A composition comprising at least 5% by mass of titanium dioxide, an α-cyanodiphenyl acrylate derivative, and 4-hydroxybenzylidenemalonate or a 4-hydroxycinnamate derivative.

Abstract

The present invention relates to a composition comprising: 1) at least one inorganic UV filter selected from titanium dioxide; 2) at least one α-cyanodiphenylacrylate derivative of the given formula; and 3) at least one 4-hydroxybenzylidenemalonate or 4-hydroxycinnamate derivative of the given formula. The present invention also relates to a cosmetic method for treating skin against UV radiation using said composition.

Description

[Technical Field]

[0001] The present invention relates to a composition comprising at least 5% by mass of at least one inorganic UV shielding agent selected from titanium dioxide, based on the total mass of the composition, at least one α-cyanodiphenyl acrylate derivative of a defined formula, and at least one hydroxybenzylidene malonate or 4-hydroxycinnamate derivative of a defined formula. [Background technology]

[0002] The present invention also relates to a cosmetic method for applying a treatment to the skin to protect it from UV radiation using the composition.

[0003] Light radiation with wavelengths between 280 and 400 nm can cause browning of the human epidermis. Light with wavelengths between 280 and 320 nm, known as UVB rays, can cause erythema and burns in the skin, which can be detrimental to the progression of browning. Light with wavelengths between 320 and 400 nm, known as UVA rays, has the power to cause harmful changes in the skin, particularly leading to premature aging through loss of elasticity and the appearance of wrinkles.

[0004] Therefore, UV rays should be blocked. Cosmetic compositions for protecting human epidermis that contain UV shielding agents active in blocking UVA and UVB radiation already exist.

[0005] Mineral pigments and organic shading agents are commercially available as various types of sunscreens to block UVA and UVB rays. These shading agents must be able to absorb or block harmful rays from sunlight while remaining harmless to the user.

[0006] Accordingly, numerous organic sunscreens capable of selectively absorbing harmful UV rays have been proposed in the cosmetics field to date. However, for various reasons, these sunscreens have not been completely satisfactory.

[0007] Therefore, there is an increasingly strong need to avoid the use of such organic shielding agents by prioritizing the use of mineral pigments, which primarily act as sunscreens by scattering / reflecting UV rays, while also providing greater safety for the user.

[0008] In this regard, titanium dioxide is currently the most widely used mineral pigment, and its shielding properties are well known.

[0009] Furthermore, since other mineral-based sunscreens such as zinc oxide are harmful to the environment, it is particularly desirable to propose sun protection products containing titanium dioxide as sunscreens.

[0010] However, in order to obtain a suitable protective coefficient, it is necessary to be able to incorporate TiO2 in a high proportion, particularly 5% by mass or more, into the antisun protection composition.

[0011] However, it has been observed that when TiO2 is used in such concentrations, compositions containing these pigments in an oxygen-free medium become unstable to light, resulting in a blue coloration. This light-induced coloration, also known as photoblueing, is clearly undesirable from an aesthetic standpoint.

[0012] To explain in detail, titanium dioxide, which is used in sunscreens, has semiconductor properties. The photoblueing phenomenon observed when it is exposed to ultraviolet light indicates that a chemical reaction is occurring that can generate free radicals that may cause harmful effects on the skin.

[0013] Therefore, it is desirable to propose a sun protection product that contains titanium dioxide in a high concentration as a standalone sunscreen, providing a high level of protection without causing any photoblueing.

[0014] (Patent Document 1) proposes using deformable hollow particles to limit the photobleaching of a sunscreen composition containing titanium oxide. However, such particles are regarded as microplastics and are undesirable components in sunscreen products.

Prior Art Documents

Patent Documents

[0015]

Patent Document 1

Summary of the Invention

Problems to be Solved by the Invention

[0016] Therefore, there is a need for an inorganic sunscreen-based composition that is highly efficient and has photo-stability.

Means for Solving the Problems

[0017] In accordance with this, the inventors have found that by introducing a α-cyanodiphenyl acrylate derivative of a defined formula and a hydroxybenzylidene malonate or 4-hydroxycinnamate derivative of a defined formula into a composition containing a TiO2 pigment, the photobleaching inherent in the composition is significantly reduced.

[0018] This discovery forms the basis of the present invention.

[0019] Therefore, one subject of the present invention is, in particular, 1) at least one inorganic UV blocker selected from titanium oxide; 2) the following formula (I):

Chemical Formula

Chemical formula

[0020] The composition according to the invention can block UV rays with high efficiency, thereby protecting the skin better.

[0021] The composition according to the invention has light stability, and a composition containing a pigment of such a titanium oxide species does not show a blue coloration in an oxygen-free medium.

[0022] Furthermore, the composition of the invention is stable over a long period of time.

[0023] Furthermore, the composition of the invention has good workability. It spreads easily and can be applied uniformly without forming a whitish film on the skin.

[0024] Furthermore, the composition of the invention has good cosmetic properties, particularly from the viewpoint of not being overly shiny, not being greasy, and not being sticky after application to the skin.

[0025] The subject matter of the present invention also relates to a cosmetic method for treating skin, particularly human skin, to protect it from UV radiation, the method comprising applying the composition according to the present invention to the skin.

[0026] According to a first specific embodiment, the composition according to the present invention does not contain piseid (polydatin).

[0027] According to a second specific embodiment, when the composition according to the present invention comprises Piseid(Polydatin), 2-ethylhexyl 2-cyano-3-(4-methoxyphenyl)-3-phenylpropenoate, and diethylhexylsyringylidene malonate, the total mass of Piseid(Polydatin), 2-ethylhexyl 2-cyano-3-(4-methoxyphenyl)-3-phenylpropenoate, and diethylhexylsyringylidene malonate is not 3% by mass of the total mass of the composition.

[0028] According to a third specific embodiment, the composition according to the present invention does not contain piseid (polydatin), resveratrol, piceatannol, or pterostilbene.

