Compositions containing a UV-absorbing system including a physical UV-attenuating material and a flavone
The combination of physical UV attenuating materials and flavones in sunscreen compositions addresses the challenge of achieving high UV protection without greasiness or whitening, providing effective and aesthetically pleasing skin coverage.
Patent Information
- Authority / Receiving Office
- FR · FR
- Patent Type
- Utility models
- Current Assignee / Owner
- LOREAL SA
- Filing Date
- 2024-12-10
- Publication Date
- 2026-06-12
AI Technical Summary
Existing sunscreen compositions struggle to provide high UV protection against both UVA and UVB radiation without being greasy, leaving white marks, and maintaining a pleasant texture.
Compositions comprising a UV-absorbing system with a physical ultraviolet attenuating material and flavones, formulated to be non-greasy and non-bleaching, enhancing UV efficiency and maintaining skin appearance.
The compositions achieve high UV protection with balanced UVA and UVB efficacy, maintaining a pleasant texture and avoiding white marks, while ensuring long-lasting color stability.
Abstract
Description
Title of the invention: Compositions containing a UV-absorbing system comprising a material UV ATTACHMENT PHYSICS AND A FLAVONE FIELD OF INVENTION
[0001] This disclosure relates to compositions comprising a UV-absorbing system including at least one physical ultraviolet (UV) attenuating material and at least one flavone, as well as methods for making and using such compositions. DISCUSSION OF THE CONTEXT
[0002] Exposure to radiation with wavelengths between 290 nm and 400 nm, known as UV radiation or simply "UVR," is implicated in a number of skin diseases and conditions. Exposure to radiation with wavelengths between 290 and 320 nm, also known as UVB radiation, can lead to numerous adverse changes in the biomechanical properties, appearance, and health of the epidermis, resulting in erythema (sunburn), immediate darkening of the skin, the appearance of wrinkles leading to premature skin aging (i.e., photoaging), and various other skin health problems that may include melanoma or other photocancers of the skin.
[0003] UVA rays with wavelengths between 320 and 400 nm penetrate the skin more deeply than UVB rays. Exposure to UVA rays can cause immediate and persistent tanning of the skin, as well as other changes in skin texture or appearance. Daily exposure to UVA rays, even for a short period under normal conditions, can damage collagen and elastin fibers, resulting in changes in the skin's microrelief, the appearance of wrinkles, and uneven pigmentation (spots, uneven skin tone).
[0004] Numerous studies show the need for effective protection against UVA and UVB to prevent sunburn, photoaging and other skin conditions or diseases related to UVR exposure.
[0005] In order to obtain a product with high protection against UVR, it is generally necessary to combine a large number of sunscreens and / or a large quantity of UV filters to achieve high levels of filtration efficiency.
[0006] However, high levels of UV filters do not lend themselves to the easy preparation of stable compositions with a pleasant texture. It is possible to obtain a high UV protection using one or more organic UV filters; however, organic UV filters are often very oily and unpleasant when applied to the skin, especially when used at high levels in a sunscreen formulation required for high UV protection efficacy.
[0007] Mineral UV filters such as titanium dioxide or zinc oxide are alternative UV filters to organic UV filters that can provide more pleasant textures; however, when one or more mineral UV filters are used, the resulting sunscreen formulation is far too whitening (leaving "white streaks") when applied to the skin. When mineral UV filters are used at lower levels, it may be possible to produce sunscreen formulations with little or no whitening when applied to the skin; however, such formulations, containing low levels of mineral UV filters, are unable to produce the desired high levels of UV protection.
[0008] Finally, it can be difficult to combine an organic UV filter and a mineral UV filter in a single composition, especially in order to obtain a non-greasy, pleasant, non-whitening and high UV protection sunscreen formulation, particularly taking into account the need to balance the effectiveness of UVA and UVB protection.
[0009] Potentially relevant art includes:
[0010] US 2020 / 0101002, which relates to mineral sunscreen compositions having improved efficacy, containing (a) one or more mineral UV filtering agents; (b) one or more stilbenoids; (c) ethylhexyl methoxycrylene; (d) diethylhexyl syringylidene malonate; and (e) a cosmetically acceptable carrier;
[0011] US 10,993,897, which relates to a topical formulation containing maqui berry or a maqui berry extract containing anthocyanins having a very high oxygen radical scavenging capacity; and
[0012] US 11,491,226, which relates to novel soluble forms of planar ring-structured organic compounds, including flavonoids, and their production
[0013] There remains a need in the art of improved sunscreen compositions which have high UV protection and balanced UVA and UVB protection, which are not greasy, are pleasant to apply and do not leave white marks when applied to the skin.
[0014] Therefore, one aspect of the present disclosure is a composition that is not greasy, that does not whiten when applied to the skin, and that has high protection against UVR, both against UVA and UVB radiation. Summary of the invention
[0015] This disclosure relates to compositions comprising a UV-absorbing system including at least one physical ultraviolet (UV) attenuating material and at least one flavone. Preferably, the compositions are non-greasy and / or non-bleaching (i.e., the compositions do not leave white residue) upon application.
[0016] This disclosure also relates to processes for the treatment, care, protection, enhancement of appearance and / or makeup of keratinous material, including the application of compositions of this disclosure to keratinous material in sufficient quantity to treat the keratinous material, care for it, enhance its appearance and / or make it up.
[0017] This disclosure also relates to methods of producing non-greasy and / or non-bleaching compositions comprising at least one ultraviolet (UV) attenuating physical material by combining at least one ultraviolet (UV) attenuating physical material and at least one flavone in the compositions during the formation of the compositions to produce non-greasy and / or non-bleaching compositions.
[0018] This disclosure also relates to methods of increasing UV efficiency, preferably of the FPS and / or critical wavelength, of compositions comprising at least one physical ultraviolet (UV) attenuating material, wherein the methods include the addition of at least one flavone during the formation of the compositions.
[0019] It is understood that both the preceding general description and the following detailed description are provided only by way of example and explanation and not as a limitation of disclosure. DETAILED DESCRIPTION OF THE INVENTION
[0020] In the following description and the claims annexed thereto, it shall be understood that the terms used have their ordinary and usual meanings in the art, unless otherwise specified.
[0021] “Approximately”, as used herein, means to within 10% of the stated number (for example, “ "Approximately 10%" means from 9% to 11% and "approximately 2%" means from 1.8% to 2.2%.
[0022] “Film-forming”, “film-forming polymer” or “film-forming agent” as used herein means a polymer or resin that is capable of leaving a film on the substrate to which it is applied, for example, after a solvent accompanying the film-forming agent has evaporated, been absorbed into the substrate and / or dissipated on it.
[0023] “Substitute” as used herein means comprising at least one substitute. Non-exhaustive examples of substituents include atoms, such as atoms oxygen and nitrogen atoms, as well as functional groups, such as hydroxyl groups, ether groups, alkoxy groups, acyloxyalkyl groups, oxyalkylene groups, polyoxyalkylene groups, carboxylic acid groups, amine groups, acylamino groups, amide groups, halogen-containing groups, ester groups, thiol groups, sulfonate groups, thiosulfate groups, siloxane groups, and polysiloxane groups. The substituent(s) may, in addition, be substituted.
[0024] “Volatile”, as used here, means having a flash point of less than about 115 °C.
[0025] “Non-volatile”, as used here, means having a flash point greater than approximately 115 °C.
[0026] “Polymer” as used herein means a compound that is made up of at least two monomers.
[0027] “Exempt” or “substantially exempt” or “devoid of”, as used herein This means that, although it is preferable for no quantity of the specific component to be present in the composition, it is possible for very small quantities of it to be present in the compositions of the disclosure, provided that these quantities do not materially affect at least one, preferably most, of the advantageous properties of the compositions of the disclosure. Thus, for example, "oil-free" means that an effective quantity (i.e., greater than trace amounts) of oil(s) is omitted from the composition (i.e., about 0% by weight), "substantially oil-free" means that one or more oils are present in quantities not exceeding 0.1% by weight, and "oil-free" means that one or more oils are present in quantities not exceeding 0.25% by weight, based on the total weight of the composition.The same nomenclature applies to all other ingredients identified throughout the application and in this paragraph, such as, for example, specific UV filters and / or surfactants (the compositions in the disclosure that are "free of oxybenzone and / or octinoxate," "substantially free of oxybenzone and / or octinoxate," and "devoid of oxybenzone and / or octinoxate," as well as "free of surfactants," "substantially free of surfactants," and "devoid of surfactants" have meanings consistent with the discussion in this paragraph), even if they are not specifically mentioned for each ingredient identified in the application. The examples mentioned of the use of such language as that in this paragraph are intended to be provided by way of example, and not as a limitation.
[0028] “UV Filters” as used herein means the active sunscreen agents approved by a government regulatory agency such as the Food and Drug Administration (FDA) in the United States or the European Commission in Europe and include organic UV filters such as avobenzone, octocrylene, benzophenones, benzotriazoles and merocyanines, as well as physical ultraviolet (UV) attenuation materials.
[0029] “Whitening” or “white marks” as used herein refers to the appearance The visually white appearance of the keratinous substance after application of a composition to the keratinous material compared to the appearance of the keratinous material before application of the composition. A composition is "non-bleaching" if it provides a minimal or no visually white appearance (preferably no visually white appearance) of the keratinous material upon application.
[0030] “Anhydrous” as used here means that the compositions of the disclosure contain less than 3% water, which means that compositions may also contain less than 2% water, and less than 1% water, as well as being "water-free", "substantially water-free" and "water-free", as defined above.
