Skin topical composition

Abstract

The present invention provides a composition for external use on the skin that can maintain high moisturizing properties on the skin even after washing it off with water. SOLUTION: The topical skin composition of the present invention contains crosslinked hyaluronic acid beads, and in particular, the crosslinked hyaluronic acid beads are a crosspolymer of polyethylene glycol glycidyl ether and sodium hyaluronate.

Description

[Technical Field]

[0001] The present invention relates to a topical skin composition, and more particularly to a topical skin composition containing crosslinked hyaluronic acid beads. [Background technology]

[0002] Cosmetic compositions containing hyaluronic acid are known. Hyaluronic acid is used as a moisturizing agent and / or can smooth the texture of cosmetics and improve the feel when applied to the skin.

[0003] For example, Patent Document 1 discloses a facial cleanser containing hyaluronic acid and its derivatives, which has excellent foam elasticity and foam durability, and is comfortable and safe to use.

[0004] Furthermore, Patent Document 2 discloses inorganic powder for cosmetics in which the moisturizing effect is enhanced by coating the inorganic powder with hyaluronic acid.

[0005] Furthermore, as described in Patent Documents 3 and 4, it is known to use cross-linked hyaluronic acid beads as a composition for skin injection. [Prior art documents] [Patent documents]

[0006] [Patent Document 1] Japanese Patent Publication No. 2022-126195 [Patent Document 2] Japanese Patent Application Laid-Open No. 2009-263249 [Patent Document 3] International Publication No. 2009 / 077620 [Patent Document 4] Special Publication No. 2020-512061 Summary of the Invention [Problem to be solved by the invention]

[0007] The present invention aims to provide a composition for external use on the skin that can maintain high moisturizing properties on the skin even after rinsing with water. [Means for solving the problem]

[0008] The present invention has the following aspects: <<Aspect 1>> A composition for topical application to the skin containing cross-linked hyaluronic acid beads. <<Aspect 2>> 2. The topical skin composition of claim 1, wherein the crosslinked hyaluronic acid beads comprise a crosspolymer of polyethylene glycol glycidyl ether and sodium hyaluronate. Aspect 3 The topical skin composition according to aspect 1, further comprising a cationic polymer. Aspect 4 The composition for external application to skin according to Aspect 1, which is in the form of an oily liquid, a cosmetic oil, a balm, a skin lotion, a lotion, an emulsion, a cream, a gel, or a pack cosmetic. Aspect 5 Aspect 5. The topical skin composition according to aspect 4, which is in the form of an aqueous gel. Aspect 6 The topical skin composition according to aspect 5, which is a cleansing agent. Aspect 7 A wipe sheet having a substrate impregnated with the topical skin composition according to embodiment 1. [Effects of the Invention]

[0009] The present invention can provide a composition for external use on the skin that can maintain high moisturizing properties on the skin even after rinsing with water. DETAILED DESCRIPTION OF THE INVENTION

[0010] The topical skin composition of the present invention contains crosslinked hyaluronic acid beads.

[0011] The present inventors have discovered that by incorporating crosslinked hyaluronic acid beads, which have not been conventionally used in the field of cosmetics, into a topical skin composition, it is possible to provide the skin with a high level of moisturizing properties that cannot be achieved by incorporating other forms of hyaluronic acid.Furthermore, it has been found that the crosslinked hyaluronic acid beads function as a scrubbing material in the form of beads, but do not cause a rough or prickly feeling to the skin when massaging the skin during face washing, etc., and can provide the topical skin composition with an excellent usability.

[0012] <Cross-linked hyaluronic acid beads> As used herein, crosslinked hyaluronic acid beads refer to hyaluronic acid in the form of beads that have been crosslinked. Here, hyaluronic acid includes all modifications of hyaluronic acid, hyaluronate, or hyaluronan, as well as combinations of these modifications.

[0013] Hyaluronic acid can be crosslinked, for example, by a crosslinking agent having a bifunctional epoxy group. Examples of crosslinking agents having a bifunctional epoxy group include 1,4-butanediol diglycidyl ether, poly(ethylene glycol) diglycidyl ether, poly(propylene glycol) diglycidyl ether, poly(tetramethylene glycol) diglycidyl ether, polyglycerol polyglycidyl ether, glycerol diglycidyl ether, triethylene diglycidyl ether, trimethylolpropane triglycidyl ether, ethylene diglycidyl ether, neopentyl glycol diglycidyl ether, and 1,6-hexanediol diglycidyl ether, and particularly poly(ethylene glycol) diglycidyl ether. Therefore, crosslinked hyaluronic acid beads can contain crosspolymers of hyaluronic acid and these crosslinking agents. As commercially available crosslinked hyaluronic acid beads, "HA BEADS" manufactured by HYUNDAI BIOLAND Co., Ltd. can be preferably used. It was found that these crosslinked hyaluronic acid beads, when incorporated into topical skin compositions, remain on the skin easily and provide high moisturizing properties. This is thought to be because the crosslinked hyaluronic acid beads are cross-polymerized, resulting in the presence of hydrophobic moieties in some parts, which enhances their affinity with the skin.

