A composition comprising a UV shielding agent, at least 1% by mass of ascorbic acid, and scleroglucan gum.
Patent Information
- Authority / Receiving Office
- JP · JP
- Patent Type
- Applications
- Current Assignee / Owner
- LOREAL SA
- Filing Date
- 2024-06-11
- Publication Date
- 2026-07-24
AI Technical Summary
Existing cosmetic compositions with high UV shielding agents and ascorbic acid face issues of instability, phase separation, and unpleasant texture, making it difficult to achieve high sun protection while maintaining sensory characteristics like non-greasy feel and stability.
Incorporating at least 1% by mass of ascorbic acid and scleroglucan gum in cosmetic compositions stabilizes the formulation, allowing for high photoprotective power and a refreshing, non-greasy texture.
The composition maintains stability and provides effective sun protection with a pleasant feel, overcoming the challenges of phase separation and texture issues.
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Abstract
Description
[Technical Field]
[0001] The present invention relates to compositions comprising at least one UV shielding agent, at least 1% by mass, preferably at least 5% by mass, of ascorbic acid and at least one scleroglucan gum based on the total mass of the composition, particularly cosmetic or dermatological compositions, and to the use of said compositions in the fields of beauty and dermatology, particularly for caring for and treating keratinous substances, especially for caring for, protecting and / or applying makeup to the skin of the body or face, or for hair care. [Background technology]
[0002] It is known that light emission with wavelengths of 280-400 nm can brown the human epidermis. More specifically, wavelengths of 280-320 nm, known as UVB light, can cause erythema and burns in the skin and interfere with the natural progression of tanning.
[0003] For this reason, and for aesthetic reasons, there is a certain demand for means of controlling natural tanning and controlling skin color. Therefore, UVB radiation should be blocked. It is also known that UVA light with wavelengths of 320-400 nm, which causes skin browning, can cause harmful changes to the skin, especially if the skin is sensitive or if it is continuously exposed to solar radiation. UVA light, in particular, causes loss of skin elasticity and the appearance of wrinkles, resulting in premature skin aging.
[0004] Therefore, an increasing number of people desire to limit the effects of UVA light on their skin for aesthetic and cosmetic reasons, such as maintaining the skin's natural elasticity. Consequently, it is desirable that UVA radiation also be blocked.
[0005] To protect skin and keratinous substances from UV radiation, photoprotective compositions containing organic shielding agents effective in the UVA and UVB ranges are widely used.
[0006] Many cosmetic compositions intended for skin photoprotection have been proposed so far. These compositions generally contain one or more organic molecules capable of absorbing ultraviolet light, which are soluble in an oily phase and / or an aqueous phase in an emulsified liquid carrier (preferably an oil-in-water emulsion). Mineral pigments of metal oxides such as titanium dioxide are increasingly frequently used in such sun protection compositions. This is because these particles are not visible to the naked eye due to their small size and it is possible to increase the protection index of the composition containing them.
[0007] It is also known that a high content of sunscreen is required to achieve a high level of shielding efficiency.
[0008] However, a high content of UV sunscreen is not suitable for the easy manufacture of a composition having a stable and pleasant texture.
[0009] Therefore, formulations having a high shielding power generally have unpleasant or uncomfortable sensory aspects, masking the freshness and pleasantness of the formulation. In particular, the weakness of a photoprotective formulation having a high protection index is often very greasy and sticky to the touch, thus lacking the lightness of the resulting texture, and also having a white appearance upon application and thus being visible on the skin.
[0010] Furthermore, introducing a high content of UV sunscreen generally causes problems of destabilization. This instability can in some cases cause phase separation of the emulsion and / or loss of the viscosity of the composition, making the formulation inefficient or even unusable.
[0011] One of the main drawbacks of these photoprotective emulsions containing organic and / or inorganic sunscreens is the difficulty of reconciling good product stability, easy product application, effective sunburn prevention, and a fresh and non-greasy feel.
[0012] Furthermore, the market for everyday sun protection is expanding rapidly. While hybrid products combining skincare and SPF 15-20 protection are on the rise, the challenge remains of achieving higher SPF values, such as 30 or above, or even 50 or above, while maintaining a comfortable feel for everyday use. The skincare sector still differs significantly from the sun protection sector in terms of consumer experience, which increases the complexity of formulation development.
[0013] Therefore, there is a need for skincare products that offer high sun protection while maintaining the sensory characteristics of skincare: appearance, texture, viscosity, and sensory aspects.
[0014] In cosmetic applications, ascorbic acid (vitamin C) is commonly added as an active ingredient to regenerate the skin by promoting collagen synthesis, which is responsible for skin elasticity, or as a whitening ingredient that suppresses melanin production, which causes melasma. Ascorbic acid is also known for its antioxidant properties.
[0015] However, when ascorbic acid is introduced into an aqueous medium (emulsion or serum) at a high concentration (i.e., for example, more than 1% by mass, preferably more than 5% by mass), it becomes unstable and the color changes dramatically, making formulation difficult.
[0016] For this reason, serums or aqueous compositions containing ascorbic acid in powder form that dissolves upon use are commercially available. The drawback of this type of product is that vitamin C eventually decomposes in the aqueous medium. Therefore, from a practical standpoint, these products lose their appeal because consumers prefer serums that require no pretreatment, guarantee color stability, and do not undergo chemical degradation.
[0017] Furthermore, introducing high concentrations of vitamin C into cosmetic compositions can lead to instability of the formulation. For example, in emulsion form, phase separation accompanied by the release of the oily phase may be observed. [Overview of the Initiative] [Problems that the invention aims to solve]
[0018] Therefore, there is a need for a cosmetic composition containing a UV shielding agent and ascorbic acid that is stable, that is, maintains the same color (generally white) and texture as the original, does not degrade the active ingredients, and exhibits high photoprotective properties.
[0019] Surprisingly, the applicant has found that the presence of one or more scleroglucan gums in the shielding composition makes it possible to introduce a high vitamin C content into the composition while simultaneously maintaining effective sun protection and high stability of the composition. [Means for solving the problem]
[0020] Therefore, the subject of the present invention is compositions, particularly cosmetic or dermatological compositions: a) at least one UV shielding agent; b) at least 1% by mass, preferably at least 5% by mass, of ascorbic acid relative to the total mass of the composition; c) at least one type of scleroglucan gum and It is a composition containing [the specified ingredient].
[0021] Contrary to all expectations, the inventors have found that by using at least one occlusive agent, at least 1% by mass, preferably at least 5% by mass, of ascorbic acid and at least one scleroglucan gum in a cosmetic composition, it is possible to obtain a composition that spreads easily, has high photoprotective power, is stable over time, and further possesses good cosmetic properties such as a refreshing feeling and a non-greasy and non-sticky texture.
[0022] In another aspect, the subject of the present invention is also the use of keratinous substances, particularly the compositions defined above, for the care of the skin of the body and / or face.
[0023] In yet another aspect of the present invention, another subject matter is a non-therapeutic cosmetic method for makeup and / or care of keratinous material, particularly the skin of the body and / or face, the method comprising at least the application of the cosmetic composition defined above to the keratinous material.
[0024] The present invention also relates to a non-therapeutic cosmetic method for inhibiting skin darkening and / or improving the uniformity of color and / or complexion, which includes applying at least one cosmetic composition as defined above to the surface of a keratinous substance.
[0025] The present invention also relates to non-therapeutic cosmetic methods for preventing and / or treating signs of aging of keratinous material, comprising applying at least one cosmetic composition defined above to the surface of keratinous material.
[0026] The compositions according to the present invention exhibit good stability. This stability can be evaluated macroscopically and / or microscopically after storage at ambient temperature (25°C), 4°C, 45°C, or 55°C for 24 hours, 1 week, 1 month, or 2 months. Stable compositions generally maintain their comfort and sensory properties over time. More specifically, the stability of a composition can be evaluated qualitatively, for example, by the absence of any phase separation or crystal formation, or quantitatively by monitoring changes in parameters such as viscosity or pH.
[0027] According to the present invention, the term "stable over time" is understood to mean that, after being stored at a temperature in the range of 4°C to 45°C for one month, preferably two months, the composition exhibits only slight macroscopic changes, such as changes in color, odor, viscosity, or pH, or only slight changes in microscopic appearance.
[0028] In relation to the present invention, shielding efficiency is evaluated from the evaluation of SPF and UVAPF.
[0029] With regard to the object of this invention, the term "SPF" means: a sun protection factor that measures the level of protection against UVB radiation. The SPF value corresponds to the ratio of the shortest time required to get sunburned when using the photoprotective composition to the shortest time required when not using the product. More specifically, the term "SPF" is defined in the paper A new substrate to measure sunscreen protection factors throughout the ultraviolet spectrum, J. Soc. Cosmet. Chem., 40, 127-133 (May / June 1989).