[0029] According to a fourth specific embodiment, the composition according to the present invention is stilbenoide-free.

[0030] Stilbenoids are by-products in the formation of tree heartwood and possess phytoalexin properties. From a chemical standpoint, they are stilbene derivatives and often contain one or more phenolic functional groups. From a biochemical standpoint, they belong to the group of phenylalanine derivatives, also known as phenylpropanoids. Their biosynthetic pathways are largely shared with those of aromatic chalcones and other aromatic chalcones.

[0031] One of the most well-characterized plant stilbenoids is resveratrol (3,5,4'-trihydroxy-trans-stilbene), a resorcinol derivative first isolated from Veratrum album in 1939, found in the skins of red grapes and other fruits and nuts, including berries and peanuts. Non-limiting examples of stilbenoids include piceatannol, pterostilbene, and mixtures thereof. [Modes for carrying out the invention]

[0032] Other subjects, features, embodiments, and advantages of the present invention will become even clearer by reading the following description and examples.

[0033] In the following text, unless otherwise specified, boundary values ​​of a range are included within that range, particularly expressions such as "between ~" and "from ~ to ~".

[0034] Furthermore, as used herein, the expressions "at least one" and "at least" are equivalent to the expressions "one or more" and "more than or equal to," respectively.

[0035] The degree of sun protection, as determined by the ultraviolet protection factor (SPF), is expressed numerically as the ratio of the exposure time required to reach the erythema threshold with UV protection to the exposure time required to reach the erythema threshold without UV protection.

[0036] This can be evaluated in vivo, in particular, in accordance with the ISO 24444 method.

[0037] This can also be measured according to the in vitro method described in BLDiffey in J.Soc.Cosmet.Chem. 40, 127-133, (1989).

[0038] For the purposes of this patent application, the term “highly efficient shielding composition” refers to a composition capable of achieving an ultraviolet protection factor (SPF) value of at least 30, preferably at least 50.

[0039] The appearance of blue light, to varying degrees, is observed while the composition is exposed to light. The evaluation principle consists of exposing the test specimen to an irradiation source whose spectral distribution is well defined and whose emitted energy is well quantified. A CPS-Sun-Test apparatus is used, and irradiation is performed with a xenon lamp in the 300-800 nm range.

[0040] Next, photoblueing can be evaluated with the naked eye.

[0041] Photoblueing can also be evaluated by colorimetric values ​​measured using a Minolta CM1000 colorimeter: the first measurement is recorded immediately before exposure to UV (T0), and the second is recorded one hour after exposure to UV (T1H).

[0042] The results are expressed in the (L, a, b) system, where L represents brightness, a represents the red-green axis (-a = green, +a = red), and b represents the yellow-blue axis (-b = blue, +b = yellow).

[0043] The values ​​of interest in evaluating photoblueing are Δb, which indicates the change in blue color; ΔL, which indicates the darkening of the composition; and ΔE, which indicates the change in the overall color. More precisely, Δb and ΔL are given by Δb = b T1H -b T0 and ΔL=L T1H -L T0 It is defined as follows. The smaller the value of Δb, the greater the protective effect against photoblueing. ΔE can be calculated from the changes ΔL, Δa, and Δb according to the following formula:

number

[0044] The term "stable over a long period of time" according to the present invention refers to a state in which, even after storing the composition at a temperature in the range of 4°C to 45°C for one month, preferably two months, no macroscopic changes are observed in color, odor, or viscosity, the pH remains unchanged, and the microscopic appearance also remains unchanged.

[0045] The compositions according to the present invention are intended for topical application and therefore contain physiologically acceptable media. The term "physiologically acceptable media" as used herein means media that are compatible with keratinic substances.

[0046] In relation to the present invention, the term "keratinous material" means, in particular, keratin fibers such as skin, scalp, eyelashes, eyebrows, head hair, and body hair, nails, and mucous membranes such as lips, and more specifically, skin (of the body, face, area around the eyes, or eyelids, preferably of the body or face).

[0047] Mineral UV shielding agent The composition according to the present invention comprises one or more mineral UV shielding agents selected from titanium dioxide.

[0048] The term "UV shielding agent" according to the present invention is synonymous with the term "photoprotective agent."

[0049] The titanium dioxide pigment may or may not be coated.

[0050] Coated pigments are pigments that have been surface-treated to have one or more 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, (titanium or aluminum) metal alkoxides, polyethylene, silicone, proteins (collagen, elastin), alkanolamines, silicon dioxide, metal oxides, or sodium hexametaphosphate.

