Patent Application
20140134120
The present invention relates to a photoprotective composition for topical use containing an association of baicalin or an extract containing same with at least one system filtering UVA radiation. The invention particularly relates to the field of cosmetics and/or beauty products.
The present invention also relates to the cosmetic, non-therapeutic, use of baicalin, or an extract containing same, in association with at least one system filtering UVA radiation comprising at least one bis-resorcinyl triazine for protecting the skin and/or lips and/or hair against solar radiation.
It is known that UV-A rays, having wavelengths between 320 and 400 nm, which cause the skin to tan, are liable to induce damage thereof, particularly in the case of sensitive skin or skin continually exposed to solar radiation. UV-A rays particular cause a loss of skin elasticity and the appearance of wrinkles giving rise to premature skin ageing. In this way, for esthetic and cosmetic reasons, such as preserving natural skin elasticity, for example, an increasing number of people are seeking to control the effect of UV-A rays on their skin. It is thus desirable to filter UV-A radiation.
It is also known that light radiation with wavelengths between 280 nm and 400 nm enables tanning of the human epidermis, and that rays having wavelengths more specifically between 280 and 320 nm, known as UV-B, impede the development of a natural tan. For these reasons and for esthetic reasons, there is a constant demand for means for controlling natural tanning with a view to controlling skin color; it is thus necessary to filter UV-B radiation.
In order to protect the skin and keratin material against UV radiation, sunscreen compositions comprising organic filters, active in the UV-A range and active in the UV-B range, are generally used. The majority of these filters are lipophilic, although they also include hydrophilic compounds.
There is scope for further enhancement of existing photoprotective compositions in respect of protecting the skin against UV radiation, particularly in respect of UVA, but also UVB, radiation.
The development of cosmetic compositions suitable for combating premature skin ageing effectively involves the use of sun filters, particularly those absorbing in the UVA range. These filters make it possible to reduce excess photoinduced free radicals. However, with the majority of compositions containing UV filters, particularly UVA filters, complete protection is not provided. In this way, following repeated exposure, the residual amount of free radicals persisting in spite of UVA filter protection may, in the long-term, cause photoactinic ageing phenomena. One solution may consist of increasing the amounts of UVA filters, but it is not recommended to use excessively high levels of filters in cosmetic products for everyday use.
Indeed, with the majority of filters, a maximum protection factor is reached, which is very difficult to improve by increasing the proportion of filters.
In this way, research on solutions, aiming to find a means other than that consisting of using large amounts of UV filters, particularly UVA filters, for protecting the skin against sun rays and combating premature skin ageing effectively under conditions of use and in concentrations acceptable for those skilled in the art, is still of interest.
In the prior art, the use of baicalin in cosmetic compositions, and particularly in photoprotective compositions, has already been suggested. This particularly stems from a number of publications and patents such as the patent application JP 63083017 relating to the filtering action of some compounds including baicalin.
The publications by Shengzhao et al. (Study of application of baicalin in functional cosmetics, Shengzhao Gong; Yuke Jie; Shuiming Yuan, Riyong Huaxue Gongye (2003), 33(3), 200-203) and Feng-jiao et al. (Technology for preparation of sunscreen cream containing baicalin, Feng-jiao Sun; Ke-jian Liao; Yu-feng Cong; Yue-ling Dai; Feng Yan, Riyong Huaxue Gongye (2009), 39(4), 257-259) also relate to cosmetic compositions, and more specifically sun protection compositions, containing baicalin.
The patent application DE102009037900 also describes a cosmetic composition comprising baicalin in association with various active ingredients. This document also describes the possible additional presence of UV filtering agents, but with no particular conclusion in this respect.
The international application WO 98/196651 describes a composition comprising mineral (non-chemical) filters in the presence of proanthocyanidins, ferulic acid oryzanol and/or an ester containing same and optionally a scutellaria extract. The possibility of using baicalin is mentioned; however, it is clear from the examples that the very specific association of ethyl ferulate, pycnogenol, oryzanol and scutellaria extract improves the skin protection factor (SPF). However, these photoprotective compositions comprising baicalin require further enhancement in terms of protecting the skin against solar radiation, particularly UV.
There is thus still a need to identify compositions, particularly cosmetic compositions protecting the skin against damage induced by sun rays.
The aim of the invention is that of solving the technical problem consisting of providing a photoprotective composition for topical use and particularly a cosmetic composition.
The aim of the invention is also that of solving the technical problem consisting of improving photoprotective compositions in terms of protection of the skin and/or hair and/or lips against solar radiation, particularly UV.
A further aim of the invention is that of finding a means other than that consisting of using large amounts of UV filters, particularly UVA filters, for combating premature ageing of the skin and/or lips and/or hair effectively under conditions of use and in concentrations acceptable for those skilled in the art.
A further aim of the invention is that of preventing and/or combating premature ageing of the skin and/or lips due to ultraviolet radiation and protecting the skin and/or lips and/or hair against this form of radiation and free radicals.
The invention thus proposes to solve these various technical problems
The Applicant has now discovered, surprisingly, that, by associating baicalin, or an extract containing same, with at least one system filtering UVA radiation comprising at least one bis-resorcinyl triazine derivative, it was possible to enhance the protection of the skin and/or lips and/or hair against UV, particularly in respect of UVA radiation.
In this way, according to one of the aims of the present invention, a photoprotective composition for topical use comprising baicalin or an extract containing same, and at least one system filtering UVA radiation comprising at least one bis-resorcinyl triazine derivative. The invention particularly relates to a cosmetic composition. The system filtering UVA radiation advantageously further comprises at least one UVA filter selected from a dibenzoylmethane derivative, a compound filtering UVA derived from benzylidene camphor and a mixture of these two types of derivatives.