[0030] SPF (Sun Protection Factor) can be evaluated in vitro using a Labsphere® spectrophotometer. The plate is a material to which a photoprotective composition has been applied. For this protocol, poly(methyl methacrylate) (PMMA) plates have been found to be ideal. The specific protocol has been approved by ISO under the name ISO Committee Draft 23675.
[0031] The sun protection factor (SPF) of a composition can also be evaluated in vivo according to the ISO 24444:2019 protocol, “Cosmetics - Sun protection test methods - In vivo determination of the sun protection factor (SPF)”.
[0032] With respect to the purposes of this invention, the term "UVAPF" is understood to mean an index that characterizes protection against UVA radiation. In particular, this index can be measured in vivo by the skin color observed 2–4 hours after exposure to UVA radiation, according to the "PPD" (Persistent Pigment Darkening) method, protocol ISO-24442:2022. Protection against UVA radiation can also be evaluated in vitro using a Labsphere spectrophotometer®. The plate is a material to which a sun protection composition has been applied. For this protocol, poly(methyl methacrylate) (PMMA) plates have been found to be ideal. The ISO24443:2021 protocol describes such an in vitro method.
[0033] Other features, embodiments, and advantages of the present invention will become apparent from the detailed description that follows.
[0034] The compositions according to the present invention are intended for topical application and therefore contain a physiologically acceptable medium. The term "physiologically acceptable medium" as used herein means a medium compatible with keratinic substances.
[0035] 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, as well as mucous membranes such as nails and lips, and more particularly skin and mucous membranes (body, face, area around the eyes, eyelids, lips, preferably body, face and lips).
[0036] In the text below, unless otherwise specified, boundary values of a range are included in that range, particularly in expressions such as "between ~" and "from ~ to ~".
[0037] Furthermore, the expressions "at least one" and "at least" as used in this disclosure are synonymous with "one or more" and "more than or equal to," respectively.
[0038] The terms "preventing" or "prevention" in the present invention mean reducing the risk of or delaying the occurrence of a given phenomenon, namely, the signs of aging of keratinous material according to the present invention.
[0039] The term "organic UVA shielding agent" refers to any organic chemical molecule capable of absorbing UVA radiation in the wavelength range of at least 320–400 nm; furthermore, the molecule may also absorb UVB radiation in the wavelength range of 280–320 nm.
[0040] The term "organic UVB shielding agent" refers to any organic molecule that can absorb only UVB radiation in the wavelength range of 280-320 nm.
[0041] According to a specific embodiment of the present invention, the composition is in emulsion form.
[0042] The term "emulsion" refers to any kinetically stable, macroscopically homogeneous composition comprising at least two immiscible phases, one of which is a dispersing continuous phase and the other being dispersed in droplet form within the continuous phase. The two phases can typically be kinetically stabilized by at least one emulsion system, which usually comprises at least one emulsifying surfactant.
[0043] The difference lies between oil-in-water emulsions ("direct"), which consist of a continuous aqueous dispersion phase and a discontinuous oily dispersion phase, and water-in-oil emulsions ("inverse"), which consist of a continuous oily dispersion phase and a discontinuous aqueous dispersion phase. Multiple emulsions, such as water-in-oil or oil-in-water, also exist. [Modes for carrying out the invention]
[0044] UV shielding agent The composition according to the present invention comprises at least one UV shielding agent.
[0045] UV shielding agents can be selected from lipophilic organic UV shielding agents, hydrophilic organic UV shielding agents, and inorganic UV shielding agents.
[0046] Lipophilic organic UV shielding agent The term “organic lipophilic shielding agent” is intended to mean any cosmetic or dermatological organic compound that shields against UV radiation, which may be completely dissolved in molecular form in a liquid lipid phase, or in colloidal form (e.g., in micelle form) in a liquid lipid phase.
[0047] Lipophilic organic shielding agents include, in particular, cinnamic compounds; anthranilate compounds; salicylic acid compounds; dibenzoylmethane compounds; benzylidene camphor compounds; benzophenone compounds; β,β-diphenyl acrylate compounds; triazine compounds; benzotriazole compounds; benzalmalonate compounds, particularly those cited in U.S. Patent No. 5,624,663; benzimidazole derivatives; imidazoline compounds; bisbenzazolyl compounds described in European Patent No. 669323 and U.S. Patent No. 2,463,264; methylenebis(hydro) compounds described in U.S. Patent No. 5,237,071, U.S. Patent No. 5,166,355, British Patent No. 2,303,549, German Patent No. 1,972,6184 and European Patent No. 893,119. A selection of compounds including cyphenylbenzotriazole compounds; benzoxazole compounds described in European Patent No. 0832642, European Patent No. 1027883, European Patent No. 1300137 and German Patent No. 10162844; shielding polymers and shielding silicones, particularly those described in International Publication No. 93 / 04665; α-alkylstyrene dimers, such as those described in German Patent No. 19855649; 4,4-diarylbutadiene compounds described in European Patent No. 0967200, German Patent No. 19746654, German Patent No. 19755649, European Patent Application Publication No. A-1008586, European Patent No. 1133980 and European Patent No. 133981; and mixtures thereof.
[0048] Preferably, the lipophilic organic shielding agent is selected from salicylic acid compounds; dibenzoylmethane compounds; benzylidene camphor compounds; benzophenone compounds; triazine compounds; benzotriazole compounds; and mixtures thereof.
[0049] Examples of lipophilic organic photoprotective agents include those represented by the following INCI names and / or chemical names.
[0050] Cinnamic acid compounds: In particular, ethylhexyl methoxycinnamate, sold by DSM Nutritional Products under the trademark name Parsol® MCX; Isoamyl p-methoxycinnamate, sold by Symrise under the trademark name Neo Heliopan E 1000 (registered trademark).
[0051] Dibenzoylmethane compounds: In particular, Butyl Methoxydibenzoylmethane, sold by DSM Nutritional Products under the trademark name Parsol® 1789.
[0052] Salicylic acid compounds: Homosalate, sold by DSM Nutritional Products under the name Parsol(registered trademark)HMS. Ethylhexyl salicylate, marketed by Symrise under the name Neo Heliopan® OS.
[0053] β,β-diphenylacrylate compounds: In particular, octocrylene, which is sold by BASF under the trademark name Uvinul® N 539 T.
[0054] Benzophenone compounds: Benzophenone-3 or oxybenzone, marketed by BASF under the trademark name Uvinul(registered trademark) M 40. Diethylamino hydroxybenzoyl hexyl benzoate, marketed by BASF under the trademark name Uvinul® A Plus, or as a mixture with ethylhexyl methoxycinnamate under the trademark name Uvinul® A Plus B.
[0055] Benzylidene camphor compounds: 4-methylbenzylidene camphor, marketed by Merck under the name Eusolex® 6300.
[0056] Phenylenbenzotriazole compounds: Drometrizole trisiloxane, manufactured by Novell under the name Mexoryl(registered trademark)XL.
[0057] Methylenebis(hydroxyphenylbenzotriazole) compounds: Methylenebis-benzotriazolyltetramethylbutylphenol, especially in solid form, such as the product sold by Fairmount Chemical under the trademark name MIXXIM BB / 100 (registered trademark).
[0058] Triazine compounds: - Its INCI name is phenylenebis-diphenyltriazine, 3,3'-(1,4-phenylene)bis(5,6-diphenyl-1,2,4-triazine). - Bis-ethylhexyloxyphenol methoxyphenyl triazine, marketed by DSM under the trademark name Parsol Shield® and by BASF under the trademark name Tinosorb® S. - In particular, ethylhexyl triazone, marketed by BASF under the trademark name Uvinul(registered trademark) T150. - Diethylhexyl butamide triazone, sold by 3V Sigma under the trademark name Uvasorb(registered trademark)HEB. - Symmetrical triazine shielding agents substituted with naphthalenyl or polyphenyl groups, as described in U.S. Patent No. 6,225,467, International Publication No. 2004 / 085412 (see compounds 6 and 9), or in the document "Symmetrical Triazine Derivatives" IP.COM IPCOM000031257 Journal, Inc. West Henrietta, NY, US (September 20, 2004).
[0059] Anthranilic acid compounds: Menthyl anthranilate, sold by Symrise under the trademark name Neo Heliopan (registered trademark) MA.
[0060] Benzalmalonate compounds: Polyorganosiloxanes containing benzalmalonate functional groups, such as Polysilicone-15, marketed by Hoffmann-La Roche under the trademark name Parsol SLX®.
[0061] According to certain embodiments, the composition according to the present invention comprises bis-ethylhexyloxyphenol methoxyphenyl triazine.