[0051] The coated pigment is, more specifically, titanium dioxide coated with the following: - Silica, for example, Sunveil from Ikeda Bussan Co., Ltd., Eusolex T-AVO from Merck, and Sunsil TIN 50 from Sunjin; - Silica and iron oxide, for example, product Sunveil F from Ikeda Bussan Co., Ltd. - Silica and alumina, for example, Microtitanium Dioxide MT 500 SA and Microtitanium Dioxide MT 100 SA from Tayca Corporation, and Tioveil from Croda Corporation; - Alumina, for example, products Tipaque TTO-55(B) and Tipaque TTO-55(A) from Ishihara Sangyo Co., Ltd., and UVT 14 / 4 from Sachtleben Pigments; - Stearic acid and aluminum hydroxide, for example, products from Teika Corporation: Microtitanium Dioxide MT 100 TV, MT 100 TX, MT 100 Z, MT-01, and MT 900Z; - Stearic acid and alumina, for example, product Solaveil XT-300-LQ from Croda; - Aluminum stearate and alumina, for example, products from Croda, Solaveil CT-10 W, Solaveil CT 100-LQ, Solaveil CT 200-LQ, and Solaveil CT-300 LQ; - Silica, alumina, and alginate, for example, product MT-100 AQ from Teika Co., Ltd.; - Alumina and aluminum laurate, for example, Microtitanium Dioxide MT 100 S from Teika Co., Ltd. - Iron oxide and iron stearate, for example, product Microtitanium Dioxide MT 100 F from Teika Co., Ltd. - Silica and alumina (and treated with silicone), for example, products from Teika Corporation such as Microtitanium Dioxide MT 600 SAS, Microtitanium Dioxide MT 500 SAS, or Microtitanium Dioxide MT 100 SAS; - Silica, alumina, and aluminum stearate (and treated with silicone), for example, Titan Kogyo's product STT-30-DS. - Silica (and treated with silicone), for example, UV-Titan X 195 from Sachtleben Pigments and Parsol TX from DSM Nutritional Products; - Alumina (and treated with silicone), for example, product Typeque TTO-55(S) from Ishihara Sangyo Co., Ltd. or product UV Titan M 262 from Sachtleben Pigments; - Triethanolamine, for example, product STT-65-S from Titanium Industries Co., Ltd.; - Stearic acid, for example, product Typeque TTO-55(C) from Ishihara Sangyo Co., Ltd. - Sodium hexametaphosphate, for example, Microtitanium Dioxide MT 150 W from Teika Corporation; - TiO2 treated with octyltrimethylsilane, particularly the one sold by Degussa Silices under the trade name T 805; - TiO2 treated with polydimethylsiloxane, particularly the product sold by Cardre under the trade name 70250 Cardre UF TiO2SI3; - Anatase / rutile-type TiO2 treated with polydimethylhydrogensiloxane, particularly the product sold by Color Techniques under the trade name Microtitanium Dioxide USP Grade Hydrophobic.

[0052] 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 triglycerides.

[0053] The oily dispersion of titanium dioxide particles may also contain one or more dispersants, such as sorbitan esters, such as sorbitan isostearate, or fatty acid esters of polyoxyalkylene-modified glycerol, such as triPPG-3 myristyl citrate, and polyglyceryl-3 polyricinoleate. Preferably, the oily dispersion of titanium dioxide particles contains at least one dispersant selected from fatty acid esters of polyoxyalkylene-modified glycerol. More specifically, examples include oily dispersions (INCI names: titanium dioxide, tri-PPG-3 myristyl ether citrate, polyglyceryl-3 ricinoleate, and sorbitan isostearate) obtained by dispersing manganese-doped TiO2 particles in caprylic / capric triglyceride in the presence of triPPG-3 myristyl citrate and polyglyceryl-3 polyricinoleate, as well as sorbitan isostearate), particularly the product sold by Croda under the trade name Optisol TD50.

[0054] Uncoated titanium oxide pigments are sold, for example, by Teika Corporation under the trade names Microtitanium Dioxide MT 500 B or Microtitanium Dioxide MT 600 B, by Degussa under the name P 25, by Wackher under the name Transparent titanium oxide PW, by Miyoshi Kasei Co., Ltd. under the name UFTR, by Tomen Corporation under the name ITS, and by Tioxide under the name Tioveil AQ.

[0055] According to certain embodiments of the present invention, titanium dioxide nanoparticles will be utilized.

[0056] According to a preferred embodiment, the number-mean primary particle size of the titanium dioxide particles, as determined by a transmission electron microscope (TEM) or scanning electron microscope (SEM), is less than 100 nm, preferably less than 50 nm.

[0057] By optionally including larger-sized titanium dioxide in combination with iron oxide in this composition, taking advantage of its whitening properties, it is also possible to obtain a lightly tinted foundation-type product or a concealer product that whitens the skin.

[0058] Titanium dioxide is present in the composition according to the present invention in an amount of 5% by mass or more, preferably 10% by mass or more, and more preferably 15% by mass or more, based on the total mass of the composition.

[0059] According to a particular embodiment of the present invention, titanium dioxide is present in an amount ranging from 5% to 25% by mass, preferably 10% to 20% by mass, and more preferably 12% to 18% by mass, based on the total mass of the composition.

[0060] According to a particular embodiment of the present invention, the composition contains an organic UV shielding agent in an amount of less than 5% by mass, preferably less than 2% by mass, based on the total mass of the composition. Advantageously, the composition according to the present invention does not contain an organic UV shielding agent.

[0061] According to other specific embodiments of the present invention, the composition contains an inorganic UV shielding agent other than titanium dioxide in an amount of less than 5% by mass, preferably less than 2% by mass, based on the total mass of the composition. Advantageously, the composition according to the present invention does not contain an inorganic UV shielding agent other than titanium dioxide.

[0062] α-Cyanodiphenyl acrylate derivatives This composition is represented by the following formula (I): [ka] (In the formula, R1 and R2 independently represent a hydrogen atom, a linear or branched C1-C30 alkyl group, or a linear or branched C1-C30 alkoxy group; R3 comprises at least one α-cyanodiphenyl acrylate derivative represented by a linear or branched C1-C30, preferably C1-C24, and more preferably C1-12 alkyl group.

[0063] According to a particular embodiment of the present invention, R1 and R2 are independently selected from a hydrogen atom and a linear or branched C1-C30, preferably C1-C8 alkoxy group.

[0064] In a preferred embodiment, one of the R1 and R2 groups represents a hydrogen atom, and the other represents a linear C1-C8, preferably C1-C4, alkoxy group. More preferably, R1 represents a hydrogen atom, and R2 represents a linear C1-C4 alkoxy group, preferably a methoxy group.

[0065] According to other specific embodiments of the present invention, R3 represents a linear or branched C2-C20 alkyl group.

[0066] In a preferred embodiment, R3 represents a branched C3-C10 alkyl group. Preferably, R3 represents a 2-ethylhexyl group.

[0067] An example of an α-cyanodiphenyl acrylate derivative that can be used in connection with the present invention is 2-ethylhexyl 2-cyano-3-(4-methoxyphenyl)-3-phenylpropenoic acid, in which R1 is a hydrogen atom, R2 is a methoxy group, R3 is a 2-ethylhexyl group, and the INCI name is ethylhexyl methoxycrylene, for example, Solastay® R1, a product sold by The Hallstar Company.

