Aqueous cosmetic or dermatological composition containing merocyanine and a water-soluble UV shielding agent

Abstract

The present invention relates to an aqueous cosmetic or dermatological composition comprising: a) at least one merocyanine corresponding to formula (3) in an amount of less than 3% by mass of the total mass of the composition, and its geometric isomer form, particularly the E / E- or E / Z- geometric isomer form: (wherein A is -O- or -NH-, R can have one or more oxygen atoms interrupted, C1-C) 22 Alkyl alkyl groups, C2-C 22 Alkenyl group, C2~C 22 Alkynyl group, C3~C 22 Cycloalkyl groups or C3-C 22 The present invention relates to an aqueous cosmetic or dermatological composition comprising (a) a cycloalkenyl group and (b) at least one water-soluble organic UV shielding agent. TIFF2026522364000034.tif30170

Description

[Technical Field]

[0001] The present invention relates to an aqueous cosmetic or dermatological composition comprising at least one merocyanine of formula (3) as defined in detail below and at least one water-soluble UV shielding agent. [Background technology]

[0002] Radiation with wavelengths of 280nm to 400nm is capable of causing sunburn in human epidermis, and radiation with wavelengths of 280 to 320nm, known as UV-B rays, is known to adversely affect the development of natural sunburn. Exposure also tends to induce a decline in the biomechanical properties of the epidermis, which is reflected in the development of wrinkles, leading to premature skin aging.

[0003] UV-A rays, with wavelengths of 320-400 nm, are known to penetrate deeper into the skin than UV-B rays. UV-A rays cause immediate and persistent browning of the skin. Under normal circumstances, even short-term exposure to UV-A rays can degrade collagen and elastin fibers, which manifests as changes in the skin's surface texture, the appearance of wrinkles, and uneven pigmentation (melasma or uneven skin tone).

[0004] Therefore, protection against UVA and UVB radiation is necessary. Effective photoprotective products must provide protection against both UVA and UVB radiation.

[0005] Many photoprotective compositions have been proposed to overcome the effects induced by UVA and / or UVB radiation. These generally contain organic and / or inorganic UV shielding agents, which function by absorbing, reflecting, or scattering UV radiation according to their own chemical properties and characteristics. These typically contain mixtures of lipid-soluble organic shielding agents and / or water-soluble UV shielding agents combined with metal oxide pigments such as titanium dioxide and zinc oxide.

[0006] Furthermore, the majority of organic UV shielding agents consist of aromatic compounds that absorb in the wavelength range of 280–370 nm. In addition to their solar radiation shielding ability, the desired photoprotective compounds must also possess good cosmetic properties, good solubility in ordinary solvents, particularly in lipids, e.g., oils, or in water, and good photostability, either alone or in combination with other UV shielding agents. They should also be colorless or have at least a cosmetically acceptable color to consumers.

[0007] One of the main drawbacks of these compositions known to date is that these shielding systems are insufficiently effective against UV radiation, particularly long UVA radiation with wavelengths exceeding 370 nm, for the purpose of controlling photo-induced pigmentation and its occurrence by shielding against UV radiation across the entire UV spectrum.

[0008] Of all the compounds recommended for this purpose, a favorable family of UV shielding agents composed of carbonized merocyanine derivatives has been proposed, as described in (Patent Document 1), (Patent Document 2), and the document published on April 3, 2004 (Non-Patent Document 1). These compounds exhibit very good shielding properties over long UVA irradiation ranges, but their solubility in conventional solvents in both aqueous and fatty phases is only slightly satisfactory, and some merocyanines have insufficient photostability.

[0009] In an effort to find other merocyanines with better solubility and better photostability in conventional solvents, (Patent Document 3) proposes merocyanines containing polar groups composed of hydroxyl and ether functional groups, which exhibit good, long-lasting UVA shielding efficiency. However, the solubility of these particular merocyanines is still not entirely satisfactory and often requires cumbersome compounding processes. Furthermore, the large amount of solvent required to dissolve this type of merocyanine may cause cosmetic discomfort, such as a sticky, tacky feel when applied.

[0010] Therefore, there is still a need to improve the solubility of these merocyanines in cosmetic compositions, especially in photoprotective formulations, in both the aqueous and fatty phases while still obtaining good cosmetic properties.

[0011] Furthermore, there is also a need to improve the solubility of merocyanines in the presence of organic screening agents. In fact, the addition of additional screening agents can potentially render the composition containing merocyanines unstable.

[0012] UV screening agents are mainly carried in the oily phase and / or the aqueous phase as anti-UV active agents and are generally proposed in the form of emulsions or gel types.

[0013] It is also known that a high content of screening agent is required to achieve a high level of screening efficiency.

[0014] However, a high content of UV screening agent is not useful for the easy manufacture of a composition having a stable and pleasant texture.

[0015] Therefore, formulations having a high screening power can generally have unpleasant or even repulsive sensory aspects that mask the freshness and comfort of the formulation. In particular, the weakness of photoprotective formulations having a high protection factor can often be a strong stickiness and thus a lack of lightness of the resulting texture, but also have a white appearance upon application and thus be not unobtrusive on the skin.

[0016] Furthermore, the introduction of a high content of UV screening agent generally brings about problems of destabilization. This destabilization can even cause phase separation of the emulsion and / or a decrease in the viscosity of the composition, rendering the formulation inefficient or unusable.

[0017] To overcome the above-mentioned undesirable effects, aqueous formulation forms have already been considered, especially to obtain an effect of freshness on application and an unobtrusive effect on the skin. However, these aqueous compositions containing UV screening agents are generally sticky and thus unpleasant.

[0018] Therefore, there is a need for an aqueous cosmetic or dermatological composition that has good long-wavelength UVA shielding efficiency, good cosmetic properties, and is completely stable and homogeneous, i.e., does not undergo demixing.

[0019] There is also a need for an aqueous photoprotective composition that has good shielding efficiency across the entire wavelength spectrum from 280 to 400 nm, possesses good cosmetic properties, and is completely stable and homogeneous, i.e., does not undergo demixing.

[0020] There is still a need for water-based cosmetic or dermatological compositions that have good long-wavelength UVA shielding efficiency and are also transparent. Furthermore, there is a need for cosmetic or dermatological compositions that remain transparent even after application to the skin.

[0021] In particular, there is still a need for aqueous cosmetic or dermatological compositions that have good shielding efficiency between 370nm and 400nm, and in some cases high levels of UV protection across the entire wavelength spectrum between 280nm and 400nm, possess good cosmetic properties when applied, are particularly easy to apply, do not leave an oily or sticky finish on the skin after drying, and have a pleasant sensory effect embodied particularly by the smoothness during application. [Prior art documents] [Patent Documents]

[0022] [Patent Document 1] U.S. Patent No. 4195999 [Patent Document 2] International Publication No. 2004 / 006878 Brochure [Patent Document 3] International Publication No. 2013 / 011094 Pamphlet [Non-patent literature]

[0023] [Non-Patent Document 1] IP COM Journal 4(4),16 No.IPCOM000011179D [Overview of the project] [Problems that the invention aims to solve]

[0024] The objective of this invention is to propose a new cosmetic or dermatological composition that solves these problems.

[0025] The applicant has surprisingly discovered that the addition of at least one water-soluble shielding agent, which must be solubilized in water itself rather than being a solvent, makes it possible to significantly increase the water solubility of the above-mentioned merocyanine.

[0026] This makes it possible to solubilize these specific merocyanines in essentially water-based sunscreen products without adding any additional solvents.

[0027] This discovery forms the basis of the present invention. [Means for solving the problem]

[0028] Therefore, according to one of the subjects of the present invention, an aqueous cosmetic or dermatological composition is proposed herein, and the aqueous cosmetic or dermatological composition is a) At least one merocyanine of formula (3) as defined in detail below, in an amount less than 3% by mass of the total mass of the composition; and b) At least one water-soluble UV shielding agent Includes.

[0029] Therefore, the water solubility of merocyanine is improved in the presence of at least one water-soluble UV shielding agent.

[0030] The applicant has surprisingly discovered that, even in the presence of further organic UV shielding agents, it is possible to substantially improve the solubility of these merocyanines in the aqueous phase by using at least one water-soluble UV shielding agent.

[0031] The applicant also found that the use of at least one such merocyanine in combination with at least one water-soluble UV shielding agent makes it possible to obtain good cosmetic properties of a merocyanine-containing composition, which is particularly non-greasy and non-sticky.

[0032] Furthermore, the present invention makes it possible to obtain a transparent composition even after application to the skin.

[0033] The present invention relates to a non-therapeutic cosmetic method for caring for and / or making up a keratinous substance, and also to a non-therapeutic cosmetic method comprising applying at least one cosmetic composition according to the present invention as defined above to the surface of the keratinous substance.

[0034] The present invention also relates to a non-therapeutic cosmetic method for inhibiting skin darkening and / or improving the uniformity of color and / or complexion, comprising applying at least one cosmetic composition as defined above to the surface of a keratinous substance.

[0035] The present invention also relates to a non-therapeutic cosmetic process for preventing and / or treating signs of aging of keratinous material, comprising applying at least one of the previously defined cosmetic compositions to the surface of keratinous material.

[0036] The present invention also relates to the use of at least one water-soluble UV shielding agent for solubilizing merocyanine of formula (3) as defined below in an aqueous phase.

[0037] Other features, embodiments, and advantages of the present invention will become apparent from the detailed description that follows.