According to one preferred embodiment, the composition according to the invention further comprises at least one UVB filter, particularly of the β,β′-diphenylacrylate type.
The composition according to the invention more specifically covers a composition comprising baicalin, or an extract containing same; at least one system filtering UVA radiations comprising at least one bis-resorcinyl triazine derivative, at least one dibenzoylmethane derivative, and at least one compound filtering UVA derived from benzylidene camphor; and at least one UVB filter particularly of the β,β′-diphenylacrylate type, and preferably a composition comprising baicalin, or an extract containing same; and at least one system filtering UVA radiations comprising at least Bis-Ethylhexylphenol Methoxyphenyltriazine, Avobenzone, Terephthalylidene Dicamphor Sulfonic Acid; said composition further comprising octocrylene.
The composition according to the invention more specifically further comprises compounds filtering UVA and/or UVB. The composition according to the invention preferably further comprises cosmetically acceptable excipients.
The invention also relates to a multi-constituent agent for the photoprotection of human keratin material (skin, lips, hair, eyelashes, eyebrows, nails) comprising a composition A and a composition B packaged separately; said composition A comprising, in a cosmetically acceptable medium, at least baicalin or an extract;
said composition B comprising, in a cosmetically acceptable medium, at least one system filtering UVA radiation comprising at least one bis-resorcinyl triazine derivative;
said composition A and said composition B being applied either simultaneously or sequentially on the surface of the keratin material.
In the case of sequential application, composition A comprising baicalin is preferably applied first. The time interval between the applications of composition A and composition B preferably varies from 1 hour to 48 hours and more preferentially from 1 hour to 24 hours. The filtering composition B could be applied immediately prior to UV and particularly solar radiation exposure.
The system filtering UVA radiation advantageously further comprises at least one UVA filter selected from a dibenzoylmethane derivative, a compound filtering UVA derived from benzylidene camphor and a mixture of these two types of derivatives.
Composition B according to the invention specifically contains at least one system filtering UVA radiation comprising at least one bis-resorcinyl triazine derivative, at least one dibenzoylmethane derivative, and at least one compound filtering UVA derived from benzylidene camphor.
According to one preferred embodiment, the composition according to the invention further comprises at least one UVB filter, particularly of the β,β′-diphenylacrylate type.
According to one preferred embodiment, composition B according to the invention comprises at least one system filtering UVA radiation comprising at least Bis-Ethylhexylphenol Methoxyphenyltriazine, Avobenzone, Terephthalylidene Dicamphor Sulfonic Acid; said composition further comprising octocrylene.
Composition B according to the invention more specifically further comprises compounds filtering UVA and/or UVB. The composition according to the invention preferably further comprises cosmetically acceptable excipients.
A further aim of the invention relates to the cosmetic, non-therapeutic, use of baicalin, or an extract containing same, in association with at least one system filtering UVA radiation comprising at least one bis-resorcinyl triazine for protecting the skin and/or lips and/or hair against solar radiation, and/or for combating or preventing photoinduced premature ageing of the skin and/or lips and/or hair.
The present invention also relates to a cosmetic and/or beauty treatment method comprising the topical application on human keratin material (skin, lips, hair, eyelashes, eyebrows, nails) of a composition or a multi-constituent agent according to the invention, for combating or preventing photoinduced premature ageing of human keratin material (skin, lips, hair, eyelashes, eyebrows, nails).
The present invention also relates to a cosmetic and/or beauty treatment method comprising the topical application on human keratin material (skin, lips, hair, eyelashes, eyebrows, nails) of a composition or a multi-constituent agent as defined, for protecting the human keratin material (skin, lips, hair, eyelashes, eyebrows, nails) against solar radiation.
Further features, aspects and advantages of the invention will emerge on reading the detailed description hereinafter.
The term system filtering UV (UVA and/or UVB) radiation refers to a substance capable of absorbing at least a portion of UV (UVA and/or UVB) radiation emitted by the sun for protecting the skin and/or lips and/or hair against the harmful effects of this radiation.
UVA radiation wavelengths are different to UVB radiation wavelengths. UVA radiation wavelengths are between 400 nm and 315 nm and for UVB between 315 nm and 280 nm.
The term “associate” compounds or “association” of compounds refers to the presence, in the same composition, or in separate compositions applied sequentially or simultaneously, of the compounds to which reference is made.
The term “cosmetically acceptable” means compatible with the skin and/or integuments thereof, having a pleasant color, odor and texture and not giving rise to unacceptable discomfort (tingling, tightness, redness), liable to dissuade the consumer from using the composition.
The compositions according to the invention, particularly compositions A and/or B, may additionally comprise further complementary organic or inorganic UV filters active in the UVA and/or UVB range, which are hydrophilic or lipophilic or insoluble in routine cosmetic solvents.
The term “lipophilic UV filter” refers to any cosmetic or dermatological filter liable to be completely dissolved in the molecular state in a liquid fat phase or be solubilized in colloidal form (for example in micellar form) in a liquid fat phase.
The term “hydrophilic UV filter” refers to any cosmetic or dermatological filter liable to be completely dissolved in the molecular state in a liquid aqueous phase or be solubilized in colloidal form (for example in micellar form) in a liquid aqueous phase.