[0062] Hydrophilic organic UV shielding agent In relation to the spirit of this invention, the term "hydrophilic organic UV shielding agent" is understood to mean a water-soluble organic UV shielding agent or a water-dispersible organic UV shielding agent.
[0063] The term "water-soluble organic shielding agent" means any organic shielding agent that can be completely dissolved in a liquid aqueous phase in molecular form or in a colloidal form (e.g., in micelle form) in a liquid aqueous phase.
[0064] The term "water-dispersible organic shielding agent" is understood to mean any organic shielding agent capable of forming a homogeneous suspension of particles with a volume-average diameter of less than 100 microns in a liquid aqueous phase. The volume-average diameter is determined by laser diffraction particle size analysis.
[0065] Among the water-soluble organic UVA screening agents that can be used in accordance with the present invention, mention may be made of benzene-1,4-bis(3-methylene-10-camphorsulfonic) acid (INCI name: terephthalylidene dicamphor sulfonic acid) and its various salts, in particular those described in French Patent Application Publication No. 2528420A and French Patent Application Publication No. 2639347A. In particular, mention may be made of benzene-1,4-bis(3-methylene-10-camphorsulfonic acid) (INCI name: terephthalylidene dicamphor sulfonic acid), such as the product manufactured under the name Mexoryl® SX by Noveal.
[0066] These screening agents correspond to the following general formula (I): [Chemical formula] (wherein F represents a hydrogen atom, an alkali metal or NH(R1)3 + group (wherein the R1 groups may be the same or different and represent a hydrogen atom, a C1-C4 alkyl group or a hydroxyalkyl group or Mn + and Mn + represents a polyvalent metal cation, n is 2 or 3 or 4, and Mn + is preferably Ca 2+ Zn 2+ Mg 2+ Ba 2+ Al 3+ and Zr 4+ represents a metal cation selected from). The compounds of formula (I) above can give rise to "cis-trans" isomers around one or more double bonds, and it is clearly understood that all the isomers are relevant to the present invention.
[0067] Among the water-soluble organic UVA shielding agents that can be used in accordance with the present invention, examples include compounds containing at least two benzazolyl groups having a sulfonic acid group, such as those described in European Patent Application Publication No. A-0669323.
[0068] These are also described in U.S. Patent No. 2,463,264 and European Patent Application Publication No. A-0669323, and are prepared according to the synthesis shown therein.
[0069] A compound comprising at least two benzazolyl groups according to the present invention is shown in the following general formula (II): [ka] (In the formula, - Z represents an (l+n) valence organic residue containing one or more double bonds, arranged to complete a system of at least two benzazolyl double bonds defined within the square brackets, and to form a fully conjugated aggregate; - X' is S, O, or NR 6 It represents; - R 1 These are hydrogen atoms, C1~C 18 Alkyl, C1-C4 alkoxy, C5-C 15 Aryl, C2~C 18 Represents an acyloxy group, an SO3Y group, or a COOY group; - R 2 , R 3 , R 4 and R 5 The groups may be the same or different, and may be a nitro group or R 1 Represents the base; - R 6 represents a hydrogen atom, a C1-C4 alkyl group, or a C1-C4 hydroxyalkyl group; - Y represents a cation produced by neutralizing a hydrogen atom, Li, Na, K, NH4, 1 / 2Ca, 1 / 2Mg, 1 / 3Al, or a free acid group with an organic nitrogen base; - m is either 0 or 1; - n is a number between 2 and 6; - l is a number between 1 and 4; - However, the value of l+n does not exceed 6.
[0070] Among these compounds, most specifically, 1,4-bis-benzimidazolyl-phenylene-3,3',5,5'-tetrasulfonic acid (INCI name: disodium phenyldibenzimidazoletetrasulfonate) or its salt, which has the following structure (III) and is sold by Symrise under the name Neo Heliopan® AP, is preferred. [ka]
[0071] Preferably, the water-soluble shielding agent capable of absorbing UVA rays is benzene-1,4-bis(3-methylidene-10-camphor sulfonic acid) (INCI name: Terephthalylidene Dicamphor Sulfonic Acid), such as the product manufactured by Novell under the name Mexoryl SX.
[0072] Water-soluble organic UVB shielding agents that can be used in accordance with the present invention are selected from water-soluble cinnamic acid derivatives, such as ferulic acid or 3-methoxy-4-hydroxycinnamic acid; water-soluble benzylidene camphor compounds; water-soluble phenylbenzimidazole compounds; water-soluble p-aminobenzoic acid (PABA) compounds; water-soluble salicylic acid compounds and mixtures thereof.
[0073] Examples of water-soluble organic UVB shielding agents include phenylbenzimidazole compounds, such as 2-phenyl-1H-benzimidazole-5-sulfonic acid (INCI name: phenylbenzimidazole sulfonic acid), particularly the one sold by Merck under the trademark name Eusolex 232®.
[0074] The composition according to the present invention may also include at least one mixed water-soluble shielding agent capable of absorbing UVA and UVB rays.
[0075] If the water-soluble UV shielding agent is of the sulfonic acid type, it is preferably accompanied by an organic base such as an alkanolamine.
[0076] The term "alkanolamine" refers to a C2-C group containing at least one primary, secondary, or tertiary amine group and at least one alcohol, usually a primary alcohol group. 10 This refers to a compound. Suitable alkanolamines include 2-amino-2-(hydroxymethyl)-1,3-propanediol (INCI name: tromethamine) and triethanolamine.
[0077] Among water-dispersible organic shielding agents, the following shielding agents can be listed.
[0078] Benzophenone compounds: For example, 1,1'-(1,4-piperazinediyl)bis[1-[2-[4-(diethylamino)-2-hydroxybenzoyl]phenyl]methanone] (CAS 919803-06-8), as described in International Publication No. 2007 / 071584; this compound is advantageously used in granular form (volume average diameter of 0.02-2 μm) (which can be obtained, for example, by following the pulverization process described in British Publication No. A-2303549 and European Patent Application Publication No. A-893119), particularly in the form of an aqueous dispersion.
[0079] Methylenebis(hydroxyphenylbenzotriazole) compounds: An aqueous dispersion of finely powdered particles of methylenebis(benzotriazolyl)tetramethylbutylphenol having a volume-average particle size in the range of 0.01 to 5 μm, more preferably in the range of 0.01 to 2 μm, and more specifically in the range of 0.020 to 2 μm, C n H 2n+1O(C6H 10 O5) x H(wherein n is an integer between 8 and 16, and x is (C6H) 10 In the form of an aqueous dispersion containing at least one alkyl polyglycoside surfactant having a structure with an average degree of polymerization of 05 units, which is in the range of 1.4 to 1.6, for example, the aqueous dispersion described in UK Patent Application Publication No. 2303549A, in particular the product sold by BASF under the trade name Tinosorb® M, or An aqueous dispersion of finely powdered particles having a volume-average particle size in the range of 0.02 to 2 μm, more preferably 0.01 to 1.5 μm, and more specifically 0.02 to 1 μm, wherein at least one mono(C8~C) has a degree of polymerization of glycerol of at least 5. 20 ) In the form of aqueous dispersions containing alkyl polyglycerol esters, for example, aqueous dispersions described in International Publication No. 2009 / 063392, in particular the product marketed by BASF under the name Tinosorb WPGL.
[0080] Triazine compounds: - A water-dispersible bis-ethylhexyloxyphenol methoxyphenyl triazine, whose INCI name is bis-ethylhexyloxyphenol methoxyphenyl triazine (and) acrylates / C12-22 alkyl methacrylate copolymer, and which is a trademark of BASF, known as Tinosorb® S LiteAqua. - Symmetric triazine shielding agents substituted with naphthalenyl or polyphenyl groups, used in a pulverized form (average particle size 0.02-3 μm), which can be obtained using the pulverization processes described in, for example, British Patent Application Publication No. 2303549A and European Patent Application Publication No. A-893119, particularly in the form of aqueous dispersions, especially 2,4,6-tris(biphenyl)triazine and 2,4,6-tris(terphenyl)triazine, which are sold by BASF under the name Tinosorb® A2B and are included in International Publication Nos. 06 / 035000, 06 / 034982, 06 / 034991, 06 / 035007, 2006 / 034992 and 2006 / 034985.
[0081] Benzoxazole compounds: CAS number 904-39-2, 2-[4-(1,3-benzoxazole-2-yl)phenyl]-1,3-benzoxazole.
[0082] Inorganic UV shielding agent The inorganic UV shielding agents that can be used in accordance with the present invention are metal oxide pigments. More preferably, the inorganic UV shielding agents of the present invention are metal oxide particles having an average primary particle size of 0.5 μm or less, more preferably 0.005 to 0.5 μm, even more preferably 0.01 to 0.2 μm, better preferably 0.01 to 0.1 μm, and more specifically 0.015 to 0.05 μm. They are, in particular, listed in Annex VI of EU Regulation No. 1223 / 2009 relating to cosmetics, as updated on 22 September 2021, but are not limited to this list.