[0014] When the number of ethylene oxide units in the poly(ethylene glycol) diglycidyl ether used as the crosslinking agent is in the range of 3 to 20, 5 to 15, or 8 to 12, the crosslinked hyaluronic acid beads can have appropriate physical properties such as elasticity.

[0015] The average particle size of the crosslinked hyaluronic acid beads may be, for example, 0.1 mm or more, 0.3 mm or more, 0.5 mm or more, 1.0 mm or more, or 1.5 mm or more, or 10 mm or less, 5.0 mm or less, 3.0 mm or less, 2.0 mm or less, or 1.5 mm or less. The average particle size can be determined by observing with an optical microscope, selecting 100 or more particles of a representative size, and measuring the major axis of the 100 or more particles.

[0016] The crosslinked hyaluronic acid beads may be contained in the topical skin composition at 0.01% by mass or more, 0.03% by mass or more, 0.05% by mass or more, or 0.10% by mass or more, or at 3.0% by mass or less, 1.0% by mass or less, 0.50% by mass or less, 0.30% by mass or less, 0.20% by mass or less, 0.10% by mass or less, or 0.05% by mass or less.

[0017] <Cationic polymer> The topical skin composition of the present invention can further contain a cationic polymer. The present inventors have found that the use of crosslinked hyaluronic acid beads together with a cationic polymer can provide a particularly high moisturizing effect to the skin. This is thought to be because the cationic polymer adheres to the skin, which is mainly anionic, and the crosslinked hyaluronic acid beads then adhere to the cationic polymer.

[0018] Examples of cationic polymers include water-soluble cationic polymers, such as polyquaterniums, cationized cellulose derivatives, cationized gums, cationized chitosan, cationized protein derivatives, and cationized hydrolyzed collagen.

[0019] The cationic polymer may be contained in the topical skin composition at 0.01% by mass or more, 0.03% by mass or more, 0.05% by mass or more, or 0.10% by mass or more, or at 3.0% by mass or less, 1.0% by mass or less, 0.50% by mass or less, 0.30% by mass or less, 0.20% by mass or less, 0.10% by mass or less, or 0.05% by mass or less.

[0020] The cationic polymer may be contained in the topical skin composition in an amount of 10 parts by mass or more, 30 parts by mass or more, 50 parts by mass or more, or 100 parts by mass or more, or 300 parts by mass or less, 200 parts by mass or less, 100 parts by mass or less, 50 parts by mass or less, or 30 parts by mass or less, per 100 parts by mass of crosslinked hyaluronic acid beads.

[0021] <Dosage form> The formulation of the topical skin composition is not particularly limited. For example, the topical skin composition may be in various forms such as an oily composition, an aqueous composition, an emulsion, a cream, a gel, or a pack cosmetic. The topical skin composition may also be in the form of a wipe sheet impregnated into a substrate. The topical skin composition may be a so-called leave-on cosmetic or a leave-off cosmetic, such as a cleanser composition that is washed off with water.

[0022] <Dosage form - oily composition> The topical composition for skin can be an oily liquid composition, an oily semi-solid composition, etc. Oily compositions, particularly oily semi-solid cleanser compositions, can provide moisturizing properties to the skin by leaving oil behind even after rinsing with water, and although there was no idea of ​​adding hyaluronic acid or the like for further moisturizing properties, it has been found that they can provide high moisturizing properties.

[0023] The oily composition may be a liquid cosmetic oil, or may be a semi-solid balm or cleanser.

[0024] When the topical composition for skin is an oily liquid composition, it can contain liquid oil, a nonionic surfactant, the cationic polymer, and / or crosslinked hyaluronic acid beads. For example, the topical composition for skin can contain 60 to 95% by mass of liquid oil and further contain 3 to 30% by mass of a nonionic surfactant.

[0025] When the topical skin composition is an oily semi-solid, it can contain solid oil, liquid oil, a nonionic surfactant, the cationic polymer, and / or crosslinked hyaluronic acid beads. For example, the topical skin composition can contain 1 to 30% by mass of solid oil and 50 to 95% by mass of liquid oil, and can further contain 3 to 30% by mass of a nonionic surfactant.

[0026] The solid oil may be an oil that is solid at room temperature (25° C.), and serves as a thickener in an oily semi-solid composition to make the composition semi-solid.