The term “insoluble UV filter” refers to any cosmetic or dermatological filter which is not defined as a lipophilic UV filter or as a hydrophilic UV filter, in particle form in liquid aqueous or fat phase.
The invention is detailed hereinafter with reference to the more general description of the invention.
Baicalin has the following formula:
Baicalin is available from MMP or Guilin Layn Natural Ingredients Corp. for example. This compound is particularly described in the application WO 2008/140440 particularly in stable solution form. Baicalin may be used in stable solution form comprising a glycol alkyl having 2 to 7 carbon atoms, a polyol ether, and at least one anti-oxidant.
Such an organic compound may be obtained as described in EP 1 400 579 (US2004/0067894) relating to the synthesis of tetrahydroxyflavones wherein the general formula comprises baicalin.
Baicalin may be used in the form of an extract of plant origin. Baicalin is a polyphenol (flavone) particularly extracted from skull cap root (scutellaria and particularly scutellaria baicalensis), based on traditional Chinese medicine.
The bis-resorcinyl triazine compounds according to the present invention preferably comply with the following formula (I):
in which:
(i) the radicals R1 and R2, which are identical or different, refer to a C3-C18 alkyl radical; a C2-C18 alkenyl radical or a residue having the formula —CH2—CH(OH)—CH2—OT1 where T1 is a hydrogen atom or a C1-C8 alkyl radical;
(ii) the radicals R1 and R2, which are identical or different, may also refer to a residue having the following formula (1):
in which:
where R10 is a C1-C5 alkyl radical;
in which:
In formulas (I) and (1) to (5) described above:
The bis-resorcinyl triazine derivatives having formula (I) according to the invention are filters already known per se. They are described and prepared according to the synthesis processes given in the patent applications EP-A-0775 698.
Examples of compounds having formula (I) suitable for use include:
More specifically, at least the compound 2,4-bis {[4-(2-ethyl-hexyloxy)-2-hydroxy]-phenyl}-6-(4-methoxy-phenyl)-1,3,5-triazine or Bis-Ethylhexyloxyphenol Methoxyphenyl Triazine (INCI name) such as the product sold under the trade name “TINOSORB S” by CIBA GEIGY.
The bis-resorcinyl triazine compound(s) having formula (I) are generally present in the filtering compositions according to the invention at a concentration ranging from 0.1 to 20% by weight and more preferentially from 1 to 10% by weight and more specifically from 2 to 8% by weight with respect to the total weight of the composition.
The dibenzoylmethane derivatives particularly include, but are not limited to:
Of the dibenzoylmethane derivatives mentioned above, 4-isopropyl-dibenzoylmethane, sold under the trade name “EUSOLEX 8020” by MERCK, and complying with the formula below is used for example:
Particular preference is placed on the use of at least 4-(ter.-butyl) 4′-methoxy dibenzoylmethane or Butyl Methoxy Dibenzoylmethane or avobenzone, marketed under the trade name “PARSOL 1789” by DSM Nutritional Products, Inc; this filter complies with the following formula:
The dibenzoylmethane derivative(s) may be present in the compositions according to the invention at contents preferably varying from 0.01 to 10% by weight and more preferentially from 0.1 to 6% by weight with respect to the total weight of the composition.
The benzylidene camphor derivatives include:
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,
Polyacrylamidomethyl Benzylidene Camphor manufactured under the name “MEXORYL SW” by CHIMEX.
The use of at least Terephthalylidene Dicamphor Sulfonic Acid marketed under the name MEXORYL SX by CHIMEX is preferred.
The invention may further comprise at least one UVB filter and particular at least one β,β′-diphenylacrylate derivative. Lipophilic UVB filters are preferred.
The β,β′-diphenylacrylate derivatives include etocrylene, particularly sold under the trade name “UVINUL N35” by BASF. The use of at least octocrylene as a UVB filter is preferred. Octocrylene is particularly sold under the trade name “UVINUL N539” by BASF.
The compositions according to the invention may additional comprise complementary organic or inorganic photoprotective agents, also known as filtering agents or filters, filtering wavelengths within the UVA and/or UVB ranges, which are hydrophilic or lipophilic or insoluble in routine cosmetic solvents.
The complementary organic filters are particularly selected from anthranilics; cinnamic derivatives; salicylic derivatives; benzophenone derivatives; phenyl benzotriazole derivatives; benzalmalonate derivatives particularly those cited in the patent U.S. Pat. No. 5,624,663; phenyl benzimidazole derivatives; imidazolines; 4,4-diarylbutadiene derivatives; bis-benzoazolyle derivatives as described in the patents EP669323 and U.S. Pat. No. 2,463,264; p-aminobenzoic acid (PABA) derivatives; methylene bis-(hydroxyphenyl benzotriazole) derivatives as described in the applications U.S. Pat. No. 5,237,071, U.S. Pat. No. 5,166,355, GB2303549, DE 197 26 184 and EP893119; benzoxazole derivatives as described in the patent applications EP0832642, EP1027883, EP1300137 and DE10162844; filter polymers and filter silicones such as those particularly described in the application WO-93/04665; dimers derived from α-alkylstyrene such as those described in the patent application DE19855649; 4,4-diarylbutadienes as described in the applications EP0967200, DE19746654, DE19755649, EP-A-1008586, EP1133980 and EP133981; merocyanine derivatives such as those described in WO04006878, WO05058269 and WO06032741 and the mixtures thereof.