[0083] These can be selected from titanium dioxide, zinc oxide, iron oxide, zirconium oxide, and cerium oxide, or mixtures thereof.
[0084] Such coated or uncoated metal oxide pigments are described in particular in European Patent Application Publication A-0518773. Commercially available pigments include those sold by Croda, Tayca, and Merck.
[0085] Metal oxide pigments may be coated or uncoated.
[0086] 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, metal (titanium or aluminum) alkoxides, polyethylene, silicone, proteins (collagen, elastin), alkanolamines, silicon dioxide, metal oxides, or sodium hexametaphosphate.
[0087] The coated pigment is, more specifically, titanium dioxide coated as follows: - Coated with hydrated silica, for example, MT-100WP from Tayca. - Coated with silica and iron oxide, for example, Sunveil F (registered trademark), a product from Ikeda. - Coated with silica and alumina, for example, Tayca's products MT-500SA® and MT-100SA® and Croda's product Tioveil® AQ-N. - Coated with alumina, for example, TTO-55(A) (registered trademark), a product from Ishihara. - Coated with alumina and aluminum stearate, for example, Tayca products MT-100TV(registered trademark), MT-100Z(registered trademark) and MT-01(registered trademark), Croda product Solaveil(trademark) CT100(registered trademark), and Merck product Eusolex T-AVO(registered trademark). - Coated with silica, alumina, and alginate, for example, MT-100 AQ (registered trademark), a product from Tayca. - Coated with alumina and aluminum laurate, - Coated with iron oxide and iron stearate, - Coated with zinc oxide and zinc stearate, - Coated with silica and alumina and treated with silicone, for example, MTY-500SAS® or Microtitanium Dioxide MT-100SAS SAS® from Tayca. - Coated with silica, alumina, and aluminum stearate, and treated with silicone. - Coated with silica and treated with silicone, - Coated with alumina and treated with silicone, for example, TTO-55(S) (registered trademark), a product from Ishihara. - Coated with triethanolamine, - Coated with stearic acid, for example, TTO-55(C) (registered trademark), a product from Ishihara. - Coated with sodium hexametaphosphate, -Coated with TiO2 treated with octyltrimethylsilane, - Coated with TiO2 treated with polydimethylsiloxane, - Coated with anatase / rutile-type TiO2 treated with polydimethylhydrogensiloxane, - TiO2 coated with alumina, triethylhexanoin, aluminum stearate, and is sold by Croda under the trademark name Solaveil(trademark) CT-200. - TiO2 coated with aluminum stearate, alumina, and silicone, sold by Croda under the trademark name Solaveil(trademark) CT-12W. - Coated with TiO2 coated with lauroyllysine, - C9~C 15 TiO2 coated with fluoroalcohol phosphate and aluminum hydroxide.
[0088] Examples include at least one transition metal, such as iron, zinc, or manganese, and more specifically, manganese-doped TiO2 pigments. Preferably, the doped pigment is in the form of an oily dispersion. The oil present in the oily dispersion is preferably selected from triglycerides such as capric / caprylic acid triglycerides. The oily dispersion system of titanium dioxide particles may contain one or more dispersants, such as sorbitan esters, such as sorbitan isostearate, or polyoxyalkylene fatty acid esters of glycerol, such as Tri-PPG-3 myristyl ether citrate and polyglyceryl-3 polyricinoleate. Preferably, the oily dispersion of titanium dioxide particles contains at least one dispersant selected from polyoxyalkylene fatty acid esters of glycerol. More specifically, examples include oily dispersions in which manganese-doped TiO2 particles having the INCI names titanium dioxide (and) triPPG-3 myristyl citrate (and) polyglyceryl-3 ricinoleate (and) sorbitan isostearate are dispersed in caprylic / capric triglyceride in the presence of tri-PPG-3 myristyl citrate, polyglyceryl-3 polycinoleate and sorbitan isostearate, or products sold by Croda under the trademark name Optisol (OTP-1).
[0089] Uncoated titanium dioxide pigments are sold, for example, by Tayca under the trademark names MT-500B and MT-600B®, or by Evonik under the trade name Degussa P25.
[0090] Uncoated zinc oxide pigments include, for example, the following: - Products sold by BASF under the name Z-Cote® (registered trademark); - Sold by Nanophase Technologies under the name NanoArc(registered trademark) Zinc Oxide.
[0091] Examples of coated zinc oxide pigments are shown below: - ZnO coated with polymethylhydrosiloxane; - Benzoic acid C 12 -C 15 Solaveil® CZ-100 (INCI: Zinc Oxide, C12-15 Alkyl Benzoate, Polyhydroxystearic Acid, and Isostearic Acid) from Croda, dispersed in an alkyl ester); - Sold by Daito Kasei under the name Daitopersion Zn-60VA (registered trademark) (contains dispersant, C9~C 12 Dispersion in alkanes; - Sold by Shin-Etsu under the name SPD-Z5 (registered trademark) (a product in which ZnO coated with a silicone-grafted acrylic polymer is dispersed in cyclodimethylsiloxane).
[0092] Uncoated cerium oxide pigments can be, for example, those sold by Solvay under the name Rhodigard® W15.
[0093] Examples of metal oxide mixtures include, in particular, mixtures of titanium dioxide and cerium dioxide, such as an equal mass mixture of titanium dioxide and cerium dioxide (coated with silica), and mixtures of titanium dioxide and zinc dioxide (coated with alumina, silica and silicone or alumina, silica and glycerol).
[0094] When the composition according to the present invention contains an inorganic UV shielding agent, coated or uncoated titanium dioxide pigments are particularly preferred.
[0095] According to a particular embodiment, the total amount of UV shielding agent present in the composition is 15% by mass or more of the total mass of the composition. According to a preferred embodiment, the total amount of UV shielding agent present in the composition is 15% to 35% by mass, preferably 16% to 25% by mass, of the total mass of the composition.
[0096] In relation to the spirit of this invention, the term "total amount of UV shielding agent" means the sum of the concentrations of the active substances of the UV shielding agents present in the composition, particularly lipophilic organic UV shielding agents, hydrophilic organic UV shielding agents, and inorganic UV shielding agents.
[0097] Ascorbic acid For the purposes of the present invention, ascorbic acid is preferably L-ascorbic acid or vitamin C, which has the structure of formula (IV). [ka]
[0098] The composition according to the present invention contains at least 1% by mass, preferably at least 5% by mass, and more preferably at least 7% by mass of ascorbic acid, based on the total mass of the composition.
[0099] Preferably, the composition contains 1% to 30% by mass, preferably 5% to 25% by mass, more preferably 7% to 20% by mass, and even more preferably 8% to 15% by mass of ascorbic acid, based on the total mass of the composition.
[0100] Scleroglucan gum The composition according to the present invention comprises one or more types of scleroglucan gum.
[0101] Scleroglucan gum is a microbial polysaccharide produced by fungi of the genus Sclerotium, particularly Sclerotium rolfsii. These polysaccharides are composed solely of glucose units.
[0102] Scleroglucan gum may be denatured or undenatured. Preferably, the scleroglucan gum used in the present invention is undenatured.
[0103] Non-limiting examples of scleroglucan gums that can be used in the present invention include products marketed by Sanofi Bio Industries under the name Actigum CS, particularly Actigum CS 11, and products marketed by Alban Mueller International under the name Amigum or Amigel.
[0104] Other scleroglucan gums, such as the glyoxal-treated gum described in French Patent Application Publication No. 2633940, can also be used.
[0105] The scleroglucan gum that can be used in accordance with the present invention preferably represents a total content in the range of 0.01% to 10% by mass, more preferably 0.05% to 5% by mass, and even more preferably 0.1% to 3% by mass, based on the total mass of the composition.
[0106] Lipophilic polymers According to a particular embodiment of the present invention, the composition comprises at least one lipophilic polymer containing monomer units of formulas (A) and (B): [ka] (In the formula, R1 is independently selected from an alkyl group or an alkenyl group; At least 60% by mass of the R1 groups are selected from stearyl and behenyl groups, and this mass percentage is relative to the total of all R1 groups present in the polymer; The mass ratio of the total hydroxyethyl acrylate units to the total acrylate units having an R1 group is in the range of 1:30 to 1:1; The sum of units A and B is at least 95% by mass of the total mass of the polymer. Includes.
[0107] Preferably, R1 is an alkyl group, preferably C 16 ~C 22 Alkyl alkyl groups, more preferably stearyl(C) 18 ) group, or behenyl (C 22 It is composed of ) groups.