[0027] The content of solid oil in the composition for external use on skin may be 1% by mass or more, 3% by mass or more, 5% by mass or more, 7% by mass or more, or 10% by mass or more, and may be 30% by mass or less, 20% by mass or less, 15% by mass or less, or 10% by mass or less. The content of solid oil in the composition for external use on skin can be, for example, 1% by mass or more and 30% by mass or less, 3% by mass or more and 20% by mass or less, or 5% by mass or more and 15% by mass or less.

[0028] The melting point of the solid oil may be 40°C or higher, 50°C or higher, 60°C or higher, or 70°C or higher, or 120°C or lower, 110°C or lower, 100°C or lower, or 90°C or lower. Here, the melting point of the solid oil can be measured by Melting Point Determination Method 2, a general testing method in the Standards for Quasi-drug Ingredients. The melting point of the solid oil can be, for example, 40°C or higher and 120°C or lower, 50°C or higher and 110°C or lower, or 60°C or higher and 100°C or lower.

[0029] When the content and melting point of the solid oil are within the above ranges, the liquid oil can be solidified uniformly, the storage stability and shape retention are sufficient, and the product can be given an appropriate hardness when used.

[0030] Specifically, the solid oil may be any solid oil used in ordinary oily semi-solid compositions, such as hydrocarbon waxes such as paraffin wax, polyethylene wax, and Fischer-Tropsch wax, carnauba wax, candelilla wax, rice wax, beeswax (beeswax), hydrogenated jojoba oil, hardened oils, higher alcohols, and silicone waxes, and two or more of these may be combined. Oily semi-solid compositions for external use on skin must be heated for a long time during the process of filling them into containers, and hydrocarbon waxes are preferred from the viewpoint of oxidation resistance during heating.

[0031] Examples of liquid oils include oils that are fluid at room temperature (25°C) and semi-solid oils with a melting point of less than 50°C or less than 40°C.

[0032] The content of liquid oil in the composition for external use on skin may be 50% by mass or more, 55% by mass or more, 60% by mass or more, 65% by mass or more, or 70% by mass or more, or may be 95% by mass or less, 90% by mass or less, 85% by mass or less, or 80% by mass or less. The content of liquid oil in the composition for external use on skin can be, for example, 50% by mass or more and 95% by mass or less, 55% by mass or more and 90% by mass or less, or 60% by mass or more and 85% by mass or less.

[0033] When the content of the liquid oil is within the above range, the composition for external use on skin can be provided with properties such as easy compatibility with other cosmetics and easy spreadability when applied to the skin.

[0034] The mass ratio of solid oil to liquid oil may be 0.05 or more, 0.10 or more, 0.15 or more, 0.20 or more, or 0.25 or more, and may be 0.50 or less, 0.40 or less, 0.30 or less, 0.25 or less, or 0.20 or less. For example, the mass ratio may be 0.05 or more and 0.50 or less, or 0.10 or more and 0.30 or less.

[0035] Specifically, the liquid oil may be any liquid oil used in ordinary oily liquid compositions or oily semi-solid compositions, and may be any of animal oil, vegetable oil, or synthetic oil. For example, tri(caprylic / capric acid)glyceryl, triethylhexanoin, diglyceryl triisostearate, decaglyceryl decaisostearate, cetyl isooctanoate, isopropyl myristate, isopropyl palmitate, cholesterol fatty acid esters, jojoba oil and other esters; hydrocarbons such as volatile isoparaffin, polybutene, polyisobutylene, squalane, petrolatum; oils and fats such as olive oil, castor oil, mink oil, macadamia nut oil and other; fatty acids such as isostearic acid, oleic acid and other; higher alcohols such as oleyl alcohol, isostearyl alcohol and other; silicone oils such as low-polymerization dimethylpolysiloxane, methyl trimethicone, caprylyl trimethicone, fluorine-modified polysiloxane and other; fluorine-based oils such as perfluoropolyether; lanolin, lanolin acetate, lanolin fatty acid isopropyl, lanolin alcohol and other lanolin derivatives; and the like, and two or more of these may be combined.

[0036] The HLB value of the nonionic surfactant used may be, for example, 3.0 or more, 5.0 or more, 7.0 or more, 8.0 or more, or 9.0 or more, or 15.0 or less, 14.0 or less, 13.0 or less, 12.0 or less, 11.0 or less, or 10.0 or less. The HLB value range of the nonionic surfactant may be, for example, 5.0 or more and 15.0 or less, 7.0 or more and 13.0 or less, or 8.0 or more and 11.0 or less. Here, for example, "the HLB value range of the nonionic surfactant is 5.0 or more and 15.0 or less" means a single nonionic surfactant having an HLB value in the range of 5 to 15, a combination of multiple nonionic surfactants having HLB values ​​in that range, or a combination of multiple nonionic surfactants having two or more different HLB values, resulting in a weighted average HLB value in the range of 5 to 15.