Examples of organic UV filters include those referred to hereinafter using the INCI name thereof:
Classification According to UVA and/or UVB Radiation Wavelength Range
n-hexyl 2-(4-diethylamino-2-hydroxybenzoyl)-benzoate particularly sold under the trade name “UVINUL A+” by BASF;
1,1′-(1,4-piperazinediyl)bis[1-[2-[4-(diethylamino)-2-hydroxybenzoyl]phenyl]-methanone (CAS 919803-06-8)
Menthyl anthranilate particularly sold under the trade name “NEO HELIOPAN MA” by SYMRISE;
4,4-diarylbutadiene Derivatives:
1,1-dicarboxy(2,2′-dimethyl-propyl)-4,4-diphenylbutadiene;
Octyl-5-N,N-diethylamino-2-phenysulfonyl-2,4-pentadienoate;
Within the scope of the invention, and according to one particular embodiment, the following lipophilic filters are used:
The bis-benzoazolyl derivatives as described in the patents EP 669 323, and U.S. Pat. No. 2,463,264 and more specifically the compound Disodium Phenyl Dibenzimidazo tetra-sulfonate sold under the trade name “NEO HELIOPAN AP” by SYMRISE;
The preferred hydrophilic UVA filter is Terephthalylidene Dicamphor Sulfonic Acid.
Ethylhexyl Dimethyl PABA (ESCALOL 507 from ISP);
Homosalate particularly sold under the name “Eusolex HMS” by Rona/EM Industries;
Ethylhexyl Salicylate particularly sold under the name “NEO HELIOPAN OS” by SYMRISE;
Dipropyleneglycol Salicylate particularly sold under the name “DIPSAL” by SCHER;
TEA Salicylate sold under the name “NEO HELIOPAN TS” by SYMRISE;
Ethylhexyl Methoxycinnamate particularly sold under the trade name “PARSOL MCX” by DSM Nutritional Products, Inc.;
Isopropyl Methoxy cinnamate;
Isoamyl Methoxy cinnamate particularly sold under the trade name “NEO HELIOPAN E 1000” by SYMRISE;
β,β′-diphenylacrylate Derivatives:
Etocrylene, particularly sold under the trade name “UVINUL N35” by BASF;
3-Benzylidene camphor manufactured under the name “MEXORYL SD” by CHIMEX;
Methylbenzylidene camphor sold under the name “EUSOLEX 6300” by MERCK;
Polyacrylamidomethyl Benzylidene Camphor manufactured under the name “MEXORYL SW” by CHIMEX;
Ethylhexyl triazone particularly sold under the trade name “UVINUL T150” by BASF;
Diethylhexyl Butamido Triazone particularly sold under the trade name “UVASORB HEB” by SIGMA 3V;
2,4,6-tris(dineopentyl 4′-amino benzalmalonate)-s-triazine;
2,4,6-tris(diisobutyl 4′-amino benzalmalonate)-s-triazine;
2,4-bis(dineopentyl 4′-amino benzalmalonate)-6-(n-butyl 4′-aminobenzoate)-s-triazine;
2,4-bis(n-butyl 4′-amino benzoate)-6-(aminopropyltrisiloxane)-s-triazine;
the symmetrical triazine filters described in the patent U.S. Pat. No. 6,225,467, the application WO 2004/085412 (see compounds 6 and 9) or the document “Symmetrical Triazine Derivatives” IP.COM Journal, IP.COM INC WEST HENRIETTA, N.Y., US (Sep. 20, 2004) particularly 2,4,6-tris-(biphenyl)-1,3,5-triazine (particularly 2,4,6-tris(biphenyl-4-yl-1,3,5-triazine) and 2,4,6-tris(terphenyl)-1,3,5-triazine, the latter two filters being described in the BEIERSDORF applications WO 06/035000, WO 06/034982, WO 06/034991, WO 06/035007, WO 2006/034992, WO 2006/034985).
Polyorganosiloxanes with a benzalmalonate function such as Polysilicone-15 particularly sold under the trade name “PARSOL SLX” by DSM Nutritional Products, Inc.;
Di-neopentyl 4′-methoxybenzalmalonate;
Within the scope of the invention, and according to one particular embodiment, the following lipophilic UV-B filters are used in the composition according to the invention:
Ethylhexyl triazone.
The following p-aminobenzoic acid (PABA) derivatives:
PEG-25 PABA particularly sold under the trade name “UVINUL P25” by BASF.
Phenylbenzimidazole Sulfonic Acid particularly sold under the trade name “EUSOLEX 232” by MERCK,
ferulic acid,
salicylic acid,
DEA methoxycinnamate,
Benzylidene Camphor Sulfonic Acid manufactured under the name “MEXORYL SL” by CHIMEX,
Camphor Benzalkonium Methosulfate manufactured under the name “MEXORYL SO” by CHIMEX,
The preferred hydrophilic UVB filter is Phenylbenzimidazole Sulfonic Acid.
Benzophenone-1 particularly sold under the trade name “UVINUL 400” by BASF;
Benzophenone-2 particularly sold under the trade name “UVINUL D50” by BASF;
Benzophenone-3 or Oxybenzone particularly sold under the trade name “UVINUL M40” by BASF;
Benzophenone-6 particularly sold under the trade name “Helisorb 11” by Norquay;
Benzophenone-8 particularly sold under the trade name “Spectra-Sorb UV-24” by American Cyanamid;
Drometrizole Trisiloxane particularly sold under the name “Silatrizole” by RHODIA CHIMIE or manufactured under the name “Meroxyl XL” by CHIMEX;
Methylene bis-Benzotriazolyl Tetramethylbutylphenol, sold in solid form particularly under the trade name “MIXXIM BB/100” by FAIRMOUNT CHEMICAL or in micronized form in aqueous dispersion particularly under the trade name “TINOSORB M” by CIBA SPECIALTY CHEMICALS;
Benzoxazole derivatives:
2,4-bis-[5-1(dimethylpropyl)benzoxazol-2-yl-(4-phenyl)-imino]-6-(2-ethylhexyl)-imino-1,3,5-triazine particularly sold under the name Uvasorb K2A by Sigma 3V.