[0108] Preferably, at least 70% by mass, preferably at least 80% by mass, and more preferably at least 90% by mass of the R1 group are stearyl groups or behenyl groups.
[0109] In one preferred embodiment, all R1 groups are behenyl groups.
[0110] In other preferred embodiments, all R1 groups are stearyl groups.
[0111] Preferably, the mass ratio is in the range of 1:15 to 1:1, and more preferably in the range of 1:10 to 1:4.
[0112] Advantageously, the polymer units present in the polymer are composed of the above-mentioned units (A) and (B).
[0113] According to a particular embodiment of the present invention, the polymer has a number-average molecular weight Mn in the range of 2000 to 9000 g / mol, and preferably in the range of 5000 to 9000 g / mol. The number-average molecular weight can be measured by gel permeation chromatography, for example, according to the method described in the following example.
[0114] Preferably, the melting point of the polymer is in the range of 40°C to 70°C, and more preferably in the range of 45°C to 67°C. The melting point is measured by differential scanning calorimetry (DSC), for example, by the method described later in the examples.
[0115] According to the first embodiment, when at least 60% by mass of the R1 groups of the polymer are stearyl groups, the melting point of the polymer is generally in the range of 40 to 60°C, and preferably in the range of 45 to 55°C.
[0116] According to the second embodiment, when at least 60% by mass of the R1 groups of the polymer are behenyl groups, the melting point of the polymer is generally in the range of 60 to 70°C, and preferably in the range of 63 to 67°C.
[0117] The polymer used in accordance with the present invention can be prepared by polymerizing a monomer of the formula CH2=CH-COO-R1 (where R1 is the same as above) and 2-hydroxyethyl acrylate.
[0118] Polymerization can be carried out according to known methods such as solution polymerization or emulsion polymerization.
[0119] Polymerization is described, for example, in U.S. Patent Application Publication No. 2007 / 0264204.
[0120] The lipophilic polymers described above used in connection with the present invention may be present in the composition such that the amount of active substance is in the range of 0.05% to 10% by mass, preferably 0.1% to 5% by mass, and more preferably 0.2% to 3% by mass, based on the total mass of the composition.
[0121] aqueous phase The composition according to the present invention comprises at least one aqueous phase.
[0122] The aqueous phase contains water and, optionally, another organic solvent that is water-soluble or water-miscible at 25°C.
[0123] The water used may include sterilized desalinated water and / or floral water, such as rose water, cornflower water, chamomile water, or lime water, and / or natural hot spring water or mineral water.
[0124] Suitable aqueous phases for the present invention may include, for example, natural spring water, such as water from La Roche-Posay, water from Vittel, water from Saint-Gervais Mont Blanc, or water from Vichy, or water selected from floral waters.
[0125] Suitable water-soluble or water-miscible solvents for the present invention include short-chain monoalcohols, such as C1-C4 monoalcohols, such as ethanol or isopropanol; diols or polyols, such as ethylene glycol, 1,2-propylene glycol, 1,3-butylene glycol, hexylene glycol, diethylene glycol, dipropylene glycol, 2-ethoxyethanol, diethylene glycol monomethyl ether, triethylene glycol monomethyl ether, glycerol, and sorbitol, as well as mixtures thereof.
[0126] According to one particular embodiment of the present invention, the entire aqueous phase in the composition, including all hydrophilic substances soluble in the aqueous phase and a hydrophilic barrier, accounts for 40% to 80% by mass, preferably 55% to 75% by mass, of the total mass of the composition.
[0127] fatty phase The composition according to the present invention may contain at least one fatty phase.
[0128] The fatty phase may consist of all fatty substances conventionally used in the fields of cosmetic medicine and dermatology; in particular, it may include at least one oil. The fatty phase also includes a lipophilic shielding agent present in the composition according to the present invention.
[0129] The term "oil" is intended to mean any lipid that is in liquid form at ambient temperature (20-25°C) and atmospheric pressure (760 mmHg). Oils may be volatile or non-volatile.
[0130] In this invention, the term "volatile oil" refers to an oil that, upon contact with skin or keratin fibers, can evaporate in less than one hour at ambient temperature and atmospheric pressure. The volatile oil of this invention is liquid at ambient temperature and has a vapor pressure other than zero at ambient temperature and atmospheric pressure, particularly 0.13 Pa to 40000 Pa (10 -3 This is a volatile cosmetic oil exhibiting a vapor pressure 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).
[0131] The term "non-volatile oil" refers to an oil that remains on the skin or keratin fibers for at least several hours under ambient temperature and atmospheric pressure, and in particular has a vapor pressure of 10. -3 This refers to oil with a pH of less than mmHg (0.13 Pa).
[0132] With respect to the object of the present invention, the term "hydrocarbon oil" means any oil that mainly contains carbon atoms and hydrogen atoms, and optionally contains one or more heteroatoms, particularly nitrogen and oxygen. Accordingly, these oils may contain one or more ester groups, ether groups, fluoro groups, carboxylic acid groups and / or alcohol groups.
[0133] The term "silicone oil" is intended to mean an oil containing at least one silicon atom, and moreover, at least one Si-O group.
[0134] In particular, the following can be mentioned as non-volatile hydrocarbon-based oils that may be used in accordance with the present invention: (i) Hydrocarbon oils of plant origin, such as glyceride triesters, generally fatty acids and glycerol triesters (these fatty acids are C4-C4). 24(These chains may have varying lengths, and these chains may be straight or branched, saturated or unsaturated.) These oils are, 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, almond oil, palm oil, rapeseed oil, cottonseed oil, hazelnut oil, macadamia oil, jojoba oil, alfalfa oil, poppy oil, red pumpkin oil, pumpkin oil, blackcurrant oil, evening primrose oil, millet oil, barley oil, quinoa oil, rye oil, safflower oil, candlenut oil, passionflower oil, or musk rose oil; or caprylic / capric acid notriglycerides, for example, those sold by Stearineries Dubois, or those sold by Dynamit Nobel under the names Miglyol 810®, 812®, and 818®; (ii) Synthetic ethers having 10 to 40 carbon atoms; (iii) Straight-chain or branched hydrocarbons of mineral or synthetic origin, such as liquid petrolatum, polydecene, hydrogenated polyisobutene such as parleam, squalane, and mixtures thereof; (iv) Synthetic esters, for example, oils of the formula RCOOR' (wherein R represents a linear or branched fatty acid residue containing 1 to 40 carbon atoms, and R' represents a hydrocarbon chain containing 1 to 40 carbon atoms, especially a branched hydrocarbon chain, provided that R + R' ≥ 10), for example Purcellin oil (cetostearyl octanoate), isopropyl myristate, isopropyl palmitate, C 12 ~C 15Alkyl benzoate (products sold by Witco under the trade names Finsolv TN® or Witconol TN®, or by Evonik Goldschmidt under the trade name Tegosoft TN®, etc.), 2-ethylphenyl benzoate (products marketed by ISP under the name X-Tend 226®, etc.), isopropyl lanolinate, hexyl laurate, diisopropyl adipate, isononyl isononanoate, oleyl erucate, 2-ethylhexyl palmitate, isostearyl isostearate, diisopropyl sebacate (from Stearinerie Dubois under the trade name "Dub Products sold under the name "Dis", etc.; octanoic acid esters, decanoic acid esters, or ricinoleic acid esters of alcohols or polyhydric alcohols (e.g., propylene glycol dioctanoate); hydroxylated esters (e.g., isostearyl lactate, diisostearyl malate); pentaerythritol esters; citrate esters or tartaric acid esters (e.g., di(linear C) tartaric acid); 12 ~C 13 In addition to alkyl esters (such as those sold by Enichem Augusta Industriale under the name Cosmacol ETI®), ditartrate (linear C) 14 ~C 15 Alkyl esters (such as those sold by the company under the name Cosmacol ETL®); acetate esters; (v) Fatty alcohols, aliphatic alcohols that are liquid at ambient 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) Carbonates, for example, dicaprylyl carbonate, for example, products marketed by Cognis under the name Cetiol CC®; and mixtures thereof.
[0135] Among the non-volatile hydrocarbon oils that can be used in accordance with the present invention, more specifically, glyceride triesters, particularly caprylic / capric triglyceride, synthetic esters, particularly diisopropyl adipate, diisopropyl sebacate, isopropyl palmitate, dicaprylyl carbonate, isononyl isononanoate, oleyl erucate, alkyl (C12-15) benzoate, 2-ethylphenyl benzoate, and fatty alcohols, particularly octyldodecanol, are preferred. Preferably, the non-volatile hydrocarbon oil is selected from diisopropyl adipate, diisopropyl sebacate, isopropyl palmitate, and dicaprylyl carbonate.