[0038] The compositions according to the present invention are intended for topical application and therefore contain a physiologically acceptable medium. The term "physiologically acceptable medium" as used herein means a medium compatible with keratinic substances.

[0039] In relation to the present invention, the term "keratin material" means, in particular, keratin fibers such as skin, scalp, eyelashes, eyebrows, hair, and body hair, nails, mucous membranes such as lips, and more particularly skin and mucous membranes (body, face, area around the eyes, eyelids, lips, preferably body, face and lips).

[0040] In the text below, unless otherwise specified, boundary values ​​of a range are included in that range, especially in expressions such as "between ~" and "from ~ to ~".

[0041] Furthermore, the expressions "at least one type" and "at least" as used in this disclosure are synonymous with the expressions "one or more types" and "one or more types," respectively.

[0042] The terms "preventing" or "prevention" in the present invention mean reducing the risk of or delaying the occurrence of a given phenomenon, namely, the signs of aging of keratinous material according to the present invention.

[0043] The term "organic UVA shielding agent" refers to any organic chemical molecule capable of absorbing UVA radiation in the wavelength range of at least 320–400 nm, and which may also absorb UVB radiation in the wavelength range of 280–320 nm.

[0044] The term "organic UVB shielding agent" is understood to mean any organic chemical molecule that can exclusively absorb UVB radiation in the wavelength range of 280–320 nm.

[0045] For the purposes of the present invention, the term "transparent or translucent composition" refers to a composition having a turbidity value of less than 1000 NTU, preferably less than 800 NTU, more preferably less than 500 NTU, even better less than 200 NTU, preferably less than 150 NTU, and particularly less than 100 NTU. Preferably, the turbidity of the composition is equal to at least 1 NTU.

[0046] NTU (Turbidimetric Turbidity Unit) is a unit for measuring the turbidity of a composition. Turbidity is measured using, for example, a Hach 2100P model turbidimeter, and the tube used for measurement should be referred to AR397A cat 24347-06. Measurements are performed at ambient temperature (20°C to 25°C).

[0047] According to a particular embodiment of the present invention, the composition is transparent and has a turbidity value between 1 and 200 NTU, preferably between 1 and 150 NTU, and preferably less than 100 NTU.

[0048] Preferably, the composition is transparent after being applied to the skin, that is, it does not leave a white residue after being spread on the skin. [Modes for carrying out the invention]

[0049] Merocyanine According to the present invention, a family of merocyanines corresponding to the following formula (3), and their geometric isomer forms, particularly the E / E- or E / Z- geometric isomer forms, are used. [ka] During the ceremony, A is -O- or -NH-, R can be interrupted by one or more O's, C1~C 22 Alkyl alkyl groups, C2-C 22 Alkenyl group, C2~C 22 Alkynyl group, C3~C 22 Cycloalkyl groups or C3-C 22 It is a cycloalkenyl group.

[0050] The merocyanine compound of the present invention may also be in the form of its E / E- or E / Z geometric isomer. [ka]

[0051] A more preferable compound is the one in formula (3): A is -O-, and R is C1~C 22 It is an alkyl group, which may be interrupted by one or more oxygen atoms.

[0052] Among the compounds of formula (3), those selected from the following group, and their geometric isomer forms, particularly the E / E- or E / Z- geometric isomer forms, are used more specifically.

[0053] [Table 1]

[0054] [Table 2]

[0055] [Table 3]

[0056] According to a more particularly preferred embodiment of the present invention, the compound 2-ethoxyethyl(2Z)-cyano{3-[(3-methoxypropyl)amino]cyclohexa-2-ene-1-ylidene}ethanoate (25) having an E / E- and / or E / Z-geometric configuration is used.

[0057] The E / Z configuration has the following structure: [ka]

[0058] The E / E configuration has the following structure: [ka]

[0059] The shielding merocyanine according to the present invention is present in the composition in an amount of less than 3% by mass, preferably 2.5% by mass or less, preferably 0.01% to 2.5% by mass, and more preferably 0.5% to 1.5% by mass, based on the total mass of the composition.

[0060] Compounds of formula (3) that form a carbocyclic ring containing six carbon atoms can be prepared according to the protocols described in International Publication No. 2007 / 071582, IP.com Journal (2009), 9(5A), 29-30 IPCOM000182396D, title “Process for producing 3-amino-2-cyclohexan-1-ylidene compounds” and U.S. Patent No. 4,749,643, columns 13, lines 66-14, lines 57, and the references cited herein.

[0061] In particular, compounds of formula (3), such as compound 2-ethoxyethyl(2Z)-cyano{3-[(3-methoxypropyl)amino]cyclohexa-2-ene-1-ylidene}ethanoate (25), can be synthesized by the synthetic scheme described in the publication "A cyclic merocyanine UV-A absorber: mechanism of formation and crystal structure" by B. Winkler et al., Tetrahedron Letters, 55 (2014) 1749-1751, and the compounds of formula (3) are shown below. [ka] More details are provided for compound 25, as listed in Table 1. [ka]

[0062] Water-soluble organic UV shielding agent The composition according to the present invention comprises at least one water-soluble organic UV shielding agent.

[0063] The term "water-soluble organic screening agent" is understood to mean any organic screening agent that can be completely dissolved in molecular form or in colloidal form (e.g., micellar form) in an aqueous liquid phase.

[0064] Among the water-soluble organic UVA screening agents that can be used according to the present invention, mention may be made of benzene-1,4-bis(3-methylidene-10-camphorsulfonic) acid (INCI name: terephthalylidenedicamphorsulfonic acid) and its various salts, in particular those described in French Patent Application Publication Nos. 2528420 and 2639347. Particular mention may be made of benzene-1,4-bis(3-methylidene-10-camphorsulfonic acid) (INCI name: terephthalylidenedicamphorsulfonic acid) such as that manufactured under the name Mexoryl® SX by Noveal.

[0065] These screening agents correspond to the following general formula (I),

Chemical formula

[0066] Among the water-soluble organic UVA shielding agents that can be used in accordance with the present invention, compounds containing at least two benzazolyl groups having a sulfonic acid group, such as those described in European Patent Application Publication No. A-0669323, can also be mentioned.

[0067] These are also described in U.S. Patent No. 2,463,264 and European Patent Application Publication No. A-0669323, and are prepared according to the synthesis shown therein.

[0068] The compound comprising at least two benzazolyl groups according to the present invention corresponds to the following general formula (II): [ka] During the ceremony, - Z represents an organic residue with valence (l+n) containing one or more double bonds arranged to complete a system of double bonds of at least two benzazolyl groups defined within the square brackets, so as to form a fully conjugated aggregate. - X' is S, O, or NR 6 This represents, - R 1 These are hydrogen atoms, C1~C 18 Alkyl, C1-C4 alkoxy, C5-C 15 Aryl, C2~C 18 Represents an acyloxy group, an SO3Y group, or a COOY group. - R 2 , R 3 , R 4 and R 5 The groups may be the same or different, and may be a nitro group or R 1 Represents the basis, - R 6 This represents a hydrogen atom, a C1-C4 alkyl group, or a C1-C4 hydroxyalkyl group. - Y represents a cation produced by neutralizing a hydrogen atom, Li, Na, K, NH4, 1 / 2Ca, 1 / 2Mg, 1 / 3Al, or a free acid group with an organic nitrogen base. - m is 0 or 1, - n is a number between 2 and 6. - l is a number between 1 and 4. - However, l+n does not exceed the value of 6.

[0069] Among these compounds, 1,4-bis-benzimidazolyl-phenylene-3,3',5,5'-tetrasulfonic acid (INCI name: disodium phenyldibenzimidazole tetrasulfonate) or its salt having the following structure (III) is particularly marketed by Symrise under the name Neo Heliopan® AP. [ka]

[0070] Preferably, the water-soluble shielding agent capable of absorbing UVA rays is benzene-1,4-bis(3-methylidene-10-camphor sulfonic acid) (INCI name: terephthalylidene dicamphor sulfonic acid), such as the product manufactured by Novell under the name Mexoryl SX.

[0071] Water-soluble organic UVB shielding agents that can be used in accordance with the present invention are selected from water-soluble cinnamic acid derivatives, such as ferulic acid or 3-methoxy-4-hydroxycinnamic acid; water-soluble benzylidene camphor compounds; water-soluble phenylbenzimidazole compounds; water-soluble p-aminobenzoic acid (PABA) compounds; water-soluble salicylic acid compounds and mixtures thereof.

[0072] Examples of water-soluble organic UVB shielding agents include phenylbenzimidazole compounds such as 2-phenyl-1H-benzimidazole-5-sulfonic acid (INCI name: phenylbenzimidazole sulfonic acid), which is sold by Merck under the trade name Eusolex 232 (registered trademark).

[0073] The compositions according to the present invention may also include at least one mixed water-soluble shielding agent capable of absorbing UVA and UVB rays.

[0074] If the water-soluble UV shielding agent is of the sulfonic acid type, it is preferable that it is associated with an organic base such as an alkanolamine, or an inorganic base such as sodium hydroxide or potassium hydroxide.

[0075] The term "alkanolamine" refers to a C2-C group containing at least one primary, secondary, or tertiary amine group and at least one alcohol, usually a primary alcohol group. 10 This refers to a compound. Suitable alkanolamines include 2-amino-2-(hydroxymethyl)-1,3-propanediol (INCI name: tromethamine) and triethanolamine.

[0076] A water-soluble organic UV shielding agent may be present in the composition according to the present invention at a concentration of 0.1% to 19% by mass, preferably 0.5% to 12% by mass, and more preferably 3% to 10% by mass, relative to the total mass of the composition.