The preferential lipophilic organic UVA and UVB filters are selected from:
Methylene bis-Benzotriazolyl Tetramethylbutylphenol;
Benzophenone derivatives comprising at least one sulfonic radical such as
Benzophenone-4 particularly sold under the trade name “UVINUL MS 40” by BASF,
The composition according to the invention may also comprise mineral filters which are pigments. The pigments may be coated or uncoated.
The coated pigments are pigments which have undergone one or a plurality of chemical, electronic, mechanochemical and/or mechanical surface treatments with compounds as described for example in Cosmetics & Toiletries, February 1990, Vol. 105, p. 53-64, such as amino acids, beeswax, fatty acids, fatty alcohols, anionic surfactants, lecithins, sodium, potassium, zinc, iron or aluminum salts of fatty acids, metal (titanium or aluminum) alkoxides, polyethylene, silicones, proteins (collagen, elastin), alkanolamines, silicon oxides, metal oxides or sodium hexametaphosphate.
According to the prior art, the silicones are organosilicate polymers or oligomers with a linear or cyclic, branched or cross-linked structure, with a variable molecular weight, obtained by polymerization and/or polycondensation of suitably functionalized silanes, and essentially consisting of a repetition of primary structural units wherein the silicon atoms are interconnected by oxygen atoms (siloxane bond), optionally substituted hydrocarbon radicals being directly bound via a carbon atom on said silicon atoms.
The term “silicones” also covers the silanes required for the preparation thereof, particularly, alkyl silanes.
The silicones used for coating pigments suitable for the present invention are preferably selected from the group containing alkyl silanes, polydialkylsiloxanes, and polyalkylhydrogen siloxanes. More preferentially, the silicones are selected from the group containing octyl trimethyl silane, polydimethylsiloxanes and polymethylhydrogen siloxanes.
Obviously, prior to the treatment thereof with silicone, the metal oxide pigments may have been treated with other surface agents, particularly cerium oxide, alumina, silica, aluminum compounds, silicon compounds, or mixtures thereof.
The coated pigments are, for example, titanium oxides coated with:
Further titanium oxide pigments treated with a silicone are for example TiO2 treated with octyl trimethyl silane such as that sold under the trade name “T 805” by DEGUSSA SILICES, TiO2 treated with a polydimethylsiloxane such as that sold under the trade name “70250 Cardre UF TiO2SI3” by CARDRE, anatase/rutile TiO2 treated with a polydimethylhydrogen siloxane such as that sold under the trade name “MICRO TITANIUM DIOXYDE USP GRADE HYDROPHOBIC” by COLOR TECHNIQUES.
The uncoated titanium oxide pigments are for example sold by TAYCA under the trade names “MICROTITANIUM DIOXIDE MT 500 B” or “MICROTITANIUM DIOXIDE MT600 B”, by DEGUSSA under the name “P 25”, by WACKHER under the name “Oxyde de titane transparent PW”, by MIYOSHI KASEI under the name “UFTR”, by TOMEN under the name “ITS” and by TIOXIDE under the name “TIOVEIL AQ”.
The uncoated zinc oxide pigments are for example
The coated zinc oxide pigments are for example
The uncoated cerium oxide pigments are sold for example under the name “COLLOIDAL CERIUM OXIDE” by RHONE POULENC.
The uncoated iron oxide pigments are for example sold by ARNAUD under the names “NANOGARD WCD 2002 (FE 45B)”, “NANOGARD IRON FE 45 BL AQ”, “NANOGARD FE 45R AQ, “NANOGARD WCD 2006 (FE 45R)”, or by MITSUBISHI under the name “TY-220”.
The coated iron oxide pigments are for example sold by ARNAUD under the names “NANOGARD WCD 2008 (FE 45B FN)”, “NANOGARD WCD 2009 (FE 45B 556)”, “NANOGARD FE 45 BL 345”, “NANOGARD FE 45 BL”, or by BASF under the name “TRANSPARENT IRON OXIDE”.
It is also possible to cite metal oxide mixtures, particularly of titanium dioxide and cerium dioxide, including the mixture of equal weights of titanium dioxide and cerium dioxide coated with silica, sold by IKEDA under the name “SUNVEIL A”, and the mixture of titanium dioxide and zinc dioxide coated with alumina, silica and silicone such as the product “M 261” sold by KEMIRA or coated with alumina, silica and glycerin such as the product “M 211” sold by KEMIRA.
The pigments may be introduced into the compositions according to the invention as is or in pigment paste form, i.e. in a mixture with a dispersion agent, as described for example in the document GB-A-2206339.
The additional UV filters are generally present in the compositions according to the invention in proportions ranging from 0.01 to 20% by weight with respect to the total weight of the composition, and preferably ranging from 0.1 to 10% by weight with respect to the total weight of the composition.
The composition may further comprise at least one additional ingredient intended to provide an immediate visual effect. This particularly includes fillers with a soft-focus effect or agents promoting naturally pink skin color.
