuvin® 3 12 sold by the company BASF, having the respective structures:
B/ Triazines
Among the insoluble UV-screening agents of the triazine type in accordance with
the invention, mention may also be made of those corresponding to formula (II)
below:
in which T3, T and T5, independently, are phenyl, phenoxy or pyrrolo, in which the
phenyl, phenoxy and pyrrolo are unsubstituted or substituted with one, two or
three substituents chosen from OH, Ci-Cisalkyl or Ci-Cisalkoxy, Ci-
Ciscarboxyalkyl, Cs-Cscycloalkyl, a methylbenzylidenecamphor group, a group -
(CH=CH)n(CO)-OT 6, with T6 being either Ci-Cisalkyl or cinnamyl.
These compounds are described in WO 97/03642, GB 2286774, EP 743309, WO
98/22447 and GB 231 9523.
Among the UV-screening agents of the triazine type in accordance with the
invention, mention may also be made of insoluble s-triazine derivatives bearing
benzalmalonate and/or phenylcyanoacrylate groups such as those described in
patent application EP-A-0 790 243 (forming an integral part of the content of the
description).
Among these insoluble UV-screening agents of the triazine type, mention will be
made more particularly of the following compounds:
- 2,4,6-tris(diethyl 4'-aminobenzalmalonate)-s-triazine,
- 2,4,6-tris(diisopropyl 4'-aminobenzalmalonate)-s-triazine,
- 2,4,6-tris(dimethyl 4'-aminobenzalmalonate)-s-triazine,
- 2,4,6-tris(ethyl a-cyano-4-aminocinnamate)-s-triazine.
Among the UV-screening agents of the triazine type in accordance with the
invention, mention may also be made of insoluble s-triazine derivatives bearing
benzotriazole and/or benzothiazole groups such as those described in patent
application WO 98/25922 (forming an integral part of the content of the
description).
Among these compounds, mention may be made more particularly of:
- 2,4,6-tris[(3'-benzotriazol-2-yl-2'-hydroxy-5'-methyl)phenylamino]-s-triazine,
- 2,4,6-tris[(3'-benzotriazol-2-yl-2'-hydroxy-5'-tert-octyl)phenylamino]-s-triazine.
Mention may also be made of the symmetrical triazines 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 Journal, IP.COM 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.
C/ Benzotriazoles
Among the insoluble organic UV-screening agents of the benzotriazole type in
accordance with the invention, mention may be made of those of formula (III)
below as described in patent application WO 95/22959 (forming an integral part of
the content of the description):
in which T7 denotes a hydrogen atom or a C 1-C18 alkyl radical; T8 and T9, which
may be identical or different, denote a C 1-C18 alkyl radical optionally substituted
with a phenyl.
As examples of compounds of formula (III), mention may be made of the
commercial products Tinuvin 328, 320, 234 and 350 from the company BASF,
having the following structure:
Among the insoluble organic UV-screening agents of the benzotriazole type in
accordance with the invention, mention may be made of the compounds as
described in patents US 5 687 521 ,
US5 373 037 and US 5 362 881 and in particular [2,4'-dihydroxy-3-(2Hbenzotriazol-
2-yl)-5-(1 ,1 ,3,3-tetramethylbutyl)-2'-n-octoxy-5'-
benzoyl]diphenylmethane sold under the name Mixxim PB30® by the company
Fairmount Chemical, having the structure:
Among the insoluble organic UV-screening agents of the benzotriazole type in
accordance with the invention, mention may be made of the
methylenebis(hydroxyphenylbenzotriazole) derivatives having the following
structure:
in which the radicals T 0 and Tn, which may be identical or different, denote a Ci-
Ci8 alkyl radical possibly substituted with one or more radicals chosen from Ci-C 4
alkyl and C 5-C12 cycloalkyl or an aryl residue. These compounds are known per se
and are described in patent applications US 5237 071 , US 5 166 355, GB-A-2 303
549, DE 197 26 184 and EP-A-893 119 (forming an integral part of the
description).
In formula (I) defined above, the C1-C18 alkyl groups may be linear or branched
and are, for example, methyl, ethyl, n-propyl, isopropyl, n-butyl, isobutyl, tert-butyl,
tert-octyl, n-amyl, n-hexyl, n-heptyl, n-octyl, isooctyl, n-nonyl, n-decyl, n-undecyl,
n-dodecyl, tetradecyl, hexydecyl or octadecyl; the C 5-C12 cycloalkyl groups are, for
example, cyclopentyl, cyclohexyl or cyclooctyl; the aryl groups are, for example,
phenyl or benzyl.
Among the compounds of formula (IV), mention may be made of those having the
following structure:
compound (a)
compound b)
compound c)
Compound (a) with the nomenclature 2,2'-methylenebis[6-(2H-benzotriazol-2-yl)-4-
( 1 , 1 ,3,3-tetramethylbutyl)phenol] is especially sold under the trade name Mixxim
BB/200® by the company Fairmount Chemical.
Compound (c) with the nomenclature 2,2'-methylenebis[6-(2H-benzotriazol-2-yl)-4-
(methyl)phenol] is especially sold in solid form under the trade name Mixxim
BB/200® by the company Fairmount Chemical.
D/ Vinylamides
Among the insoluble organic screening agents of the vinylamide type, mention
may be made, for example, of the compounds having the following formulae,
which are described in application WO 95/22959 (forming an integral part of the
content of the description):
-(Y)r-C(=0)-C(T 13)=C(T 4)-N(Ti5)(Ti6)
in which T 2 is a C1-C18, preferably C1-C5, alkyl radical or a phenyl group optionally
substituted with one, two or three radicals chosen from OH, C1-C18 alkyl, Ci-Cs
alkoxy or a group - C(=O)-OTi7 where T 7 is a C1-C18 alkyl group; T 13, T , T15 and
T16, which may be identical or different, denote a C1-C18 and preferably C1-C5 alkyl
radical, or a hydrogen atom; Y is Nor O and r is 0 or 1.
Among these compounds, mention will more particularly be made of:
- 4-octylamino-3-penten-2-one;
- ethyl 3-octylamino-2-butenoate;
- 3-octylamino-1 -phenyl -2-buten-1 -one;
- 3-dodecylamino-1 -phenyl -2-buten-1 -one.
E/ Cinnamides
Among the insoluble organic screening agents of the cinnamide type in
accordance with the invention, mention may also be made of the compounds as
described in patent application WO 95/22959 (forming an integral part of the
content of the description) and corresponding to the following structure:
in which OTi8 is a hydroxyl or Ci-C4 alkoxy radical, preferably methoxy or ethoxy;
Tig is hydrogen, Ci-C4 alkyl, preferably methyl or ethyl; T2o is a group -(CONH)sphenyl
in which s is 0 or 1 and the phenyl group may be substituted with one, two
or three groups chosen from OH, C1-C18 alkyl, Ci-Cs alkoxy or a group -C(=O)-
OT21 in which T2i is a C1-C18 alkyl and more preferentially T2i is a phenyl, 4-
methoxyphenyl or phenylaminocarbonyl group.
Mention may also be made of cinnamide dimers such as those described in patent
US 5 888 481 , for instance the compound of structure:
F/ Benzazoles
Among the insoluble organic screening agents of the benzazole type, mention may
be made of those corresponding to one of the following formulae:
in which each of the symbols X independently represents an oxygen or sulfur atom
or a group NR2, each of the symbols Z independently represents a nitrogen atom
or a CH group,
each of the symbols Ri independently represents an OH group, a halogen atom, a
linear or branched Ci-Csalkyl group optionally containing a silicon atom, or a linear
or branched Ci-Csalkoxy group,
each of the numbers m is independently 0, 1 or 2,
n represents an integer between 1 and 4, inclusive,
p is equal to 0 or 1,
each of the numbers q is independently equal to 0 or 1,
each of the symbols R2 independently represents a hydrogen atom, a benzyl
group or a linear or branched Ci-Cs alkyl group optionally containing a silicon
atom,
A represents a radical of valency n chosen from those having the formulae:
(m) ( ) ( )
in which each of the symbols R 3 independently represents a halogen atom or a
linear or branched Ci-4 alkyl or alkoxy, or hydroxyl, group, R4 represents a
hydrogen atom or a linear or branched Ci-4 alkyl group, c = 0 - 4, d = 0 - 3, e = 0 or
1, and f = 0 - 2 .