[0037] HLB is an index that shows the balance between hydrophilicity and lipophilicity using a value from 0 to 20, with the closer to 0 the higher the lipophilicity and the closer to 20 the higher the hydrophilicity. There are various known methods for calculating the HLB value, and the values ​​are also listed in catalogs provided by manufacturers. A nonionic surfactant with an appropriate HLB value can be selected according to the polarity of the solid oil and liquid oil.

[0038] The content of the nonionic surfactant in the composition for topical skin application may be 3% by mass or more, 5% by mass or more, 7% by mass or more, 10% by mass or more, or 15% by mass or more, or 30% by mass or less, 25% by mass or less, 20% by mass or less, 15% by mass or less, or 10% by mass or less. The content of the nonionic surfactant in the composition for topical skin application may be, for example, 3% by mass or more and 30% by mass or less, 5% by mass or more and 25% by mass or less, or 7% by mass or more and 20% by mass or less.

[0039] When the content of the liquid oil is within the above range, the composition for external use on skin can be provided with properties such as easy compatibility with other cosmetics and easy spreadability when applied to the skin.

[0040] The mass ratio of the nonionic surfactant to the solid oil may be 0.5 or more, 0.8 or more, 1.0 or more, 1.2 or more, or 1.5 or more, and may be 5.0 or less, 4.0 or less, 3.0 or less, 2.5 or less, or 2.0 or less. For example, this mass ratio may be 0.5 or more and 5.0 or less, or 0.80 or more and 3.0 or less.

[0041] The mass ratio of the nonionic surfactant to the liquid oil may be 0.05 or more, 0.10 or more, 0.15 or more, 0.20 or more, or 0.25 or more, or 0.60 or less, 0.50 or less, 0.40 or less, 0.30 or less, or 0.25 or less. For example, this mass ratio may be 0.05 or more and 0.60 or less, or 0.10 or more and 0.30 or less.

[0042] Specifically, the nonionic surfactant may be any of the nonionic surfactants used in ordinary oily liquid compositions or oily semi-solid compositions, and examples thereof include polyoxyethylene sorbitan fatty acid esters, polyoxyethylene glycerin fatty acid esters, polyoxyethylene alkyl ethers, polyoxyethylene castor oil, polyoxyethylene hydrogenated castor oil, polyoxyethylene sorbit fatty acid esters, polyoxyethylene polyoxypropylene alkyl ethers, polyglycerin fatty acid esters, and polyethylene glycol fatty acid esters, and two or more of these may be used in combination.

[0043] The oily composition may contain water in an amount of 0.1% by weight or more, 0.5% by weight or more, or 1.0% by weight or more, and 3.0% by weight or less, 2.0% by weight or less, or 1.0% by weight or less.

[0044] For example, an oily liquid composition (particularly, a cosmetic oil) preferably contains water in an amount of 0% by mass to 5.0% by mass or 0.5% by mass to 3.0% by mass, liquid oil in an amount of 50% by mass to 90% by mass or 60% by mass to 85% by mass, nonionic surfactant in an amount of 10.0% by mass to 30% by mass or 15% by mass to 25% by mass, cationic polymer in an amount of 0.01% by mass to 0.30% by mass, and crosslinked hyaluronic acid beads in an amount of 0.03% by mass to 1.0% by mass.

[0045] For example, an oily semi-solid composition (particularly, a cleansing balm) preferably contains water in an amount of from 0% to 3.0% by mass, or from 0.5% to 2.0% by mass, solid oil in an amount of from 3% to 20% by mass, or from 5% to 10% by mass, liquid oil in an amount of from 50% to 90% by mass, or from 60% to 85% by mass, nonionic surfactant in an amount of from 5.0% to 20% by mass, or from 10% to 20% by mass, cationic polymer in an amount of from 0.01% to 0.30% by mass, and crosslinked hyaluronic acid beads in an amount of from 0.03% to 1.0% by mass.

[0046] The oily composition may contain components commonly used in cosmetics, such as water, dyes, oil-based gelling agents, oil-soluble resins, polyhydric alcohols, lower alcohols, ultraviolet absorbers, ultraviolet scattering agents, moisturizing agents, fragrances, antioxidants, preservatives, antifoaming agents, and various extracts, as long as the effects of the present invention are not impaired.

[0047] When the topical composition for skin application is an oily semi-solid, it does not exhibit fluidity at room temperature (25°C) and normal pressure (1 atmosphere), and its shape is not particularly limited, and specific examples of the shape include a stick, rod, plate, and a product cast into a container.

[0048] The oily semi-solid topical skin composition can be prepared by a conventional method, for example, by heating all raw materials to above their melting points, mixing them uniformly, pouring the molten mixture into a predetermined container such as a jar, or into a metal or resin dish, and then cooling to obtain the oily semi-solid topical skin composition.