[0031] A “UV-absorbing system containing essentially at least one physical ultraviolet (UV) attenuating material,” as used herein, means that the disclosure compositions contain less than 3% of UV filters other than physical ultraviolet (UV) attenuating materials, in particular less than 3% of organic UV filters, which means that, within the framework of this definition, by way of subcategories, we find compositions containing less than 2% of UV filters other than physical ultraviolet (UV) attenuating materials, in particular less than 2% of organic UV filters, and less than 1% of UV filters other than physical UV attenuating materials, in particular less than 1% of organic UV filters, as well as those “free of UV filters other than a physical ultraviolet (UV) attenuating material,”"substantially free of UV filters other than a physical ultraviolet (UV) attenuating material" and "devoid of UV filters other than a physical ultraviolet (UV) attenuating material" as defined above.
[0032] “System” and “component” are used interchangeably in the present request.
[0033] “Primary particle” as used in relation to the description of the material Ultraviolet (UV) attenuation physics here refers to inorganic or organic particles (structures) that can be held together by molecular or atomic bonding to form an ultraviolet (UV) attenuation physics material.
[0034] “Primary particle size” means the size of a non-aggregated primary particle in a physical material for attenuating ultraviolet (UV).
[0035] “Passive” as used in relation to the description of a physical material Ultraviolet (UV) attenuation here refers to a material that has been treated in a way to ensure that the potential for the release of ionic species when in contact with water is reduced compared to the same non-passivated material.
[0036] “Keratinous materials” or “keratinous substance” means nails (nails of the fingers and / or toes), skin such as the body, face and eye area, scalp, keratinous fibers such as eyelashes, eyebrows and hair and mucous membranes such as lips.
[0037] “Physiologically acceptable” means compatible with keratinous materials and having a pleasant color, smell and feel, and which does not cause unacceptable discomfort (tingling or pulling) likely to discourage a consumer from using the composition.
[0038] “UV protection efficiency” or “filtration efficiency” in the context of This disclosure is evaluated based on one or more of the following: FPS, FPUVA, critical wavelength, and UVA-I / UV ratio.
[0039] The "SPF" (Sun Protection Factor) measures the level of protection against erythema provided by a composition. The SPF value corresponds to the ratio between the minimum erythematous dose (MED) measured on skin covered with the composition and the MED measured on bare skin. The term "SPF" is known in the art of sunscreens and is defined, for example, in "A new substrate to measure sunscreen protection factors throughout the ultraviolet spectrum," J. Soc. Cosmet. Chem., 40, 127-133 (May / June 1989).
[0040] The evaluation of the SPF (Sun Protection Factor) can be carried out, for example, in vitro with a spectrophotometer from Labsphere (North Sutton, NH, USA). In such an evaluation, the plate is the material onto which the composition under test is applied. For such an evaluation, polymethyl methacrylate (PMMA) plates can be used. An example of an acceptable protocol is currently undergoing ISO accreditation under the name ISO Committee Draft 23675.
[0041] The evaluation of the sun protection factor (SPF) can also be performed in vivo in accordance with ISO 24444:2019 “Cosmetics-Sun protection test methods-In-vivo determination of the sun protection factor (SPF).” It can also be determined in accordance with FDA protocols, as described in the document “Labeling and Effectiveness Testing; Sunscreen Drug Products for Over-the-Counter Human Use” published in the U.S. Federal Register on May 7, 2011 (https: / / www.federalregister.gov / d / 2011-14766); 21 CFR Part 352 Subpart D § 352.72, updated and revised by the 2011 publication in the Federal Register.
[0042] “UVA protection factor” refers to an index characterizing the UVA protection provided by a composition. For example, the UPF / VA index can be measured in vivo according to the "PPD" (Persistent Pigment Darkening) method of the protocol ISO-24442:2022, measuring skin color observed 2 to 4 hours after UVA exposure. It can also be determined according to FDA protocols, as described again in 21 CFR Part 352 Subpart D § 352.72 as mentioned above in relation to SPF.
[0043] UVA protection can also be assessed in vitro using the Labsphere® spectrophotometer under conditions such as those mentioned above in relation to the SPF. ISO 24443:2021 describes such an in vitro procedure.
[0044] FDA broad-spectrum test procedures, particularly "critical wavelength" test procedures, are also available in 21 CFR Part 352 Subpart D § 352.72. In addition, broad-spectrum test procedures include the determination of the UVA1 / UV ratio as described in "Sunscreen Drug Products for Over-the-Counter-Human-Use" published in the Federal Register https: / / www.federalregister.gov / documents / 2019 / 02 / 26 / 2019-03019 / sunscreen-drug-products-for-over-the-counter-human-use.
[0045] According to this disclosure, the compositions in this disclosure preferably have one or more of the following properties:
[0046] The compositions have a critical wavelength, as determined by FDA critical wavelength procedures, of at least 370 nm;
[0047] The compositions have an FPS value of at least 15, preferably at least 30, preferably at least 50 and preferably at least 70;
[0048] The compositions have an FPUVA / FPS ratio of at least 1 / 3, and preferably of at least 2 / 5 and / or
[0049] The compositions have a UVA1 / UV ratio of 0.7 or more, preferably 0.75 or more, and preferably 0.8 or more.
[0050] “Makeup result”, as used herein, refers to compositions where The color remains the same or substantially the same as at the time of application, as observed with the naked eye, after a prolonged period. The "makeup result" can be evaluated by assessing the long-lasting properties using any method known in the art for evaluating such properties. For example, long-lasting performance can be assessed by a test involving the application of a composition to a keratinous material such as skin and evaluating the color of the composition after a prolonged period. For example, the color of a composition can be evaluated immediately after application to a keratinous material such as skin, and these characteristics can then be re-evaluated and compared after a certain duration. Furthermore, these characteristics can be evaluated in relation to other compositions, such as commercially available compositions.
[0051] “Natural” as in the expression “natural compound” means any compound derived directly from a natural substance such as a plant without having undergone chemical modification.
[0052] “Compound of natural origin” means any compound derived from a natural compound which has undergone one or more chemical modifications, for example by organic synthesis reaction, without the properties of the natural compound having been modified.
[0053] “Synthetic compound” means any compound that is neither a natural compound nor a composed of natural origin.
[0054] “Room temperature” means approximately 20-25 °C.
[0055] “Atmospheric pressure” means approximately 760 mmHg, i.e. approximately 105 pascals.
[0056] “UV filter” and “sunscreen agent” are used interchangeably in the present request.
[0057] “UV efficiency” and “Efficiency against UV” and “Efficiency of UV protection” " are used interchangeably in this application and refer to the ability to provide protection against UVB radiation, UVA radiation and / or UV radiation (UVR) in general.
[0058] The compositions and methods of the present invention may include, consist of, or consist essentially of the essential elements and limitations of the disclosure described herein, as well as any additional or optional ingredients, components, or limitations described herein or otherwise useful. For example, the UV (ultraviolet) absorbing system of the compositions in the disclosure may "consist essentially of" at least one physical ultraviolet (UV) attenuating material.
[0059] For the purposes of this disclosure, the "fundamental novel property" associated with compositions, components and processes relating to UV protection properties that "consist essentially of" identified ingredients or actions is "UV efficacy".
[0060] For the purposes of this disclosure, the "fundamental novel property" associated with compositions, components and processes relating to properties of the composition when applied to keratinous material which "consist essentially of" identified ingredients or actions is "non-bleaching".
[0061] The compositions of this disclosure may be in any form suitable for use as a personal care composition, such as a stick, paste, cream, anhydrous composition, emulsion (oil-in-water, water-in-oil, multiple emulsion such as water-in-oil-in-water), nanoemulsion, gel, liquid, solid, etc. These compositions may be used for any personal care purpose in cosmetic and / or dermatological products such as, for example, a sunscreen, a foundation complexion products, lip balms, lipsticks, concealers, mascaras, leave-in hair products, eyeshadows, powders, etc.
[0062] Reference is made herein to trade names of materials including, but not limited to, materials such as polymers and optional components. Materials are not intended to be limited by the materials described and referenced herein by a particular trade name. Equivalent materials (for example, those obtained from a different source under a different name or catalogue (reference) number) to those referenced by a trade name may be substituted for and used in the processes described and claimed herein.
[0063] Unless otherwise stated, all percentages and ratios are calculated by weight. Unless otherwise stated, all percentages are calculated relative to the total weight of a composition. All component or composition rates refer to the active rate of that component or composition and are understood to be exclusive of impurities, for example, residual solvents or by-products, which may be present in commercially available sources. COMPOSITION UV attenuating physical material
[0064] According to this disclosure, compositions comprising at least one ultraviolet (UV) attenuating physical material are proposed. "UV attenuating physical material" as used herein refers to solid inorganic ingredients that absorb incoming ultraviolet (UV) light and may optionally scatter incoming ultraviolet (UV) light, when present in the compositions disclosed herein. The physical UV attenuation material preferably comprises one or more metal oxides such as, for example, oxides of titanium, chromium, zinc, tin, alumina, cerium, and / or iron. Specific examples of suitable metal oxide(s) include, but are not limited to, at least one metal oxide selected from the group consisting of titanium dioxide, zinc oxide, iron oxide, chromium oxide, tin oxide, alumina, cerium oxide, and mixtures thereof.