These compounds are in particular described in patents DE 676 103 and CH 350
763, patent US 5 501 850, patent US 5 961 960, patent application EP 0 669 323,
patent US 5 518 7 13, patent US 2 463 264, the article in J. Am. Chem. Soc, 79,
5706 - 5708, 1957, the article in J. Am. Chem. Soc, 82, 609 - 5,61 1, 1960, patent
application EP 0 921 126 and patent application EP 071 2855.
As examples of preferred compounds of formula (VII) of the 2-arylbenzazole
family, mention may be made of 2-benzoxazol-2-yl-4-methylphenol, 2-(1 Hbenzimidazol-
2-yl)-4-methoxyphenol or 2-benzothiazol-2-ylphenol, it being
possible for these compounds to be prepared, for example, according to the
processes described in patent CH 350 763.
As examples of preferred compounds of formula (VII) of the
benzimidazolylbenzazole family, mention will be made of 2,2'-bis-benzimidazole,
5,5',6,6'-tetramethyl-2,2'-bisbenzimidazole, 5,5'-dimethyl-2,2'-bisbenzimidazole, 6-
methoxy-2,2'-bisbenzimidazole, 2-(1 H-benzimidazol-2-yl)benzothiazole, 2-(1 Hbenzimidazol-
2-yl)benzoxazole and N,N'-dimethyl-2,2'-bisbenzimidazole, it being
possible for these compounds to be prepared according to the procedures
described in patents US 5 961 960 and US 2 463 264.
As examples of preferred compounds of formula (VII) of the phenylenebenzazole
family, mention will be made of 1,4-phenylenebis(2-benzoxazole), 1,4-
phenylenebis(2-benzimidazole), 1,3-phenylenebis(2-benzoxazole), 1,2-
phenylenebis(2-benzoxazole), 1,2-phenylenebis(benzimidazole), 1,4-
phenylenebis(N-2-ethylhexyl-2-benzimidazole) and 1,4-phenylenebis(Ntrimethylsilylmethyl-
2-benzimidazole), it being possible for these compounds to be
prepared according to the procedures described in patent US 2 463 264 and in the
publications J. Am. Chem. Soc, 82, 609 (1960) and J. Am. Chem. Soc, 79, 5706 -
5708 ( 1957).
As examples of preferred compounds of formula (VII) of the
benzofuranylbenzoxazole family, mention will be made of 2-(2-
benzofuranyl)benzoxazole, 2-(benzofuranyl)-5-methylbenzoxazole and 2-(3-
methyl-2-benzofuranyl)benzoxazole, it being possible for these compounds to be
prepared according to the procedures described in patent US 5 5 18 713.
As preferred compounds of formula (VIII), mention may be made, for example, of
2,6-diphenyl-1 ,7-dihydrobenzo[1 ,2-d;4,5-d']diimidazole corresponding to the
formula:
or 2,6-distyryl-1 ,7-dihydrobenzo[1 ,2-d; 4,5-d']diimidazole or else 2,6-di(p-tertbutylstyryl)-
1 ,7-dihydrobenzo[1 ,2-d; 4,5-d']diimidazole, which can be prepared
according to the processes described in application EP 0 669 323.
As preferred compound of formula (IX), mention may be made of 5,5'-bis-[(phenyl-
2)benzimidazole] having the formula:
the preparation of which is described in J. Chim. Phys., 64, 1602 ( 1967).
Among these UV radiation-screening organic insoluble compounds, 2-(1 Hbenzimidazol-
2-yl)benzoxazole, 5 ole, 6-methoxy-2,2'-bisbenzimidazole, 2-(1 Hbenzimidazol-
2-yl)benzothiazole, 1,4-phenylenebis(2-benzoxazole), 1,4-
phenylenebis(2-benzimidazole), 1,3-phenylenebis(2-benzoxazole), 1,2-
phenylenebis(2-benzoxazole), 1,2-phenylenebis(2-benzimidazole) and 1,4-
phenylenebis(N-trimethylsilylmethyl-2-benzimidazole) are most particularly
preferred.
G/ Aryl vinylene ketones
Among the insoluble organic screening agents of the aryl vinylene ketone type,
mention may be made of those corresponding to one of the following formulae (X)
and (XI):
in which:
n' = 1 or 2,
B, in formula (X) when n' = 1 or in formula (XI), is an aryl radical chosen from the
following formulae (a') to (d') or in formula (X) when n' = 2, is a radical chosen from
the following formulae (e') to (h'):
(e' ( ) (g') (tV)
in which:
each of the symbols Rs independently represents an OH group, a halogen atom, a
linear or branched C1-C6 alkyl group optionally containing a silicon atom, a linear
or branched C1-C6 alkoxy group optionally containing a silicon atom, a linear or
branched C1-C5 alkoxycarbonyl group, or a linear or branched C1-C6
alkylsulfonamide group optionally containing a silicon atom or an amino acid
function,
p' represents an integer between 0 and 4 inclusive,
q' represents 0 or 1,
R5 represents hydrogen or an OH group,
R 6 represents hydrogen, a linear or branched C 1-C6 alkyl group optionally
containing a silicon atom, a cyano group, a C 1-C6 alkylsulfonyl group or a
phenylsulfonyl group,
R7 represents a linear or branched C 1-C6 alkyl group optionally containing a silicon
atom or a phenyl group which can form a bicycle and which is optionally
substituted with one or two R4 radicals,
or R6 and R together form a C2-10 monocyclic, bicyclic or tricyclic hydrocarbonbased
residue, optionally interrupted with one or more nitrogen, sulfur and oxygen
atoms, and possibly containing another carbonyl, and optionally substituted with a
linear or branched C i -Cs alkylsulfonamide group,
and optionally containing a silicon atom or an amino acid function; on condition
that when n' = 1, R6 and R do not form a camphor nucleus.