[0049] <Dosage form - aqueous composition> The topical composition for skin application can be an aqueous composition. The aqueous composition may be a leave-off product such as a liquid cleanser, or a leave-on product such as a lotion. Such aqueous compositions can be used to replenish moisture and moisturizing ingredients to the stratum corneum of the skin and to support the physiological functions of the skin. Specific examples of aqueous compositions include lotions and lotions, and more specific examples include cleansing lotions, astringent lotions, softening lotions, and multi-layered lotions, as well as skin lotions, body lotions, hand lotions, and emollient lotions.

[0050] The aqueous composition may contain the cationic polymer and / or crosslinked hyaluronic acid beads in addition to water and / or alcohol. The aqueous composition may also contain other moisturizing ingredients in addition to the crosslinked hyaluronic acid beads. Furthermore, the aqueous composition may contain emollients (softening agents), solubilizers, buffers, thickeners, etc. depending on its purpose and function.

[0051] The aqueous composition may contain water in an amount of 30% by weight or more, 50% by weight or more, or 70% by weight or more, and 95% by weight or less, 90% by weight or less, or 80% by weight or less. The aqueous composition may also contain alcohol in an amount of 1% by weight or more, 3% by weight or more, or 5% by weight or more, and 20% by weight or less, 15% by weight or less, or 10% by weight or less. Examples of alcohol include ethanol and isopropanol.

[0052] The aqueous composition may further contain a polyhydric alcohol as a base, such as ethylene glycol, propylene glycol, dipropylene glycol, butylene glycol, propanediol, glycerin, etc. The aqueous composition may contain the base in an amount of, for example, 5% by weight or more, 10% by weight or more, or 15% by weight or more, and 40% by weight or less, 30% by weight or less, or 25% by weight or less.

[0053] The aqueous composition may contain moisturizing ingredients other than the crosslinked hyaluronic acid beads in an amount of 1% by weight or more, 3% by weight or more, or 5% by weight or more, and 20% by weight or less, 15% by weight or less, or 10% by weight or less.

[0054] As the emollient (softening agent), substances known as emollients (softening agents) for aqueous compositions, such as ester oil, vegetable oil, etc. The aqueous composition may contain the emollient (softening agent) in an amount of 0.01% by mass or more, 0.05% by mass or more, or 0.1% by mass or more, and 1.0% by mass or less, 0.5% by mass or less, or 0.3% by mass or less.

[0055] The aqueous composition may contain, as a solubilizing agent, a nonionic surfactant such as polyoxyethylene oleyl alcohol ether, polyoxyethylene alkyl ether, polyoxyethylene fatty acid ester, polyoxyethylene sorbitan fatty acid ester, glycerin fatty acid ester, polyglycerin fatty acid ester, polyoxyethylene glycerin fatty acid ester, polyoxyethylene hydrogenated castor oil, polyoxyethylene sorbitol fatty acid ester, etc. The aqueous composition may contain the solubilizing agent in an amount of 0.1% by weight or more, 0.5% by weight or more, or 1.0% by weight or more, and 3.0% by weight or less, 2.0% by weight or less, or 1.0% by weight or less.

[0056] The aqueous composition may contain, as a buffer, citric acid, lactic acid, an amino acid, etc. An appropriate amount of these may be added to the aqueous composition to adjust the pH.

[0057] The aqueous composition may contain as a thickener alginate, cellulose derivative, quince seed gum, pectin, pullulan, xanthan gum, veegum, carboxyvinyl polymer, acrylic acid polymer, laponite, etc. These may be blended into the aqueous composition in an appropriate amount to adjust the viscosity, for example, at 0.1% by mass or more, 0.5% by mass or more, or 1.0% by mass or more, and at 3.0% by mass or less, 2.0% by mass or less, or 1.0% by mass or less.

[0058] The aqueous composition may further contain other ingredients such as fragrances, preservatives, browning agents, etc., as known in the art.

[0059] <Dosage form - emulsion> The topical skin composition may be an emulsion. An emulsion is an emulsion with properties intermediate between a lotion and a cream. Except in special cases, emulsions have a smaller amount of oil phase than creams and are fluid emulsions, so they are also known as "liquid creams." Emulsions are either O / W or W / O types, but are generally O / W types, which have a high proportion of aqueous phase and spread thinly when applied to the skin, giving a moist feel.

[0060] The emulsion can contain water and oil as a base, an emulsifier, the above-mentioned cationic polymer, and / or the above-mentioned crosslinked hyaluronic acid beads. The emulsion can also contain other moisturizing ingredients in addition to the above-mentioned crosslinked hyaluronic acid beads. Furthermore, the emulsion can contain a thickener or the like depending on its purpose and function. Furthermore, the emulsion can contain the polyhydric alcohol described above for the aqueous composition as a base.

[0061] The emulsion may contain 30% by weight or more, 50% by weight or more, 60% by weight or more, or 70% by weight or more, and 95% by weight or less, 90% by weight or less, or 80% by weight or less of water. The emulsion may contain the above-described bases in the amounts described for the aqueous compositions above.