[0077] Additional UV shielding agent The composition according to the present invention may also contain merocyanine of formula (3) and at least one additional UV shielding agent other than the water-soluble organic UV shielding agent described above.

[0078] Additional UV shielding agents can be selected from lipophilic organic UV shielding agents, water-dispersible organic UV shielding agents, and inorganic UV shielding agents.

[0079] According to certain embodiments, additional UV shielding agents can be selected from water-dispersible organic UV shielding agents and inorganic UV shielding agents.

[0080] Lipophilic organic UV shielding agent The term "organic lipophilic shielding agent" is intended to mean any cosmetic or dermatological organic compound for shielding UV radiation that can be completely dissolved in a liquid lipid phase in molecular form or in a colloidal form (e.g., in micelle form).

[0081] Lipophilic organic shielding agents include, in particular, cinnamic compounds; anthranilate compounds; salicylic acid compounds; dibenzoylmethane compounds; benzylidene camphor compounds; benzophenone compounds; β,β-diphenyl acrylate compounds; triazine compounds; benzotriazole compounds; benzalmalonate compounds, particularly those cited in U.S. Patent No. 5,624,663; benzimidazole derivatives; imidazoline compounds; bisbenzazolyl compounds described in European Patent No. 669323 and U.S. Patent No. 2,463,264; methylenebis(hi) described in U.S. Patent No. 5,237,071, U.S. Patent No. 5,166,355, British Patent No. 2,303,549, German Patent No. 1,972,6184 and European Patent No. 893,119. A selection of compounds including droxyphenylbenzotriazole compounds; benzoxazole compounds described in European Patent No. 0832642, European Patent No. 1027883, European Patent No. 1300137 and German Patent No. 10162844; shielding polymers and shielding silicones, particularly those described in International Publication No. 93 / 04665; α-alkylstyrene dimers, such as those described in German Patent No. 19855649; 4,4-diarylbutadiene compounds described in European Patent No. 0967200, German Patent No. 19746654, German Patent No. 19755649, European Patent Application Publication No. A-1008586, European Patent No. 1133980 and European Patent No. 133981; and mixtures thereof.

[0082] Preferably, the lipophilic organic shielding agent is selected from salicylic acid compounds; dibenzoylmethane compounds; benzylidene camphor compounds; benzophenone compounds; triazine compounds; benzotriazole compounds; and mixtures thereof.

[0083] Examples of lipophilic organic photoprotective agents include those represented by the following INCI names and / or chemical names:

[0084] Cinnamic acid compounds: Ethylhexyl methoxycinnamate, especially the product sold by DSM Nutritional Products under the trade name Parsol® MCX,

[0085] Isoamyl p-methoxycinnamate, sold by Symrise under the trade name Neo Heliopan E 1000 (registered trademark),

[0086] Dibenzoylmethane compounds: Butyl methoxydibenzoylmethane (especially the one sold by DSM Nutritional Products under the trade name Parsol 1789®),

[0087] Salicylic acid compounds: Homosalate, sold by DSM Nutritional Products under the name Parsol(registered trademark) HMS, Ethylhexyl salicylate, sold by Symrise under the name Neo Heliopan® OS,

[0088] β,β-diphenylacrylate compounds: In particular, octocrylene sold by BASF under the trade name Uvinul(registered trademark)N 539 T,

[0089] Benzophenone compounds: Oxybenzone-3 or oxybenzone, sold by BASF under the trade name Uvinul(registered trademark) M 40,

[0090] Diethylamino hydroxybenzoyl hexyl benzoate, sold by BASF under the trade name Uvinul® A Plus, or as a mixture with ethylhexyl methoxycinnamate under the trade name Uvinul® A Plus B,

[0091] Benzylidene camphor compounds: - 4-methylbenzylidene camphor, sold by Merck under the name Eusolex(registered trademark) 6300,

[0092] Phenylenbenzotriazole compounds: Drometrizole trisiloxane, manufactured by Noveal under the name Mexoryl(registered trademark)XL,

[0093] Methylenebis(hydroxyphenylbenzotriazole) compounds: Products such as those sold by Fairmount Chemical under the trade name MIXXIM BB / 100 (registered trademark), particularly solid-state methylenebis-benzotriazoltetramethylbutylphenol,

[0094] Triazine compounds: - 3,3'-(1,4-phenylene)bis(5,6-diphenyl-1,2,4-triazine), whose INCI name is phenylenebis-diphenyltriazine, - Bis-ethylhexyloxyphenol methoxyphenyl triazine, sold by DSM Nutritional Products under the trade name Parsol Shield® and by BASF under the trade name Tinosorb® S. - Ethylhexyltriazone (especially sold by BASF under the trade name Uvinul T 150®), - Diethylhexyl butamide triazone, sold by 3V Sigma under the trade name Uvasorb(registered trademark)HEB, - Symmetrical triazine shielding agents substituted with naphthalenyl or polyphenyl groups, as described in U.S. Patent No. 6,225,467, International Publication No. 2004 / 085412 (see Compounds 6 and 9), or in the document “Symmetrical triazine derivatives” (IP.COM) IPCOM000031257 Journal, Inc. West Henrietta, NY, US (September 20, 2004).

[0095] Anthranilic acid ester compounds: Methyl anthranilate, sold by Symrise under the trade name Neo Heliopan(registered trademark)MA.

[0096] Benzalmalonate ester compounds: Polyorganosiloxanes containing benzal malonate functional groups, such as polysilicone-15, sold by Hoffmann-La Roche under the trade name Parsol SLX (registered trademark).

[0097] Water-dispersible organic UV shielding agent The term "water-dispersible organic shielding agent" refers to any organic shielding agent capable of forming a homogeneous suspension of particles with a volume-average diameter of less than 100 microns in a liquid aqueous phase. The volume-average diameter is determined by laser diffraction particle size analysis.

[0098] Among water-dispersible organic shielding agents, the following shielding agents can be listed.

[0099] Benzophenone compounds: As described in International Publication No. 2007 / 071584, 1,1'-(1,4-piperazinediyl)bis[1-[2-[4-(diethylamino)-2-hydroxybenzoyl]phenyl]methanone](CAS919803-06-8); this compound is advantageously used in a micronized form (volume average size of 0.02-2 μm), which can be obtained particularly in the form of an aqueous dispersion, according to the micronization process described, for example, in British Patent No. A-2303549 and European Patent No. A-893119.

[0100] Methylenebis(hydroxyphenylbenzotriazole) compounds: An aqueous dispersion of finely particulated particles of methylenebis(benzotriazolyl)tetramethylbutylphenol having a volume-average particle size in the range of 0.01 to 5 μm, more preferably in the range of 0.01 to 2 μm, and more specifically in the range of 0.020 to 2 μm, C n H 2n+1 O(C6H 10 O5) x H(wherein n is an integer between 8 and 16, and x is the unit (C6H) 10 In the form of an aqueous dispersion containing at least one alkyl polyglycoside surfactant having a structure with an average degree of polymerization of O5) which is in the range of 1.4 to 1.6, for example, the aqueous dispersion described in UK Patent Application Publication No. 2303549, in particular the product sold by BASF under the trade name Tinosorb® M, or An aqueous dispersion of fine particles having a volume-average particle size in the range of 0.02 to 2 μm, more preferably 0.01 to 1.5 μm, and more specifically 0.02 to 1 μm, wherein the degree of polymerization of glycerol is at least 5, and at least one mono(C8 to C) 20 ) In the form of aqueous dispersions containing alkyl polyglycerol esters, for example, aqueous dispersions described in International Publication No. 2009 / 063392, in particular the product marketed by BASF under the name Tinosorb WPGL,

[0101] Triazine compounds: - Tinosorb® S LiteAqua is a trade name of BASF, and its INCI name is Bis-ethylhexyloxyphenol methoxyphenyl triazine (and) acrylate / C12-22 alkyl methacrylate copolymer, and is a water-dispersible form thereof. - For example, symmetric triazine shielding agents substituted with naphthalenyl or polyphenyl groups, used in particulate form (average particle size 0.02-3 μm), which can be obtained by the particulate process described in British Patent No. A-2303549 and European Patent No. A-893119, particularly in aqueous dispersion form, and are sold by BASF under the name Tinosorb® A2B, and are included in the patent application brochures International Publication No. 06 / 035000, International Publication No. 06 / 034982, International Publication No. 06 / 034991, International Publication No. 06 / 035007, International Publication No. 2006 / 034992, and International Publication No. 2006 / 034985, using 2,4,6-tris(biphenyl)triazine and 2,4,6-tris(terphenyl)triazine.

[0102] Benzoxazole compounds: It has 2-[4-(1,3-benzoxazole-2-yl)phenyl]-1,3-benzoxazole, CAS number 904-39-2.

[0103] Inorganic UV shielding agent The inorganic UV shielding agents that can be used in accordance with the present invention are metal oxide pigments. More preferably, the inorganic UV shielding agents of the present invention are metal oxide particles having an average primary particle size of 0.5 μm or less, more preferably 0.005 to 0.5 μm, even more preferably 0.01 to 0.2 μm, even more preferably 0.01 to 0.1 μm, and more specifically 0.015 to 0.05 μm. They are, in particular, listed in Annex VI of EU Regulation No. 1223 / 2009 relating to cosmetics, as updated on 22 September 2021, but are not limited to this list.