[0068] The α-cyanodiphenyl acrylate derivative of formula (I) can be present in the composition according to the present invention at a concentration of 0.5% by mass or more, preferably 2% by mass or more, and more preferably 3% by mass or more, based on the total mass of the composition.

[0069] According to a particular embodiment, the α-cyanodiphenyl acrylate derivative of formula (I) may be present in the composition according to the present invention at a concentration of 0.5% to 5% by mass, preferably 2% to 4% by mass, and more preferably 2.5% to 3.5% by mass, based on the total mass of the composition.

[0070] 4-Hydroxybenzylidenemalonate or 4-hydroxycinnamate derivative This composition is given by the following formula (II): [ka] (In the formula, A is a UV-absorbing chromophore group containing two monovalent groups having carbonyl functional groups; R4 represents a hydrogen atom, a linear or branched C1-C8 alkyl group, or a linear or branched C1-C8 alkoxy group; R5 comprises at least one 4-hydroxybenzylidenemalonate or 4-hydroxycinnamate derivative (where R5 represents a hydrogen atom or a linear or branched C1-C8 alkyl group).

[0071] According to a particular embodiment of the present invention, the following formula (IIa): [ka] (In the formula, R4 represents a hydrogen atom, a linear or branched C1-C8 alkyl group, or a linear or branched C1-C8 alkoxy group; R5 represents a hydrogen atom or a linear or branched C1-C8 alkyl group; R6 is selected from -C(O)CH3, -CO2R8, -C(O)NH2, and -C(O)N(R9)2; R7 is a straight chain or branched C1~C 30 Represents an alkyl group; R8 is a straight chain or branched C1~C 20 Represents an alkyl group; Each R9 independently represents a linear or branched C1-C8 alkyl group; A compound of X (where X represents O or NH) will be used.

[0072] Among these compounds, the following formulas (IIb) or (IIc) are preferred: [ka] (In the formula, R6 represents -CO2R8; R7 represents a linear or branched C1-C8 alkyl group; R8 represents a linear or branched C1-C8 alkyl group; A compound of X (where X represents O) will be used.

[0073] Examples of compounds of formula (II) that can be used include ethyl α-cyano-3,5-dimethoxy-4-hydroxycinnamate, ethyl α-acetyl-3,5-dimethoxy-4-hydroxycinnamate, isopropyl α-acetyl-3,5-dimethoxy-4-hydroxycinnamate, isoamyl α-acetyl-3,5-dimethoxy-4-hydroxycinnamate, 2-ethylhexyl α-acetyl-3,5-dimethoxy-4-hydroxycinnamate, and 3,5-dimethoxy-4-hydroxybenzylidenmalone. Examples include diethyl acid, bis(2-ethylhexyl) 3,5-dimethoxy-4-hydroxybenzylidenemalonate, diisoamyl 3,5-dimethoxy-4-hydroxybenzylidenemalonate, didodecyl 3,5-dimethoxy-4-hydroxybenzylidenemalonate, dipalmitoyl 3,5-dimethoxy-4-hydroxybenzylidenemalonate, diisopropyl 3,5-dimethoxy-4-hydroxybenzylidenemalonate, and diethylhexylsyringylidene malonate.

[0074] In particular, the following formula: [ka] Diethylhexyl syringylidenemalonate (INCI name: Diethylhexyl Syringylidenemalonate), for example, a product marketed by Merck under the trade name Oxynex ST, containing 90% of the active substance in tri(caprylic / capric acid) glyceryl, would likely be used.

[0075] The 4-hydroxybenzylidenemalonate or 4-hydroxycinnamate derivative of formula (II) may be present in the composition according to the present invention at a concentration of 0.5% by mass or more, preferably 1.5% by mass or more, and more preferably 2.5% by mass or more, based on the total mass of the composition.

[0076] According to certain embodiments, the 4-hydroxybenzylidenemalonate or 4-hydroxycinnamate derivative of formula (II) may be present in the composition according to the present invention at a concentration of 0.5% to 5% by mass, preferably 2% to 4% by mass, and more preferably 2.5% to 3.5% by mass, based on the total mass of the composition.

[0077] Provided form The composition according to the present invention may be in the form of an aqueous solution, an aqueous gel, an anhydrous product, or an oil-in-water or water-in-oil emulsion.

[0078] The amount of the oily phase is generally in the range of 1% to 100% by mass, preferably 5% to 90% by mass, and more preferably 10% to 80% by mass, relative to the total mass of the composition.

[0079] According to a first specific embodiment, the composition according to the present invention is aqueous and is in the form of an aqueous solution or an aqueous gel.

[0080] For the purposes of this invention, the term "aqueous" refers to a composition containing a fatty phase in an amount of less than 5% by mass, preferably less than 2% by mass, relative to the total mass of the composition. Advantageously, the composition according to the present invention is basically aqueous, i.e., does not contain a fatty phase.

[0081] According to a second specific embodiment, the composition according to the present invention is anhydrous.

[0082] The term "anhydrous" specifically means that, while it is preferable that water is not intentionally added to the composition, trace amounts of water may be present in the various compounds used in the composition.

[0083] According to a third specific embodiment, the composition according to the present invention is in the form of an oil-in-water emulsion (also known as a direct emulsion, or abbreviated as O / W emulsion) comprising droplets of oil dispersed in a continuous aqueous phase.

[0084] According to a fourth specific embodiment, the composition according to the present invention is in the form of a water-in-oil emulsion (also known as a reverse emulsion, or abbreviated as W / O emulsion) comprising droplets of an aqueous phase dispersed in a continuous oily phase.

[0085] Preferably, the composition according to the present invention is in the form of a water-in-oil emulsion.