[0065] The UV attenuating physical material may be subjected to a surface treatment agent to improve the sensoriality, performance, and / or compatibility of the compositions disclosed herein. Suitable surface treatment agents may include hydrophobic or hydrophilic surface treatment agents such as, for example, those described in Cosmetics & Toiletries, February 1990, Vol. 105, pp. 53-64, including, but not limited to, specific examples such as amino acids, beeswax, fatty acids, fatty acid salts, fatty alcohols, anionic surfactants, lecithin, lecithin derivatives, metal alkoxides, polyethylene, silicones, Proteins, alkanolamines, silicon oxides, metal oxides, sodium hexametaphosphate, alumina and / or glycerol. Preferably, the physical UV attenuation material is passivated.
[0066] Preferably, the UV attenuation physical material comprises one or more zinc oxides and / or titanium dioxides. Preferably, the UV attenuation physical material comprising one or more zinc oxides and / or titanium dioxides is passivated.
[0067] According to preferred embodiments, the UV attenuating physical material comprises titanium dioxide. The titanium dioxide may be present in any form in the compositions disclosed herein. Furthermore, the TiO2 may be treated (coated) or untreated.
[0068] According to preferred embodiments, the UV attenuating physical material comprises zinc oxide. The zinc oxide may be present in any form (for example, as wurtzite or a zinc mixture) in the compositions disclosed herein. Furthermore, the zinc oxide may be treated (coated) or untreated.
[0069] Preferably, the UV attenuation physical material comprises zinc oxide. Preferably, the zinc oxide is passivated.
[0070] Preferably, the UV attenuation physical material comprises titanium dioxide. Preferably, the titanium dioxide is passivated.
[0071] Preferably, the average primary particle size of the ultraviolet (UV) attenuating material is from 1 nm to 500 nm, preferably from 5 nm to 250 nm, preferably from 10 nm to 100 nm, and preferably from 20 nm to 50 nm, including all intermediate ranges and sub-ranges such as, for example, 25 nm to 40 nm, 10 nm to 75 nm and 15 nm to 150 nm.
[0072] Suitable examples of coated pigments include, but are not limited to, titanium dioxides that have been coated such as titanium dioxides:
[0073] - of hydrated silica, such as Tayca's MT-100WP product,
[0074] - of silica and iron oxide, such as the Sunveil F® product from Ikeda;
[0075] - of silica and alumina, such as Tayca's MT-500SA® and MT-100SA® products and Croda's Tioveil™ AQ-N,
[0076] - of alumina, such as Ishihara's TTO-55 (A)® product,
[0077] - of alumina and aluminum stearate, such as MT-100TV® products, Tayca's MT-100Z® and MT-01®, Croda's Solaveil™ CT 100® and Merck's Eusolex T-AVO®,
[0078] - of silica, alumina and alginic acid, such as Tayca's MT-100AQ® product,
[0079] - of alumina and aluminum laurate,
[0080] - of iron oxide and iron stearate,
[0081] - of zinc oxide and zinc stearate,
[0082] - of silica and alumina and treated with a silicone, such as the products MTY-500SAS® or Microtitanium Dioxide MT-100SAS® from Tayca,
[0083] - of silica, alumina and aluminum stearate and treated with a silicone,
[0084] - of silica and treated with a silicone,
[0085] - of silica and treated with a silicone, such as Ishihara's TTO-55(S)® product;
[0086] - of triethanolamine,
[0087] - of stearic acid, such as Ishihara's TTO-55 (C)® product,
[0088] - of sodium hexametaphosphate,
[0089] - with octyltrimethylsilane,
[0090] - with a polydimethylsiloxane, with anatase / rutile TiO2 treated with a polydimethylhydrogenosiloxane
[0091] - with triethylhexanoin, with aluminium stearate and with alumina sold under the trade name Solaveil™ CT-200 by Croda,
[0092] - with aluminum stearate, with alumina and with silicone, marketed under the trade name Solaveil™ CT-12W by Croda,
[0093] - with lauroyl lysine and / or
[0094] - with C9-Ci5 fluoroalcohol phosphate and with aluminium hydroxide.
[0095] Other examples include TiO2 pigments doped with at least one transition metal such as iron, zinc, or manganese, preferably manganese. Preferably, the doped pigments are in the form of an oily dispersion. The oil in the oily dispersion is preferably selected from triglycerides such as, for example, capric / caprylic acids. The oily dispersion of titanium dioxide particles may also include one or more dispersants, for example, a sorbitan ester, such as sorbitan isostearate, or a polyoxyalkylated fatty acid ester of glycerol, such as tri-PPG-3 myristylether citrate and polyglyceryl-3 polyricinoleate. Preferably, the oily dispersion of titanium dioxide particles includes at least one dispersant selected from polyoxyalkylated fatty acid esters of glycerol.One example is the oily dispersion of manganese-doped TiO2 particles in capric / caprylic acid triglyceride in the presence of tri-PPG-3 myristyl ether citrate and polyglyceryl-3 polyricinoleate and sorbitan isostearate, having the INCI name: titanium dioxide (and) TRLPPG-3 myristyl ether citrate (and) polyglyceryl-3 ricinoleate (and) sorbitan isostearate, for example the product sold under the trade name Optisol™ OTP-1 by Croda.
[0096] Suitable uncoated titanium oxide includes, but is not limited to, those sold by Tayca under the trade names MT-500B or MT-600B®, or by Evonik under the name Degussa P 25.
[0097] Appropriate examples of uncoated zinc oxide include, but are not limited to, zinc oxide marketed under the name "Z-COTE"® by BASF, zinc oxide marketed under the name "NanoArc® Zinc Oxide" by Nanophase Technologies, zinc oxide marketed under the name "MZ-500", "MZ-300", "MZ-200" or "MZ-150" by TAYCA.
[0098] Treated (coated) zinc oxide compounds are compounds that have undergone one or more surface treatments of a chemical, electronic, mechanochemical and / or mechanical nature with compounds such as described, for example, in Cosmetics & Toiletries, February 1990, Vol. 105, pp. 53-64, such as amino acids, beeswax, fatty acids, fatty alcohols, anionic surfactants, lecithins, sodium, potassium, zinc, iron or aluminum salts of fatty acids, metal alkoxides (titanium or aluminum), polyethylene, silicones, hydrated silica, proteins (collagen, elastin), alkanolamines, silicon oxides, triethoxycaprylylsilane, metal oxides or sodium hexametaphosphate.
[0099] Examples of suitable coated zinc oxide include, but are not limited to, polymethylhydrogenosiloxane-coated zinc oxide; zinc oxide dispersed in Cl2-15 alkyl benzoate (INCI: Zinc Oxide (and) Cl2-15 Alkyl Benzoate (and) Polyhydroxystearic Acid (and) Isostearic Acid), marketed by Croda under the trade name Solaveil CZ-100; zinc oxide dispersions in C9-12 alkane with a dispersing agent, marketed under the trade name "DAITOPERSION Zn-60VA"® by Daito Kasei; silicone-grafted acrylic polymer-coated ZnO dispersed in cyclodimethylsiloxane, marketed under the name "SPD-Z5®" by Shin-Etsu; ZnO coated with hydrated silica, marketed by TAYCA under the name "MZ-500HP"; ZnO coated with hydrated silica, triethoxysilylethyl polydimethylsiloxyethyl hexyl dimethicone and hydrogenodimethicone (H-Me-Si), marketed by TAYCA under the name MZ-510 HPSX;stearic acid-coated or isostearic acid-coated ZnO, such as those marketed by TAYCA under the name "MZ-505T", "MZY-505EX" or "MZY-304EX"; silicone oil-coated ZnO, such as those marketed by TAYCA under the name "MZX-510HPS", "MZY-505S", "MZY-510M3S", "MZ-505M", "MZY-303S", "MZY-303M", "MZY-203S", "MZY-210M3S" or "MZY-153S"; triethoxycaprylylsilane coated ZnO, such as those marketed by BASF under the name Z-COTE HP1, or by TAYCA under the name "MZX-508OTS", "MZY-203OTS" or "MZX-304OTS" or by DSM; under the name PARSOL ZX; for example: ZnO marketed under the brand name "Zinc Oxide CS-5" by Toshiba (ZnO coated with polymethylhydrosiloxane); ZnO marketed under the brand name "Nanogard Zinc Oxide FN" by Nanophase Technologies (as a 40% dispersion in Finsolv TN, C12-C15 alkyl benzoate); ZnO marketed under the brand names "Daitopersion Zn-30" and "Daitopersion Zn-50" by Daito (dispersions in polydimethylsiloxane / oxyethylenated cyclopolymethylsiloxane comprising 30% or 50% of zinc nanooxides coated with silica and polymethylhydrosiloxane); ZnO marketed under the brand name "NFD Ultrafine ZnO" by Daikin (ZnO coated with perfluoroalkyl phosphate and a perfluoroalkylethyl copolymer dispersed in cyclopentasiloxane); ZnO marketed under the brand name "SPD-Z1" by Shin-Etsu (ZnO coated with a silicone-grafted acrylic polymer dispersed in cyclodimethylsiloxane);ZnO marketed under the brand name "Escalol Z100" by ISP (alumina-treated ZnO dispersed in an ethylhexyl methoxycinnamate / PVP-hexadecene methicone copolymer mixture); ZnO marketed under the brand name "Fuji ZnO-SMS-10" by Fuji Pigment (ZnO coated with silica and polymethylsilsesquioxane); and ZnO marketed under the brand name "Nanox Gel TN" by Elementis (ZnO dispersed at 55% in C12-C15 alkyl benzoate with hydroxystearic acid polycondensate); ZnO marketed under the brand name Finex by SAKAI such as FINEX-50LP, FINEX-50S-LP2 and FINEX-30S-LPT (ZnO coated with hydrogenodimethicone); FINEX-33W (coated ZnO of hydrated silica), FINEX-52W-LP2 and FINEX-33W-LP2 (ZnO coated with hydrogenodimethicone and hydrated silica), FINEX-50-OTS and FINEX-30-OTS (ZnO coated with triethoxycaprylysilane). ;
[0100] Preferred zinc oxide coatings preferably comprise one or more of the following: hydrated silica, triethoxysilylethyl polydimethylsiloxyethyl, hexyl dimethicone, hydrogenodimethicone and / or triethoxycaprylysilane.