[0062] The oil may be a liquid oil or a solid oil, such as stearic acid, cetyl alcohol, petrolatum, squalane, cetyl alcohol, beeswax, dimethylpolysiloxane, liquid paraffin, lanolin, etc. The emulsion may contain 3% by mass or more, 5% by mass or more, 10% by mass or more, 20% by mass or more, or 30% by mass or more of the oil, and 60% by mass or less, 50% by mass or less, 40% by mass or less, 30% by mass or less, or 20% by mass or less of the oil.

[0063] Examples of the emulsifier include nonionic surfactants such as polyoxyethylene oleyl alcohol ether, polyoxyethylene alkyl ether, polyoxyethylene fatty acid ester, polyoxyethylene sorbitan fatty acid ester, glycerin fatty acid ester, polyglycerin fatty acid ester, polyoxyethylene glycerin fatty acid ester, polyoxyethylene hydrogenated castor oil, polyoxyethylene sorbitol fatty acid ester, polysorbate, sorbitan stearate, etc. The emulsion may contain the emulsifier in an amount of 1.0% by mass or more, 1.5% by mass or more, 2.0% by mass or more, or 3.0% by mass or more, and 10% by mass or less, 7.0% by mass or less, 5.0% by mass or less, or 3.0% by mass or less.

[0064] The type and amount of the thickener used in the emulsion can be referenced to the type and amount of the thickener described for the aqueous composition.

[0065] For example, the emulsion preferably contains 50% by mass to 90% by mass or 60% by mass to 80% by mass of water, 3% by mass to 30% by mass or 10% by mass to 20% by mass of liquid oil, 1.0% by mass to 10% by mass or 1.5% by mass to 5.0% by mass of emulsifier, 0.1% by mass to 1.0% by mass of thickener, 0.01% by mass to 0.30% by mass of cationic polymer, and 0.03% by mass to 1.0% by mass of crosslinked hyaluronic acid beads.

[0066] The emulsion may further contain other ingredients known in the art, such as moisturizers, fragrances, preservatives, antioxidants, neutralizing agents, coloring agents, and the like, in addition to the crosslinked hyaluronic acid beads.

[0067] <Formulation: Cream> The topical skin composition may be a cream. Creams generally have a larger amount of oil phase than emulsions and are therefore non-fluid emulsions. The purpose of creams, like emulsions, is to cleanse the skin, remove makeup, protect the skin, moisturize and soften it, and promote blood circulation in the skin. More specific examples of creams include cleansing creams, emollient creams, nourishing creams, night creams, base creams, vanishing creams, moisture creams, massage creams, cold creams, and lip creams.

[0068] The cream may contain water and oil as a base, an emulsifier, the cationic polymer, and / or the cross-linked hyaluronic acid beads. The types of oil, nonionic surfactant, and emulsifier can be referenced to those described above for the emulsion. Furthermore, the cream may also contain a polyhydric alcohol as a base, as described above for the aqueous composition.

[0069] The cream may contain water in an amount of 10% by mass or more, 20% by mass or more, 30% by mass or more, 50% by mass or more, or 60% by mass or more, and 80% by mass or less, 70% by mass or less, or 50% by mass or less. The cream may contain oil in an amount of 20% by mass or more, 30% by mass or more, 40% by mass or more, 50% by mass or more, or 60% by mass or more, and 80% by mass or less, 60% by mass or less, 50% by mass or less, 40% by mass or less, or 30% by mass or less. The contents of the polyhydric alcohol and emulsifier in the cream can be referenced to the amounts described for the aqueous composition or the emulsion above.

[0070] The type and amount of the thickener used in the cream can be referenced to the type and amount of the thickener described for the aqueous composition.

[0071] For example, the cream preferably contains 50% by mass or more and 80% by mass or less, or 60% by mass or more and 70% by mass or less, liquid oil 5% by mass or more and 30% by mass or less, or 10% by mass or more and 20% by mass or less, emulsifier 1.0% by mass or more and 10% by mass or more and 2.0% by mass or more and 5.0% by mass or less, thickener 0.1% by mass or more and 1.0% by mass or less, cationic polymer 0.01% by mass or more and 0.30% by mass or less, and crosslinked hyaluronic acid beads 0.03% by mass or more and 1.0% by mass or less.

[0072] The cream may further contain other ingredients known in the art, such as moisturizers, chelating agents, fragrances, preservatives, antioxidants, neutralizing agents, coloring agents, and the like, in addition to the crosslinked hyaluronic acid beads.

[0073] <Dosage form - gel> The composition for external application to skin may be a gel. Gels have a uniform appearance, are transparent to translucent, and provide a moist feel. Gels include aqueous gels and oily gels, with aqueous gels containing a large amount of water and oily gels containing a large amount of oil.