[0086] aqueous phase The compositions according to the present invention preferably comprise at least one aqueous phase.

[0087] The aqueous phase comprises water and optionally at least one water-soluble or water-miscible organic solvent.

[0088] Suitable aqueous phases for use in the present invention may include, for example, water selected from natural spring water or floral water such as water from La Roche-Posay, water from Vittel, or water from Vichy.

[0089] Suitable water-soluble or water-miscible solvents for use in the present invention include short-chain monoalcohols, such as C1-C4 monoalcohols like ethanol or isopropanol; diols or polyols such as ethylene glycol, 1,2-propylene glycol, 1,3-butylene glycol, hexylene glycol, diethylene glycol, dipropylene glycol, 1,3-propanediol, pentylene glycol, hexylene glycol, caprylyl glycol, glycerol (glycerin), and sorbitol; ethers such as 2-ethoxyethanol, diethylene glycol monomethyl ether, and triethylene glycol monomethyl ether; and mixtures thereof.

[0090] In preferred embodiments, more specifically, ethanol, propylene glycol, glycerol, 1,3-propanediol, or mixtures thereof can be used.

[0091] According to certain embodiments of the present invention, the aqueous phase accounts for 10% to 90% by mass, preferably 20% to 70% by mass, and more preferably 30% to 50% by mass, based on the total mass of the composition.

[0092] oily phase The composition according to the present invention may include at least one oily phase.

[0093] For the purposes of this invention, the term "oily phase" means a phase comprising at least one oil and any lipid-soluble and lipophilic components and fatty substances used to formulate the composition of this invention.

[0094] The term "oil" refers to any fatty substance that is in liquid form at room temperature (20-25°C) and atmospheric pressure (760 mmHg). Suitable oils for use in this invention may be volatile or non-volatile.

[0095] This oil can be selected from hydrocarbon oils, silicone oils, fluorinated oils, and mixtures thereof. Suitable hydrocarbon oils for use in the present invention may be animal hydrocarbon oils, vegetable hydrocarbon oils, mineral hydrocarbon oils, or synthetic hydrocarbon oils. Advantageously, suitable oils for use in the present invention can be selected from inorganic hydrocarbon oils, vegetable hydrocarbon oils, synthetic hydrocarbon oils, silicone oils, and mixtures thereof.

[0096] For the purposes of this invention, the term "silicone oil" means an oil containing at least one silicon atom, and in particular, at least one Si-O group.

[0097] The term "hydrocarbon oil" primarily refers to oils that contain hydrogen and carbon atoms.

[0098] The term "fluorinated oil" refers to an oil that contains at least one fluorine atom.

[0099] Hydrocarbon oils suitable for use in the present invention may optionally contain oxygen atoms, nitrogen atoms, sulfur atoms, and / or phosphorus atoms, for example, in the form of hydroxyl, amine, amide, ester, ether, or acidic groups, particularly in the form of hydroxyl, ester, ether, or acidic groups.

[0100] For the purposes of this invention, the term "volatile oil" means an oil that, upon contact with skin or keratin fibers, can evaporate in less than one hour at room temperature and atmospheric pressure. The volatile oil of this invention is liquid at room temperature and at room temperature and atmospheric pressure, particularly 0.13 Pa to 40000 Pa (10 -3 It is a volatile cosmetic oil whose vapor pressure is not zero in the range of ~300 mmHg, particularly in the range of 1.3 Pa to 13000 Pa (0.01 to 100 mmHg), and more specifically in the range of 1.3 Pa to 1300 Pa (0.01 to 10 mmHg).

[0101] The term "non-volatile oil" refers to an oil that remains on the skin or keratin fibers for at least several hours at room temperature and atmospheric pressure, particularly with a vapor pressure of 10. -3 This refers to oil with a pH of less than mmHg (0.13 Pa).

[0102] hydrocarbon oils Examples of non-volatile hydrocarbon oils that can be used in accordance with the present invention include, in particular, those listed below. (i) Hydrocarbon oils of plant origin, such as glyceride triesters (generally triesters of fatty acids and glycerol, the fatty acids having chain lengths that can vary between C4 and C24, and these chains may be straight or branched, saturated or unsaturated). These oils include, in particular, wheat germ oil, sunflower oil, grape seed oil, sesame seed oil, corn oil, apricot oil, castor oil, shea butter oil, avocado oil, olive oil, soybean oil, sweet almond oil, palm oil, rapeseed oil, cottonseed oil, hazelnut oil, macadamia oil, jojoba oil, alfalfa oil, poppy oil, pumpkin oil, sesame seed oil, mallow oil, rapeseed oil, blackcurrant seed oil, evening primrose oil, millet oil, barley oil, quinoa seed oil, rye oil, safflower oil, candlenut oil, passionflower oil, and rosehip oil; or tri(caprylic / capric acid)glyceride, for example, those sold by Stearinerie Dubois, or by Sasol under the names Miglyol 810, 812, and 818; (ii) Synthetic ethers containing 10 to 40 carbon atoms; (iii) Straight-chain or branched hydrocarbons of mineral or synthetic origin, such as petrolatum, polydecene, hydrogenated polyisobutene such as Parleam, squalane, and mixtures thereof; (iv) Synthetic esters, for example, oils of formula RCOOR' (wherein R represents a linear or branched fatty acid residue containing 1 to 40 carbon atoms, and R' represents a particularly branched hydrocarbon chain containing 1 to 40 carbon atoms, provided that R+R' is >10), for example, parcelin oil (cetostearyl octanonate), isopropyl myristate, isopropyl palmitate, alkyl benzoates (C12-C15), for example, products sold by Innospec Active Chemicals under the trade names Finsolv TN or Witconol TN, or by Evonik Goldschmidt under the trade name Tegosoft TN, 2-ethylphenyl benzoate, for example, X-Tend from ISP. Products marketed under the name 226, isopropyl lanolinate, hexyl laurate, diisopropyl adipate, isononyl isononanoate, oleyl erucate, 2-ethylhexyl palmitate, isostearyl isostearate, diisopropyl sebacate, for example, products sold by Stearinerie Dubois under the name Dub Dis, octanoates, decanoates, or ricinoleates of alcohols or polyalcohols, for example, propylene glycol dioctanoate; hydroxylated esters, for example, isostearyl lactate or diisostearyl malate; and pentaerythritol esters; citrate or tartaric acid esters, for example, di(linear C12-C13 alkyl) tartrate, for example, those sold by Sasol under the name Cosmacol ETI, and di(linear C14-C15 alkyl) tartrate, for example, Cosmacol Products sold by the company under the name ETL; acetate; (v) Fatty alcohols that are liquid at room temperature and have branched and / or unsaturated carbon chains containing 12 to 26 carbon atoms, such as octyldodecanol, isostearyl alcohol, oleyl alcohol, 2-hexyldecanol, 2-butyloctanol, or 2-undecylpentadecanol; (vi) higher fatty acids, such as oleic acid, linoleic acid, or linolenic acid; (vii) Carbonates, for example, dicaprylyl carbonate, for example, a product sold by BASF under the name Cetiol CC; (viii) Fatty amides, for example, N-lauroyl sarcosin isopropyl, for example, the product sold by Ajinomoto Co., Inc. under the trade name Eldew SL 205, and mixtures thereof.