[0101] According to preferred embodiments of this disclosure, zinc oxide may be in the form of wafers, and may be coated or uncoated. Suitable examples of such forms are sold by Croda under the name Solaveil (MicNo), such as Solaveil MXP3, MZP7, MZP8, MZ3-100, MZ3-300, and MZ7-100. Preferably, the zinc oxide wafers useful according to this disclosure (1) have a median specific area of more than 25 square meters per gram, preferably greater than 30 square meters per gram, and / or (2) are transparent (i.e., transmission >30% at 600 nm). Suitable examples of such wafer forms may also be found in US Patent 11,608,275.
[0102] Suitable examples of other coated oxides include, but are not limited to, coated oxides preferably having amphiphilic properties such as:
[0103] - titanium oxides coated with cetyl phosphate and silica, such as the product " Eusolex® T-EASY” from Merck;
[0104] - titanium oxides coated with polyglyceryl-10 oleate and stearic acid, such as as “MTY-200STW” from Tayca;
[0105] - zinc oxides coated with polyglyceryl-10 oleate and isostearic acid, such as as “MZY-505EXW” from Tayca;
[0106] - titanium oxides coated with polysorbate 80 and isostearic acid, such as " Tayca's MT-10EXW; and
[0107] - zinc oxides coated with polysorbate 80 and isostearic acid, such as " Tayca's MZY-304EXW.
[0108] Preferably, the at least one ultraviolet (UV) attenuating physical material is present in the compositions of this disclosure in an amount of at least 5% by weight, preferably at least about 10% by weight, preferably at least about 12% by weight, preferably at least about 14% by weight, and preferably at least about 15% by weight, the upper end of the range of the at least one ultraviolet (UV) attenuating physical material present being preferably about 40% by weight (e.g., about 5 to 40%, about 10 to 40%, about 12 to 40%, etc.), preferably about 30% by weight (e.g., about 5 to 30%, about 10 to 30%, about 12 to 30%, etc.), preferably about 25% by weight (e.g., about 5 to 25%, about 10 to 25%, about 12 to 25%, etc.), and preferably about 20% by weight (for example, about 5 to 20%, about 10 to 20%, about 12 to 20%, etc.), all weights being based on the total weight of the composition.
[0109] According to preferred embodiments, the compositions of this disclosure contain a UV-absorbing system comprising essentially one or more ultraviolet (UV) attenuating physical material(s) as defined above. Flavone
[0110] According to this disclosure, compositions comprising at least one flavone are proposed. In preferred embodiments, the at least one flavone is present in compositions of this disclosure in an amount that increases the UV, UVA, and / or UVB efficiency of at least one UV attenuating physical material present in the composition.
[0111] Flavones are a class of polyphenols and flavonoids based on the general structure of 2-phenylchromene-4-one and have antioxidant properties. Examples of suitable flavones include, but are not limited to, luteolin, apigenin, and Baicalin and baicalein. Preferably, the compositions of this disclosure include at least one flavone selected from the group consisting of luteolin, baicalin, baicalein and mixtures thereof.
[0112] The flavones of this disclosure may be derived or extracted from plants.
[0113] According to preferred embodiments, the compositions of this disclosure may optionally further comprise at least one other ingredient that also enhances the UV, UVB, and / or UVA efficiency of at least one ultraviolet (UV) attenuating physical material present in the compositions. However, the compositions of this disclosure may also "consist essentially of" or "consist of" flavones for the purpose of enhancing the UV, UVA, and / or UVB efficiency of at least one ultraviolet (UV) attenuating physical material present in the compositions.
[0114] According to preferred embodiments, at least one flavone is present in the compositions of this disclosure in an amount that enhances UV efficiency, an amount that enhances UVA efficiency, and / or an amount that enhances UVB efficiency, such as, for example, from about 0.1% to about 10% by weight relative to the total weight of the composition, from about 0.25% to about 7.5% by weight, from about 0.5% to about 5% by weight, and from about 1% to about 3% by weight, including all intermediate ranges and sub-ranges such as, for example, from about 4.5% to about 10% by weight, and from about 1% to about 5% by weight, from about 2% to about 6% by weight, from about 5.5% to about 8% by weight, from about 1.7% to about 3.9% by weight, etc., all weights being based on the total weight of the composition.
[0115] According to preferred embodiments, at least one ultraviolet (UV) attenuating physical material and at least one flavone are present in the compositions of this disclosure in a weight % ratio of about 40:1 to about 1:10, preferably about 20:1 to about 1:7.5, preferably about 10:1 to about 1:5, and preferably about 6:1 to about 1:1, including all intermediate ranges and sub-ranges, such as, for example, 5:1 to 2:1, 1:2 to 5:1, 8:1 to 1.5:1, 1:1.5 to 1:8, etc., all weights being based on the weight % of ultraviolet (UV) attenuating physical material(s) and the weight % of flavone present in the composition. Preferably, a higher weight % of ultraviolet (UV) attenuating physical material(s) is present in the compositions than of flavone. Polymers and waxes
[0116] According to preferred embodiments of this disclosure, compositions optionally comprising at least one polymer and / or at least one wax are proposed. Appropriate examples of polymers and waxes include, but are not limited to, hydrophilic and / or lipophilic polymers and waxes.
[0117] Appropriate specific examples of polymers include, but are not limited to, bis-Peg-12 dimethicone candelillate, VP eicosene copolymer, tricontanyl / PVP, C30-38 isopropyl olefin / MA maleate copolymer, bis-hydroxyethoxypropyl dimethicone, styrene / acrylates copolymer, PVP / dimethiconylacrylate / polycarbamyl / polyglycol ester / acrylates / methacryloyloxyethyl phosphate copolymer, and mixtures thereof. Preferably, however, the compositions in this disclosure are "substantially free," "free," or "devoid" of styrene / acrylates copolymer.
[0118] Additional examples of waxes include, but are not limited to, hydrocarbon waxes, silicone waxes and / or fluoro waxes, and may be of vegetable, animal, mineral and / or synthetic origin. Examples of hydrocarbon waxes include beeswax, lanolin wax or Chinese insect wax; rice wax, carnauba wax, candelilla wax, ouricury wax, esparto wax, cork fiber wax, sugar cane wax, Japanese wax, laurel berry wax, lacquer wax and sumach wax, helichane annuus (sunflower) seed wax, montan wax, microcrystalline waxes, paraffins, ozokerite, polyethylene waxes, polymethylene waxes, waxes obtained by Fisher-Tropsch synthesis and waxy copolymers, as well as their esters.Examples include beeswax, for example the product sold under the name White beeswax BR G889 by Koster Keunen, carnauba wax, for example sold under the name Cerauba Tl Bio or Cerauba T3 by Baerlocher or under the name Mexoryl SAP by Noveal, Helianthus annuus (sunflower) wax sold under the name Sunflower Wax by Koster Keunen, ORYZA SATIVA (RICE) BRAN WAX, for example sold under the name NC 1710 by Cera Nica Noda, or one of their mixtures. Additional sunscreen agents
[0119] According to preferred embodiments of this disclosure, compositions optionally further comprising at least one additional UV filter (in addition to at least one physical ultraviolet (UV) attenuating material) selected from the group consisting of organic UV filters are provided. However, as noted above, preferred embodiments of this disclosure include compositions of this disclosure containing a UV-absorbing system containing little or no UV filter as defined above.
[0120] The additional organic UV filter(s) may be hydrophilic or lipophilic. “Hydrophilic organic UV filter” means a water-soluble organic UV filter or a water-dispersible organic UV filter (in colloidal form). “Lipophilic organic UV filter” means a UV filter that is dissolved or dispersed in colloidal form in a liquid oil phase.
[0121] Suitable organic UV filters may be selected from the following non-exhaustive list of compounds: cinnamic compounds; anthranilate compounds; para-aminobenzoic acid compounds; salicylic compounds; dibenzoylmethane compounds; camphor compounds; benzophenone compounds; [3,[3-diphenylacrylate] compounds; triazine compounds such as bis-ethylhexyloxyphenol methoxyphenyl triazine; benzotriazole compounds; benzalmalonate compounds, including those cited in US patent 5624663; benzimidazole derivatives; imidazoline compounds; bis-benzoazolyl compounds as described in patents EP669323 and US 2,463,264; the compounds methylene bis(hydroxyphenylbenzotriazole) as described in applications US 5 237 071, US 5 166 355, GB2303549, DE197 26 184 and EP893119; the compounds benzoxazole as described in patent applications EP0832642, EP1027883, EP1300137 and DE10162844;Polymer filters and silicone filters such as those described in particular in application WO 93 / 04665; alkylstyrene-derived dimers such as those described in patent application DE19855649; 4,4-diarylbutadiene compounds such as those described in applications EP0967200, DE19746654, DE19755649, EP-A-1008586, EPI 133980 and EP133981, and mixtures thereof. Preferably, lipophilic organic UV filters are selected from salicylic compounds, dibenzoylmethane compounds, benzylidene camphor compounds; benzophenone compounds; triazine compounds; benzotriazole compounds; as well as other categories of compounds identified herein; and mixtures thereof.