As examples of insoluble UV radiation-screening compounds of formula (X) in
which n' = 1, with a mean particle size of between 10 nm and 5 nm, mention may
be made of the following families:
- compounds of the styryl ketone type as described in patent application
JP 04 134 042, such as 1-(3,4-dimethoxyphenyl)-4,4-dimethylpent-1 -en-3-one:
- compounds of the benzylidene cineole type such as those described in the article
by E. Mariani et al., 16th IFSCC Congress, New York ( 1990), such as 1,3,3-
trimethyl-5-(4-methoxybenzylidene)-2-oxabicyclo[2.2.2]octan-6-one:
- compounds of the benzylidene chromanone type such as those described in
patent application JP 04 134 043, for instance 3-(4-methoxybenzylidene)-
2,3,4a,8a-tetrahydrochromen-4-one:
- compounds of the benzylidene thiochromanone type such as those described in
patent application JP 04 134 043, for instance 3-(4-methoxybenzylidene)-
2,3,4a,8a-tetrahydrochromene-4-thione:
- compounds of the benzylidene quinuclidinone type such as those described in
patent application EP 0 576 974, for instance 4-methoxybenzyliden-1 -
azabicyclo[2.2.2]octan-3-one:
- compounds of the benzylidene cycloalkanone type such as those described in
patent application FR 2 395 023, for instance 2-(4-
methoxybenzylidene)cyclopentanone and 2-(4-
methoxybenzylidene)cyclohexanone:
- compounds of the benzylidene hydantoin type such as those described in patent
application JP 0 1 158 090, for instance 5-(3,4-
dimethoxybenzylidene)imidazolidine-2,4-dione:
- compounds of the benzylidene hydantoin type such as those described in patent
application JP 04 134 043, for instance 2-(4-methoxybenzylidene)indan-1-one:
- compounds of the benzylidene tetralone type such as those described in patent
application JP 04 134 043, for instance 2-(4-methoxybenzylidene)-3,4-dihydro-2Hnaphthalen-
1 -one:
- compounds of the benzylidene furanone type such as those described in patent
application EP 0 390 683, for instance 4-(4-methoxybenzylidene)-2, 2,5,5-
tetramethyldihydrofuran-3-one:
- compounds of the benzylidene benzofuranone type such as those described in
patent application JP 04 134 041 , for instance 2-benzylidenebenzofuran-3-one:
- compounds of the benzylidene indanedione type such as 2-(3,5-di-tert-butyl-4-
hydroxybenzylidene)indane-1 ,3-dione:
- compounds of the benzylidene benzothiofuranone type such as those described
in patent application JP 04 134 043, for instance 2-benzylidenebenzo[b]thiophen-
3-one:
compounds of the benzylidene barbituric type such as 5-(4-
methoxybenzylidene)-1 ,3-dimethylpyrimidine-2,4,6-trione:
compounds of the benzylidene pyrazolone type such as 4-(4-
methoxybenzylidene)-5-methyl-2-phenyl-2,4-dihydropyrazol-3-one:
- compounds of the benzylidene imidazolone type such as 5-(4-
methoxybenzylidene)-2-phenyl-3,5-dihydroimidazol-4-one:
- compounds of the chalcone type such as 1-(2-hydroxy-4-methoxyphenyl)-3-
phenylpropenone:
- the benzylidene one compounds as described in document FR 2 506 156 for
instance 3-hydroxy-1 -(2-hydroxy-4-methoxyphenyl)-3-phenylpropenone:
As examples of insoluble UV radiation-screening compounds of formula (X) in
which n' = 2, with a mean particle size of between 10 nm and 5 miti , mention may
be made of the following families:
- compounds of the phenylene bis methylidene-nor-camphor type such as those
described in document EP 0 693 471 , for instance 1,4-phenylenebis{3-
methylidenebicyclo[2.2.1]heptan-2-one}:
- compounds of the phenylene bis methylidene camphor type such as those
described in document FR 2 528 420, for instance 1,4-phenylenebis{3-
methylidene-1 ,7,7-trimethylbicyclo[2.2.1 ]heptan-2-one}:
or 1,3-phenylenebis{3-methylidene-1 ,7,7-trimethylbicyclo[2.2.1]heptan-2-one}:
- compounds of the phenylene bis methylidene camphor sulfonamide type such as
those described in document FR2 529 887, for instance ethyl or 2-ethylhexyl 1,4-
phenylenebis(3,3'-methylidenecamphor-1 0,10'-sulfonamide):
- compounds of the phenylene bis methylidene cineole type such as those
described in the article by E. Mariani et al., 16th IFSCC Congress, New York
( 1990), such as 1,4-phenylenebis{5-methylidene-3,3-dimethyl-2-
oxabicyclo[2.2.2]octan-6-one}:
- compounds of the phenylene bis methylidene ketotricyclodecane type such as
those described in patent application EP 0 694 521 , for instance 1,4-
phenylenebis(octahydro-4,7-methano-6-inden-5-one):
- compounds of the phenylene bis alkylene ketone type such as those described in
patent application JP 04 134 041 , for instance 1,4-phenylenebis(4,4-dimethylpent-
1-en-3-one):
- compounds of the phenylene bis methylidene furanone type such as those
described in patent application FR 2 638 354, for instance 1,4-phenylenebis(4-
methylidene-2,2,5,5-tetramethyldihydrofuran-3-one):
- compounds of the phenylene bis methylidene quinuclidinone type such as those
described in patent application EP 0 714 880, for instance 1,4-phenylenebis{2-
methylidene-1 -aza-bicyclo[2.2.2]octan-3-one}:
As compounds of formula (XI), mention may be made of the following families:
- compounds of the bis benzylidene cycloalkanone type such as 2,5-
dibenzylidenecyclopentanone:
- compounds of the gamma pyrone type such as those described in document JP
04 290 882, for instance 2,6-bis(3,4-dimethoxyphenyl)pyran-4-one:
Among these insoluble organic UV radiation-screening compounds of the aryl
vinylene ketone type, the ones most particularly preferred are the compounds of
formula (X) in which n' = 2 .
H/ Phenylene bis-benzoxazinones
Among the insoluble organic screening agents of the phenylene bisbenzoxazinone
type, mention may be made of those corresponding to formula
(XII) below:
with R representing a divalent aromatic residue chosen from the following
formulae e) to (h):
in which:
each of the symbols Rg independently represents an O H group, a halogen atom, a
linear or branched C 1-C6 alkyl group optionally containing a silicon atom, a linear
or branched C 1-C6 alkoxy group optionally containing a silicon atom, a linear or
branched C 1-C5 alkoxycarbonyl group, or a linear or branched C 1-C6
alkylsulfonamide group optionally containing a silicon atom or an amino acid
function,
p" represents an integer between 0 and 4, inclusive,
q" represents 0 or 1.
As examples of insoluble UV radiation-screening compounds of formula (XII), with
a mean particle size of between 10 nm and 5 miti , mention may be made of the
following derivatives:
- 2,2'-p-phenylenebis(3,1 -benzoxazin-4-one), the commercial product Cyasorb
UV-3638® from the company Cytec,
- 2,2'-(4,4'-biphenylene)bis(3,1 -benzoxazin-4-one),
- 2,2'-(2,6-naphthylene)bis(3,1-benzoxazin-4-one).
I/ Acrylonitrile amide, sulfonamide or carbamate derivatives
Among the insoluble organic screening agents of the acrylonitrile amide,
sulfonamide or carbamate type, mention may be made of those corresponding to
formula (XIII) below:
in which:
Rio represents a linear or branched Ci-Cs alkyl group,
n'" is 0, 1 or 2,
X2 represents a divalent radical of formula -(C=O)-Rn-(C=O)-, -SO2-R11-SO2- or -
(C=O)-O-Rii-O-(C=O)-,
Y represents a radical -(C=O)-Ri2 or -SO2R13,
R11 represents a single bond or a linear or branched divalent C1-C30 alkylene or
C3-C30 alkenylene radical, which may bear one or more hydroxyl substituents and
which may contain in the carbon chain one or more heteroatoms chosen from
oxygen, nitrogen and silicon atoms,
R12 represents a radical -ORi 4 or -NHRi ,
Ri3 represents a linear or branched C1-C30 alkyl radical, or a phenyl nucleus which
is unsubstituted or substituted with Ci-C 4 alkyl or alkoxy radicals,
Ri4 represents a linear or branched C1-C30 alkyl or C3-C30 alkenyl radical, which
may bear one or more hydroxyl substituents and which may contain in the carbonbased
chain one or more heteroatoms chosen from oxygen, nitrogen and silicon
atoms.
Although in formula (XIII) above only the isomers in which the cyano substituent is
in the cis position relative to the para-aminophenyl substituent are represented,
this formula should be understood as also encompassing the corresponding trans
isomers; for each of the two double bonds, and independently, the cyano and
para-aminophenyl substituents may be in the cis or trans configuration relative to
each other.
An example that may be mentioned is the 2-ethylhexyl 2-cyano-3-[4-
(acetylamino)phenyl]acrylate dimer of formula:
J/ Polyvalent metals
Another particular family of insoluble organic screening agents in accordance with
the invention is that of polyvalent metal salts (for example of Ca2+, Zn2+, Mg2+,
Ba2+, Al3+ or Zr4+) of sulfonic or carboxylic organic screening agents, such as the
polyvalent metal salts of sulfonic derivatives of benzylidenecamphor, such as
those described in patent application FR-A 2 639 347; the polyvalent metal salts of
sulfonic derivatives of benzimidazole such as those described in patent application
EP-A-893 119; the polyvalent metal salts of cinnamic acid derivatives, such as
those described in application JP-87 166 5 17 .