Agents promoting naturally pink skin color include, for example, self-tanning agents, i.e. an agent which, applied on the skin, particularly on the face, makes it possible to obtain a tanning effect more or less similar to that liable to result from prolonged exposure to the sun (natural tan) or a UV lamp;
Examples of self-tanning agents particularly include:
dihydroxyacetone (DHA),
erythrulose, and
the association of a catalytic system formed from:
manganese and/or zinc salts and oxides, and
alkaline and/or alkaline earth hydrogen carbonates.
The self-tanning agents are generally selected from mono or polycarbonyl compounds such as for example isatin, alloxan, ninhydrin, glyceraldehyde, mesotartaric aldehyde, glutaraldehyde, erythrulose, pyrazolin-4,5-dione derivatives as described in the patent application FR 2 466 492 and WO 97/35842, dihydroxyacetone (DHA), 4,4-dihydroxypyrazolin-5-one derivatives as described in the patent application EP 903 342. DHA is preferably used.
DHA may be used in free and/or encapsulated form for example in lipid vesicles such as liposomes, particularly described in the application WO 97/25970.
As a general rule, the self-tanning agent, particularly DHA, is present in an amount ranging from 0.01 to 20% by weight, and preferably in an amount between 0.1 and 10% of the total weight of the composition.
Further colorants suitable for modifying the color produced by the self-tanning agent may be used.
These colorants may be selected from synthetic or natural direct colorants.
These colorants may be selected for example from red or orange fluorane type colorants such as those described in the patent application FR2840806. For example, this includes the following colorants:
These colorants may also be selected from anthraquinones, caramel, carmine, carbon black, azulene blues, methoxalene, trioxalene, guajazulene, chamuzulene, rose bengal, cosine 10B, cyanosin, daphinin.
These colorants may also be selected from indole derivatives such as monohydroxyindoles as described in the patent FR2651126 (i.e.: 4-, 5-, 6- or 7-hydroxyindole) or di-hydroxyindoles as described in the patent EP-B-0425324 (i.e.: 5,6-dihydroxyindole, 2-methyl 5,6-dihydroxyindole, 3-methyl 5,6-dihydroxyindole, 2,3-dimethyl 5,6-dihydroxyindole).
The compositions according to the present invention may further comprise conventional cosmetic adjuvants particularly selected from fatty substances, particularly oils, waxes, organic solvents, ionic or non-ionic thickeners, hydrophilic or lipophilic, softeners, moistening agents, opacifiers, stabilizers, emollients, silicones, anti-foaming agents, perfumes, preservatives, anionic, cationic, non-ionic, zwitterionic or amphoteric surfactants, active substances, fillers, polymers, propellants, alkalinizing or acidifying agents or any other ingredient routinely used in the cosmetic and/or dermatological field.
The fatty substances may consist of an oil or a wax or mixtures thereof. The term oil refers to a liquid compound at ambient temperature. The term wax refers to a solid or substantially solid compound at ambient temperature, wherein the melting point is generally greater than 35.
The oils include, for example mineral oils (paraffin oil); vegetable oils (sweet almond, macadamia, blackcurrant seed, jojoba); synthetic oils such as perhydrosqualene, fatty alcohols, fatty amides (such as isopropyl lauroyl sarcosinate sold under the name “Eldew SL-205” by Ajinomoto), fatty acids or esters such as C12-C15 alcohol benzoate sold under the trade name “Finsolv TN” or “Witconol TN” by WITCO, 2-ethylphenyl benzoate such as the commercial product sold under the name X-TEND 226® by ISP, octyl palmitate, isopropyl lanolate, triglycerides including those of capric/caprylic acids, dicaprylyl carbonate sold under the name “Cetiol CC” by Cognis), oxyethylene or oxypropylene fatty esters and ethers; silicone oils (cyclomethicone, polydimethysiloxanes or PDMS) or fluorinated oils, polyalkylenes, trialkyl trimellitates such as tridecyl trimellitate.
The waxes include, for example, carnauba wax, beeswax, hydrogenated castor oil, polyethylene waxes and polymethylene waxes such as that sold under the name Cirebelle 303 by SASOL.
The organic solvents include, for example lower alcohols and polyols. These may be selected from glycols and glycol ethers such as ethylene glycol, propylene glycol, butylene glycol, dipropylene glycol or diethylene glycol.
The hydrophilic thickeners include, for example, carboxyvinyl polymers such as Carbopols (Carbomers) and Pemulens (acrylate/C10-C30-alkylacrylate copolymer); polyacrylamides such as for example cross-linked copolymers sold under the names Sepigel 305 (C.T.F.A. name: polyacrylamide/C13-14 isoparaffin/Laureth 7) or Simulgel 600 (C.T.F.A. name: acrylamide/sodium acryloyldimethyltaurate copolymer/isohexadecane/polysorbate 80) by Seppic; 2-acrylamido 2-methylpropane sulfonic acid polymers and copolymers, optionally cross-linked and/or neutralized, such as poly(2-acrylamido 2-methylpropane sulfonic acid) marketed by Hoechst under the trade name “Hostacerin AMPS” (CTFA name: ammonium polyacryloyldimethyl taurate or SIMULGEL 800 marketed by SEPPIC (CTFA name: sodium polyacryolyldimethyl taurate/polysorbate 80/sorbitan oleate); 2-acrylamido 2-methylpropane sulfonic acid and hydroxyethyl acrylate copolymers such as SIMULGEL NS and SEPINOV EMT 10 marketed by SEPPIC; cellulose derivatives such as hydroxyethylcellulose; polysaccharides and particularly gums such as Xanthan gum; hydrophilic or hydro-dispersible silicone derivatives such as acrylic silicones, silicone polyethers and cationic silicones and mixtures thereof.