[0104] These can be selected from titanium dioxide, zinc oxide, iron oxide, zirconium oxide, and cerium oxide, or mixtures thereof.

[0105] Such coated or uncoated metal oxide pigments are described in particular in European Patent Application Publication A-0518773. Commercially available pigments include those sold by Croda, Tayca, and Merck.

[0106] Metal oxide pigments may be coated or uncoated.

[0107] Coated pigments are pigments that have been surface-treated to one or more of the chemical, electronic, mechanochemical, and / or mechanical properties using compounds such as amino acids, beeswax, fatty acids, fatty alcohols, anionic surfactants, lecithin, sodium, potassium, zinc, iron, or aluminum salts of fatty acids, metal (titanium or aluminum) alkoxides, polyethylene, silicone, proteins (collagen, elastin), alkanolamines, silicon dioxide, metal oxides, or sodium hexametaphosphate.

[0108] The coated pigment is, more specifically, titanium dioxide coated as follows: - Hydrated silica, for example, product MT-100WP from Tayca. - Silica and iron oxide, such as Sunveil F (registered trademark), a product from Ikeda. - Silica and alumina, for example, Tayca products MT-500SA® and MT-100SA®, and Croda's Tioveil® AQ-N, - Alumina, for example, Ishihara's product TTO-55(A) (registered trademark), - Alumina and aluminum stearate, for example, Tayca products MT-100TV®, MT-100Z®, and MT-01®, Croda product Solaveil® CT100, and Merck product Eusolex T-AVO®. - Silica, alumina, and alginate, for example, Tayca's product MT-100AQ (registered trademark), - Alumina and aluminum laurate, - Iron oxide and iron stearate, - Zinc oxide and zinc stearate, - Coated with silica and alumina, then treated with silicone such as Tayca's MT-500SAS® or Microtitanium Dioxide MT-100SAS®. - Coated with silica, alumina and aluminum stearate, treated with silicone. - Coated with silica and treated with silicone. - Coated with silica and treated with silicone, for example, Ishihara's product TTO-55(S) (registered trademark). - Coated with triethanolamine, - Stearic acid, for example, TTO-55(C) (registered trademark), a product from Ishihara. - Sodium hexametaphosphate, - TiO2 treated with octyltrimethylsilane, - TiO2 treated with polydimethylsiloxane, - Anatase / rutile-type TiO2 treated with polydimethylhydrogensiloxane, - Triethylhexanoin, aluminum stearate, and alumina-coated TiO2, sold by Croda under the trade name Solaveil (trademark) CT-200. - TiO2 coated with aluminum stearate, alumina, and silicone, sold by Croda under the trade name Solaveil (trademark) CT-12W. - TiO2 coated with lauroyllysine, - C9~C 15 TiO2 coated with fluoroalcohol phosphate and aluminum hydroxide.

[0109] Examples include at least one transition metal, such as iron, zinc, or manganese, and more specifically, manganese-doped TiO2 pigments. Preferably, the doped pigment is in the form of an oily dispersion. The oil present in the oily dispersion is preferably selected from triglycerides such as capric / caprylic acid triglycerides. The oily dispersion of titanium dioxide particles may contain one or more dispersants, such as sorbitan esters, such as sorbitan isostearate, or polyoxyalkylene fatty acid esters of glycerol, such as Tri-PPG-3 myristyl ether citrate and polyglyceryl-3 polyricinoleate. Preferably, the oily dispersion of titanium dioxide particles contains at least one dispersant selected from polyoxyalkylene fatty acid esters of glycerol. More specifically, an oily dispersion (for example, a product sold by Croda under the trade name Optisol® OTP-1) can be cited, which is obtained by dispersing manganese-doped TiO2 particles having the INCI names titanium dioxide (and) triPPG-3 myristyl citrate (and) polyglyceryl-3 ricinoleate (and) sorbitan isostearate (and) in caprylic / capric triglyceride in the presence of TRI-PPG-3 myristyl citrate ether, polyglyceryl-3 polycinoleate, and sorbitan isostearate.

[0110] Uncoated titanium dioxide pigments are sold, for example, by Tayca under the trade names MT-500B or MT-600B (registered trademark), or by Evonik under the trade name DegussaP25.

[0111] Uncoated zinc oxide pigments include, for example, the following: - Products sold by BASF under the name Z-Cote®; - This product is sold by Nanophase Technologies under the name NanoArc(registered trademark) ZincOxide.

[0112] Examples of coated zinc oxide pigments are shown below: - ZnO coated with polymethylhydrosiloxane; - Alkyl benzoate (C 12 ~C 15 ) dispersed in Croda's Solaveil (trademark) CZ-100 (INCI: Zinc Oxide (and) Alkyl Benzoate (C12-15) (and) Polyhydroxystearic Acid (and) Isostearic Acid); - Products sold by Daito Kasei under the name Daitopersion Zn-60VA (registered trademark) (containing dispersant C9~C 12 Dispersion in alkanes; - Sold by Shin-Etsu under the name SPD-Z5 (registered trademark) (a dispersion of ZnO and cyclodimethylsiloxane coated with a silicone-grafted acrylic polymer).

[0113] Uncoated cerium oxide pigments can be, for example, those sold by Solvay under the name Rhodigard® W185.

[0114] Metal oxides, particularly mixtures of titanium dioxide and cerium dioxide, including a mixture of equal masses of titanium dioxide and cerium dioxide coated with silica, as well as mixtures of titanium dioxide and zinc dioxide coated with alumina, silica and silicone, or with alumina, silica and glycerol.

[0115] When the composition according to the present invention contains an inorganic UV shielding agent, coated or uncoated titanium dioxide pigments are particularly preferred.

[0116] According to a particular embodiment, the total amount of additional UV shielding agent present in the composition is 20% by mass or less, preferably 10% by mass or less, and more preferably 5% by mass or less, relative to the total mass of the composition.

[0117] According to a preferred embodiment, the total amount of additional UV shielding agent present in the composition is 0.1% to 20% by mass, preferably 0.5% to 10% by mass, and more preferably 1% to 5% by mass, relative to the total mass of the composition.

[0118] According to a particular embodiment, the only UV shielding agents present in the composition are a water-soluble organic shielding agent and merocyanine of formula (3).

[0119] For the purposes of the present invention, the term "total amount of additional UV shielding agents" means the sum of the concentrations of the active substances of each UV shielding agent present in the composition other than the merocyanine and water-soluble organic UV shielding agent of formula (3) above.

[0120] aqueous phase The composition according to the present invention comprises at least one aqueous phase.

[0121] The aqueous phase comprises water and optionally other water-soluble or water-miscible organic solvents.

[0122] Suitable aqueous phases for the present invention may include, for example, natural spring water, such as water selected from La Roche-Posay, water from Vittel, water from Saint-Gervais Mont-Blanc, or water from Vichy, or floral water.

[0123] The aqueous phase may include, for example, at least one other organic solvent soluble in water at 25°C, selected from the following: - C1-C4 monoalkanols. The term "C1-C4 monoalkanol" means any linear or branched saturated alkane compound containing 1 to 4 carbon atoms and just one hydroxyl (OH) functional group. The C1-C4 monoalkanols present in the compositions of the present invention may be selected from methanol, ethanol, propanol, isopropanol, and butanol, or mixtures thereof. More specifically, ethanol would be selected. - Particularly includes polyols having 2 to 20 carbon atoms, such as glycerol, diglycerol, propylene glycol, isoprene glycol, dipropylene glycol, butylene glycol, hexylene glycol, caprylyl glycol, 1,3-propanediol, pentylene glycol, ethylene glycol or diethylene glycol, 2-ethoxyethanol, diethylene glycol monomethyl ether, triethylene glycol monomethyl ether, sorbitol, simple sugars, water-soluble polyalkylene glycols; preferably, polyols having 2 to 8 carbon atoms; and mixtures thereof.

[0124] According to one particular embodiment, the composition according to the present invention comprises at least one C1-C4 monoalkanol, more specifically ethanol.

[0125] Monoalkanols are generally present in concentrations ranging from 0.2% to 90% by mass, more preferably 0.5% to 50% by mass, and more preferably 1% to 15% by mass, relative to the total mass of the composition.

[0126] According to another specific embodiment, the composition according to the present invention comprises at least one polyol, particularly as described above. Preferably, it comprises at least 1% by mass of polyol relative to the total mass of the composition, preferably at least 5% by mass of polyol, preferably 5% to 20% by mass, and preferably 10% to 15% by mass of polyol relative to the total mass of the composition.

[0127] Preferably, the composition according to the present invention comprises, as a polyol, glycerol, butylene glycol, propylene glycol, or dipropylene glycol, and mixtures thereof.

[0128] The compositions according to the present invention are aqueous. For the purposes of the present invention, the term "aqueous" refers to a composition having an amount of fat phase of less than 10% by mass, preferably less than 5% by mass, and more preferably less than 2% by mass, based on the total mass of the composition. Advantageously, the compositions according to the present invention are basically aqueous; that is, they do not contain a fat phase.

[0129] According to a particular embodiment of the present invention, the composition has a pH of 3 to 8. Advantageously, the pH of the composition is 5 to 7.5.

[0130] According to certain embodiments, the cosmetic composition according to the present invention may contain an acidifying agent and / or a basicizing agent.

[0131] Examples of acidifying agents include inorganic or organic acids, such as hydrochloric acid, orthophosphoric acid, sulfuric acid, carboxylic acids, such as acetic acid, tartaric acid, citric acid, lactic acid, and sulfonic acid.