Mention may also be made of metal or ammonium or substituted ammonium
complexes of UV-A and/or UV-B organic screening agents, such as those
described in patent applications WO 93/1 0753, WO 93/1 1095 and WO 95/051 50.
Among the insoluble organic UV-screening agents, mention may also be made of
compound 1, 1 '-(1 ,4-piperazinediyl)bis[1-[2-[4-(diethylamino)-2-
hydroxybenzoyl]phenyl]methanone (CAS 919803-06-8) having the following
structure:
as described in patent application WO 2007/071 584; this compound
advantageously being 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 in particular in the
form of an aqueous dispersion.
According to a particularly preferred form of the invention, use will be made of
insoluble organic UV-screening agents chosen from
(i) symmetrical triazine screening agents substituted by naphthalenyl groups or
polyphenyl groups described in patent US 6 225 467, patent application WO
2004/08541 2 (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
06/035000, WO 06/034982, WO 06/034991 , WO 06/035007, WO 2006/034992
and WO 2006/034985, these compounds advantageously being used in the
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 the form of an aqueous
dispersion;
(ii) the methylenebis(hydroxyphenylbenzotriazole) compounds of formula (IV)
below:
in which the radicals T 0 and Tn, which may be identical or different, denote a Ci-
Ci8 alkyl radical possibly substituted with one or more radicals chosen from Ci-C 4
alkyl and C 5-C12 cycloalkyl or an aryl residue;
(iii) and mixtures thereof.
According to a particularly preferred form of the invention, the
methylenebis(hydroxyphenylbenzotriazole) compounds of formula (IV) are in the
form of an aqueous dispersion of particles with a mean particle size which ranges
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 surfactant of structure CnH2n+i O(C6HioO5)xH
in which n is an integer from 8 to 16 and x is the average degree of polymerization
of the unit (C6H10O5) and ranges from 1.4 to 1.6 as defined previously. The said
surfactant is preferably used at a concentration ranging from 1% to 50% by weight
and more preferentially from 5% to 40% by weight relative to the benzotriazole
screening agent and the amount of benzotriazole screening agent of formula (I) in
the aqueous dispersion preferably ranges from 10% to 50% by weight and more
preferentially from 30% to 50% by weight relative to the total weight of the
dispersion.
The mean particle diameter is measured with a particle size distribution analyser
such as the Coulter N4 Plus® machine manufactured by Beckman Coulter Inc.
According to a particularly preferred form of the invention, the
methylenebis(hydroxyphenylbenzotriazole) compounds of formula (IV) may be in
the form of an aqueous dispersion of 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 miti , 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.
As examples of polyglyceryl mono(C8-C2o)alkyl ester surfactants, mention may be
made of decaglyceryl caprate, decaglyceryl laurate, decaglyceryl myristate,
decaglyceryl oleate, decaglyceryl stearate, decaglyceryl isostearate, hexaglyceryl
caprate, hexaglyceryl laurate, hexaglyceryl myristate, hexaglyceryl oleate,
hexaglyceryl stearate, hexaglyceryl isostearate, pentaglyceryl caprate,
pentaglyceryl laurate, pentaglyceryl myristate, pentaglyceryl oleate, pentaglyceryl
stearate and pentaglyceryl isostearate.
Use will be made in particular of:
- decaglyceryl caprate such as the products sold under the following trade
names: Sunsoft Q10Y®, Sunsoft Q 10S®, Sunsoft Q 12Y®, Sunsoft Q 12S®,
Sunsoft M 12J® by the company Taiyo Kagaku Co. Ltd., Nikkol Decaglyn 1-
L by the company Nikko Chemicals Co. Ltd, Ryoto-Polyglyceryl ester L-
10D® and L-7D® by the company Mitsubishi-Kagaku Co. Ltd.,
- decaglyceryl laurate such as the products sold under the following trade
names: Sunsoft Q14Y®, Sunsoft Q14S®, Sunsoft Q 12Y®, Sunsoft Q12S®,
Sunsoft M12J® by the company Taiyo Kagaku Co. Ltd., Nikkol Decaglyn 1-
M® by the company Nikko Chemicals Co. Ltd, Ryoto-Polyglyceryl ester M-
10D® and M-7D® by the company Mitsubishi-Kagaku Co. Ltd.,
- decaglyceryl stearate such as the products sold under the following trade
names: Sunsoft Q18Y®, Sunsoft Q 18S®, Sunsoft Q 12Y®, Sunsoft Q 12S®,
Sunsoft M12J® by the company Taiyo Kagaku Co. Ltd., Nikkol Decaglyn 1-
SV by the company Nikko Chemicals Co. Ltd, Ryoto-Polyglyceryl ester S-
15D® by the company Mitsubishi-Kagaku Co. Ltd.,
- hexaglyceryl caprate such as the products sold under the following trade
names: Nikkol Hexaglyn 1-L® by the company Nikko Chemicals Co. Ltd,
Glysurf 6ML by the company Aoki Oil Industrial Co. Ltd., Unigly GL-1 06® by
the company Nippon Oil & Fats Co. Ltd.,
- hexaglyceryl myristate such as the products sold under the following trade
names: Nikkol Hexaglyn 1-M®, Nikkol Hexaglyn 1-OV® by the company
Nikko Chemicals Co. Ltd, Glysurf 6ML® by the company Aoki Oil Industrial
Co. Ltd., Unigly GL-1 06 by the company Nippon Oil & Fats Co. Ltd.,
- hexaglyceryl stearate such as the products sold under the following trade
names: Nikkol Hexaglyn 1-M®, Nikkol Hexaglyn 1-SV® by the company
Nikko Chemicals Co. Ltd, Emalex MSG-6K® by the company NihonEmulsion
Co. Ltd., Unigly GL-1 06 by the company Nippon Oil & Fats Co.
Ltd.,
- hexaglyceryl isostearate such as the product sold under the following trade
name: Matsumate MI-61 0® by the company Matsumoto Fine Chemical Co.
Ltd,
- pentaglyceryl caprate such as the product sold under the following trade
name: Sunsoft A10E® by the company Taiyo Kagaku Co. Ltd.,
- pentaglyceryl laurate such as the products sold under the following trade
names: Sunsoft A 12E®, Sunsoft A 12 1E® by the company Taiyo Kagaku
Co. Ltd.,
- pentaglyceryl myristate such as the products sold under the following trade
names: Sunsoft A14E®, Sunsoft A141 E® by the company Taiyo Kagaku
Co. Ltd.,
- pentaglyceryl oleate such as the products sold under the following trade
names: Sunsoft A 17E®, Sunsoft A 17 1E® by the company Taiyo Kagaku
Co. Ltd.,
- pentaglyceryl stearate such as the products sold under the following trade
names: Sunsoft A 18E®, Sunsoft A 18 1E® by the company Taiyo Kagaku
Co. Ltd.
Among these surfactants, use is preferably made of those with an HLB of greater
than or equal to 14.5 and more preferentially greater than or equal to 15 . As
examples of polyglyceryl mono(C8-C2o)alkyl ester surfactants with a degree of
polymerization of glycerol of at least 5 and and with an HLB of greater than or
equal to 14.5, mention may be made of decaglyceryl caprate, decaglyceryl laurate,
decaglyceryl myristate, decaglyceryl oleate, decaglyceryl stearate, decaglyceryl
isostearate, hexaglyceryl laurate, pentaglyceryl caprate, pentaglyceryl laurate,
pentaglyceryl myristate, pentaglyceryl oleate and pentaglyceryl stearate. As
examples of polyglyceryl mono(C8-C2o)alkyl ester surfactants with a degree of
polymerization of glycerol of at least 5 and and with an HLB of greater than or
equal to 15, mention may be made of decaglyceryl caprate and decaglyceryl
laurate.