[0122] Specific reference may be made to suitable salicylate compounds including Homosalate (homomentyl salicylate), for example marketed under the brand name "Eusolex HMS" by Rona / EM Industries; and ethylhexyl salicylate, for example marketed under the brand name "Neo Heliopan OS" by Symrise; and glycol salicylate. Other examples of salicylate compounds include phenyl salicylate; dipropylene glycol salicylate, for example marketed under the brand name "Dipsal" by Scher; and TEA salicylate, for example marketed under the brand name "Neo Heliopan TS" by Symrise.
[0123] Examples of suitable [3,[3-diphenylacrylate compounds include Octocrylene, for example marketed under the brand name "Uvinul N539" by BASF; and Etocrylene, for example marketed under the brand name "Uvinul N35" by BASF.
[0124] Suitable anthranilic compounds may include menthyl anthranilates, for example marketed under the brand name "Neo Heliopan MA" by Symrise.
[0125] Examples of dibenzoylmethane compounds include butyl methoxydibenzoylmethane, for example marketed under the brand name "Parsol 1789" by DSM; and isopropyl dibenzoylmethane.
[0126] Suitable cinnamyl compounds include ethylhexyl methoxycinnamate, marketed for example under the brand name "Parsol MCX" by DSM; isopropyl methoxycinnamate; isopropoxyl methoxycinnamate; isoamyl methoxycinnamate, marketed for example under the brand name "Neo Heliopan E 1000" by Symrise; cinoxate (2-ethoxyethyl-4-methoxycinnamate); DEA methoxycinnamate; diisopropyl methylcinnamate; and glyceryl dimethoxycinnamate ethylhexanoate.
[0127] Examples of camphor compounds include benzylidenecamphor derivatives: 3-benzylidene camphor, for example marketed under the brand name "Mexoryl SD" by Chimex; 4-methylbenzylidene camphor, for example marketed under the brand name "Eusolex 6300" by Merck; benzylidene camphor sulfonic acid, for example marketed under the brand name "Mexoryl SL" by Noveal; benzalkonium camphor methosulfate, for example marketed under the brand name "Mexoryl SO" by Noveal; terephthalylidene dicamphre sulfonic acid, for example marketed under the brand name "Mexoryl SX" by Noveal; and polyacrylamidomethyl benzylidene camphor, for example marketed under the brand name "Mexoryl SW" by Noveal.
[0128] Suitable benzophenone compounds include benzophenone-1 (2,4-dihydroxybenzophenone), such as that marketed under the brand name "Uvinul 400" by BASF; benzophenone-2 (tetrahydroxybenzophenone), such as that marketed under the brand name "Uvinul D50" by BASF; benzophenone-3 (2-hydroxy-4-methoxybenzophenone) or oxybenzone, such as that marketed under the brand name "Uvinul M40" by BASF; benzophenone-4 (hydroxymethoxybenzophonene sulfonic acid), such as that marketed under the brand name "Uvinul MS40" by BASF; benzophenone-5 (sodium hydroxymethoxybenzophenone sulfonate); benzophenone-6 (dihydroxy dimethoxybenzophenone), such as that marketed under the brand name "Helisorb 11" by Norquay; benzophenone-8, such as that marketed under the brand name "Spectra-Sorb UV-24" by American Cyanamid;benzophenone-9 (Disodium dihydroxy dimethoxy benzophenonedisulfonate), such as that marketed under the brand name "Uvinul DS-49" by BASF, benzophenone-12 and n-hexyl 2-(4-diethylamino-2-hydroxybenzoyl)benzoate (such as that marketed under the brand name UVINUL A+ by BASF).
[0129] Examples of triazine compounds include 4-bis-{[4-(2-ethylhexyloxy)-2-hydroxy]-phenyl]-6-(4-methoxyphenyl)-1,3,5-triazine (INCI name: Bis-Ethylhexyloxyphenol Methoxyphenyl Triazine (BEMT)), diethylhexyl butamido triazone, such as that marketed under the brand name "Uvasorb HEB" by Sigma 3V; 2,4,6-tris(dineopentyl 4'-aminobenzalmalonate)-s-triazine, bis- ethylhexyloxyphenol methoxyphenyl triazine, such as that marketed under the brand name "TINOSORB S" by BASF, and ethylhexyl triazone, such as that marketed under the brand name "UVTNUL T150" by BASF.
[0130] Suitable benzotriazole compounds include phenylbenzotriazole derivatives: 2-(2H-benzotriazole-2-yl)-6-dodecyl-4-methylpheno, branched and linear, and those described in USP 5240975.
[0131] Suitable benzalmalonate compounds include dineopentyl 4'-methoxybenzalmalonate and polyorganosiloxane comprising benzalmalonate functional groups, such as polysilicone-15, such as that marketed under the brand name "Parsol SLX" by Hoffmann-LaRoche.
[0132] Examples of benzimidazole compounds include, in particular, phenylbenzimidazole derivatives such as phenylbenzimidazole sulfonic acid, such as that marketed in particular under the brand name "Eusolex 232" by Merck, and phenyl dibenzimidazole tetrasulfonate disodium, such as that marketed under the brand name "Neo Heliopan AP" by Symrise.
[0133] Suitable imidazoline compounds include ethylhexyl dimethoxybenzylidene propionate dioxoimidazoline.
[0134] Examples of bis-benzoazolyl compounds include the compounds described in EP-669 323 and US patent no. 2 463 264.
[0135] Suitable para-aminobenzoic acid compounds include PABA (p-aminobenzoic acid), ethyl PABA, ethyl dihydroxypropyl PABA, pentyl dimethyl PABA, ethylhexyl dimethyl PABA, such as that marketed under the brand name "Escalol 507" by ISP, glyceryl PABA, and PEG-25 PABA, such as that marketed under the brand name "Uvinul P25" by BASF.
[0136] Suitable methylene bis-(hydroxyphenylbenzotriazole) compounds include 2,2'-methylenebis[6-(2H-benzotriazol-2-yl)-4-methylphenol] such as that marketed under the brand name "Mixxim BB / 200" by Fairmount Chemical, 2,2'-methylenebis[6-(2H-benzotriazol-2-yl)-4-(1,1,3,3-tetramethylbutyl)phenol] such as that marketed in micronized aqueous dispersion form under the brand name "Tinosorb M" by BASF or under the brand name "Mixxim BB / 100" by Fairmount Chemical, and derivatives as described in US patents Nos. 5,237,071 and 5,166,355, GB-2,303,549, DE-197,26184 and EP-893,119, and drometrizole trisiloxane, such as that marketed under the brand name "Silatrizole" by Rhodia Chimie or - "Mexoryl XL" by L'Oréal.
[0137] Examples of benzoxazole compounds include 2,4-bis [5-1 (dimethylpropyl)benzoxazol-2-yl-(4-phenyl)imino]-6-(2-ethylhexyl)imino-l,3,5-triazine, such as that marketed under the brand name Uvasorb K2A by Sigma 3V.
[0138] Suitable examples of protective polymers and protective silicones include the silicones described in WO 93 / 04665.
[0139] Suitable α-alkylstyrene derived dimers include the dimers described in DE-19855649.
[0140] Examples of 4,4-diarylbutadiene compounds include l,l-dicarboxy(2,2'-dimethylpropyl)-4,4-diphenylbutadiene.
[0141] If present, at least one additional organic UV filter is preferably present in the compositions of this disclosure in an amount of at least about 1% by weight, preferably at least about 5% by weight, preferably at least about 10% by weight, preferably at least about 12.5% by weight, and preferably at least about 15% by weight, the upper end of the range of additional UV filter present preferably being about 40% by weight (such as about 1 to 40%, about 10 to 40%, about 12.5 to 40%, etc.), preferably about 30% by weight (such as about 5 to 30%, about 10 to 30%, about 15 to 30%, etc.), preferably about 25% by weight (such as about 5 to 25%, about 10 to 25%, about 15 to 25%, etc.), and preferably of about 20% by weight (such as about 1 to 20%, about 5 to 20%, about 10 to 20%, etc.), all weights being based on the total weight of the composition.
[0142] According to preferred embodiments, the compositions of this disclosure comprise 10% or less by weight relative to the total weight of the composition of such optional additional UV filters, preferably less than 7.5% by weight relative to the total weight of the composition, preferably less than 5% by weight relative to the total weight of the composition, preferably less than 3% by weight relative to the total weight of the composition, and preferably less than 1% by weight relative to the total weight of the composition.
[0143] According to preferred embodiments, the compositions of this disclosure further comprise at least one additional organic UV filter selected from the group consisting of 4-bis-{ [4-(2-ethylhexyloxy)-2-hydroxy]-phenyl]-6-(4-methoxyphenyl)-1,3,5-triazine (INCI name: Bis-Ethylhexyloxyphenol Methoxyphenyl Triazine), avobenzone (butyl methoxydibenzoylmethane), octisalate (ethylhexyl salicylate), ensulizole (phenylbenzimidazole sulfonic acid), homosalate, octocrylene and mixtures thereof. In such embodiments, the UV-absorbing system may "consist of" or "consist essentially of" (1) at least one physical ultraviolet (UV) attenuating material and (2) at least one organic UV filter selected from the group consisting of 4-bis-[4-(2-ethylhexyloxy)-2-hydroxy]-phenyl]-6-(4-methoxyphenyl)-1,3,5-triazine (INCI name: Bis-Ethylhexyloxyphenol Methoxyphenyl Triazine), avobenzone (butyl methoxydibenzoylmethane), octisalate (ethylhexyl salicylate), ensulizole (phenylbenzimidazole sulfonic acid), homosalate, octocrylene and mixtures thereof.