[0074] The aqueous gel may contain water, a nonionic surfactant, a thickener, the cationic polymer, and / or the crosslinked hyaluronic acid beads, and preferably contains the cationic polymer. The oily gel may contain an oil, a nonionic surfactant, an emulsifier, and the crosslinked hyaluronic acid beads. The types of oil and emulsifier can be referenced to those described above for the emulsion. The gel may also contain a polyhydric alcohol as a base, as described above for the aqueous composition.

[0075] The aqueous gel may contain water at 30% by mass or more, 50% by mass or more, or 70% by mass or more, and 95% by mass or less, 90% by mass or less, 85% by mass or less, 80% by mass or less, or 75% by mass or less. The aqueous gel may contain a nonionic surfactant at 1% by mass or more, 3% by mass or more, 5% by mass or more, 7% by mass or more, or 10% by mass or more, and may contain a nonionic surfactant at 30% by mass or less, 20% by mass or less, 15% by mass or less, or 10% by mass or less. The content of polyhydric alcohol in the aqueous gel can be determined by referring to the amount described above for the aqueous composition.

[0076] Thickeners used in aqueous gels include water-soluble polymers other than the above-mentioned cationic polymers, such as agar, agarose, alginic acids, carrageenan, dextrin, methyl cellulose, ethyl cellulose, hydroxyethyl cellulose, hydroxypropyl cellulose, polyvinyl alcohol, polyacrylic acid, polymethacrylic acid, carboxyvinyl polymer, (acrylic acid / C10-30 alkyl acrylate) copolymer, xanthan gum, carboxymethyl chitin, chitosan, etc.

[0077] The aqueous gel may contain, for example, 0.1% by weight or more, 0.5% by weight or more, or 1.0% by weight or more of a thickener, and 3.0% by weight or less, 2.0% by weight or less, 1.5% by weight or less, or 1.0% by weight or less of a thickener.

[0078] The oily gel may contain 30% by mass or more, 50% by mass or more, or 70% by mass or more of oil, and 95% by mass or less, 90% by mass or less, or 80% by mass or less of oil. The contents of the emulsifier and polyhydric alcohol in the oily gel can be referenced to the amounts described above for the emulsion.

[0079] For example, the aqueous gel preferably contains water at 50% by mass to 85% by mass or 60% by mass to 80% by mass, polyhydric alcohol at 10% by mass to 30% by mass or 15% by mass to 25% by mass, nonionic surfactant at 3% by mass to 15% by mass or 5% by mass to 10% by mass, thickener at 0.5% by mass to 2.0% by mass, cationic polymer at 0.01% by mass to 0.30% by mass, and crosslinked hyaluronic acid beads at 0.03% by mass to 1.0% by mass.

[0080] The gel may further contain other ingredients known in the art, such as moisturizers, fragrances, preservatives, antioxidants, neutralizing agents, coloring agents, and the like, in addition to the crosslinked hyaluronic acid beads.

[0081] <Form: Pack cosmetics> The composition for external application to the skin may be a pack cosmetic. The pack cosmetic may be a coating type that is applied to the skin to form a film, or may be a patch type that is contained in a substrate such as a nonwoven fabric.

[0082] The pack cosmetic can contain water, alcohol, polyhydric alcohol, thickener, oil, powder, the cationic polymer, and / or the crosslinked hyaluronic acid beads. Here, for the water, alcohol, and polyhydric alcohol, the types and amounts described for the aqueous composition can be referenced, for the thickener, the types and amounts described for the aqueous gel can be referenced, and for the oil, the types and amounts described for the emulsion can be referenced.

[0083] Examples of powders used in pack cosmetics include kaolin, talc, titanium oxide, zinc oxide, spherical cellulose, etc. Pack cosmetics can contain 5% by mass or more, 10% by mass or more, or 15% by mass or more of powder, and 30% by mass or less, 20% by mass or less, or 15% by mass or less of powder.

[0084] The pack cosmetic may further contain other ingredients known in the art, such as moisturizers, fragrances, preservatives, antioxidants, neutralizing agents, coloring agents, etc., in addition to the crosslinked hyaluronic acid beads.

[0085] <Dosage form - Wipe sheet> The topical skin composition may be in the form of a wipe sheet in which the substrate is impregnated with the above-mentioned cosmetic oil, balm, toner, lotion, emulsion, cream, and / or gel.

[0086] The substrate may be a substrate commonly used in this field, for example, a woven fabric or a nonwoven fabric, and the nonwoven fabric may be a water-decomposable nonwoven fabric.

[0087] The present invention will be explained in more detail in the following examples, but the present invention is not limited thereto. [Example]

[0088] 《Manufacturing》 Each of the components listed in Tables 1 and 2 was dissolved by heating according to the dosage form, and cooled to room temperature while stirring to prepare each of the skin external compositions.