The amount of methylenebis(hydroxyphenylbenzotriazole) compound of formula
(IV) in the aqueous dispersion preferably ranges from 10% to 50% by weight and
more preferentially from 30% to 50% by weight relative to the total weight of the
dispersion.
Preferentially, the weight ratio of methylenebis(hydroxyphenylbenzotriazole)
compound/polyglyceryl mono(C8-C2o)alkyl ester ranges from 0.05 to 0.5 and more
preferentially from 0.1 to 0.3.
Use will be made more preferentially in these aqueous dispersions, as
methylenebis(hydroxyphenylbenzotriazole) compound of formula (IV), of the
compound 2,2'-methylenebis[6-(2H-benzothazol-2-yl)-4-(1 ,1 ,3,3-
tetramethylbutyl)phenol] of structure:
compound (a)
such as the commercial product sold under the name Tinosorb M® by BASF,
which is an aqueous dispersion comprising decylglucoside, xanthan gum and
propylene glycol (INCI name: Methylene Bis-Benzotriazolyl
Tetramethylbutylphenol (and) Aqua (and) Decyl Glucoside (and) Propylene Glycol
(and) Xanthan Gum).
The insoluble organic UV-screening agent(s) of the invention are present in an
active material concentration preferably ranging from about 0.1 % to 15% by weight
and more particularly from 0.5% to 10% by weight relative to the total weight of the
composition.
INSOLUBLE INORGANIC UV-SCREENING AGENTS
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 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 0.01 5 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,
- Ί O 2 treated with a polydimethylsiloxane, sold under the trade name 70250
Cardre UF TiO2SI3 by the company Cardre,
- anatase/rutile Ί O 2 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-PPG3 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 Wackherr 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, C 12-C1 5 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 C 12-C1 5 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 non-coated iron oxide pigments are sold, for example, by 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 Mitsubishi under the name
TY-220.
The coated iron oxide pigments are sold, for example, by 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 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 insoluble inorganic UV-screening agents of the invention are preferably
present in the compositions according to the invention in a content ranging from
0.1 % to 30% by weight, more particularly from 0.5% to 20% by weight and in
particular 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" is understood 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.
The term "oil" is understood to mean any fatty substance in the liquid form at room
temperature (20 - 25°C) and at atmospheric pressure (760 mmHg).
An oil suitable for the invention can be volatile or non-volatile.
An oil suitable for the invention can be chosen from hydrocarbon-based oils,
silicone oils, fluorinated oils and mixtures thereof.
A hydrocarbon-based oil suitable for the invention can be an animal hydrocarbonbased
oil, a vegetable hydrocarbon-based oil, a mineral hydrocarbon-based oil or
a synthetic hydrocarbon-based oil.
An oil suitable for the invention can advantageously be chosen from mineral
hydrocarbon-based oils, vegetable hydrocarbon-based oils, synthetic
hydrocarbon-based oils, 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" is understood to mean an oil comprising mainly
hydrogen and carbon atoms.
The term "fluorinated oil" is understood to mean an oil comprising at least one
fluorine atom.
A hydrocarbon-based oil suitable for the invention can in addition 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 or agents, 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" is understood to mean an oil which remains on the skin
or the keratinous fibre, at room temperature and atmospheric pressure, for at least
several hours and which has in particular a vapour pressure of less than 10 3
mmHg (0.13 Pa).
Hydrocarbon-based oils
Mention may in particular be made, as non-volatile hydrocarbon-based oils which
can be used according to the invention, 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 seed 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®, 812® and 818®
by Dynamit Nobel,
(ii) synthetic ethers having 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 (cetearyl 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, such as the product sold under the
name Cetiol CC® by 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.
Preference will more particularly be given, among the non-volatile hydrocarbon oils
which can be used according to the invention, 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.
Mention may in particular be made, as volatile hydrocarbon oils which can be used
according to the invention, of hydrocarbon oils having 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 patent applications of
Cognis WO 2007/068371 or WO 2008/1 55059 (mixtures of distinct alkanes
differing by at least one carbon). These alkanes are obtained from fatty alcohols,
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 WO2008/1 55059 from Cognis. Mention may also be made of
n-dodecane (C12) and n-tetradecane (Ci4) , sold by Sasol respectively under the
references Parafol 12-97® and Parafol 14-97®, and also their mixtures.
Use may also be made of other volatile hydrocarbon oils, such as petroleum
distillates, in particular those sold under the name Shell Solt® by Shell. According
to one embodiment, the volatile solvent is chosen from volatile hydrocarbon-based
oils having from 8 to 16 carbon atoms, and mixtures thereof.
Silicone oils
The non-volatile silicone oils can 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 have 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 silicones, 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):
where R represents an alkyl group comprising from 2 to 4 carbon atoms, one or
more hydrogen atoms of which can be replaced by a fluorine or chlorine atom.
Mention may be made, among the oils of general formula (I), of:
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.
Fluorinated oils
Use may also be made of volatile fluorinated oils, such as
nonafluoromethoxybutane, decafluoropentane, tetradecafluorohexane,
dodecafluoropentane, and mixtures thereof.
An oily phase according to the invention can additionally comprise other fatty
substances, mixed with or dissolved in the oil.
Another fatty substance which can be present in the oily phase can 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.
Preferably, 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 preferably from 10% to 80% by weight, relative to the total
weight of the composition.
AQUEOUS PHASE
The compositions according to the invention can in addition comprise at least one
aqueous phase.
The aqueous phase comprises water and optionally other water-soluble or watermiscible
organic solvents.
An aqueous phase suitable for the invention can 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-C 4 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 preferably from 10% to
80% by weight, relative 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 or lipophilic organic UVscreening
agents. It will preferentially consist of at least one hydrophilic, lipophilic
or insoluble organic UV-screening 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 state 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 additional organic UV-screening agents are chosen in particular from
cinnamic compounds; anthranilate compounds; salicylic compounds;
dibenzoylmethane 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, such as described in patents EP 669 323 and US 2 463 264; paminobenzoic
acid (PABA) compounds; benzoxazole compounds, such 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; dimers derived from c -
alkylstyrene, such as those described in patent application DE 198 55 649; 4,4-
diarylbutadiene compounds, such 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.
Mention may be made, as examples of organic photoprotective agents, of those
denoted hereinbelow under their INCI names:
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 in particular 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 D 50® by BASF,
Benzophenone-3 or Oxybenzone, sold under the trade name Uvinul M 40® by
BASF,
Benzophenone-4, sold under the trade name Uvinul MS 40® by BASF,
Benzophenone-5,
Benzophenone-6, sold under the trade name Helisorb 11® by Norquay,
Benzophenone-8, sold under the trade name Spectra-Sorb UV-24® by American
Cyanamid,
Benzophenone-9, sold under the trade name Uvinul DS 49® by BASF,
Benzophenone-1 2,
n-Hexyl 2-(4-diethylamino-2-hydroxybenzoyl)benzoate, sold under the trade name
Uvinul A Plus® or, as a mixture with octyl methoxycinnamate, under the trade
name Uvinul A Plus B® by BASF.
Benzylidenecamphor compounds:
3-Benzylidene Camphor, manufactured under the name Mexoryl SD® by Chimex,
4-Methylbenzylidene Camphor, sold under the name Eusolex 6300® by Merck,
Benzylidene Camphor Sulfonic Acid, manufactured under the name Mexoryl SL®
by Chimex,
Camphor Benzalkonium Methosulfate, manufactured under the name Mexoryl
SO® by Chimex,
Terephthalylidene Dicamphor Sulfonic Acid, manufactured under the name
Mexoryl SX® by Chimex,
Polyacrylamidomethyl Benzylidene Camphor, manufactured under the name
Mexoryl SW® by Chimex.