[0136] As volatile hydrocarbon-based oils that can be used in accordance with the present invention, in particular hydrocarbon-based oils containing 8 to 16 carbon atoms, especially branched C8-C6 16 Alkanes, for example, petroleum-derived C8-C 16 Isoalkanes (also known as isoparaffins), such as isododecane (also known as 2,2,4,4,6-pentamethylheptane), isodecane or isohexadecane, oils sold under the brand names Isopar or Permethyl, branched C8-C 16 Esters, isohexyl neopentanoate, and mixtures thereof may be mentioned.
[0137] Other examples include alkanes (mixtures of different alkanes differing by at least one carbon) described in Cognis' patent application international publication brochure 2007 / 068 371 or international publication brochure 2008 / 155 059. These alkanes are obtained from fatty alcohols, which themselves are obtained from coconut kernel oil or palm oil. n-undecane (C) obtained in Examples 1 and 2 of Cognis' patent application international publication brochure 2008 / 155 059. 11 ) and n-tridecane (C 13 A mixture of n-dodecane (C) may be used. These are sold by Sasol under product numbers Parafol 12-97 and Parafol 14-97 (registered trademarks). 12) and n-tetradecane (C 14 ), and mixtures thereof may also be cited.
[0138] Other volatile hydrocarbon oils, such as petroleum distillates, particularly those sold by Shell under the name Shell Solt®, can also be used. According to one embodiment, the volatile solvent is selected from volatile hydrocarbon oils having 8 to 16 carbon atoms and mixtures thereof.
[0139] Non-volatile silicone oils may be selected from, in particular, non-volatile polydimethylsiloxane (PDMS), polydimethylsiloxane containing alkyl or alkoxy groups (each group having 2 to 24 carbon atoms) that are side chains and / or terminals of the silicone chain, or phenylated silicones, such as phenyl trimethicone, phenyl dimethicone, phenyl(trimethylsiloxy)diphenylsiloxane, diphenyl dimethicone, diphenyl(methyldiphenyl)trisiloxane, or (2-phenylethyl)trimethylsiloxysilicate.
[0140] Examples of volatile silicone oils include volatile linear or cyclic silicone oils, particularly those with a viscosity of 8 centistokes (8 × 10⁻¹⁰). -6 m 2 The silicones are of the form ( / s), and particularly those containing 2 to 7 silicon atoms, and these silicones optionally contain alkyl or alkoxy groups containing 1 to 10 carbon atoms. Volatile silicone oils that can be used in the present invention include octamethylcyclotetrasiloxane, decamethylcyclopentasiloxane, dodecamethylcyclohexasiloxane, heptamethylhexyltrisiloxane, heptamethyloctyltrisiloxane, hexamethyldisiloxane, octamethyltrisiloxane, decamethyltetrasiloxane, dodecamethylpentasiloxane, and mixtures thereof.
[0141] Examples of volatile linear alkyltrisiloxane oils 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 can be cited as an example.
[0142] Volatile fluorinated oils such as nonafluoromethoxybutane, decafluoropentane, tetradecafluorohexane, dodecafluoropentane, and mixtures thereof may also be used.
[0143] The fatty phase according to the present invention may also additionally include other fatty substances that are mixed with or dissolved in the oil.
[0144] Other fatty substances that can be present in the oily phase include, for example, the following: - Fatty acids such as stearic acid, lauric acid, palmitic acid, or oleic acid, which contain 8 to 30 carbon atoms; preferably, C, such as oleic acid, linoleic acid, or linolenic acid. 12 ~C 22 higher fatty acids; - Waxes selected from lanolin, beeswax, carnauba or candelilla wax, paraffin wax, lignite 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.
[0145] If present, the entire fatty phase of the composition, including all lipophilic substances soluble in the oily phase and lipophilic shielding agents, accounts for 20% to 60% by mass, preferably 25% to 45% by mass, of the total mass of the composition.
[0146] beauty active ingredients The composition of the present invention may contain at least one cosmetic active ingredient.
[0147] Examples of beauty active ingredients include moisturizers; natural extracts; vitamins other than vitamin C and their derivatives (especially esters); vitamin C derivatives (especially esters); urea; caffeine; salicylic acid and its derivatives; alpha-hydroxy acids such as lactic acid or glycolic acid and their derivatives; retinoids; extracts of algae, fungi, plants, yeast and bacteria; enzymes; tonics; agents that act on the microcirculation; and mixtures thereof.
[0148] Additional auxiliaries or additives The compositions of the present invention may also contain conventional cosmetic auxiliaries or additives, such as fragrances, chelating agents (e.g., tetrasodium glutamate diacetate and disodium EDTA), preservatives (e.g., chlorphenesin and phenoxyethanol) and bactericidal agents, additional thickeners (e.g., (acrylamide / sodium acryloyldimethyltaurate) copolymer, polysaccharides other than scleroglucan, especially xanthan gum), pH adjusters (e.g., triethanolamine, citric acid and sodium hydroxide), fillers (e.g., aluminum starch octenylsuccinate and polymethylsilsesquioxane) and mixtures thereof.
[0149] Those skilled in the art will select the amounts of the cosmetic active ingredient and auxiliary agents or additives so as not to adversely affect the final use of the composition of the present invention.
[0150] Dosage form The compositions according to the present invention can be prepared according to techniques well known to those skilled in the art.
[0151] The compositions according to the present invention may be in the form of single-phase or complex emulsions (O / W type, W / O type, O / W / O type, or W / O / W type), such as creams or lotions, gel creams, serums, or liquids.
[0152] According to certain embodiments of the present invention, the composition is in emulsion form. This can be in particular an oil-in-water emulsion (normal phase emulsion) form or an oil-in-water emulsion (reverse phase emulsion) form. Preferably, the composition is in oil-in-water emulsion form.
[0153] For compositions in the form of oil-in-water or water-in-oil emulsions, paddle-type, impeller-type, rotor-stator-type, and HPH-type emulsification processes can be used.
[0154] To obtain a stable emulsion when the polymer content is low (oil / polymer ratio > 25), it is possible to prepare a dispersion in a concentrated phase and then dilute the dispersion with the remaining aqueous phase.
[0155] By using HPH (50-800 bar), it is possible to obtain stable dispersions with a suitable droplet size of about 100 nm.
[0156] The emulsion may contain at least one emulsifier selected from amphoteric, anionic, cationic, or nonionic emulsifiers, used alone or in mixtures. The emulsifier is appropriately selected depending on the emulsion to be obtained (W / O type or O / W type).
[0157] Examples of W / O type emulsifying surfactants include alkyl esters or ethers of sorbitan, glycerol, polyol, or sugar; silicone surfactants, e.g., dimethicone copolyol, e.g., a mixture of cyclomethicone and dimethicone copolyol sold by Dow Corning under the name DC 5225 C®; and alkyl dimethicone copolyol, e.g., lauryl methicone copolyol sold by Dow Corning under the name Dow Corning 5200 Formulation Aid; cetyl dimethicone copolyol, e.g., a product sold by Goldschmidt under the name Abil EM 90R® and a mixture of cetyl dimethicone copolyol, polyglyceryl isostearate (4 mol), and hexyl laurate sold by Goldschmidt under the name Abil WE O9®. One or more emulsifying agents, which can be advantageously selected from the group including polyol alkyl esters, may also be added.
[0158] Non-silicone emulsifying surfactants, particularly alkyl esters or ethers of sorbitan, glycerol, polyol, or sugar, can also be mentioned.
[0159] Examples of polyol alkyl esters include polyethylene glycol esters, such as PEG-30 dipolyhydroxystearate, for example, the product sold by ICI under the name Arlacel P135 (registered trademark).
[0160] Glycerol esters and / or sorbitan esters that may be mentioned include polyglyceryl isostearate, e.g., a product marketed by Goldschmidt under the name Isolan GI 34®; sorbitan isostearate, e.g., a product marketed by ICI under the name Arlacel 987®; sorbitan glyceryl isostearate, e.g., a product marketed by ICI under the name Arlacel 986®; and mixtures thereof.