[0144] However, according to other preferred embodiments, the compositions of this disclosure are "free", "substantially free" or "devoid" as defined above of one or more additional organic UV filters selected from the group consisting of 4-bis-{[4-(2-ethylhexyloxy)-2-hydroxy]-phenyl]-6-(4-methoxyphenyl)-1,3,5-triazine (INCI name: Bis-Ethylhexyloxyphenol Methoxyphenyl Triazine), avobenzone (butyl methoxydibenzoylmethane), octisalate (ethylhexyl salicylate), ensulizole (phenylbenzimidazole sulfonic acid), homosalate, and octocrylene, preferably two or more, preferably three or more, preferably four or more, or preferably all five of these sunscreen-forming agents.
[0145] According to preferred embodiments, the compositions of this disclosure are "free", "substantially free" or "devoid", as defined above, of one or more additional organic UV filters selected from the group consisting of OXYBENZONE (benzophenone-3), OCTINOXATE (ethylhexyl methoxycinnamate), ETHYLHEXYL TRIAZONE, DROMETRIZOLE TRISILOXANE, METHYLENE BIS-BENZOTRIAZOLYL TETRAMETHYLBUTYL PHENOL, DIETHYLAMINO HYDROXYBENZOYL HEXYL BENZOATE, DIETHYLHEXYL BUTAMIDO TRIAZONE, ISOAMYL P-METHOXYCINNAMATE, POLYSILICONE-15, 4-METHYLBENZYLIDENE CAMPHOR, PHENYL DIBENZIMIDAZOLE DISODIUM TETRASULFONATE, METHOXYPROPYLAMINO CYCLOHEXENYLIDENE METHOXYETHYLCYANOACETATE, 4-bis-{[4-(2-ethylhexyloxy)-2-hydroxy]-phenyl]-6-(4-methoxyphenyl)-1,3,5-triazine (INCI name: Bis-Ethylhexyloxyphenol Methoxyphenyl Triazine), preferably two or more, preferably three or more, preferably four or more, etc.and preferably "free", "significantly free" or "devoid" of all these sunscreen agents.
[0146] According to preferred embodiments, the compositions of this disclosure are "free", "substantially free" or "devoid" of OXYBENZONE (benzophenone-3) and / or OCTINOXATE (ethylhexyl methoxycinnamate) and / or 4-bis-{[4-(2-ethylhexyloxy)-2-hydroxy]-phenyl]-6-(4-methoxyphenyl)-1,3,5-triazine (INCI name: Bis-Ethylhexyloxyphenol Methoxyphenyl Triazine).
[0147] According to preferred embodiments, the UV-absorbing system of the compositions of this disclosure may "consist of" or "consist essentially of" at least one ultraviolet (UV) attenuating physical material.
[0148] According to preferred embodiments, this disclosure envisages omitting one or more of the specific UV filters mentioned above from the UV-absorbing system of the compositions of this disclosure. By way of example, octocrylene and / or octinoxate may be omitted from the compositions. A similar omission of one or more of the specific UV filters mentioned is thus envisaged. Oil
[0149] According to preferred embodiments of this disclosure, compositions further comprising at least one oil are proposed. “Oil” means a substance that is hydrophobic and lipophilic, and is a liquid at approximately room temperature (20 to 25 °C) and approximately atmospheric pressure (760 mm Hg).
[0150] Suitable oils include volatile and / or non-volatile oils. These oils may be any acceptable oil, including, but not limited to, silicone oils and / or hydrocarbon oils.
[0151] According to certain embodiments, the compositions of this disclosure preferably comprise one or more volatile silicone oils. Examples of such volatile silicone oils include linear or cyclic silicone oils having from 2 to 7 silicon atoms, these silicones optionally being substituted with alkyl or alkoxy groups of 1 to 10 carbon atoms. Specific oils that may be used in the disclosure include octamethyltetrasiloxane, decamethylcyclopentasiloxane, dodecamethylcyclohexasiloxane, heptamethyloctyltrisiloxane, hexamethyldisiloxane, decamethyltetrasiloxane, dodecamethylpentasiloxane, and mixtures thereof. Other volatile oils that may be used include KF 96A with a viscosity of 6 cSt, a commercial product from Shin Etsu with a flash point of 94 °C. Preferably, volatile silicone oils have a flash point of at least 40°C.
[0152] Non-limiting examples of volatile silicone oils are listed in Table 1 below.
[0153] [Tables 1] Compound Flash Point (°C) Viscosity (cSt) Octyltrimethicone 93 1.2 Hexyltrimethicone 79 1.2 Decamethylcyclopentasiloxane 72 4.2 (cyclopentasiloxane or D5) Octamethylcyclotetrasiloxane (cyclotetramethylsiloxane or D4) 55 2.5 Dodecamethylcyclohexasiloxane (D6) 93 7 Decamethyltetrasiloxane (L4) 63 1.7 KF-96 A from Shin Etsu 94 6 PDMS (polydimethylsiloxane) DC 200 (1.5 cSt) from Dow Corning 56 1.5 PDMS DC 200 (2 cSt) from Dow Corning 87 2
[0154] In addition, a linear volatile silicone oil may be used in this disclosure. Suitable linear volatile silicone oils include those described in US Patent No. 6,338,839 and in WO03 / 042221. In one embodiment, the linear volatile silicone oil is decamethyltetrasiloxane. In another embodiment, decamethyltetrasiloxane is further combined with another solvent that is more volatile than decamethyltetrasiloxane.
[0155] According to certain embodiments of this disclosure, the composition preferably comprises one or more non-silicone volatile oils and may be selected from volatile hydrocarbon oils, volatile esters, and volatile ethers. Examples of such non-silicone volatile oils include, but are not limited to, volatile hydrocarbon oils having 8 to 16 carbon atoms and mixtures thereof, and in particular, C8-Ci6 branched alkanes such as C8-Ci6 isoalkanes (also known as isoparaffins), isohexadecane, isododecane, isodecane, and, for example, oils sold under the trade names Isopar or Permethyl. Preferably, the non-silicone volatile oils have a flash point of at least 40 °C.
[0156] Non-limiting examples of non-silicone volatile oils are given in Table 2 below.
[0157] [Tables2] Compound Flash Point (°C) Isododecane 43 Propylene glycol n-butyl ether 60 Ethyl 3-Ethoxypropionate 58 Propylene glycol acetate methyl ether 46 Isopar L (Cn-Ci3 isoparaffin) 62 Isopar H (Cn-Ci2 isoparaffin) 56
[0158] According to certain embodiments of this disclosure, the composition comprises at least one non-volatile oil. Examples of non-volatile oils that may be used in this disclosure include, but are not limited to, polar oils such as, for example:
[0159] - esters and ethers, in particular fatty acids, such as oils of formula R1COOR2, in which RI represents the remainder of a fatty acid having from 8 to 29 carbon atoms, and R2 represents a hydrocarbon chain, branched or unbranched, containing from 3 to 30 carbon atoms, such as, for example, Purcellin oil, ethyl oleate, ethyl stearate, isononyl isononanoate, isopropyl myristate, ethyl-2-hexyl palmitate, octyl-2-dodecyl stearate, octyl-2-dodecyl erucate, isostearyl isostearate; hydroxylated esters such as isostearyl lactate, octylhydroxy stearate, octyldodecyl hydroxystearate, diisostearyl malate, triisocetyl citrate, heptanoates, octanoates, fatty alcohol decanoates; polyol esters, such as propylene glycol dioctanoate, neopentyl glycol diheptanoate and diethylene glycol diisononanoate;glycerin triesters such as glycerol and C12-C22 fatty acid triesters, preferably C16-C18 fatty acid triesters, preferably Cl8 fatty acid triesters, such as glycerin and isostearic acid triester (triisostearine), glycerin and stearic acid triester (tristearine), glycerin and oleic acid triester (triolein), glyceryl tripalmitate, glyceryl trilaurate, etc.; and pentaerythritol esters such as pentaerythrityl tetraisostearate or dipentaerythrityl pentaisononanoate;
[0160] - ethers containing 10 to 40 carbon atoms;
[0161] - liquid C8 to C26 fatty alcohols, for example oleyl alcohol, alcohol cetyl alcohol, stearyl alcohol and cetearyl alcohol;
[0162] - hydrocarbon oils of animal origin, such as perhydrosqualene;
[0163] - vegetable hydrocarbon oils, such as liquid triglycerides fatty acids with 4 to 10 carbon atoms such as heptanoic or octanoic acid triglycerides, for example, sunflower, corn, soybean, cucurbit, grapeseed, sesame, hazelnut, apricot, macadamia oil, ara, sunflower, castor oil, avocado, caprylic / capric acid triglycerides, such as those sold by Stéarineries Dubois or those sold under the names Miglyol 810, 812, and 818 by Dynamit Nobel, coco-caprylate / caprate (esterified coconut oil), jojoba oil, shea butter oil; and
[0164] - their mixtures.