Phenylbenzimidazole compounds:
Phenylbenzimidazole Sulfonic Acid, sold in particular under the trade name
Eusolex 232® by Merck.
Bis-benzazolyl compounds:
Disodium Phenyl Dibenzimidazole Tetrasulfonate, sold under the trade name Neo
Heliopan AP® by Haarmann and Reimer.
Phenylbenzotriazole compounds:
Drometrizole Trisiloxane, sold under the name Silatrizole® by Rhodia Chimie.
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,
silicone tnazines 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 comprising benzalmalonate functional groups, 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-diphenylbutadiene.
Benzoxazole compounds:
2,4-Bis[4-[5-(1 , 1 -dimethylpropyl)benzoxazol-2-yl]phenylimino]-6-[(2-
ethylhexyl)imino]-1 ,3,5-triazine, sold under the name of Uvasorb K2A® by Sigma
3V.
The preferred organic screening agents are chosen from:
Ethylhexyl methoxycinnamate,
Ethylhexyl salicylate,
Homosalate,
Octocrylene,
Phenylbenzimidazole Sulfonic Acid,
Benzophenone-3,
Benzophenone-4,
Benzophenone-5,
n-Hexyl 2-(4-diethylamino-2-hydroxybenzoyl)benzoate,
4-Methylbenzylidenecamphor,
Terephthalylidenedicamphorsulfonic acid,
Disodium phenyldibenzimidazoletetrasulfonate,
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'-aminobenzalnnalonate)-6-(n-butyl 4'-aminobenzoate)-striazine,
2,4-Bis(n-butyl 4'-aminobenzalmalonate)-6-[(3-{1 ,3,3,3-tetramethyl-l -
[(trimethylsilyl)oxy]disiloxanyl}propyl)amino]-s-tnazine,
Drometrizole trisiloxane,
Polysilicone-1 5,
1, 1 -Dicarboxy(2,2'-dinnethylpropyl)-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,
n-Hexyl 2-(4-diethylamino-2-hydroxybenzoyl)benzoate,
Terephthalylidenedicamphorsulfonic acid,
Bis(ethylhexyloxyphenol)methoxyphenyltriazine,
Ethylhexyl Triazone,
Diethylhexyl Butamido Triazone,
2,4-Bis(n-butyl 4'-aminobenzalmalonate)-6-[(3-{1 ,3,3,3-tetramethyl-l -
[(trimethylsilyl)oxy]disiloxanyl}propyl)amino]-s-triazine,
Drometrizole Trisiloxane,
and mixtures thereof.
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 Ci-C 4
monoalcohols as defined above and in particular short-chain C2-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, such
as, for example, 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 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 Hoechst under the trade name Hostacerin AMPS ® (CTFA name:
ammonium polyacryloyldimethyl taurate) or Simulgel 800®, sold by 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 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.
Mention may be made, among the basifying agents, by way of example, of
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.
Mention may be made, among the active agents for the care of keratinous
substances, such as the skin, lips, scalp, hair, eyelashes or nails, of, for example:
- 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 decomposition;
- agents for stimulating fibroblast proliferation;
- agents for stimulating keratinocytes proliferation;
- muscle relaxants;
- refreshing agents;
- tensioning agents;
- mattifying agents;
- depigmenting agents;
- propigmenting agents;
- keratolytic agents;
- desquamating agents;
- moisturizers;
- anti-inflammatory agents;
- antimicrobial agents;
- slimming agents;
- agents acting on the energy metabolism of cells;
- insect repellents;
- substance P or CGRP antagonists;
- hair-loss counteractants;
- antiwrinkle agents;
- anti-ageing agents.
A person skilled in the art will choose said active agent(s) according to the desired
effect on the skin, hair, eyelashes, eyebrows or 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).
FORMULATION FORMS
The compositions according to the invention can be prepared according to the
techniques 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 can also be provided in the anhydrous form, such as, for example, in the
form of an oil. The term "anhydrous composition" is understood to mean a
composition comprising less than 1% by weight of water, indeed even less than
0.5% of water, and in particular devoid of water, the water not being added during
the preparation of the composition but corresponding to the residual water
contributed by the mixed ingredients. They can optionally be packaged as an
aerosol and be provided in the form of a foam or of a spray.
In the case of compositions in the form of oil-in-water or water-in-oil emulsions, the
emulsification processes which can be used are of the paddle or propeller, 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, via HPH (between 50 and 800 bar), to obtain stable dispersions
with droplet 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 provided in the form of
an oil-in-water 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.
Mention may be made, as examples of W/O emulsifying surfactants, of alkyl esters
or ethers of sorbitan, of glycerol, of polyol or of sugars; or silicone surfactants,
such as dimethicone copolyols, for example the mixture of cyclomethicone and
dimethicone copolyol sold under the name DC 5225 C® by Dow Corning, and alkyl
dimethicone copolyols, such as lauryl methicone copolyol, sold under the name
Dow Corning 5200 Formulation Aid by Dow Corning, or cetyl dimethicone
copolyol, such as the product sold under the name Abil EM 90R® by Goldschmidt
and the mixture of cetyl dimethicone copolyol, polyglycerol (4 mol) isostearate and
hexyl laurate sold under the name Abil WE 09® by Goldschmidt. It is also possible
to add thereto one or more coemulsifiers which, advantageously, can 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.
Mention may in particular be made, as polyol alkyl esters, of polyethylene glycol
esters, such as PEG-30 Dipolyhydroxystearate, such as the product sold under
the name Arlacel P 135® by ICI.
Mention may be made, as glycerol and/or sorbitan esters, for example, of
polyglycerol isostearate, such as the product sold under the name Isolan Gl 34®
by Goldschmidt; sorbitan isostearate, such as the product sold under the name
Arlacel 987® by ICI; sorbitan glyceryl isostearate, such as the product sold under
the name Arlacel 986® by ICI, and mixtures thereof.
Mention may be made, for the O/W emulsions, for example, as nonionic
emulsifying surfactants, of 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 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 Henkel under the respective
names Plantaren 2000® and Plantaren 1200®, cetearyl glucoside, optionally as a
mixture with cetearyl alcohol, sold, for example, under the name Montanov 68® by
SEPPIC, under the name Tegocare CG90® by Goldschmidt and under the name
Emulgade KE3302® by 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 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 self-emulsifying
composition, for example as described in document WO-A-92/06778.
According to a particularly preferred form, the compositions are provided in the oilin-
water form.
When it is an emulsion, the aqueous phase of the latter can 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 the
cosmetic treatment of 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 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 as an aerosol and be provided in the
form of a foam or of 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 as an aerosol in accordance with the invention
generally comprise 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 being unsealed; and
ii) a make-up and/or care composition in accordance with the invention placed
inside the said compartment(s).
The container can, for example, be in the form of a pot or a case.
The closing member can 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 make-up and/or care composition or compositions.