[0132] Examples of basicizing agents include aqueous ammonia, alkali metal carbonates, alkanolamines such as mono-, di-, and triethanolamines and their derivatives, sodium hydroxide, or potassium hydroxide.

[0133] Preferably, the cosmetic composition contains one or more basicizing agents selected from alkanolamines, particularly triethanolamine, sodium hydroxide, and potassium hydroxide.

[0134] Hydrophilic gelling agent The composition according to the present invention may contain at least one hydrophilic gelling agent (or hydrophilic thickener).

[0135] For the purposes of the present invention, the term "hydrophilic gelling agent" (or "hydrophilic thickening agent") means a compound that can gel the aqueous phase of a composition according to the present invention.

[0136] In particular, in the context of this patent application, the term “thickener” means an agent that increases the viscosity of a mixture containing 1% by mass of the agent, 0.9% by mass of triethanolamine, and water by at least 10 times, preferably at least 15 times, and preferably at least 20 times, at a temperature of 25°C.

[0137] According to a particular embodiment of the present invention, the hydrophilic gelling agent is polymeric.

[0138] The hydrophilic gelling agent can be selected from anionic synthetic thickening polymers, nonionic thickening polysaccharides, sulfate-based thickening polysaccharides, and carboxylic acid branched thickening polysaccharides.

[0139] The term "carboxylic acid" means that a substance contains at least one carboxylic acid functional group.

[0140] Preferably, the composition according to the present invention is substantially free of (i.e., contains less than 0.4% by mass, preferably less than 0.3% by mass, preferably less than 0.2% by mass, and even better less than 0.1% by mass, based on the total mass of the composition), preferably completely free of (i.e., contains less than 0.4% by mass, preferably less than 0.3% by mass, preferably less than 0.2% by mass, and even better less than 0.1% by mass) thickeners selected from clay, mica, modified starches such as starch phosphate, and gellan gum.

[0141] Anionic synthetic thickening polymers The composition according to the present invention may contain an anionic synthetic thickening polymer.

[0142] Preferably, the anionic synthetic thickening polymer is non-aromatic. This means it does not contain aromatic monomers.

[0143] Among the anionic synthetic thickening polymers that can be used, either alone or in mixtures, are crosslinked homopolymers or copolymers of acrylic acid or methacrylic acid, crosslinked or non-crosslinked 2-acrylamido-2-methylpropanesulfonic acid homopolymers or salts thereof, and copolymers of acrylamide-2-methylpropanesulfonic acid or salts thereof with one or more crosslinked or non-crosslinked nonionic monomers.

[0144] The first family of thickening polymers suitable for use is represented by crosslinked acrylic acid homopolymers. Among these homopolymers, those crosslinked with sugar series allyl alcohol ethers include, for example, products sold by Lubrizol under the names Carbopol 980, 981, 954, 2984 and 5984, or products sold by 3V under the names Synthalen M and Synthalen K.

[0145] Such acrylic acid homopolymers may be present in the composition in granular or non-granular form. When present in granular form, their average size in the hydrated state is preferably 10 μm or less, and more preferably 5 μm or less. Their average size in the dry or unhydrated state is preferably 2 μm or less, and more preferably 1 μm or less.

[0146] Preferably, the acrylic acid homopolymer exists in a non-granular form.

[0147] Preferably, an acrylic acid homopolymer that has been at least partially neutralized is used. The homopolymer used in accordance with the present invention is selected in particular from sodium polyacrylate and potassium polyacrylate. Sodium polyacrylate is preferably used.

[0148] Examples that can be mentioned regarding these acrylic polymers that have already been neutralized before use include the following: - Sodium polyacrylate, such as Cosmedia SP®, which is sold by BASF and contains 90% solids and 10% water, or Cosmedia SPL®, which is sold as a reverse emulsion containing approximately 60% dry active material, oil (hydrogenated polydecene), and surfactant (PPG-5 laureth-5). - Partially neutralized sodium polyacrylate in the form of a reverse emulsion containing at least one polar oil, for example, the product marketed by BASF under the name Luvigel® EM; and - A mixture of those.

[0149] An acrylic acid polymer that has not been neutralized beforehand can also be used and then partially or completely neutralized before use by any suitable means, particularly by adding any base such as sodium hydroxide, potassium hydroxide, or an alkanolamine such as triethanolamine. Thus, sodium polyacrylate is clearly obtained. Potassium polyacrylate is also suitable for use in this invention.

[0150] The second family of thickening polymers suitable for use is (meth)acrylic acid and C1-C 30 It is represented by a crosslinked copolymer of alkyl acrylates.

[0151] Preferably, these copolymers are crosslinked copolymers of (meth)acrylic acid and C1-C6 alkyl acrylates.

[0152] The (meth)acrylic acid monomer is present in an amount of preferably 20% to 80% by mass, more specifically 25% to 70% by mass, and even more specifically 35% to 60% by mass, relative to the total mass of the copolymer.

[0153] C1-C6 alkyl acrylate monomers are present in an amount of preferably 15% to 80% by mass, more specifically 25% to 75% by mass, and even more specifically 40% to 65% by mass, relative to the total mass of the copolymer. Among these monomers, examples include methyl acrylate, ethyl acrylate, n-butyl acrylate, ethyl 2-hydroxyacrylate, styrene, acrylamide, N,N-dimethylacrylamide, tert-butylacrylamide, methyl methacrylate, ethyl methacrylate, n-butyl methacrylate, and 2-hydroxyethyl methacrylate.

[0154] Such copolymers are typically partially or entirely crosslinked with at least one conventional crosslinking agent. The crosslinking agents are particularly polyunsaturated compounds. These compounds include, in particular, polyalkenyl ethers of sucrose or polyols, diallyl phthalate, divinylbenzene, allyl (meth)acrylate, ethylene glycol di(meth)acrylate, methylene bisacrylamide, trimethylolpropane tri(meth)acrylate, diaryl itaconate, diallyl fumarate, diallyl maleate, zinc (meth)acrylate, and castor oil or polyol derivatives produced from unsaturated carboxylic acids. Unsaturated monomer compounds containing reactive groups that can react with unsaturated compounds to form crosslinked copolymers can also be used as crosslinking agents. The crosslinking agent content is generally in the range of 0.01% to 5% by mass, preferably 0.03% to 3% by mass, and more specifically 0.05% to 1% by mass, based on the total mass of the copolymer.

[0155] The preferred crosslinked copolymers of (meth)acrylic acid and C1-C6 alkyl acrylate according to the present invention are selected from crosslinked copolymers of methacrylic acid and C1-C6 alkyl acrylate, crosslinked copolymers of acrylic acid and C1-C6 alkyl acrylate, and more specifically, crosslinked copolymers of methacrylic acid and ethyl acrylate.

[0156] In a particularly preferred embodiment, the copolymer of the present invention may be in the form of an aqueous dispersion. The number-average size of the copolymer particles in the dispersion is generally 10 to 500 nm, preferably 20 to 200 nm, and more preferably 50 to 150 nm.

[0157] Among crosslinked copolymers of (meth)acrylic acid and C1-C6 alkyl acrylates, examples include a product sold by Coatex under the name Viscoatex 538C, which is a crosslinked copolymer of (meth)acrylic acid and C1-C4 ethyl acrylate in the form of an aqueous dispersion containing 38% active substance, or a product sold by Rohm & Haas under the name Aculyn 33, which is a crosslinked copolymer of acrylic acid and ethyl acrylate in the form of an aqueous dispersion containing 28% active substance. More specifically, a crosslinked methacrylic acid / ethyl acrylate copolymer in the form of a 30% aqueous dispersion manufactured and sold by Lubrizol under the name Carbopol Aqua SF-1 can be cited.

[0158] A third family of suitable thickening polymers is represented by crosslinked or non-crosslinked 2-acrylamido-2-methylpropanesulfonic acid (AMPS®) homopolymers or salts thereof. These homopolymers may or may not be crosslinked.

[0159] Such homopolymers may have a number-average molecular weight in the range of 1,000 to 2,000,000 g / mol, preferably in the range of 20,000 to 5,000,000 g / mol, and more preferably in the range of 100,000 to 1,500,000 g / mol.

[0160] More specifically, 2-acrylamido-2-methylpropanesulfonic acid, and its partially or completely neutralized forms, are used.

[0161] When the polymer is crosslinked, the crosslinking agent may be selected from polyolefin unsaturated compounds commonly used in crosslinked polymers obtained by radical polymerization. Examples of crosslinking agents that may be mentioned include divinylbenzene, diallyl ethers, dipropylene glycol diallyl ethers, polyethylene glycol diallyl ethers, triethylene glycol divinyl ethers, hydroquinone diallyl ethers, ethylene glycol di(meth)acrylate or tetraethylene glycol di(meth)acrylate, trimethylolpropane triacrylate, methylene bisacrylamide, methylene bismethacrylamide, triallylamine, triallyl cyanurate, diallyl maleate, tetraallylethylenediamine, tetraallyloxyethane, trimethylolpropane diallyl ether, allyl(meth)acrylate, allyl ethers of sugar series alcohols, or other allyl ethers or vinyl ethers of polyfunctional alcohols, and also allyl esters of phosphoric acid derivatives and / or vinylphosphonic acid derivatives, or mixtures of these compounds.

[0162] According to preferred embodiments of the present invention, the crosslinking agent is selected from methylenebisacrylamide, allyl methacrylate, and trimethylolpropane triacrylate (TMPTA). The degree of crosslinking is generally in the range of 0.01 mol% to 10 mol%, more specifically 0.2 mol% to 2 mol%, relative to the polymer.