[0089] "evaluation" Approximately 1.5 mL of each topical skin composition was applied to the entire face and evaluated on a 5-point scale. Leave-off products (cosmetics that are washed off after application) were evaluated on the skin after washing with water, and leave-on products (cosmetics that are applied to the skin) were evaluated on the skin immediately after application by 14 expert panelists, and the average score was used as the evaluation result.

[0090] <Massage effect> (Evaluation criteria) Good: There was no rough or prickly feeling on the skin, and it gave a very good massage. △: There was a slight rough or prickly feeling on the skin, but it gave a good massage. ×: There was a strong rough or prickly feeling on the skin, and it was not possible to massage very well.

[0091] <Moisturized feeling on skin after use> (Evaluation criteria) 1: Very dry 2: Slightly dry 3: Neither 4: Feels slightly moist 5: Feels naturally moisturized

[0092] <Smoothness of skin after application> (Evaluation criteria) 1: Very dry 2: Slightly dry 3: Neither 4: Feels slightly moist 5: Feels naturally moisturized

[0093] "result" The compositions and measurement results of each example are shown in Tables 1 and 2 below.

[0094] [Table 1]

[0095] [Table 2]

[0096] The (PEG-9 diglycidyl ether / sodium hyaluronate) crosspolymer is available under the trade name HA BEADS (manufactured by HYUNDAI BIOLAND); hydroxypropyltrimonium hyaluronate is available under the trade name Hyalobel (trademark)-MPF (manufactured by Kewpie Corporation); the hyaluronic acid-treated inorganic powder is produced by the method described in Patent Document 2; and acetylated sodium hyaluronate is available under the trade name PrimalHyal Ultrafiller (manufactured by Givaudan SA).

[0097] As can be seen from the results in Tables 1 and 2, the compositions of the examples containing crosslinked hyaluronic acid beads ((PEG-9 diglycidyl ether / sodium hyaluronate) crosspolymer) were able to massage the skin without any roughness or tingling sensation, compared to the comparative compositions that did not contain crosslinked hyaluronic acid but contained other types of hyaluronic acid, and were highly rated for moisturizing and smooth skin after application. This is thought to be because, while other types of hyaluronic acid fall off immediately upon washing, crosslinked hyaluronic acid beads tend to remain on the skin even after washing. The reason why crosslinked hyaluronic acid beads tend to remain on the skin is thought to be because the crosslinked hyaluronic acid beads are crosspolymerized and have hydrophobic moieties in some parts, which increases their affinity with the skin. Furthermore, it is thought that the crosslinked hyaluronic acid beads remaining on the skin formed a cosmetic film with high moisture evaporation while retaining the moisture in the formulation, thereby providing a highly moisturizing feeling. Furthermore, when cross-linked hyaluronic acid beads were used in combination with a cationic water-soluble polymer (polyquaternium), a particularly high effect was obtained. This is thought to be because the cationic water-soluble polymer adheres to the skin, which is mainly anionic, and then the cross-linked hyaluronic acid beads adhere to it. For this reason, it was suggested that the cross-linked hyaluronic acid beads have anionic properties.

[0098] Furthermore, among the formulations, a particularly high effect was obtained with the aqueous gel in Example 1. Although aqueous gels contain a lot of water due to the use of large amounts of dipropylene glycol (DPG) or nonionic surfactants, they can leave a feeling of degreasing on the skin after application, but it was found that this can be prevented by including cross-linked hyaluronic acid beads.

Claims

1. The oily semi-solid detergent composition contains 3% by mass or more and 20% by mass or less of solid oil, 50% by mass or more and 90% by mass or less of liquid oil, 5% by mass or more and 20% by mass or less of a nonionic surfactant, and crosslinked hyaluronic acid beads.

2. The facial cleansing composition is an aqueous gel containing 50% by mass or more and 80% by mass or less of water, 10% by mass or more and 30% by mass of a polyhydric alcohol, 5% by mass or more and 15% by mass or less of a nonionic surfactant, and crosslinked hyaluronic acid beads.

3. The wipe sheet has a substrate impregnated with a composition for external use on the skin, the composition containing crosslinked hyaluronic acid beads comprising a crosspolymer of polyethylene glycol diglycidyl ether and sodium hyaluronate.

4. 3. The composition of claim 1, wherein the crosslinked hyaluronic acid beads comprise a crosspolymer of polyethylene glycol diglycidyl ether and sodium hyaluronate.

5. The composition according to claim 1 or 2, further comprising a cationic polymer.

6. The wiping sheet according to claim 3 , wherein the composition for external use on skin further comprises a cationic polymer.

7. The composition according to claim 5, wherein the cationic polymer is at least one selected from the group consisting of polyquaterniums, cationized cellulose derivatives, cationized gums, cationized chitosan, and cationized protein derivatives.

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