[0161] In the case of O / W emulsions, examples of nonionic emulsifying surfactants include: esters of polyoxyalkylene (more specifically polyoxyethylene and / or polyoxypropylene) fatty acids with glycerol, e.g., polyethylene glycol stearate ester, marketed by Croda under the name Myrj S100-PA-(SG), with the INCI name PEG-100 Stearate; esters of oxyalkylene fatty acids with sorbitan; and polyoxyalkylene (especially polyoxyethylene and / or polyoxypropylene) esters of fatty acids, optionally combined with esters of fatty acids and glycerol, e.g., PEG-100 stearate / glyceryl stearate mixture, e.g., Arlacel by ICI. Products sold under the name 165; ethers of oxyalkylene (oxyethylene and / or oxypropylene) fatty alcohols; sugar esters, e.g., sucrose stearate; or fatty alcohols and sugar ethers, especially alkyl polyglucosides (APGs), e.g., decyl glucoside and lauryl glucoside, e.g., those sold by Henkel under the names Plantaren 2000 (registered trademark) and Plantaren 1200 (registered trademark), respectively; cetostearyl glucoside, optionally as a mixture with cetostearyl alcohol, e.g., those sold by SEPPIC under the name Montanov 68 (registered trademark), those sold by Goldschmidt under the name Tegocare CG90 (registered trademark), and those sold by Henkel under the name Emulgade Examples include those sold under the name KE3302®, and those sold by SEPPIC under the name Montanov 202®, which are in the form of arachidyl glucosides, such as mixtures of arachidyl alcohol and behenyl alcohol with arachidyl glucoside. According to a particular embodiment of the present invention, mixtures of the alkyl polyglucosides defined above with the corresponding fatty alcohols may take the form of self-emulsifying compositions, such as those described in, for example, International Publication No. 92 / 06778.
[0162] An anionic surfactant that enables the formation of O / W emulsions includes at least one C8-C 30 Preferably C8~C 24 Examples of surfactants include amino acids and their salts modified with hydrocarbon chains, particularly acyl glutamic acid (INCI name: acyl glutamic acid) or its salts (acyl glutamate salts), such as stearoyl glutamic acid or its salts, especially sodium stearoyl glutamate (INCI name) (INCI name).
[0163] Such compounds are marketed by Ajinomoto under the name Amisoft, particularly under the reference names Amisoft CA, Amisoft LA, Amisoft HS 11 PF, Amisoft MK-11, Amisoft LK-11, and Amisoft CK-11, or by Cognis under the alternative name Eumulgin SG.
[0164] Anionic surfactants that enable the formation of O / W emulsions include hydrophobically modified polysaccharides, particularly hydrophobic chains, such as alkylcarbamate groups, especially C8-C8. 18 Examples include inulin modified with alkylcarbamate groups, or more specifically, laurylcarbamate groups.
[0165] Examples of these compounds include, in particular, the product marketed by Creachem under the name Inutec SL1.
[0166] The composition according to the present invention may also be an aqueous solution, more preferably an aqueous solution having a slightly gelled appearance.
[0167] According to another specific embodiment, the composition according to the present invention is a single-layer aqueous composition. This composition may be called a “serum.” The term “serum” is understood to mean a flowing composition having a fluid texture and a slightly gelled appearance.
[0168] According to this embodiment, the composition is preferably substantially free of surfactants. The term "substantially free of surfactants" is understood to mean that the composition according to the present invention contains a surfactant of 2% by mass or less, preferably 1% by mass or less, relative to the total mass of the composition. The surfactant may preferably be a dissolving agent having a concentration of 0.1% to 2% by mass, which enables the dissolution of small amounts of oil or lipophilic compounds or fragrances (i.e., the concentration of the fragrance or oil or lipophilic compound is 0.05% to 2% by mass). [Examples]
[0169] The present invention will now be described in more detail using examples, but these examples do not limit the scope of the invention in any way. However, these examples can support certain features, modifications, and preferred embodiments of the present invention.
[0170] A / Synthesis example of a lipophilic polymer containing monomer units of formulas (A) and (B) according to the present invention Determination of molecular weight by gel permeation chromatography (GPC): The sample is prepared by preparing a tetrahydrofuran solution containing 10 mg / ml of polymer. The sample is placed in a 54°C oven for 10 minutes, and then shaken in a reciprocating shaker for 60 minutes to promote dissolution. Visual inspection reveals that the sample appears to be completely dissolved in the solvent.
[0171] The prepared samples were analyzed using two polypore 300 × 7.5 mm columns (Agilent Technologies), a Waters 2695 chromatography system, a tetrahydrofuran mobile phase, and refractive index detection. The samples were filtered through a 0.45 μm nylon filter before being injected into the liquid chromatograph. The calibration standard used was Agilent Technologies' Easi Vial, a polystyrene (PS) standard with a narrow molecular weight distribution.
[0172] For calibration, polystyrene standard materials ranging from 2,520,000 to 162 Daltons were used.
[0173] This system is equipped with a PSS SECcurity 1260 RI detector. The average molecular weight was determined using a polystyrene calibration curve. Chromatograms (diagrams) were recorded and various molecular weights were determined using the Win GPC Unichrom 81 program.
[0174] Measurement of melting point by differential scanning calorimetry (or DSC): This method describes a general procedure for determining the melting point of a polymer by differential scanning calorimetry. The method is based on standards ASTM E791 and ASTM D 34182, and the DSC calibration is performed according to standard ASTM E 9672.
[0175] Behenyl acrylate / 2-hydroxyethyl acrylate copolymer (polymer 1): In a four-necked flask equipped with a side-blade mixer, an internal thermometer, two funnels, a reflux condenser, and extension connections from the other two necks, oxygen was removed from the system by flushing with nitrogen for 20 minutes. Then, 40 g of isopropanol was added to 175 g of behenyl acrylate, 25 g of 2-hydroxyethyl acrylate, and 0.4 g of 2,2'-azobis(2-methylbutyronitrile) (Akzo Nobel) over 60 minutes with stirring at 80°C. The mixture was stirred at 80°C for 3 hours. The solvent was then removed by vacuum distillation, and 1 g of dilauryl peroxide was added, and the reaction was continued at 110°C for 60 minutes. This step was repeated. The mixture was then cooled to 90°C, a stream of desalted water was added, and the mixture was stirred. Water was removed by vacuum distillation. Molecular weight: Mn=7300g / mol, Mw=21000, Mw / Mn=2.8 Melting point: 65℃
[0176] Stearyl acrylate / 2-hydroxyethyl acrylate copolymer (polymer 2): In a four-necked flask equipped with a side-blade mixer, an internal thermometer, two funnels, a reflux condenser, and extension connections from the other two necks, oxygen was removed from the system by flushing with nitrogen for 20 minutes. Then, 50 g of isopropanol was added to 155 g of behenyl acrylate, 45 g of 2-hydroxyethyl acrylate, and 0.4 g of 2,2'-azobis(2-methylbutyronitrile) (Akzo Nobel) over 90 minutes with stirring at 80°C. The mixture was stirred at 80°C for 3 hours. The solvent was then removed by vacuum distillation, and 1 g of dilauryl peroxide was added, and the reaction was continued at 125°C for 60 minutes. This step was repeated. The mixture was then cooled to 90°C, a stream of desalted water was added, and the mixture was stirred. Water was removed by vacuum distillation. Molecular weight: Mn=7500g / mol, Mw=19000, Mw / Mn=2.6 Melting point: 49℃
[0177] B / Combination example The following examples are illustrative of the present invention and are not inherently limiting. In these examples, the amounts of components present in the composition are expressed as the mass percentage of the starting material (SM) or active material (AM) relative to the total mass of the composition.
[0178] Protocol for evaluating the stability of the composition of the present invention The stability of the composition is evaluated macroscopically (appearance, color, odor, pH, and viscosity) and microscopically at 4°C, 25°C, and 45°C for 24 hours, 1 month, and 2 months.
[0179] Macroscopic stability is evaluated visually, and microscopic stability is evaluated using a white light microscope.
[0180] Method for preparing a composition The process for producing the exemplified composition is conventional.
[0181] Generation within the main container: The starting material for phase A1 is introduced into the container. The container is placed under vacuum, and blade and turbine stirring is performed to homogenize phase A1, heating the turbine to a temperature of 47°C. Once this temperature is reached, heating is stopped, and the starting material for phase A2 is aspirated. Under vacuum, a turbine efficiency of 2000 rpm to 2500 rpm is applied at a temperature of 47°C. Care is taken to ensure sufficient dispersion until a homogeneous medium free of gel particles is obtained.
[0182] Once phases A1 and A2 are completely homogenized, phase B, prepared according to the manufacturing process defined below, is introduced, and the mixture is thoroughly stirred for at least 10-15 minutes at a turbine efficiency of 2500-3000 rpm, still under vacuum, at a temperature of 50-55°C, until a suitable emulsion is obtained. Once a suitable emulsion is obtained, the preparation is cooled under vacuum while stirring with a scraper blade until a temperature of below 35°C is obtained. At this stage, the starting materials for phases C1 and C2 are introduced while stirring at 2500-3000 rpm. Dispersion is carried out while stirring at 2500-3000 rpm until a suitable emulsion and good dispersion of fillers are obtained. Cooling is continued while stirring with a scraper blade, and vacuum is applied as needed. At 33°C, the manufacturing vessel is inactivated until the end of manufacturing, and then the starting materials for phase D are introduced at a temperature of below 33°C while stirring at a turbine efficiency of 2500-3000 rpm. Continue stirring under a microscope until a suitable emulsion is obtained. Once this step is reached, introduce the starting materials for phases E1, E2, and E3 in that order and stir for 15 minutes at a turbine efficiency of 2500 rpm to 3000 rpm.