[0163] Homopolymers consist only of monomers having sulfone groups, and if crosslinked, they contain one or more crosslinking agents.

[0164] Preferred 2-acrylamido-2-methylpropanesulfonic acid homopolymers are generally randomly distributed, a) The following general formula (1) for 90% to 99.9% by mass: [ka] [In the formula, X +This represents a proton, alkali metal cation, alkaline earth metal cation, or ammonium ion, but cation X + If possible, a concentration of 10 mol% or less of proton H + The unit of [is]; b) Crosslinking units (their mass ratios are defined relative to the total mass of the polymer) derived from at least one monomer containing at least two olefinic double bonds, in an amount of 0.01% to 10% by mass. Includes.

[0165] A more particularly preferred homopolymer according to the present invention contains 98% to 99.5% by mass of the unit of formula (1) and 0.2% to 2% by mass of crosslinking units.

[0166] A prime example of this type of polymer is the cross-linked, neutralized 2-acrylamido-2-methylpropanesulfonic acid homopolymer (CTFA name: ammonium polyacryldimethyltauamide), sold by Clariant under the trade name Hostacerin AMPS®.

[0167] The polymer is, for example, C6~C as described in International Publication No. 00 / 31154. 22 The amphiphilic homopolymer (i.e., hydrophobic modified homopolymer) may be selected from random amphiphilic 2-acrylamido-2-methylpropanesulfonic acid polymers (which are grafted homopolymers) modified by reaction with an n-monoalkylamine or di-n-alkylamine.

[0168] A fourth family of suitable thickening polymers is represented by copolymers of acrylamide-2-methylpropanesulfonic acid or a salt thereof and one or more nonionic monomers. These may or may not be crosslinked.

[0169] If the polymer is crosslinked, the crosslinking agent may be selected from polyolefin-based unsaturated compounds commonly used for crosslinked polymers obtained by radical polymerization. Such agents are described above.

[0170] According to a preferred embodiment of the present invention, the crosslinking agent is selected from methylenebisacrylamide, allyl methacrylate, and trimethylolpropane triacrylate (TMPTA). The degree of crosslinking is generally in the range of 0.01 mol% to 10 mol%, more specifically 0.2 mol% to 2 mol%, relative to the polymer.

[0171] Copolymers according to the present invention are obtained from AMPS®, one or more hydrophilic or hydrophobic ethylenically unsaturated nonionic monomers, and, if crosslinked, one or more crosslinking agents, for example, those defined above.

[0172] The 2-acrylamido-2-methylpropanesulfonic acid monomer of the copolymer contained in the composition according to the present invention is in a free form, or is partially or entirely neutralized with an inorganic base (sodium hydroxide, potassium hydroxide, or aqueous ammonia) or an organic base, such as mono-, di-, or triethanolamine, aminomethylpropanediol, N-methylglucamine, a basic amino acid, such as arginine and lysine, or a mixture of these compounds.

[0173] Preferably, the 2-acrylamido-2-methylpropanesulfonic acid monomer is partially or completely chlorided in the form of an ammonium salt or a sodium salt.

[0174] Preferably, the 2-acrylamido-2-methylpropanesulfonic acid monomer is completely chlorided, preferably in the form of an ammonium salt or a sodium salt.

[0175] AMPS® copolymers contain one or more nonionic monomers selected from water-soluble ethylenically unsaturated monomers, hydrophobic monomers, or mixtures thereof.

[0176] Examples of nonionic water-soluble monomers include the following: - (meth)acrylamide, - N-vinylacetamide and N-methyl-N-vinylacetamide, - N-vinylformamide and N-methyl-N-vinylformamide, - Maleic anhydride, - Vinylamine, - Cyclic alkyl groups containing 4 to 9 carbon atoms, for example, N-vinylpyrrolidone, N-butyrolactam, and N-vinylcaprolactam, N-vinyllactams, - Vinyl alcohol of formula CH2=CHOH, - Water-soluble vinyl monomer of the following formula (2): [ka] During the ceremony, - R 15 However, it is selected from H, -CH3, -C2H5 and -C3H7, - X2, -OR 16 Selected from alkyl oxides of type R 16 However, these are linear or branched, saturated or unsaturated hydrocarbon-based groups containing 1 to 6 carbon atoms, and are optionally substituted with halogen atoms (iodine, bromine, chlorine, or fluorine); hydroxyl (-OH) groups; or ethers.

[0177] For example, refer to glycidyl (meth)acrylate, hydroxyethyl (meth)acrylate, and (meth)acrylates of ethylene glycol, diethylene glycol, or polyalkylene glycol.

[0178] Preferably, the water-soluble monomer is selected from acrylamide (meth)acrylate, vinylpyrrolidone (meth)acrylate, and hydroxyalkyl (meth)acrylate, and more specifically vinylpyrrolidone (meth)acrylate.

[0179] Examples of copolymers of AMPS® according to the present invention with hydrophilic monomers that may be referred to include the following: - Copolymers of acrylamide-2-methylpropanesulfonic acid and vinylpyrrolidone, particularly commercially available products such as Aristoflex AVC sold by Clariant, - Cross-linked acrylamide / sodium acrylamide-2-methylpropanesulfonate copolymer, e.g., product Sepigel 305 (registered trademark) (INCI name: polyacrylamide / C 13 ~C 14 Products used in isoparaffin / laureth-7, or in products sold by SEPPIC under the name Simulgel 600 (registered trademark) (INCI name: acrylamide / sodium acryloyldimethyl taurate / isohexadecane / polysorbate-80); - Copolymers of AMPS® and ethyl hydroxyacrylate, e.g., sodium AMPS® / ethyl hydroxyacrylate copolymer, e.g., commercially available products sold by SEPPIC under the name Simulgel NS® (INCI name: ethyl hydroxyacrylate / sodium acryloyldimethyl taurate copolymer (and) squalane (and) polysorbate 60; - Hydrophobic modified AMPS(registered trademark) copolymers, known by their INCI name: Ammonium acryloyldimethyltaurate / steareth-25 methacrylate crosspolymer, sold by Clariant under the trade name Aristoflex HMS.

[0180] The concentration of the anionic synthetic thickening polymer (i.e., the active substance) is generally in the range of 0.05% to 35% by mass, preferably 0.1% to 20% by mass, preferably 0.2% to 10% by mass, preferably 0.25% to 5% by mass, and more specifically 0.3% to 3% by mass, based on the total mass of the composition.

[0181] Thickening polysaccharides The compositions according to the present invention may also include a thickening polymer selected from nonionic thickening polysaccharides, sulfate-based thickening polysaccharides, and carboxylic acid branched thickening polysaccharides.

[0182] Among nonionic thickening polysaccharides, nonionic cellulose-based thickening polysaccharides are particularly noteworthy.

[0183] Preferably, the cellulose that can be used in the composition according to the present invention is selected from cellulose that does not contain hydrophobic chains and nonionic cellulose that contains one or more hydrophobic chains.

[0184] Preferably, the cellulose used in accordance with the present invention is a cellulose ether. More preferably, these celluloses are nonionic hydroxyalkyl celluloses, particularly hydroxyethyl cellulose or hydroxypropyl cellulose. They may or may not contain fatty acid chains. Among nonionic celluloses that do not contain fatty acid chains, examples include hydroxyethyl cellulose, hydroxypropyl cellulose, and hydroxypropyl methyl cellulose. A particularly suitable hydroxyethyl cellulose for use is Cellosize HEC QP-4400H, sold by Amerchol (INCI name: hydroxyethyl cellulose).

[0185] Cellulose modified with a group containing one or more nonionic fatty acids that can be used according to the present invention are, in particular, the following: - The product sold by Ashland, Natrosol Plus Grade 330 CS (registered trademark), corresponds to the INCI name cetyl hydroxyethylcellulose.16 Modified with at least one fatty chain-containing group, such as an alkyl group, arylalkyl group, or alkylaryl group, or a mixture thereof, such as the product Bermocoll EHM 100 (registered trademark) sold by AkzoNobel, where the alkyl group is preferably C8-C 22 The base is nonionic hydroxyethylcellulose, - Products marketed by Amerchol, such as Amercell Polymer HM-1500(registered trademark) (nonylphenyl polyethylene glycol (15) ether), which are modified with alkylphenyl polyalkylene glycol ether groups, corresponding to the INCI name nonoxynyl hydroxyethylcellulose.

[0186] Among sulfate-based thickening polysaccharides, those that do not contain rhamnose are particularly noteworthy. These sulfate-based polysaccharides are preferably carrageenan.

[0187] Carrageenan is a polysaccharide that makes up the cell walls of various red algae (Rhodophyceae) belonging to the families Gigartinacae, Hypneaceae, Furcellariaceae, and Polyideaceae. It contains long galactan chains and anionic polyelectrolytes. Its molecular mass is 10 6 They may be larger. These linear polymers formed from disaccharide units consist of two D-galactopyranos units alternately linked by α- and β-bonds. They are highly sulfated polysaccharides (20-50%), and the α-D-galactopyranosyl residue may be in the 3',6'-anhydrous form.

[0188] First, carrageenans were divided into two families according to their solubility in potassium chloride (KCl). The fraction soluble in KCl was indicated by the prefix "kappa," while the term "lambda" was reserved for the insoluble fraction. Later, the classification was based on the number and position of sulfate groups, as well as the presence of 3',6'-anhydro bridges on β-D-galactopyranosyl residues. This yielded four main families: κ, λ, β, and ω.

