Composition with alpha-gel structure

Abstract

An object of the present invention is to provide a composition having an α - gel structure without using a surfactant, and having a small change in quality over time.SOLUTION: The present invention relates to a composition containing a combination of specific amounts of (A) a modified hyaluronic acid or a salt thereof containing a glycerin skeleton-containing group, (B) a higher alcohol, (C) an α - monoalkyl glyceryl ether, (D) an oily component other than the (B) and (C), (E) glycerin, and (F) water.SELECTED DRAWING: Figure 1

Description

[Technical Field]

[0001] The present invention relates to a composition having an α-gel structure. [Background technology]

[0002] Conventionally, emulsion compositions having a so-called α-gel structure (hexagonal crystal arrangement), in which the entire system is thickened into a gel state by α-type hydrate crystals formed by higher alcohols and surfactants, have been used to maintain emulsion stability in cosmetics, pharmaceuticals, quasi-drugs, and other products.

[0003] However, surfactants are generally not preferred for use in cosmetics and the like due to factors such as the feel during use and skin irritation, and a composition having an α-gel structure that does not require the use of surfactants has been desired. As such a composition, Patent Document 1 proposes an emulsion composition having an α-gel structure that uses an amide alcohol and a higher alcohol and does not require the use of surfactants. [Prior art documents] [Patent documents]

[0004] [Patent Document 1] Patent No. 6736190 Summary of the Invention [Problem to be solved by the invention]

[0005] However, amide-based raw materials often undergo a change in odor over time at high temperatures. Therefore, a new surfactant-free α-gel forming composition with minimal change in quality over time has been desired. In view of these circumstances, an objective of the present invention is to provide a composition having an α-gel structure that does not use a surfactant and that exhibits little change in quality over time. [Means for solving the problem]

[0006] The present inventors have conducted research to solve the above problems and have found that a composition that meets the above problems can be obtained by using a combination of specific amounts of (A) modified hyaluronic acid or its salt containing a glycerin skeleton-containing group; (B) a higher alcohol; (C) an α-monoalkyl glyceryl ether; (D) an oily component other than (B) and (C); (E) glycerin; and (F) water, and have thus completed the present invention. That is, the gist of the present invention relates to the following.

[0007] [1] The following components (A) to (F): (A) a modified hyaluronic acid or a salt thereof containing a glycerin skeleton-containing group; (B) higher alcohols; (C) α-monoalkyl glyceryl ether; (D) an oily component other than (B) and (C); (E) glycerin; and (F) Water; Including, the content ratio (mass ratio) of (B) to (C) ((B) / (C)) is 0.1 to 2.5, A composition in which the total content of (B), (C), and (D) is 20.0 to 35.0 mass% based on the total amount of the composition, The (A) to (F) form an α-gel. composition. [2] The composition, wherein (A) is a modified hyaluronic acid or a salt thereof containing a glycerin skeleton-containing group represented by the following general formula (1): -O-CH2-CHOH-CH2-OR 1 ···(1) (In the formula, R 1 represents a linear or branched alkyl or alkenyl group. [3] The composition, wherein (A) is hydrolyzed alkyl (C12-13) glyceryl hyaluronate. [4] The composition as described above, wherein (B) is a higher alcohol having 16 to 22 carbon atoms. [5] The composition as described above, wherein (B) is cetanol or behenyl alcohol. [6] The composition as described above, wherein (C) is an α-monoalkyl glyceryl ether having an alkyl group with 8 to 24 carbon atoms. [7] The composition, wherein (C) is batyl alcohol. [8] The composition as described above, wherein (D) is one or more oils selected from hydrocarbon oils, monoester oils, triglyceride oils, and silicone oils. [9] The composition, wherein (D) is one or more selected from hydrogenated polyolefins, 2-ethylhexyl palmitate, triethylhexanoin, and dimethicone.

[10] The composition, wherein the content of (A) is 0.9 to 1.8 mass% based on the total mass of the composition.

[11] The composition, wherein the content of (B) is 3.0 to 14.7% by mass based on the total mass of the composition.

[12] The composition, wherein the content of (C) is 5.5 to 13.25 mass% based on the total mass of the composition.

[13] The composition, wherein the content of (D) is 8.8 to 11.5 mass% based on the total mass of the composition.

[14] The composition, wherein the content of (E) is 23.2 to 53.1 mass% based on the total mass of the composition.

[15] The composition, wherein the content of (F) is 19.5 to 44.2 mass% of the total composition.

[16] The composition, wherein the mass ratio of the content of (B) to the content of (C) is 3.5:1.5 to 1:4.

[17] The composition, which is an oil-in-water emulsion type.

[18] The composition, which is an external preparation for skin.