The examples which follow serve to illustrate the invention without, however,
exhibiting a limiting 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 are 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 is 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 9
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-methoxy-propyl)-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-phenysulfonyl-2,4-pentadienoate
(outside the invention)
and the merocyanine compound MC1 1 disclosed in the application
WO2008/090066 (outside of invention)
Formulations 1 to 4 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
1 2
Phase Ingredients
(outside the (outside the
invention) invention)
Water qsp 100 qsp 100
Glycerin 6 6
Disodium EDTA 0.1 0.1
Thethanolamine 0.45 0.45
A Methylenebis(benzotriazolyl)-
5% active 5% active
tetramethylbutylphenol
material material
(Tinosorb M®)
Potassium cetyl phosphate
1 1
(Amphisol K®)
2-Ethylphenyl benzoate
30 29.4
(X-Tend 226®)
Octyl 5-N,N-diethylamino-2-
phenylsulfonyl-2,4- - 0.6
pentadienoate
B
Stearic Acid 1.5 1.5
Glyceryl Stearate (and) PEG-
1.5 1.5
100 Stearate (Arlacel 165 ®)
Dimethicone 0.5 0.5
Preserving agents 1.28 1.28
Isohexadecane 2 2
Xanthan gum 0.1 0.1
C Acrylates / C 10-30 Alkyl
Acrylate crosspolymer 0.25 0.25
(Pemulen TR1®)
D Thethanolamine 0.25 0.25
E Alcohol 2 2
in vitro SPF (t24h) 4.1 ± 0.3 3.8 ± 0.2
in vitro UVAPPD (t24h) 4.5 ± 0.3 6.7 ± 0.5
Formulation
Formulation
Phase Ingredients 4
(outside the
(invention)
invention)
Water qsp 100 qsp 100
Glycerin 6 6
Disodium EDTA 0.1 0.1
Thethanolamine 0.45 0.45
A Methylenebis(benzotriazolyl)-
5% active 5% active
tetramethylbutylphenol
material material)
(Tinosorb M®
Potassium Cetyl
1 1
Phosphate(Amphisol K®)
2-Ethylphenyl benzoate
29.2 29
(X-Tend 226®)
(2Z)-2-cyano-N-(3-
methoxypropyl)-2-{3-[(3-
methoxypropyl)amino]cyclo- 0.8 -
hex-2-en-1-
B ylidene}ethanamide
Compound (2) - 1
Stearic Acid 1.5 1.5
Glyceryl Stearate (and) PEG-
1.5 1.5
100 Stearate (Arlacel 165®)
Dimethicone 0.5 0.5
Preserving agents 1.28 1.28
Isohexadecane 2 2
Xanthan gum 0.1 0.1
C Acrylates / C 10-C30 Alkyl
Acrylate crosspolymer 0.25 0.25
(Pemulen TR1®)
D Thethanolamine 0.25 0.25
E Alcohol 2 2
in vitro SPF (t24h) 4.1 ± 0.1 4.1 ± 0.3
in vitro UVAPPD (t24h) 7.2 ± 0.3 7.4 ± 0.8
Formulations 5 a 9 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 compound (2Z)-2-cyano-N-(3-methoxy-propyl)-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 of inventioon) at the same content. For some
of these formulations the SPF, the UVAPPD index and the absorbance after one
week at room temperature were measured. The amounts are expressed as weight
percentages relative to the total weight of the composition
Formulation 5
Formulation 6
Phase Ingredients (outside the
(invention)
invention)
Water qsp 100 qsp 100
Glycerin 5 5
Disodium EDTA 0.1 0.1
Triethanolamine 0.45 0.45
Methylene Bis-Benzotriazolyl
A
Tetramethylbutylphenol
5 5
(Tinosorb M® % in active
material)
Potassium Cetyl
1 1
Phosphate(Amphisol K®)
Isopropyl Lauroyl Sarcosinate
30 30
(Eldew SL-205®)
(2Z)-2-cyano-N-(3-
methoxypropyl)-2-{3-[(3-
2 -
methoxypropyl)amino]cyclohe
x-2-en-1 -ylidene}ethanamide
Compound (2) 2
B 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 (Montanov 2 2
68®)
Preservatives 1 1
Isohexadecane 1 1
Gomme de xanthane 0.2 0.2
C Acrylates / C 10-C30 Alkyl
Acrylate crosspolymer 0.2 0.2
(Pemulen TR1®)
D Triethanolamine 0,2 0,2
SPF in vitro (tiw) 4.3 ± 0.6 3.6 ± 1.1
UVA PPD in vitro (tiw) 16.5 ± 2.2 .6 ± 4.3
Formulation
Formulation Formulation
Formulation 8
7 9
Phase Ingredients 6 ( outside
(outside the (ouside the
(invention) the
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
Thethanolamine 0.45 0.45 0.45 0.45
Methylene Bis-
A Benzotriazolyl
Tetramethylbutylphenol 5 5 - -
(Tinosorb M® in % active
material)
Potassium Cetyl
1 1 1 1
Phosphate(Amphisol K®)
Isopropyl Lauroyl
Sarcosinate (Eldew SL- 30 30 30 30
205®)
Compound (2) 2 - 2 -
MC1 of WO2008/090066 - 2 - 2
Stearic Acid 1.5 1.5 1.5 1.5
Glyceryl Stearate (and)
B PEG-1 00 Stearate (Arlacel 2.5 2.5 2.5 2.5
65®)
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 AlkyI
Acrylate crosspolymer 0.2 0.2 0.2 0.2
(Pemulen TR1®)
D Triethanolamine 0.2 0.2 0.2 0.2
5
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. The phases C and then D were
then successively added, with continued stirring. The emulsion was finally cooled
to room temperature. The final emulsion was characterized by drops of 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 is applied to a rough plate of PMMA, in the form of a uniform
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 PPD measurement. The mAF values were then converted into
absorbance values according to: Abs= log(mAF). The profiles may be normalized
to 320 nm.
Absorbance of the formulations measured 24 hours after formulation
Conclusions
The in vitro UVAPPD index values for formulation 1 show that for the same SPF
and a similar absorbance profile in the UVB range, from 290 to 320 nm
(Formulation 2), Tinosorb M® alone is less protecting than the Tinosorb
M®/merocyanines combinations (Formulations 2, 3 and 4).
The Tinosorb M®/Compound 2 combination (Formulation 4) of the invention differs
from the Tinosorb M®/Octyl 5-N,N-diethylamino-2-phenysulfonyl-2,4-
pentadienoate (Formulation 2) and Tinosorb M ®/(2Z)-2-cyano-N-(3-
methoxypropyl)-2-{3-[(3-methoxypropyl)amino]cyclohex-2-en-1-
ylidene}ethanamide (Formulation 3) couples by a broader absorbance profile in
the UVA range and a significantly higher absorbance at 400 nm for comparable in
vitro SPF and UVAPPD values.
Absorbance of the formulations 5 and 6 measured after storage of 1 week at
room temperature and 45 days at 45°C
The Tinosorb M®/Compound 2 combination (Formulation 6) of the invention differs
from the Tinosorb M ®/ (2Z)-2-cyano-N-(3-methoxypropyl)-2-{3-[(3-
methoxypropyl)amino]cyclohex-2-en-1 -ylidene}-ethanamide combination
(Formulation 5) by a significantly higher absorbance at 400 nm after 45 days of
storage at 45°C for comparable in vitro SPF and UVAPPD values at 1 week.
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 DE* was calculated from the variations L* , a* et
between the compound (2) and the compound MC1 1 with the following equation
(DE*)2 = (DI_*)2 + (Aa*)2 + (Ab*)2
D I_* = IL *
formulation with compound MC1 1
IL *
formulation with compound (2)
Aa* = 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 AE* > 2 .
Colorimetric measures on the formulations 6 to 9
The colorimetry results on the examples 6 to 9 show that the formulations 6 and 8
with the compound (2) are significantly less yellow than the equivalent
formulations 7 and 9 with the compound MC1 1 of the application WO2008/
090066.
Formulations'! 0 to 13
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-methoxy-propyl)-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-phenysulfonyl-2,4-pentadienoate
(outside the invention)
and the merocyanine compound MC1 1 disclosed in the application
WO2008/090066 (outside the invention)
Formulae 10 to 12 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 formulae, the SPF, the UVAPPD
index and the absorbance after 24 hours at room temperature and after 10 days at
60°C were measured. The amounts are expressed as weight percentages relative
to the total weight of the composition.