[0189] Various types of carrageenans exist not in their pure forms, but in hybrid forms. Therefore, in nature, κ- and ι-carrageenans are cappyote hybrid forms, but one of the two structures may be dominant over the other. The κ-ι-hybrid state of a structure can be elucidated by using specific enzymes that allow for the concentration or reduction of the content of one of the two forms. Carrageenans can coexist with their precursors. Carrageenans from different original families can coexist in hybrid structures.

[0190] Preferably, the composition according to the present invention comprises one or more lambda-carrageenan-type sulfate polysaccharides. The lambda-carrageenan-type sulfate polysaccharide may or may not be chemically modified. Preferably, the lambda-carrageenan-type sulfate polysaccharide is unmodified. Preferably, the molecular weight (MW) of the polysaccharide is 100,000 to 1,000,000, more preferably 250,000 to 800,000. Examples of lambda-carrageenan-type sulfate polysaccharides include Satiagum UTC10 or Satiagum VPC410 from Cargill and Welgeenan ED1039 from Eurogum.

[0191] Among carboxylic acid branched thickening polysaccharides, anionic branched polysaccharides based on glucose, mannose, acetylated mannose, pyruvate, and glucuronic acid are particularly noteworthy. Xanthan gum is preferred as such a polysaccharide.

[0192] Xanthanane is a heteropolysaccharide produced industrially by aerobic fermentation of the citrus canker bacterium Xanthomonas campestris. Its structure, like cellulose, consists of a main chain of β(1,4)-linked β-D-glucose. One of the two glucose molecules has a trisaccharide side chain composed of α-D-mannose, β-D-glucuronic acid, and terminal β-D-mannose. The internal mannose residue is generally acetylated at carbon 6. Approximately 30% of the terminal mannose residues have a pyruvate group linked in a chelated form between carbons 4 and 6. Charged pyruvate and glucuronic acid are ionic and therefore contribute to the anionic nature of xanthanane (negative charge reduced to pH equal to 1). The content of pyruvate and acetate residues varies depending on the bacterial strain, the fermentation process, and the conditions after fermentation and purification. These groups are Na + , K + or Ca 2+ It can be neutralized in ion-containing products (Satia company, 1986). The neutralized form can be converted back to the acid form by ion exchange or by dialysis of the acidic solution.

[0193] Xanthan gum has a molecular weight of 1,000,000 to 5,000,000 and a viscosity of 0.6 to 1.65 Pa.s in an aqueous composition containing 1% xanthan gum (measured at 25°C using an LVT-type Brookfield viscometer at 60 rpm).

[0194] Xanthan gum is represented, for example, by products marketed as Rhodicare® by PMC Ouvrie, as Satiaxane® by Cargill Texturizing Solutions (for the food, cosmetics, and pharmaceutical industries), as Novaxan® by ADM, and as Kelzan® and Keltrol® by CP-Kelco.

[0195] The concentration of the thickening polysaccharide used in the composition according to the present invention is in the range of 0.01% to 20% by mass, preferably 0.02% to 10% by mass, preferably 0.03% to 8% by mass, preferably 0.05% to 5% by mass, and more preferably 0.1% to 3% by mass, based on the total mass of the composition.

[0196] According to a preferred embodiment, the composition according to the present invention comprises a crosslinked acrylic acid homopolymer, a crosslinked copolymer of (meth)acrylic acid and a C1-C6 alkyl acrylate, a copolymer of acrylamide-2-methylpropanesulfonic acid and one or more nonionic monomers, a crosslinked, preferably neutralized, 2-acrylamide-2-methylpropanesulfonic acid homopolymer, and a thickener selected from hydroxyethylcellulose, carrageenan, and xanthan gum.

[0197] According to a preferred embodiment, the composition according to the present invention comprises a crosslinked acrylic acid homopolymer, a crosslinked and preferably neutralized 2-acrylamido-2-methylpropanesulfonic acid homopolymer, a thickener selected from hydroxyethylcellulose, carrageenan, and xanthan gum.

[0198] The compositions according to the present invention may also comprise several thickening polymers, typically a mixture of at least two or more thickening polymers. The compositions may typically comprise at least one anionic synthetic thickening polymer and at least one thickener selected from nonionic thickening polysaccharides, sulfate-based thickening polysaccharides, carboxylic acid branched thickening polysaccharides, and mixtures thereof.

[0199] According to a particular embodiment of the present invention, the total concentration of the thickener used in the composition is in the range of 0.01% to 50% by mass, preferably 0.1% to 20% by mass, preferably 0.2% to 10% by mass, preferably 0.3% to 8% by mass, and more preferably 0.5% to 3% by mass, based on the total mass of the composition.

[0200] additives The compositions according to the present invention may also include conventional cosmetic adjuvants selected from, in particular, softeners, moisturizers, emulsions, stabilizers, emollients, silicones, defoamers, fragrances, preservatives, anionic, cationic, nonionic, zwitterionic or amphoteric surfactants, surfactants, fillers, polymers, propellants, or any other materials commonly used in the fields of cosmetics and / or dermatology.

[0201] Examples of active agents for caring for keratinous substances such as skin, lips, scalp, hair, eyelashes, or nails include: vitamins and their derivatives or precursors (alone or in mixtures); antioxidants; free radical scavengers; anti-fouling agents; self-tanning agents; anti-glycation agents; sedatives, deodorants; essential oils; NO synthase inhibitors; agents for stimulating and / or preventing the breakdown of macromolecules in the dermis or epidermis; agents for stimulating fibroblast proliferation; agents for stimulating keratinocyte proliferation; muscle relaxants; cooling agents; tensioning agents; matting agents; bleaching agents; keratolytic agents; desquamating agents; moisturizers; anti-inflammatory agents; antimicrobial agents, weight-reducing agents; agents acting on cellular energy metabolism; insecticides; substance P antagonists or CRGP antagonists; hair loss inhibitors; anti-wrinkle agents; and anti-aging agents.

[0202] A person skilled in the art would select the appropriate activator for use on skin, hair, eyelashes, eyebrows, and nails, as desired.

[0203] Of course, those skilled in the art will select the above-mentioned optional additional compounds and / or their amounts with care, so as not to adversely affect, or substantially affect, any advantageous properties inherently associated with the compositions according to the present invention.

[0204] Presentation form The compositions according to the present invention are aqueous, that is, they contain at least one aqueous phase.

[0205] The compositions according to the present invention are in aqueous form, that is, they contain an amount of fatty phase of less than 10% by mass, preferably less than 5% by mass, and more preferably less than 1% by mass, relative to the total mass of the composition. Advantageously, the compositions according to the present invention are basically aqueous; that is, they do not contain fatty phase.

[0206] The composition according to the present invention may be in the form of an aqueous solution or an aqueous gel. In a preferred embodiment, the composition is in the form of an aqueous gel.

[0207] The compositions according to the present invention have applications in many treatments of the skin, lips and scalp, including hair, particularly in cosmetic treatments, especially for protecting and / or caring for the skin, lips and / or hair, and / or for makeup application to the skin and / or lips.

[0208] Another subject of the present invention consists of the use of the compositions according to the present invention as defined above for the manufacture of products for cosmetic treatment of the skin, lips, nails, hair, eyelashes, eyebrows and / or scalp, in particular care products, anti-sun products and makeup products.

[0209] Another subject of the present invention comprises a non-therapeutic cosmetic method for caring for and / or making up a keratin material, which comprises applying to the surface of the keratin material at least one composition according to the present invention as defined above.

[0210] Another subject of the present invention consists of the use of at least one hydrophilic organic UV shielding agent for solubilizing the merocyanine of formula (3) as defined above.

[0211] According to the present invention, the water-soluble organic UV shielding agent makes it possible to solubilize the merocyanine according to the present invention in an aqueous phase. [Examples]

[0212] Here, the present invention will be described more specifically using examples, but these do not limit the scope of the present invention in any way. However, according to this example, it is possible to support specific features, modifications, and preferred embodiments of the present invention.

[0213] A / Synthesis Example of Merocyanine of Formula (3) Example A1: Preparation of Compound (14)

Chemical Formula

[0214] The following combinations of base / solvent are used.

[0215]

Table 4

[0216] The completion of the alkylation reaction can be monitored by methods such as TLC, GC, or HPLC.

[0217] 162.30 g of compound (14) obtained in the form of a brown oil.

[0218] After crystallization, the product is obtained in the form of yellowish crystals.

[0219] Melting point: 92.7 °C.

[0220] Example A2: Preparation of Compound (15)

Chemical Formula

[0221] The base / solvent combinations shown in the table below are used.

[0222] [Table 5]

[0223] The crude product (15) is obtained in the form of a dark brown oil.

[0224] After silica gel column chromatography (eluent: 99 / 1 toluene / methanol), 81.8 g of the product was obtained in the form of yellowish crystals.

[0225] Melting point: 84.7~85.3℃.

[0226] Example A3: Preparation of compound (27) [ka] 13.09 g of 3-[(3-methoxypropyl)amino]-2-cyclohexen-1-one is alkylated with dimethyl sulfate, or alternatively with diethyl sulfate, and treated with 10.12 g of isobutyl cyanoacetate in the presence of a base and, optionally, a solvent.

[0227] The base / solvent combinations shown in the table below are used.

[0228] [Table 6]

[0229] 15.97 g of crude product (27) is obtained in the form of dark brown oil.