[0165] In addition, examples of non-volatile oils that may be used in this disclosure include, but are not limited to, non-polar oils such as branched and unbranched hydrocarbons, in particular Vaseline (petrolatum), paraffin oil, squalane, squalene, hydrogenated polyisobutene, hydrogenated polydecene, polybutene, mineral oil, pentahydrosqualene and mixtures thereof.
[0166] According to certain embodiments of this disclosure, the compositions of this disclosure may include at least one non-volatile silicone oil. Appropriate examples of such silicone oils include, but are not limited to, non-volatile silicone fluids such as, for example, polyalkyl (aryl) siloxanes. Appropriate polyalkyl siloxanes include, but are not limited to, polydimethyl siloxanes, which are designated CTFA dimethicone, polydiethyl siloxane, phenyl trimethicone, trimethyl pentaphenyl trisiloxane, phenyldimethicone, phenyltrimethylsiloxydiphenylsiloxane, diphenyldimethicone, and diphenylmethyldiphenyltrisiloxane, and the siloxanes disclosed in US Patent Application Publication No. 2004 / 0126350.Specific examples of suitable high viscosity silicone oils include, but are not limited to, PCR 15 M 30 (500 cSt) or Wacker Belsil PDM 1000 (1000 cSt) and Dow Corning 200 (350 cSt) (values in parentheses represent viscosities at 25 °C).
[0167] Particularly preferred oils include, but are not limited to, one or more of the following: diisopropyl sebacate, C12-15 alkyl benzoate, phenethyl benzoate, isopropyl lauroyl sarcosinate, diisopropyl adipate, dibutyl adipate, dicaprylyl carbonate, dicaprylate / dicaprate, coco glycerides, caprylic / capric triglyceride, isopropyl myristate, isopropyl palmitate, coco caprylate / caprate, ethylhexyl palmitate, isononyl isononanoate, octyl dodecanol, isohexadecane, isododecane, dicaprylyl ether, C15-19 alkane, and mixtures thereof.
[0168] According to preferred embodiments, at least one oil is present in the compositions of this disclosure in an amount ranging from about 1% to about 50% by weight, more preferably from about 5% to about 40% by weight, and preferably from about 10% to about 35% by weight, based on the total weight of the composition, including all ranges and sub-ranges within those ranges, such as 15% to 40%, 20% to 45%, etc. Aqueous Phase
[0169] The compositions of this disclosure may also optionally contain water. When the compositions of this disclosure contain water, they are preferably in the form of an emulsion. Preferably, when the compositions of this disclosure contain water, they are in the form of an emulsion containing an external aqueous phase such as an oil-in-water (O / W) emulsion or a water-in-oil-in-water (W / O / W) emulsion, or an emulsion containing an external oil phase such as a water-in-oil (W / O) emulsion or an oil-in-water-in-oil (W / O / O) emulsion. Preferably, when in the form of an emulsion, the oil phase may contain silicone oils (for example, Si / O or W / Si emulsion) or hydrocarbon oils.Where appropriate, water is preferably present in an amount of about 10% to about 80% by weight, preferably about 20% to about 70% by weight, preferably about 35% to about 65% by weight, including all intermediate ranges and sub-ranges, all weights being based on the total weight of the composition.
[0170] According to preferred embodiments, however, the compositions of this disclosure are water-free, substantially water-free, or water-free as defined herein. Preferably, the compositions of this disclosure are anhydrous.
[0171] If present in compositions of this disclosure, the aqueous phase may include at least one water-soluble organic solvent that is liquid at room temperature and atmospheric pressure. For example, such at least one water-soluble organic solvent may include:
[0172] C1-C5 monoalcohols having a C1-C5 alkane chain and a single hydroxyl (OH) function. Suitable C1-C5 monoalcohols include methanol, ethanol, propanol, isopropanol, butanol, and mixtures thereof;
[0173] polyols (compounds having 2 or more hydroxyl groups) having, for example, from 2 to 20 carbon atoms, preferably from 2 to 6 carbon atoms, such as, for example, glycerol, diglycerol, propylene glycol, isoprene glycol, dipropylene glycol, butylene glycol, hexylene glycol, 1,3-propanediol, pentylene glycol, simple sugars and water-soluble polyalkylene glycols;
[0174] and their mixtures.
[0175] According to preferred embodiments, at least one water-soluble organic solvent is selected from the group consisting of ethanol, dipropylene glycol, butylene glycol, propanediol and propylene glycol, and mixtures thereof.
[0176] Where appropriate, the water-soluble organic solvent(s) is / are preferably present in the compositions of this disclosure in an amount ranging from about 0.5 to about 40% by weight, preferably from about 3 to about 30% by weight, and preferably from about 5% to about 20% by weight relative to the total weight of the composition, including all intermediate ranges and sub-ranges such as, for example, 2% to 15%, 2% to 25%, 7.5% to 30%, etc. Antioxidants
[0177] According to preferred embodiments of this disclosure, the compositions of this disclosure may optionally further include at least one antioxidant. Examples of such antioxidants include, but are not limited to, vitamins, ascorbic acid, polyphenols, flavonoids, stylbenoids, and their derivatives. The antioxidants may be dissolved in oily or aqueous phases.
[0178] Appropriate specific examples of antioxidants include, but are not limited to, flavones, flavonoids, Havanas, flavanones, flavonols, stylbenoids, ascorbic acid (vitamin C), ascorbyl glucoside, ascorbyl palmitate, tocopherol (vitamin E), tocopheryl acetate, retinol, resourcinol, (octyl) methoxycrylene (SolaStay SI), diethylhexyl 2,6-naphthalate (DEHN) (Corapan TQ), phenylethyl benzoate, butyl salicylate (HallBrite BHB), diethylhexyl syringylidene malonate (Oxynex ST), polycrylene (Polyester-8), hexadecyl benzoate, Butyl chloroethylene benzoate, and their mixtures or derivatives. Optional additional ingredients
[0179] The compositions of this disclosure may also optionally include at least one additional additive or auxiliary commonly used in cosmetic compositions and known to a person skilled in the art as being capable of being incorporated into such compositions. Such additives or auxiliaries may be selected from film-forming agents, coloring agents (e.g., dyes and pigments), waxes, thixotropic agents (e.g., clays), fillers, preservatives, perfumes, surfactants, antioxidants, free radical scavengers, spreading agents, dispersing agents, antifoaming agents, neutralizing agents, stabilizing agents, active ingredients selected from essential oils, moisturizing agents, vitamins, active ingredients, proteins, ceramides, plant extracts, fibers and the like, wetting agents and mixtures thereof.However, preferably, the compositions in this disclosure are "free", "substantially free" or "devoid" of such additives.
[0180] A person skilled in the art shall ensure that the optional additional additives are chosen and / or their quantity so that the advantageous properties of the composition as disclosed are not, or are not substantially, compromised by the envisaged addition.
[0181] It goes without saying that the composition of the disclosure must be cosmetically or dermatologically acceptable, that is, it must contain a physiologically acceptable, non-toxic carrier. The composition may be in any pharmaceutical form normally used in the cosmetic and dermatological fields that is suitable for topical administration as mentioned above.
[0182] These auxiliary additives may be present in the composition in a proportion of 0% to 99% (such as 0.01% to 90%) relative to the total weight of the composition and furthermore such as 0.1% to 50% by weight (where appropriate), including all intermediate ranges and sub-ranges.
[0183] In accordance with this disclosure, the compositions of this disclosure may be a standalone product (for use alone), or they may be a product for use in conjunction with another composition, for example, a base coat composition (makeup base), a color coat composition, or a top coat composition (overcoat). It should be understood that when compositions of this disclosure are applied to keratinous materials in the form of any such composition, such application may include one or more coats of the product.Thus, for example, the application of at least one color layer composition may include one or more color layers; the application of at least one topcoat composition may include one or more topcoats; the application of at least one basecoat composition may include one or more basecoats. Preferably, such basecoat, color layer, and topcoat compositions contain three or fewer layers of compositions, preferably two or fewer layers of compositions, and preferably only one layer of compositions.
[0184] During the application of the compositions of this disclosure, a base coat (if any) is typically applied directly to the keratinous material, a color coat is typically applied either directly to the keratinous material (if no base coat is present) or to a previously applied base coat, and a top coat (if any) is typically applied to a color coat.
[0185] According to preferred embodiments of this disclosure, methods for treating, protecting, improving the appearance, caring for and / or making up keratinous material by applying compositions of this disclosure to the keratinous material in sufficient quantity to treat the keratinous material, improve its appearance, take care of it and / or make it up, are offered.
[0186] Preferably, the "makeup" of the keratinous material includes the application of a composition comprising at least one coloring agent to the keratinous material in sufficient quantity to provide color and / or an optical effect to the keratinous material.
[0187] Preferably, the "protection" of the keratinous material includes the application of a composition from this disclosure to protect the keratinous material from damage resulting from exposure to UV rays.
[0188] According to the preceding embodiments, the compositions of this disclosure are applied topically to the keratinous material in a sufficient quantity to treat, improve the appearance of, care for, and / or conceal the keratinous material. The compositions can be applied to the desired area as needed, preferably once or twice a day, more preferably once a day, and then preferably allowed to dry before being subjected to contact such as with clothing or other objects (e.g., clothing or a top coat).
[0189] According to preferred embodiments of this disclosure, methods for manufacturing non-greasy and / or non-bleaching compositions comprising at least one ultraviolet (UV) attenuating physical material by combining at least one ultraviolet (UV) attenuating physical material and at least one flavone during the formation of the compositions to produce non-greasy and / or non-bleaching compositions are provided.