[0103] Among the non-volatile hydrocarbon oils that can be used in accordance with the present invention, glyceride triesters, particularly caprylic / capric triglyceride, synthetic esters, particularly isononyl isononanoate, diisopropyl sebacate, alkyl (C12-15) benzoate, 2-ethylphenyl benzoate, and fatty alcohols, particularly octyldodecanol, are preferred.

[0104] Examples of volatile hydrocarbon oils that can be used in accordance with the present invention include hydrocarbon oils having 8 to 16 carbon atoms, particularly branched C8 to C16 alkanes, such as petroleum-derived C8 to C16 isoalkanes (also known as isoparaffins), such as isododecane (also known as 2,2,4,4,6-pentamethylheptane), isodecane or isohexadecane, oils sold under the trade names Isopar or Permethyl, branched C8 to C16 esters, isohexyl neopentanoate, and mixtures thereof.

[0105] Other examples include alkanes (mixtures of different alkanes with at least one different number of carbon atoms) described in Cognis' patent application brochure International Publication No. 2007 / 068 371 or International Publication No. 2008 / 155 059. These alkanes are obtained from fatty alcohols, which themselves are obtained from coconut kernel oil or palm oil. Other examples include the mixture of n-undecane (C11) and n-tridecane (C13) obtained in Examples 1 and 2 of Cognis' patent application brochure International Publication No. 2008 / 155 059.

[0106] In addition to n-dodecane (C12) and n-tetradecane (C14), which are sold by Sasol under the product symbols Parafol 12-97 and Parafol 14-97 respectively, mixtures thereof may also be included.

[0107] Other volatile hydrocarbon-based oils, such as petroleum distillates, particularly those sold under the name Shell Sol by Shell, may also be used.

[0108] According to one embodiment, this volatile oil is selected from volatile hydrocarbon-based oils containing 8 to 16 carbon atoms and mixtures thereof.

[0109] Silicone oil The non-volatile silicone oil can be particularly selected from non-volatile polydimethylsiloxane (PDMS), polydimethylsiloxane containing alkyl or alkoxy groups (each containing 2 to 24 carbon atoms) pendant to and / or located at the ends of the silicone chain, or phenyl silicone, such as phenyltrimethicone, phenyldimethylicone, phenyltrimethylsiloxydiphenylsiloxane, diphenyldimethylicone, diphenylmethyldiphenyltrisiloxane, or 2-phenylethyltrimethylsiloxysilicate.

[0110] Examples of volatile silicone oils include volatile linear or cyclic silicone oils, particularly those having a viscosity of 8 centistokes (8.10×10 -6 m 2The silicones are of a certain type ( / s), and particularly those containing 2 to 7 silicon atoms, and these silicones optionally contain an alkyl or alkoxy group containing 1 to 10 carbon atoms. Examples of volatile silicone oils that can be used in the present invention include, in particular, octamethylcyclotetrasiloxane, decamethylcyclopentasiloxane, dodecamethylcyclohexasiloxane, heptamethylhexyltrisiloxane, heptamethyloctyltrisiloxane, hexamethyldisiloxane, octamethyltrisiloxane, decamethyltetrasiloxane, and dodecamethylpentasiloxane, as well as mixtures thereof.

[0111] General formula (III): [ka] Volatile linear alkyltrisiloxane oils of the formula (wherein R represents an alkyl group containing 2 to 4 carbon atoms, in which one or more hydrogen atoms may be replaced by fluorine or chlorine atoms) can also be mentioned.

[0112] Among oils of general formula (III), this corresponds to oils of general formula (III) where R is a butyl group, a propyl group, or an ethyl group, respectively: Examples include 3-butyl-1,1,1,3,5,5,5-heptamethyltrisiloxane, 3-propyl-1,1,1,3,5,5,5-heptamethyltrisiloxane, and 3-ethyl-1,1,1,3,5,5,5-heptamethyltrisiloxane.

[0113] Fluorine-based oils Volatile fluorinated oils such as nonafluoromethoxybutane, decafluoropentane, tetradecafluorohexane, dodecafluoropentane, and mixtures thereof may also be used.

[0114] The oily phase may also contain other fatty substances. Other fatty substances that may be present in the oily phase include, for example: - Fatty acids containing 8 to 30 carbon atoms, such as stearic acid, lauric acid, palmitic acid, and oleic acid, selected from these; - Waxes selected from lanolin, beeswax, carnauba or candelilla wax, rice bran wax, paraffin wax, montan wax, microcrystalline wax, ceresin or ozokerite, or synthetic waxes, such as polyethylene wax or Fischer-Tropsch wax; - Rubber selected from silicone rubber (dimethiconol); - Paste-like compounds, such as polymeric or non-polymeric silicone compounds, esters of glycerol oligomers, arachidyl propionate, fatty acid triglycerides and their derivatives; - and mixtures thereof.