[0230] After silica gel column chromatography (eluent: toluene / acetone), 13.46 g of the product is obtained in the form of yellowish crystals.

[0231] Melting point: 96.3 °C.

[0232] Example A4: Preparation of Compound (25) [Chemical formula] 148.4 g of 3-[(3-methoxypropyl)amino]-2-cyclohexen-1-one is alkylated with dimethyl sulfate or alternatively with diethyl sulfate and then treated with 130.00 g of cyanoacetic acid 2-ethoxyethyl in the presence of an organic base and a solvent.

[0233] The following base / solvent combinations shown in the table are used.

[0234] [Table 7]

[0235] B / Formulation Example In these examples, the amounts of the materials present in the composition are given as mass % of the active substance relative to the total mass of the composition.

[0236] Protocol for evaluating solubility: The solubility of merocyanine in aqueous solution can be evaluated macroscopically and / or microscopically. At ambient temperature, if the solution appears to the eye to be clear and translucent and shows no visible crystals under an optical microscope or a polarizing microscope (objective lens ×20 to ×40), merocyanine is considered soluble.

[0237] In the following examples, solubility is evaluated macroscopically. It is evaluated at ambient temperature after 24 hours. During this period, the solution is stored at ambient temperature.

[0238] Example 1: Solubilization in the presence of 2-phenyl-1H-benzimidazole-5-sulfonic acid or its salt. The following solutions were prepared according to the following process:

[0239] [Table 8]

[0240] Various materials are mixed in a beaker, and the mixture is continuously stirred at ambient temperature for 2 hours using a magnetic stirrer. Then, the resulting formulation is stored at ambient temperature for 24 hours, after which a macroscopic evaluation of merocyanine solubility is performed.

[0241] These results indicate that the water-insoluble compound 25 is solubilized in the presence of 2-phenyl-1H-benzimidazole-5-sulfonic acid and / or its salt.

[0242] Example 2: Solubilization in the presence of benzene-1,4-di(3-methylidene-10-camphor sulfonic acid) and / or its salts The following solutions were prepared according to the following process:

[0243] [Table 9]

[0244] Various materials are mixed in a beaker, and the mixture is continuously stirred at ambient temperature for 2 hours using a magnetic stirrer. Then, the resulting formulation is stored at ambient temperature for 24 hours, after which a macroscopic evaluation of merocyanine solubility is performed.

[0245] These results indicate that water-insoluble compound 25 is solubilized in the presence of benzene-1,4-di(3-methylidene-10-camphor sulfonic acid) and / or its salts.

[0246] Example 3: Solubilization in the presence of 1,4-bis-benzimidazolyl-phenylene-3,3',5,5'-tetrasulfonic acid and / or its salt The following solutions were prepared according to the following process:

[0247] [Table 10]

[0248] Various materials are mixed in a beaker, and the mixture is continuously stirred at ambient temperature for 2 hours using a magnetic stirrer. Then, the resulting formulation is stored at ambient temperature for 24 hours, after which a macroscopic evaluation of merocyanine solubility is performed.

[0249] These results indicate that water-insoluble compound 25 is solubilized in the presence of 1,4-bis-benzimidazolylphenylene-3,3',5,5'-tetrasulfonic acid and / or its salts.

[0250] Example 4: Clear aqueous serum Prepare the following compositions.

[0251] [Table 11]

[0252] Adjustment mode Phase A1 is prepared at 50°C with magnetic stirring, and Phase A2 is prepared at ambient temperature with magnetic stirring. Then, Phase A2 is slowly added to Phase A1 while stirring until a clear mixture is obtained. The mixture is allowed to return to ambient temperature, and then Phase B is added while stirring.

Claims

1. A water-based cosmetic or dermatological composition, a) At least one merocyanine corresponding to the following formula (3), in an amount of less than 3% by mass of the total mass of the composition, and its geometric isomer form, particularly the E / E- or E / Z- geometric isomer form: 【Chemistry 1】 (In the formula, A is -O- or -NH-, R is C which may be interrupted by one or more O's １ to C ２２ alkyl group, C ２ to C ２２ alkenyl group, C ２ to C ２２ alkynyl group, C ３ to C ２２ cycloalkyl group or C ３ to C ２２ cycloalkenyl group); and b) At least one water-soluble organic UV shielding agent A water-based cosmetic or dermatological composition containing the following:

2. The compound in formula (3) is a compound in which A is -O- and R is C １ ~C ２２ The composition according to claim 1, wherein the alkyl group is interrupted by one or more oxygen atoms.

3. The composition according to claim 1 or 2, wherein the merocyanine of formula (3) is selected from the following compounds and their E / E- or E / Z- geometric isomer forms. Table 1 Table 2 Table 3

4. The merocyanine in formula (3) has the following structure: 【Chemistry 2】 In its E / Z geometric configuration, and / or the following structure: 【Transformation 3】 The composition according to any one of claims 1 to 3, wherein the E / E-geometric configuration having is 2-ethoxyethyl (2Z)-cyano{3-[(3-methoxypropyl)amino]cyclohexa-2-ene-1-ylidene}ethanoate (25).

5. The composition according to any one of claims 1 to 4, wherein the amount of merocyanine and its geometric isomer form, particularly its E / E- or E / Z- geometric isomer form, corresponding to the following formula (3) is 2.5% by mass or less, preferably 0.01% to 2.5% by mass or less, and more preferably 0.5% to 1.5% by mass or less, of the total mass of the composition.

6. The composition according to any one of claims 1 to 5, wherein the water-soluble organic UV shielding agent is selected from benzene-2-phenyl-1H-benzimidazole-5-sulfonic acid (INCI name: phenylbenzimidazole sulfonic acid); benzene-1,4-di(3-methylidene-10-camphor sulfonic acid) (INCI name: terephthalylidene dicamphor sulfonic acid); 1,4-bis-benzimidazolyl-phenylene-3,3',5,5'-tetrasulfonic acid (INCI name: disodium phenyldibenzimimidazole tetrasulfonate); and salts thereof.

7. The composition according to any one of claims 1 to 6, wherein the water-soluble organic UV shielding agent is present in a concentration of 0.1% to 19% by mass, preferably 0.5% to 12% by mass, and more preferably 3% to 10% by mass, based on the total mass of the composition.

8. The composition according to any one of claims 1 to 7, comprising at least one additional UV shielding agent selected from lipophilic organic UV shielding agents, water-dispersible organic UV shielding agents, and inorganic UV shielding agents, preferably selected from water-dispersible organic UV shielding agents and inorganic UV shielding agents.

9. The composition according to claim 8, wherein the lipophilic organic UV shielding agent is selected from cinnamic acid compounds; anthranilate ester compounds; salicylic acid compounds; dibenzoylmethane compounds; benzylidene camphor compounds; benzophenone compounds; β,β-diphenyl acrylate compounds; triazine compounds; benzotriazole compounds; benzalmalonic acid ester compounds; benzimidazole derivatives; imidazoline compounds; bis-benzazolyl compounds; methylenebis(hydroxyphenylbenzotriazole) compounds; benzoxazole compounds; shielding polymers and shielding silicones; dimers derived from α-alkylstyrene; 4,4-diarylbutadiene compounds; and mixtures thereof; preferably selected from salicylic acid compounds, dibenzoylmethane compounds, benzylidene camphor compounds; benzophenone compounds; triazine compounds; benzotriazole compounds; and mixtures thereof.

10. The water-dispersible organic UV shielding agent is methylenebis-benzotriazolyltetramethylbutylphenol in the form of an aqueous dispersion of fine particles having an average particle size in the range of 0.01 to 5 μm, more preferably 0.01 to 2 μm, and more specifically 0.020 to 2 μm, and has structure C ｎ H ２ｎ＋１ O(C) ６ H １０ O ５ ) ｘ H (wherein n is an integer from 8 to 16, and x is the unit (C) ６ H １０ O ５ Methylenebis-benzotriazolyltetramethylbutylphenol, comprising at least one alkyl polyglycoside surfactant having an average degree of polymerization of 1.4 to 1.6; and at least one mono(C) polyglycerol having a glycerol degree of polymerization of at least 5. ８ ~C ２０ )methylenebis-benzotriazolyltetramethylbutylphenol in the form of an aqueous dispersion of fine particles having an average particle size in the range of 0.02 to 2 μm, more preferably 0.01 to 1.5 μm, more specifically 0.02 to 1 μm, in the presence of an alkyl ester; bis-ethylhexyloxyphenol methoxyphenyl triazine in an aqueous dispersible form having the INCI name bis-ethylhexyloxyphenol methoxyphenyl triazine (and) acrylate / C12-22 alkyl methacrylate copolymer; the composition according to claim 8 or 9, which is used in a fine particle form (average particle size of 0.02 to 3 μm), particularly in an aqueous dispersion form, and is a symmetric triazine shielding agent substituted with a naphthalenyl group or a polyphenyl group, particularly selected from 2,4,6-tris(biphenyl)triazine and 2,4,6-tris(ter-phenyl)triazine.

11. The composition according to any one of claims 8 to 10, wherein the inorganic UV shielding agent is selected from coated or uncoated titanium oxide pigments.

12. The composition according to any one of claims 1 to 11, wherein the total amount of the additional UV shielding agent is 20% or less, preferably 10% or less, and more preferably 5% or less of the total mass of the composition.

13. The composition according to any one of claims 1 to 12, wherein the only UV shielding agent present in the composition is the water-soluble organic UV shielding agent and merocyanine of formula (3).

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