[0190] According to preferred embodiments of this disclosure, methods for increasing UV efficiency, preferably of the FPS and / or critical wavelength, of compositions comprising at least one ultraviolet (UV) attenuating physical material, wherein the methods include the addition of at least one flavone during the formation of the compositions, are provided.
[0191] This disclosure also considers pre-packaged kits and / or materials suitable for consumer use containing one or more composition(s) as described herein, alone or in combination with makeup products such as primers, top coats, makeup removers, etc. The packaging and application device for any subject of this disclosure may be selected and manufactured by persons skilled in the art based on their general knowledge and adapted according to the nature of the composition to be packaged. Indeed, the type of device to be used may be particularly related to the consistency of the composition, especially its viscosity; it may also depend on the nature of the constituents present in the composition, for example the presence of volatile compounds.
[0192] Unless otherwise stated, all numbers expressing quantities of ingredients, reaction conditions, etc., used in the patent memorandum and claims are to be understood as modified in all cases by the term "approximately." Accordingly, unless otherwise stated, the numerical parameters presented in the following patent memorandum and the attached claims are approximations that may vary depending on the desired properties that are sought to be obtained through this disclosure.
[0193] Although the numerical ranges and parameters defining the general scope of disclosure are approximations, the numerical values shown in the specific examples are reported as accurately as possible. However, every numerical value inherently contains some errors that necessarily result from the standard deviation found in its respective measurements. The following examples are intended to illustrate disclosure without, however, limiting its scope. Percentages are provided on a weighted basis. Example 1 - Basic sunscreen formulation
[0194] [Tables3] Ingredient % by weight Hydrocarbon oil QS Polymer thickener 1.0 Wax 1.0 Additional thickeners (clays, polymers, waxes) 1.0 UV attenuating physical material 10.0% Polyphenol (flavone or flavonoid) 1.0% Ethanol 4.5%
[0195] The above basic sunscreen formulation was prepared by mixing the polymer thickener, wax, and additional thickeners under high shear at 80 °C for 15 min before slowly cooling to room temperature under constant mixing. The polyphenol ingredient(s) a / were added to the basic sunscreen formulation by dissolving in a mixture of hydrocarbon oil and / or ethanol in an amount suitable for the complete dissolution of the polyphenol, which was then added to the basic sunscreen formulation under low shear at room temperature.
[0196] Polyphenols were evaluated against a basic control sunscreen formulation that contained no added polyphenol ingredients. The polyphenols evaluated are identified in the table below. All preparations were made in triplicate and their UV efficacy compared by measuring the in vitro FPS and the critical wavelength.
[0197] The basic sunscreen formulation prepared without physical UV attenuating material does not produce a substantially high SPF greater than 2.
[0198] The in vitro SPF was measured for all samples according to the procedure described in Miksa, S. et al. Int. J. Cosmet. Sci., 2015, 37(6), 555-566 and Miksa, S. et al. Int. J. Cosmet. Sci., 2016, 38(5), 504-511. The base sunscreen formulation was applied to three Helioscreen HD6 and Helioscreen SB6 polymethyl methacrylate plates using a robotic applicator. Each polymethyl methacrylate plate was allowed to dry at 25 °C for 15 to 30 min and measured at 9 locations using a Labsphere UV-2000S. A higher in vitro SPF is a measure of greater UVB protection efficacy.
[0199] The critical wavelength was measured for all samples according to the procedure described in 21 CFR Part 352 Subpart D § 352,72. A higher critical wavelength is a measure of higher UVA protection efficiency.
[0200] [Tables4] Composition Polyphenol Polyphenol Class Effect on in vitro SPF Effect on critical wavelength (nm) Example CONTROL None 0 0 Inventive example 1 Luteolin Flavone +49% +3.7 Inventive example 1 Baicalin Flavone +20% +1.1 Inventive example 3 Baicalein Flavone +32% +2.0 Comparative example 1 Catechin Flavane +8% 0 Comparative example 2 Naringin Flavanone +15% 0 Comparative example 3 Naringenin Flavanone +40% -1.0 Comparative example 4 Hesperetin Flavanone +22% 0 Comparative example 5 Quercetin Flavonol +27% +6.0 Comparative example 6 Rutin Flavonol +21% +2.5 Comparative example 7 Genistein Isoflavanone +12% 0 Comparative example 8 Salicylate Butyl loctyl ND +31% 0 Comparative example 9 Diethylhexyl syringyl idene malonate ND +34% 0 Comparative example 10 Ethylhexyl methoxycrylene ND +37% +0.8
[0201] Table 1 describes the inventive and comparative examples prepared using the above basic sunscreen formulation. Each comparative and inventive example was compared to the control example to calculate the effect on the in vitro SPF and the effect on the critical wavelength. The effect on the in vitro SPF is reported in Table 1 as a percentage effect relative to the in vitro SPF measurement of The control example. The effect on the critical wavelength is reported in Table 1 as a value effect compared to the measurement for the critical wavelength of the control example. Positive values for the effect on the in vitro FPS and the effect on the critical wavelength indicate that the polyphenol has a positive effect on the in vitro FPS or the critical wavelength compared to the control example. Negative values for the effect on the in vitro FPS and the effect on the critical wavelength indicate that the polyphenol has a negative effect on the in vitro FPS or the critical wavelength compared to the control example.
[0202] The effect on the in vitro FPS in Table 1 is understood as an effect on UVB efficacy. The effect on the critical wavelength in Table 1 is understood as an effect on UVA efficacy.
[0203] The results in Table 1 indicate that the inventive compositions have the highest positive effect on the in vitro FPS while also having a significant positive effect on the critical wavelength (inventive examples 1, 2, and 3). Inventive examples 1, 2, and 3 contained polyphenols that are classified in the structural family of flavones.
[0204] In contrast, other structural classifications of polyphenols have no effect on UVA efficacy (Comparative Examples 1, 2, 3, 7, 8, and 9), or even a negative effect on UVA efficacy (Comparative Example 3). The structurally related flavonol family (Comparative Examples 5 and 6) has a significant positive effect on UVA efficacy (effect on the critical wavelength), but only a moderate impact on UVB efficacy (effect on the in vitro SPF).
[0205] The compounds in Comparative Examples 8, 9 and 10 are typically added to sunscreen compositions for dispersion, UV absorption, UV scattering or homogeneity of sunscreen deposition after application to keratinous material; however, the results in Table 1 indicate a moderately strong positive impact on UVB efficacy (effect on in vitro SPF) with little or no impact on UVA efficacy (effect on critical wavelength) for these compounds.
[0206] Compared to other polyphenols, the results in Table 1 show that only the combination of flavones with UV attenuating physical materials results in a surprisingly large positive impact on UVB and UVA efficiency, suggesting a synergistic relationship between flavones and the ultraviolet (UV) attenuating physical material. Thus, the Inventive Examples have demonstrated a surprising effect of combining UV attenuating physical materials with flavones compared to combining UV attenuating physical materials with other polyphenols. The Inventive Examples have also demonstrated a surprising effect of combining UV attenuating physical materials with flavones compared to the combination of physical UV attenuating materials with other materials known in comparative examples 8-10.
Claims
Demands
1. Composition comprising a UV-absorbing system comprising at least one ultraviolet (UV) attenuating physical material, preferably at least one metal oxide selected from titanium, chromium, zinc, tin, alumina, cerium and / or iron oxides, and at least one flavone, wherein the flavone is present in an amount of about 0.1% to about 10% by weight relative to the total weight of the composition.
2. Composition according to claim 1, wherein at least one flavone is present in an amount of about 0.25% to about 7.5% by weight relative to the total weight of the composition, about 0.5% to about 5% by weight, and about 1% to about 3% by weight relative to the total weight of the composition.
3. Composition according to any one of the preceding claims, wherein at least one flavone comprises one or more luteolins, baicalins or baicalein.
4. Composition according to claim 1, wherein at least one ultraviolet (UV) attenuating physical material and at least one flavone are present in the composition in a weight ratio of about 20:1 to about 1:
1.
5. Composition according to claim 1, wherein at least one ultraviolet (UV) attenuating physical material is present in the composition in an amount of at least 5% by weight relative to the total weight of the composition, preferably from about 5% to about 40% by weight relative to the total weight of the composition.
6. Composition according to any one of the preceding claims, wherein at least one ultraviolet (UV) attenuating physical material is surface-treated with a surface treatment agent, the surface treatment agent preferably comprising at least one of amino acids, beeswax, fatty acids, fatty acid salts, fatty alcohols, anionic surfactants, lecithin compounds, metal alkoxides, polyethylene, silicones, proteins, alkanolamines, silicon oxides, metal oxides, sodium hexametaphosphate, alumina, glycerol and mixtures thereof.
7. Composition according to any one of the preceding claims, wherein at least one physical attenuating material ultraviolet (UV) includes zinc oxide and / or titanium dioxide, preferably passivated.
8. Composition according to claim 1, wherein at least one ultraviolet (UV) attenuating physical material comprises zinc oxide and / or titanium dioxide, preferably zinc oxide coated with a coating, preferably the coating comprising at least one of hydrated silica, triethoxysilylethyl polydimethylsiloxyethyl hexyl dimethicone, hydrogen dimethicone, triethoxycaprylylsilane, and mixtures thereof.
9. Composition according to claim 1, wherein at least one ultraviolet (UV) attenuating physical material has an average primary particle size of 1 nm to 500 nm, preferably 5 nm to 250 nm, preferably 10 nm to 100 nm, preferably 10 nm to 50 nm, preferably 20 nm to 40 nm.