[0115] Preferably, the oily phase accounts for 5% to 95% by mass, preferably 10% to 80% by mass, and more preferably 20% to 50% by mass, based on the total mass of the composition.

[0116] High-efficiency enhancer The compositions according to the present invention may also optionally include one or more high-efficiency enhancers.

[0117] For the purposes of this application, the term "high-efficiency enhancer" means a raw material that does not block UV radiation itself but can enhance the shielding performance of the composition of the present invention.

[0118] Examples of high-efficiency enhancers include styrene-acrylate copolymer particles, such as those sold by Dow Chemicals under the name Sunspheres Powder; waxes, such as polymethylene wax (Cirebelle 303 sold by Cirebelle); lipophilic gelling polymers, such as semi-crystalline polyacrylates sold under the names Interlimer IPA 13-1, Interlimer IPA 13-6, or Uniclear 100 VG; and mixtures thereof.

[0119] Insoluble particles The composition according to the present invention may optionally include one or more types of insoluble particles that do not have UV shielding properties or high-efficiency enhancement properties.

[0120] These particles enable the composition to acquire excellent functional or optical properties after being applied to the skin.

[0121] These particles can be selected from nylon, e.g., Orgasol 2002 sold by Arkema; ​​polymethylsilsesquioxane, e.g., methylsilsesquioxane resin microbeads sold by Momentive Performance Materials under the name Tospearl 145A; polymethyl methacrylate, e.g., hollow PMMA spheres sold by Sensient under the name Covabeads LH 85; starch, e.g., corn starch; talc; silica; cross-linked polyacrylate microspheres, e.g., Aquakeep 10 SH-NFC sold by Sumitomo Seika Co., Ltd.; perlite, e.g., Optimat 2550 OR sold by World Minerals; iron oxide pigments or titanium dioxide pigments; and mixtures thereof.

[0122] Preferably, the composition according to the present invention also includes nylon particles such as Orgasol 2002.

[0123] additives The compositions according to the present invention may optionally include one or more additives, different from the compounds of the present invention, that are commonly used in cosmetics, particularly sun protection products, skincare products, and makeup products.

[0124] The aqueous phase may optionally include surfactants; surfactants; salts; organic particles; amphoteric polymers, such as Pemulens TR1 or TR2 or Carbopol ETD2020 sold by Lubrizol; hydrophilic polymers, such as poly(N-vinylpyrrolidone); polysaccharides, such as guar gum, xanthan gum, and cellulosic derivatives; water-soluble or water-dispersible silicone derivatives, such as acrylic silicones, polyether silicones, and cationic silicones; and mixtures thereof.

[0125] Examples of active agents include, in particular, vitamins (A, C, E, K, PP, etc.) and their derivatives, either alone or in mixtures; keratolytics and / or exfoliating agents (salicylic acid and its derivatives, α-hydroxy acids, ascorbic acid and its derivatives); anti-inflammatory agents; sedatives; depigmenting agents; tightening agents such as synthetic polymers; plant proteins; optionally plant-derived polysaccharides in the form of microgels; wax dispersions; colloidal particles of mixed silicates and inorganic fillers; matting agents; agents for preventing hair loss and / or promoting hair growth; anti-wrinkle agents; and mixtures thereof.

[0126] The oily phase may also optionally include lipophilic gelling agents; surfactants; organic or inorganic particles; and mixtures thereof.

[0127] Needless to say, a person skilled in the art would carefully select these or any optional additional compounds such that the intended additions do not adversely affect, or substantially adversely affect, the advantageous properties inherently associated with the composition according to the present invention.

[0128] The additives mentioned above may generally be present in amounts of 0 to 20% by mass relative to the total mass of the composition.

[0129] The subject matter of the present invention also relates to a cosmetic method for treating skin, particularly human skin, against UV radiation, the method comprising applying a composition according to the present invention to the skin.

[0130] Preferably, UV radiation corresponds to solar radiation.

[0131] More specifically, the subject of the present invention is a cosmetic method for limiting skin darkening and / or improving complexion and / or uniformity of complexion, the method comprising applying at least one of the compositions defined above to the surface of the skin.

[0132] The subject matter of the present invention also relates to a non-therapeutic cosmetic method for preventing and / or treating signs of skin aging, which comprises applying at least one of the compositions defined above to the surface of the skin.

[0133] The subject matter of the present invention also relates to the use of the compositions defined above against UV radiation, particularly solar radiation.

[0134] The subject of the present invention also relates to the use of compositions comprising at least one inorganic UV shielding agent selected from titanium dioxide, in combination with an α-cyanodiphenyl acrylate derivative of formula (I) as defined above and a 4-hydroxybenzylidenemalonate or 4-hydroxycinnamate derivative of formula (II), for reducing photoblueing.

[0135] The following embodiments serve to illustrate the present invention, but do not limit its essence. [Examples]

[0136] Unless otherwise specified, quantities are expressed as the mass percentage of the starting material (SM) relative to the total mass of the composition. Compound names are given as chemical names or INCI names.

[0137] Method for preparing an emulsion Mix the components of the fatty phase without heating. Add titanium dioxide and homogenize the mixture until a uniform mixture is obtained. Mix the components of the aqueous phase without heating. Add the alcohol. The fatty phase and the aqueous phase are emulsified without heating.