[19] The composition is a cosmetic. [Effects of the Invention]

[0008] According to the present invention, it is possible to provide a composition having an α-gel structure that does not use a surfactant and that exhibits little change in quality over time. [Brief explanation of the drawings]

[0009] [Figure 1] 1 shows X-ray diffraction charts of emulsion compositions of Examples (Comparative Examples 2 and 3 and Examples 1 to 3 from the top). [Figure 2] 1 shows microscopic images of emulsion compositions of Examples (from top to bottom: Comparative Examples 2 and 3 and Examples 1 to 3) (photographs substituting drawings). The white bar indicates 20 μm. DETAILED DESCRIPTION OF THE INVENTION

[0010] The present invention will be described below. <Composition having α-gel structure> The present invention relates to a composition having an α-gel structure that does not use a surfactant. The present inventors conducted various studies in search of a composition that does not use a surfactant and has an α-gel structure, and that exhibits little change in quality over time.

[0011] Among them, the present inventors have succeeded in creating an excellent composition that forms α-gel structure without using surfactant and has excellent stability over time by combining and blending (A) modified hyaluronic acid or its salt containing glycerin skeleton group, (B) higher alcohol, (C) α-monoalkylglyceryl ether, (D) oily component other than (B) and (C), (E) glycerin, and (F) water in specific amounts.Based on this finding, the present invention has been completed.

[0012] Here, the α-gel structure refers to a structure formed by an association of lamellar bilayer membranes. In the composition of the present invention, the components (A) to (E) form an α-gel structure in the aqueous phase.

[0013] The α-gel structure can be confirmed by wide-angle X-ray diffraction, polarizing microscope, etc. Specifically, a composition that exhibits at least one sharp diffraction peak at a Bragg angle of approximately 21 to 22° (preferably 21.4°) in wide-angle X-ray diffraction can be determined to have an α-gel structure. Furthermore, the α-gel structure can be confirmed by observing the composition under crossed Nicols with a polarizing microscope and observing the α-gel structure by observing the α-gel structure under crossed Nicols with a polarizing microscope.

[0014] In the present invention, since the α-gel structure can be formed without using a surfactant, formulations can be made without using a surfactant, but this does not preclude the inclusion of a surfactant as a technical complement. Furthermore, formulations using a surfactant also fall within the scope of the present invention. When a surfactant is included, it can be present in an amount of, for example, 0.01 to 5.0% by mass, or 0.1 to 1.0% by mass, based on the total amount of the composition.

[0015] <Component (A) Modified Hyaluronic Acid or Salt thereof Having a Glycerin Skeleton-Containing Group> The composition of the present invention comprises the modified hyaluronic acid or its salt containing glycerin skeleton group as component (A).The modified hyaluronic acid or its salt containing glycerin skeleton group is not limited as long as it can achieve the effects of the present invention, and can be used those generally used in cosmetics, medicines, etc.

[0016] The modified hyaluronic acid that contains glycerin skeleton group that is used in the present invention is not particularly limited as long as it is pharmacologically or physiologically acceptable, and can be exemplified by the modified hyaluronic acid that hydrophobic group is introduced into hyaluronic acid by glycerin etc. Although not limited, the one that contains glycerin skeleton group that is represented by the following general formula (1) can be preferably exemplified.

[0017] -O-CH2-CHOH-CH2-OR 1 ···(1) (In the formula, R 1 represents a linear or branched alkyl or alkenyl group.

[0018] The modified hyaluronic acid containing a glycerin skeleton-containing group used in the present invention has one of the oxygen atoms that does not constitute a hydroxyl group contained in the glycerin skeleton-containing group substituted with R 1 is bonded, the hydroxyl group contained in the glycerin skeleton-containing group is a secondary hydroxyl group, and another oxygen atom contained in the glycerin skeleton-containing group that does not constitute a hydroxyl group is bonded to a carbon atom that constitutes hyaluronic acid and / or a salt thereof.

[0019] In the general formula (1), R 1 Examples of the linear or branched alkyl group represented by the formula (I) include a methyl group, an ethyl group, an n-propyl group, an isopropyl group, an n-butyl group, an isobutyl group, a tert-butyl group, an n-pentyl group, an isopentyl group, a neopentyl group, a tert-pentyl group, a 2-methylbutyl group, a 1-methylbutyl group, an n-hexyl group, an isohexyl group, a 3-methylpentyl group, a 2-methylpentyl group, a 1-methylpentyl group, an n-heptyl group, an n-octyl group, an isooctyl group, a 2-ethylhexyl group, and an n-nonyl group. Examples of the alkyl group include an n-decyl group, an n-undecyl group, an n-dodecyl group, an n-tridecyl group, an n-tetradecyl group (myristyl group), an n-hexadecyl group (palmityl group), an n-octadecyl group (stearyl group), and an n-icosyl group.