The lipophilic thickeners include, for example, synthetic polymers such as poly C10-C30 alkyl acrylates sold under the name “INTELIMER IPA 13-1” and “INTELIMER IPA 13-6” by Landec or modified clays such as hectorite and derivatives thereof, such as the products marketed under the names of Bentone.
Obviously, those skilled in the art would take care to select the optional complementary compound(s) cited above and/or the amounts thereof such that the advantageous properties intrinsically associated with the compositions according to the invention are not, or substantially not, impaired by the envisaged addition(s), particularly the enhancement in the protection of the skin and/or hair and/or lips against sun rays.
The compositions according to the invention may be prepared according to techniques well-known to those skilled in the art. They may particularly 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, milk or cream gel; in the form of an aqueous gel; in the form of a lotion. They may optionally be packaged in an aerosol and be presented in the form of a foam or spray.
The compositions according to the invention may be presented in the form of an oil-in-water or water-in-oil emulsion.
The emulsification methods suitable for use are of the blade or impeller, rotor-stator and HHP type.
It is also possible, by means of HHP (between 50 and 800 bar), to obtain stable dispersions with droplet sizes as small as 100 nm.
The emulsions generally contain at least one emulsifying surfactant selected from amphoteric, anionic, cationic or non-ionic emulsifying surfactants, used alone or in a mixture. The emulsifiers are suitably selected according to the emulsion to be obtained (W/O or O/W).
The emulsifying surfactants suitable for use for preparing W/O emulsions include, for example, alkyl esters or sorbitan, glycerol or sugar ethers; silicone surfactants such as dimethicone copolyols such as the mixture of cyclomethicone and dimethicone copolyol, sold under the name “DC 5225 C” by Dow Corning, and alkyl-dimethicone copolyols such as Laurylmethicone copolyol sold under the name “Dow Corning 5200 Formulation Aid” by Dow Corning; Cetyl dimethicone copolyol such as the product sold under the name Abil EM 90R by Goldschmidt and the mixture of cetyl dimethicone copolyol, polyglycerol isostearate (4 moles) and hexyl laurate under the name ABIL WE O9 by Goldschmidt. It is also possible to add one or a plurality of co-emulsifiers, which, advantageously, may be selected from the group comprising polyol alkyl esters.
The polyol alkyl esters particularly include polyethyleneglycol esters such as PEG-30 Dipolyhydroxystearate such as the product marketed under the name Arlacel P135 by ICI.
The glycerol and/or sorbitan esters include, for example, polyglycerol isostearate, such as the product marketed under the name Isolan GI 34 by Goldschmidt; sorbitan isostearate, such as the product marketed under the name Arlacel 987 by ICI; sorbitan isostearate and glycerol, such as the product marketed under the name Arlacel 986 by ICI, and mixtures thereof.
For the O/W emulsions, the emulsifying surfactants include, for example, non-ionic emulsifiers such as oxyalkylene (more specifically polyoxyethene) fatty acid and glycerol esters; oxyalkylene fatty acid and sorbitan esters; oxyalkylene (oxyethylene and/or oxypropylene) fatty acid esters such as the PEG-100 Stearate/Glyceryl Stearate mixture marketed for example by ICI under the name Arlacel 165; oxyalkylene (oxyethylene and/or oxypropylene) fatty alcohol ethers; sugar esters such as sucrose stearate; fatty alcohol and sugar ethers, particularly alkylpolyglucosides (APG) such as decylglucoside and laurylglucoside marketed for example by Henkel under the respective names Plantaren 2000 and Plantaren 1200, cetostearylglucoside optionally in a mixture with cetostearyl alcohol, marketed 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 arachidic and behenic alcohols and arachidylglucoside marketed under the name Montanov 202 by Seppic. According to one particular embodiment of the invention, the alkylpolyglucoside mixture as defined above with the corresponding fatty alcohol may be in the form of a self-emulsifying composition, as described for example in the document WO-A-92/06778.
In the case of an emulsion, the aqueous phase thereof may comprise a non-ionic vesicular dispersion prepared according to known methods (Bangham, Standish and Watkins. J. Mol. Biol. 13, 238 (1965), FR 2 315 991 and FR 2 416 008).
The compositions according to the invention may be applied in a large number of treatments, particularly cosmetic treatments, of the skin, lips and/or hair, including the scalp, particularly for protecting and/or treating the skin, lips and/or hair, and/or for makeup for the skin and/or lips.
The cosmetic compositions according to the invention may for example by used as a makeup product.
The cosmetic compositions according to the invention may for example be used as a treatment and/or sun protection product for the face and/or body with a liquid to semi-liquid consistency, such as milks, more or less unctuous creams, cream gels, pastes. They may optionally be packaged in an aerosol and be presented in the form of a foam or spray.
The compositions according to the invention in the form of fluid lotions suitable for vaporization according to the invention are applied on the skin or hair in the form of fine particles by means of pressurization devices. The devices suitable for 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 a propellant. The latter are described in the patents U.S. Pat. No. 4,077,441 and U.S. Pat. No. 4,850,517 (an integral part of the content of the description).
The compositions packaged in an aerosol suitable for the invention generally contain conventional propellants such as for example the hydrofluorinated compounds dichlorodifluoromethane, difluoroethane, dimethylether, isobutane, n-butane, propane, trichlorofluoromethane. They are preferably present in amounts ranging from 15 to 50% by weight with respect to the total weight of the composition.