[0138] Procedure for evaluating photoblueing The principle of this test consists of exposing the test specimen to an illumination light source whose spectral distribution is well defined and whose emitted energy is well quantified. A commonly used light source is a xenon lamp: - A platinum-plated quartz filter that deflects the direction of infrared radiation and removes it through the top of the device; - And by absorbing short-wavelength ultraviolet light, it is emitted through a glass filter, which makes it possible to simulate the radiation received through a presentation window. Use the CPS Sun-Test device: - Irradiance between 300 and 800 nm from a xenon lamp is 765 W / m². 2 Set to (the value set by the manufacturer); - Separation using optical filters is performed using quartz filters and special glass plates with IR coating.

[0139] Next, observe the color of each flask with the naked eye before and after exposure to light.

[0140] [Table 1]

[0141] [Table 2]

[0142] Composition D according to the present invention, which contains a combination of an α-cyanodiphenyl acrylate derivative (Oxynex ST) and a 4-hydroxybenzylidene malonate or 4-hydroxycinnamate derivative (Solastay S1), does not show significant photoblueing after being exposed to light for 2 hours in a clear glass flask, in contrast to comparative compositions A to C, which either do not contain either the α-cyanodiphenyl acrylate derivative (Oxynex ST) or the 4-hydroxybenzylidene malonate or 4-hydroxycinnamate derivative (Solastay S1), or contain only one of the α-cyanodiphenyl acrylate (Oxynex ST) and the 4-hydroxybenzylidene malonate or 4-hydroxycinnamate derivative (Solastay S1).

[0143] Therefore, by using a combination of α-cyanodiphenyl acrylate derivatives and 4-hydroxybenzylidenemalonate or 4-hydroxycinnamate derivatives, it becomes possible to significantly reduce photoblueing of compositions containing titanium dioxide.

Claims

1. - With at least one inorganic UV shielding agent selected from coated titanium dioxide; - The following equation (I): 【Chemistry 1】 (In the formula, R １ and R ２ Each represents, independently of the other, a hydrogen atom or a linear or branched C1-C30 alkoxy group; R ３ (This represents a linear or branched C1-C30 alkyl group.) with at least one compound of; - The following equation (IIa): 【Chemistry 2】 (In the formula, R4 represents a hydrogen atom, a linear or branched C1-C8 alkyl group, or a linear or branched C1-C8 alkoxy group; R5 represents a hydrogen atom or a linear or branched C1-C8 alkyl group; R6 is selected from -CO2R8; R7 represents a linear or branched C1-C30 alkyl group; R8 represents a linear or branched C1-C20 alkyl group; (X represents O) with at least one compound of; A composition comprising, The compound of formula (I) is present in the composition at a concentration of 0.5% by mass or more relative to the total mass of the composition. The compound of formula (IIa) is present in the composition at a concentration of 0.5% by mass or more relative to the total mass of the composition. The titanium dioxide is present in an amount of 5% by mass or more relative to the total mass of the composition.

2. The composition according to claim 1, wherein the coated titanium dioxide is a pigment that has been surface-treated with a compound to have one or more chemical, electronic, mechanochemical, and / or mechanical properties.

3. The composition according to claim 1 or 2, wherein the titanium dioxide forms particles having a number-mean primary particle diameter of less than 100 nm, as determined by a transmission electron microscope (TEM) or a scanning electron microscope (SEM).

4. In formula (I), R １ and R ２ The composition according to any one of claims 1 to 3, wherein one of the members represents a hydrogen atom and the other represents a linear C1-C8 alkoxy group.

5. In formula (I), R ３ The composition according to any one of claims 1 to 4, wherein is a linear or branched C2 to C20 alkyl group.

6. In formula (I), R ３ The composition according to any one of claims 1 to 5, wherein is a branched C3 to C10 alkyl group.

7. The composition according to any one of claims 1 to 6, wherein the compound of formula (I) is 2-ethylhexyl 2-cyano-3-(4-methoxyphenyl)-3-phenylpropenoic acid (INCI name: ethylhexyl methoxycrylene).

8. The composition according to any one of claims 1 to 7, wherein the compound of formula (I) is present at a concentration of 2% by mass or more relative to the total mass of the composition.

9. The compound of formula (IIa) is either of the following formulas (IIb) or (IIc): 【Transformation 3】 【Chemistry 4】 (In the formula, R ６ represents -CO ２ R ８ ; R ７ C is a linear or branched C １ ~C ８ Represents alkyl; R ８ C is a linear or branched C １ ~C ８ Represents alkyl; (X represents O) A composition according to any one of claims 1 to 8, selected from the compounds.

10. The composition according to any one of claims 1 to 9, wherein the compound of formula (IIa) is selected from diethyl 3,5-dimethoxy-4-hydroxybenzylidenemalonate, bis(2-ethylhexyl) 3,5-dimethoxy-4-hydroxybenzylidenemalonate, diisoamyl 3,5-dimethoxy-4-hydroxybenzylidenemalonate, didodecyl 3,5-dimethoxy-4-hydroxybenzylidenemalonate, dipalmitoyl 3,5-dimethoxy-4-hydroxybenzylidenemalonate, diisopropyl 3,5-dimethoxy-4-hydroxybenzylidenemalonate, and diethylhexylsyringylidene malonate.

11. The composition according to any one of claims 1 to 10, wherein the compound of formula (IIa) is diethylhexyl syringylidene malonate (INCI name: Diethylhexyl syringylidene malonate).

12. The composition according to any one of claims 1 to 11, wherein the compound of formula (IIa) is present at a concentration of 1.5% by mass or more relative to the total mass of the composition.

13. The composition according to any one of claims 1 to 12, wherein the amount of the organic UV shielding agent is less than 5% by mass of the total mass of the composition.

14. The composition according to any one of claims 1 to 13, wherein the amount of an inorganic UV shielding agent other than titanium dioxide is less than 5% by mass of the total mass of the composition.

15. The composition according to any one of claims 1 to 14, wherein the ultraviolet protection factor (SPF) value is at least 30.

16. A cosmetic method for treating the skin to protect it from UV radiation, comprising applying the composition described in any one of claims 1 to 15 to the skin.

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