Formulation Formulation
Formulation 10 Formulation
11 13
Phase Ingredients (outside 12
(outside the (outside the
invention) (invention)
invention) invention)
Water qsp 100 qsp 100 qsp 100 qsp 100
Glycerin 6 6 6 6
Disodium EDTA 0.1 0.1 0.1 0.1
A Triethanolamine 0.45 0.45 0.45 0.45
Potassium Cetyl
Phosphate 1 1 1 1
(Amphisol K®)
2-Ethylphenyl Benzoate
22.7 22.8 22.6 22.6
(X-Tend 226 ®)
TITANIUM DIOXIDE
(and) ALUMINUM
B
HYDROXIDE (and) R R R R
STEARIC ACID
(MICRO TITANIUM
DIOXIDE MT-100 TV ®
- TAYCA)
Octyl-5- N,N-
diethylamino-2-
1.3 - - -
phenysulfonyl-2,4-
pentadienoate
(2Z)-2-cyano-N-(3-
methoxypropyl)-2-{3-
[(3- - 1.2 - -
methoxypropyl)annino]c
yclohex-2-en-1-
ylidene}ethanamide
Compound (2) - - 1.4 -
MC1 1 of
- - - 1.4
WO2008/090066
Stearic Acid 1.5 1.5 1.5 1.5
Glyceryl Stearate (and)
PEG-1 00 Stearate 1.5 1.5 1.5 1.5
(Arlacel 65 ®)
Dimethicone 0.5 0.5 0.5 0.5
Preservatives 1.28 1.28 1.28 1.28
Isohexadecane 2 2 2 2
Xanthan gum 0.1 0.1 0.1 0.1
Acrylates / C 10-C30
c
Alky I AeryIate
0.25 0.25 0.25 0.25
crosspolymer (Pemulen
TR1®)
D Triethanolamine 0.25 0.25 0.25 0.25
E Alcohol 2 2 2 2
SPF in vitro (t24h) 5.6 ± 0.1 5.4 ± 0.7 5.7 ± 0.4
-
UVAPPD in vitro (t24h) 7.1 ± 0.6 6.0 ± 0.1 6.7 ± 0.6
SPF in vitro (ti 0d at 60°C) 6.7 ± 1.6 5.9 ± 0.8
- -
UVAPPD in vitro (ti 0d at 60°C) 5.9 ± 0.9 6.3 ± 0.5
Emulsions 10 to 13 were prepared according to the same preparation mode as for
Examples 1 to 9 .
The in vitro SPF and UVAPPD index values were measured under the same
conditions indicated previously.
Colorimetric measures on the formulations 12 and 13
The colorimetric measures were made on the formulations 12 and 13 in the same
conditions as previously indicated
The colorimetry results on the examples 12 and 13 show that the formulation 12
with the compound (2) is significantly less yellow than the equivalent formulation
13 with the compound MC1 1 of the application WO2008/ 090066.

CLAIMS
1. Cosmetic or dermatological connposition 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
substituted with one or more O, and
c) at least one insoluble organic UV-screening agent and/or one insoluble
inorganic UV-screening agent.
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 substituted 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/Z4.
Composition 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 insoluble
organic UV-screening agent is in the form of particles with a mean size ranging
from 0.01 to 5 miti , more preferentially from 0.01 to 2 miti and more particularly
from 0.020 to 2 mhh .
7. Composition according to any one of Claims 1 to 6, in which the insoluble
organic UV-screening agent is chosen from organic UV-screening agents of the
oxalanilide type, of the triazine type, of the benzotriazole type; of the vinylamide
type; of the cinnamide type; of the type comprising one or more benzazole and/or
benzofuran, benzothiophenene groups or of the indole type; of the aryl vinylene
ketone type; of the phenylene bis-benzoxazinone derivative type, or of the amide,
sulfonamide or acrylonitrile carbamate derivative type, or mixtures thereof.
8. Connposition according to any one of Clainns 1 to 7, in which the insoluble
organic UV-screening agent is chosen from:
(i) symmetrical triazines substituted with naphthalenyl groups or polyphenyl
groups, in particular 2,4, 6-tris(diphenyl)triazine and/or 2,4, 6-tris(terphenyl)triazine;
(ii) the methylenebis(hydroxyphenylbenzotriazole) compounds of formula (IV)
below:
in which the radicals T 0 and Tn, which may be identical or different, denote a Ci-
Ci8 alkyl radical possibly substituted with one or more radicals chosen from Ci-C 4
alkyl and C 5-C12 cycloalkyl or an aryl residue;
(iii) and mixtures thereof.
9. Composition according to Claim 8, in which the
methylenebis(hydroxyphenylbenzotriazole) compound of formula (IV) is in the form
of an aqueous dispersion of particles with a mean particle size which ranges from
0.01 to 5 m i h , more preferentially from 0.01 to 2 miti and more particularly from
0.020 to 2 miti in the presence of at least one surfactant of structure CnH2n+i
O(C6HioO5)xH in which n is an integer from 8 to 16 and x is the average degree of
polymerization of the unit (C6H10O5) and ranges from 1.4 to 1.6.
10. Composition according to Claim 8 or 9, in which the
methylenebis(hydroxyphenylbenzotriazole) compound of formula (IV) is in the form
of an aqueous dispersion of particles with a mean size ranging from 0.02 to 2 m i h ,
more preferentially from 0.01 to 1.5 miti and more particularly from 0.02 to 1 m i h, in
the presence of at least one polyglyceryl mono(C8-C2o)alkyl ester with a degree of
glycerol polymerization of at least 5 .
11. Composition according to Claim 10, in which the polyglyceryl mono(Cs-
C2o)alkyl ester is chosen from decaglyceryl caprate, decaglyceryl laurate,
decaglyceryl myristate, decaglyceryl oleate, decaglyceryl stearate, decaglyceryl
isostearate, hexaglyceryl caprate, hexaglyceryl laurate, hexaglyceryl myristate,
hexaglyceryl oleate, hexaglyceryl stearate, hexaglyceryl isostearate, pentaglyceryl
caprate, pentaglyceryl laurate, pentaglyceryl myristate, pentaglyceryl oleate,
pentaglyceryl stearate and pentaglyceryl isostearate, and more particularly from
decaglyceryl caprate and decaglyceryl laurate.
12. Composition according to Claim 10 or 11, in which the amount of
methylenebis(hydroxyphenylbenzotriazole) compound of formula (IV) in the
aqueous dispersion ranges from 10% to 50% by weight and more preferentially
from 30% to 50% by weight relative to the total weight of the dispersion.
13. Composition according to any one of Claims 10 to 12, in which the weight ratio
of methylenebis(hydroxyphenylbenzotriazole) compound/polyglyceryl mono(Cs-
C2o)alkyl ester ranges from 0.05 to 0.5 and more preferentially from 0.1 to 0.3.
14. Composition according to any one of Claims 9 to 13, in which the
methylenebis(hydroxyphenylbenzotriazole) compound of formula (IV) in aqueous
dispersion form is the compound 2,2'-methylenebis[6-(2H-benzotriazol-2-yl)-4-
( 1 , 1 ,3,3-tetramethylbutyl)phenol] having the following structure:
compound (a)
15. Composition according to any one of Claims 1 to 14, in which the insoluble
organic UV-screening agent(s) of the invention are present in an active material
concentration ranging from 0.1 % to 15% by weight and more particularly from
0.5% to 10% by weight relative to the total weight of the composition.
16. Composition according to any one of Claims 1 to 5, in which the insoluble
inorganic UV-screening agent is chosen from coated or uncoated metal oxide
pigments, chosen especially from titanium, zinc, iron, zirconium and cerium
oxides, or mixtures thereof.
17. Composition according to Claim 16, in which the metal oxide particles have 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
0.01 5 and 0.05 mhh .
18. Composition according to Claim 16 or 17, in which the insoluble mineral UVscreening
agent consists of coated or uncoated titanium dioxide particles.
19. Composition according to any one of Claims 1 to 5, and 16 to 18, in which the
insoluble inorganic UV-screening agent(s) are present in contents ranging from
0.1 % to 30% by weight, more particularly from 0.5% to 20% by weight and in
particular from 1% to 10% by weight, relative to the total weight of the composition.
20. 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.
2 1. 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.
22. 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.