[0183] Manufacturing process for Phase B: The starting material for phase B is introduced into the second container and heated with the thacinth to a temperature of 65-70°C. The medium is homogenized until it melts and becomes completely solubilized.
[0184] Transfer phase B to the main container for emulsification.
[0185] Comparative Examples - Compositions 1-4 Prepare compositions 1 to 4 as shown below.
[0186] [Table 1]
[0187] [Table 2]
[0188] Results obtained The stability results obtained are shown below.
[0189] [Table 3]
[0190] Compositions 1 and 2 according to the present invention exhibit better temporal stability and better temperature stability than comparative compositions 3 and 4, which do not contain scleroglucan gum.
Claims
1. Compositions, particularly cosmetic or dermatological compositions, a) At least one type of UV shielding agent, b) At least 1% by mass of ascorbic acid relative to the total mass of the composition, c) At least one type of scleroglucan gum and A composition containing the following:
2. The composition according to claim 1, wherein the UV shielding agent is selected from a lipophilic organic UV shielding agent, a hydrophilic organic UV shielding agent, and an inorganic UV shielding agent.
3. The composition according to claim 1 or 2, wherein the lipophilic organic UV shielding agent is selected from cinnamic acid compounds; anthranylate compounds; salicylic acid compounds; dibenzoylmethane compounds; benzylidene camphor compounds; benzophenone compounds; β,β-diphenyl acrylate compounds; triazine compounds; benzotriazole compounds; benzalmalonate compounds; benzimidazole derivatives; imidazoline compounds; bis-benzazolyl compounds; methylenebis(hydroxyphenyl)benzotriazole compounds; benzoxazole compounds; shielding polymers and shielding silicones; α-alkylstyrene dimers; 4,4-diarylbutadiene compounds; and mixtures thereof; preferably selected from salicylic acid compounds, dibenzoylmethane compounds, benzylidene camphor compounds; benzophenone compounds; triazine compounds; benzotriazole compounds; and mixtures thereof.
4. A composition according to any one of claims 1 to 3, comprising bis-ethylhexyloxyphenol methoxyphenyl triazine.
5. The composition according to any one of claims 1 to 4, wherein the hydrophilic organic UV shielding agent is selected from a water-soluble organic UV shielding agent and a water-dispersible organic UV shielding agent.
6. The aforementioned water-soluble UV shielding agents are benzene-1,4-bis(3-methylidene-10-camphor sulfonic acid) (INCI name: terephthalylidene dicamphor sulfonic acid); 1,4-bis-benzimidazolyl-phenylene-3,3',5,5'-tetrasulfonic acid (INCI name: phenyldibenzimidazole tetrasulfonic acid disodium); 2-phenyl-1H-benzimidazole-5-sulfonic acid (INCI name: phenyl A composition according to any one of claims 1 to 5, selected from rubenzimidazole sulfonic acid; and salts thereof; preferably selected from benzene-1,4-bis(3-methylidene-10-camphor sulfonic acid) (INCI name: terephthalylidene dicamphor sulfonic acid); 2-phenyl-1H-benzimidazole-5-sulfonic acid (INCI name: phenylbenzimidazole sulfonic acid); and salts thereof.
7. The water-dispersible organic UV screening agent is an aqueous dispersion of micronized particles having an average particle size in the range of 0.01 to 5 μm, more preferably in the range of 0.01 to 2 μm, and more particularly in the range of 0.020 to 2 μm, and C n H 2n+1 O(C 6 H 10 O 5 ) x H (where n is an integer from 8 to 16, and x is the average degree of polymerization of the (C 6 H 10 O 5 ) units and is in the range of 1.4 to 1.6) and at least one alkyl polyglycoside surfactant having a structure of methylene bis-benzotriazolyl tetramethylbutylphenol in the form of an aqueous dispersion; methylene bis-benzotriazolyl tetramethylbutylphenol in the form of an aqueous dispersion of micronized particles having an average particle size in the range of 0.02 to 2 μm, more preferably in the range of 0.01 to 1.5 μm, and more particularly in the range of 0.02 to 1 μm, and at least one polyglycerol mono(C 8 -C 20 ) alkyl ester having a degree of polymerization of glycerol of at least 5 is present; bis-ethylhexyloxyphenol methoxyphenyltriazine in a water-dispersible form and having an INCI name of bis-ethylhexyloxyphenol methoxyphenyltriazine (and) acrylates / C12-22 alkyl methacrylate copolymer; a symmetric triazine screening agent substituted with a naphthalenyl group or a polyphenyl group used in a micronized form (average particle size 0.02 to 3 μm), particularly a symmetric triazine screening agent in the form of an aqueous dispersion, particularly selected from 2,4,6-tris(biphenyl)triazine and 2,4,6-tris(terphenyl)triazine, the composition according to any one of claims 1 to 6.
8. The composition according to any one of claims 1 to 7, wherein the ascorbic acid is L-ascorbic acid.
9. The composition according to any one of claims 1 to 8, comprising at least 5% by mass, preferably at least 7% by mass, of ascorbic acid based on the total mass of the composition.
10. The composition according to any one of claims 1 to 9, comprising 1% to 30% by mass, preferably 5% to 25% by mass, more preferably 7% to 20% by mass, and even more preferably 8% to 15% by mass of ascorbic acid, based on the total mass of the composition.
11. The composition according to any one of claims 1 to 10, wherein the scleroglucan gum accounts for 0.01% to 10% by mass, more preferably 0.05% to 5% by mass, and even more preferably 0.1% to 3% by mass, based on the total mass of the composition.
12. At least one lipophilic polymer containing monomer units of formulas (A) and (B): 【Chemistry 1】 (In the formula, R 1 These are independently selected from alkyl groups or alkenyl groups; R 1 At least 60% by mass of the groups are selected from stearyl groups and behenyl groups, and this mass percentage is all of the R groups present in the polymer. 1 It is for the sum of the bases; The sum of all hydroxyethyl acrylate units versus the above R 1 The total mass ratio of all acrylate units containing the group is in the range of 1:30 to 1:1; The sum of units A and B is at least 95% by mass of the total mass of the polymer. A composition according to any one of claims 1 to 11, comprising:
13. In the aforementioned lipophilic acrylic polymer, R 1 However, alkyl groups, preferably C 16 ~C 22 The composition according to claim 12, comprising an alkyl group, more preferably a behenyl group or a stearyl group.
14. In the aforementioned lipophilic acrylic polymer, the R 1 The composition according to claim 12 or 13, wherein at least 70% by mass, preferably at least 80% by mass, and more preferably at least 90% by mass of the group is a behenyl group or a stearyl group.
15. In the aforementioned lipophilic acrylic polymer, the R 1 The composition according to any one of claims 12 to 14, wherein all of the groups are behenyl groups or stearyl groups.
16. In the aforementioned lipophilic acrylic polymer, the sum of all hydroxyethyl acrylate units is R 1 The composition according to any one of claims 12 to 15, wherein the total mass ratio of all the acrylate units having groups is in the range of 1:15 to 1:1, preferably 1:10 to 1:
4.
17. The composition according to any one of claims 12 to 16, wherein the number average molecular weight Mn of the lipophilic acrylic polymer is in the range of 5,000 to 9,000 g / mol.
18. The composition according to any one of claims 12 to 17, wherein the melting point of the lipophilic acrylic polymer is in the range of 40°C to 70°C, preferably in the range of 45°C to 67°C.
19. In the aforementioned lipophilic acrylic polymer, the R 1 The composition according to any one of claims 12 to 18, wherein at least 60% by mass of the group is a stearyl group, and the melting point of the polymer is in the range of 40 to 60°C, preferably in the range of 45 to 55°C.
20. In the aforementioned lipophilic acrylic polymer, the R 1 The composition according to any one of claims 12 to 19, wherein at least 60% by mass of the groups are behenyl groups, and the melting point of the polymer is in the range of 60°C to 70°C, preferably in the range of 63°C to 67°C.
21. The composition according to any one of claims 12 to 20, wherein the lipophilic acrylic polymer is present in an active substance content in the range of 0.05% to 10% by mass, preferably in the range of 0.1% to 5% by mass, and preferably in the range of 0.2% to 3% by mass, based on the total mass of the composition.
22. The composition according to any one of claims 1 to 21, wherein the composition is in the form of an emulsion, preferably in the form of an oil-in-water emulsion.