The compositions packaged in an aerosol suitable for the invention generally contain conventional propellants such as for example the hydrofluorinated compounds dichlorodifluoromethane, difluoroethane, dimethylether, isobutane, n-butane, propane, trichlorofluoromethane. They are preferably present in amounts ranging from 15 to 50% by weight with respect to the total weight of the composition.
In the figures:
The concrete, but in no way limiting, examples illustrating the invention will now be given. Furthermore, in the examples, all the percentages are given by weight, unless specified otherwise, and the temperature is expressed in degrees Celsius unless specified otherwise, and the pressure is atmospheric pressure, unless specified otherwise. In the examples, the amounts of the ingredients of the compositions are given as a % by weight with respect to the total weight of the composition.
The purpose of this study was to express the protection performance with respect to UVA stress. Baicalin is evaluated alone and according to the invention, in association with a sunscreen composition 1 comprising a system filtering UVA comprising at least one bis-resorcinyl triazine derivative.
Under our experimental conditions, exposure of NHF (Normal Human Fibroblasts) to UVA induces the generation of activated oxygen species, measured using the DCFH-DA test.
The culture medium as follows:
1.1.1. Conditions for Evaluating Protection Against UVA Radiation
The NHF cells are pretreated with the active substances for 24 hours before exposure to UV. During the exposure of the fibroblasts to UVA, the reference formula (“Reference filter” consisting of sunscreen composition 1) and the placebo formula (placebo composition 2) are applied on a rough PMMA plate in the form of homogeneous and regular deposition at a rate of 0.6 mg/cm2. The plate is then positioned over the culture plate. The active substances (baicalin and/or system filtering UVA comprising at least one bis-resorcinyl triazine derivative, referred to as the reference filter) under evaluation are present during the solar simulation. The following combinations are evaluated:
For the NHF cells treated with the active substance, a control plate is kept protected from light.
The absorption spectrum of the reference filter (sunscreen composition 1) tested is shown in
1.1.2. Exposure Conditions
The UVA are output with the Oriel solar simulator (Xenon lamp, 1000 Watts), equipped with a WG360/2 mm filter. To obtain the entire UVA range, the UG11 visible section is not used (however, it should be noted that the dichroic mirror of the solar simulator filters a large portion of the visible range (85%)). The UVA emitted can be referred to as long UVA as it is within the wavelengths of 340 to 400 nm.
1.1.3. DCFHDA Test: Evaluation of UVA-Induced Oxidative Stress
The protection against UVA stress is evaluated by means of a DCFH-DA test as a marker of overall intracellular oxidative stress. This makes it possible to directly evaluate the negative impact of UVA on a cellular level, and particularly on harmful oxidative stress for the skin, hair and lips, particularly on skin tissue elasticity, promoting the appearance of wrinkles giving rise to premature skin ageing.
The use of DCFH-DA as a marker of overall intracellular oxidative stress is based on the physicochemical properties thereof. It consists of an apolar and non-ionic molecule capable of diffusion via cell membranes. Once inside the cell, the DCFH-DA is hydrolyzed by intracellular esterases to a non-fluorescent compound: DCFH or 2,7-dichlorofluorescin. In the presence of activated oxygen species (H2O2; OH°), DCFH is rapidly oxidized to a highly fluorescent compound: DCF or 2,7-dichlorofluorescein.
The fibroblasts, optionally in the presence of 10 μM Baicalin for 24 hours, are rinsed with PBS+ and incubated in the presence of DCFH-DA [20 μM] for 30 minutes at 37° C. and protected from light. After removing the probes and 2 rinses, the cells are again placed in contact with the active substances (10 μM) in PBS+. PMMA plates whereon either Vaseline (filter-free control) or the reference filtering formula have been applied are deposited on top of the cells. Baicalin is introduced into the culture medium at a concentration of 10 micromoles. They are then exposed to 20 J/cm2 of UVA (WG360 filter). The fluorescence of DCF is evaluation immediately after exposure to UVA, by spectrofluorimetry (Excitation 480 nm; Emission 530 nm).
1.2/Results
The evaluation of 10 μM Baicalin in the DCFH-DA test demonstrated the following results (
In this way, these results demonstrate the surprisingly enhanced efficacy due to the association of baicalin and a filtering system comprising a UVA filter comprising at least one bis-resorcinyl triazine derivative, for protecting the skin and/or lips and/or hair against solar radiation, particularly UV.
These results provide a means other than that consisting of using large amounts of UV filters, particularly UVA filters, for combating premature ageing of the skin and/or lips and/or hair effectively under conditions of use and in concentrations acceptable for those skilled in the art.
Finally, these results particularly provide compositions, particularly cosmetic compositions, for preventing and/or combating premature ageing of the skin and/or lips due to UVA radiation and for protecting the skin and/or lips and/or hair against this form of radiation and free radicals.
SCUTELLARIA BAICALENSIS
SCUTELLARIA BAICALENSIS EXTRACT
SCUTELLARIA BAICALENSIS
SCUTELLARIA BAICALENSIS
SCUTELLARIA BAICALENSIS EXTRACT
BAICALENSIS ROOT EXTRACT
| Number | Date | Country | Kind |
|---|---|---|---|
| 1156177 | Jul 2011 | FR | national |
| Filing Document | Filing Date | Country | Kind | 371c Date |
|---|---|---|---|---|
| PCT/EP2012/063114 | 7/5/2012 | WO | 00 | 1/2/2014 |
| Number | Date | Country | |
|---|---|---|---|
| 61509338 | Jul 2011 | US |