[0020] In addition, in the general formula (1), R 1 Examples of the linear or branched alkenyl group represented by the formula (I) include a vinyl group, an allyl group, a propenyl group, an isopropenyl group, a butenyl group, an isobutenyl group, a pentenyl group, an isopentenyl group, a hexenyl group, a heptenyl group, an octenyl group, a nonenyl group, a decenyl group, an undecenyl group, a dodecenyl group, a tetradecenyl group, and an oleyl group.

[0021] Among these, the compound having R in the general formula (1) has a higher effect of repairing the skin barrier function and is more water-soluble. 1 The number of carbon atoms in the linear or branched alkyl or alkenyl group represented by the formula (I) is preferably 6 to 20, more preferably 8 to 18, and even more preferably 10 to 16. In this case, R 1 The group represented by the formula (I) is preferably an alkyl group.

[0022] In the modified hyaluronic acid that contains glycerin skeleton group used in the present invention, glycerin skeleton group can be bonded to at least one of the carbon atoms that constitute hyaluronic acid skeleton.In the present invention, " carbon atom that constitutes hyaluronic acid skeleton " refers to the carbon atom that is contained in glucuronic acid and N-acetylglucosamine that constitute hyaluronic acid.

[0023] In the modified hyaluronic acid containing a glycerin skeleton-containing group used in the present invention, the glycerin skeleton-containing group is preferably bonded to at least one selected from the carbonyl groups bonded to the carbon atom at the 6th position (C-6) of N-acetylglucosamine constituting the modified hyaluronic acid and the carbon atom at the 5th position (C-5) of glucuronic acid.

[0024] The degree of polymerization of the hyaluronic acid building block composed of glucuronic acid and N-acetylglucosamine hyaluronic acid that constitute hyaluronic acid may be 1-750, 1-50, or 1-25.

[0025] The salt of the modified hyaluronic acid containing glycerin skeleton group is also not particularly limited as long as it is pharmacologically or physiologically acceptable, and can include, for example, salts with alkali metals such as sodium, potassium, etc., alkaline earth metals such as calcium, magnesium, etc., metals such as zinc, aluminum, etc., ammonium salt, basic amino acid salt, amine salt such as triethanolamine, etc. Preferably, sodium salt, potassium salt, zinc salt are used as the salt of hyaluronic acid or its derivatives.

[0026] The modified hyaluronic acid or its salt containing glycerin skeleton group used in the present invention is specifically, for example, hydrolyzed hyaluronic acid alkyl (C12-13) glyceryl etc. The modified hyaluronic acid or its salt containing glycerin skeleton group can be commercially available. For example, commercially available products such as "Hyalopear" (Kewpie Corporation) with an average molecular weight of 10,000 or less can be exemplified.

[0027] The modified hyaluronic acid or its salt containing a glycerin skeleton group may be used in the present invention either alone or in combination of two or more.

[0028] In the composition of the present invention, the content of component (A) is not limited, but may be, for example, 0.1 mass % or more, 0.5 mass % or more, or 0.8 mass % or more, and 10.0 mass % or less, 5.0 mass % or less, or 2.0 mass % or less, or any combination thereof that is not contradictory, based on the total composition. However, it may be 0.9 to 1.8 mass %, 0.95 to 1.5 mass %, or 1.0 to 1.2 mass %. By using it within this range, it becomes particularly easy to obtain the desired effects such as good formation of α-gel and stabilization of the preparation.

[0029] When two or more kinds of components (A) are used in combination, the above content is the total amount of the two or more kinds. When two or more kinds of components (A) are combined, the mass ratio is not particularly limited.

[0030] <Component (B) higher alcohol> The composition of the present invention contains a higher alcohol as component (B). The higher alcohol is not limited as long as it exhibits the effects of the present invention, and any alcohol generally used in cosmetics, pharmaceuticals, etc. can be used.

[0031] The higher alcohol is not particularly limited, but is preferably a saturated or unsaturated, straight-chain or branched monohydric alcohol having 6 or more carbon atoms (more specifically, for example, a carbon number of 16 to 22). Specific preferred examples include myristyl alcohol, cetyl alcohol (cetanol), stearyl alcohol, isostearyl alcohol, behenyl alcohol, octyldodecanol, and cetostearyl alcohol, with cetanol and behenyl alcohol being particularly preferred.

[0032] Commercially available higher alcohols can be used. As the higher alcohol, one type or a combination of two or more types can be used in the present invention.

[0033] The content of component (B) in the composition of the present invention is not limited, and may be, for example, 3.0 mass% or more, 3.5 mass% or more, 5.0 mass% or more, 6.0 mass% or more, or 7.0 mass% or more, and 20.0 mass% or less, 17.5 mass% or less, or 15.0 mass% or less, or any compatible combination thereof, relative to the total mass of the composition. Furthermore, the content of component (B) may be 7.1 to 14.7 mass%, 7.1 to 12.6 mass%, or 7.1 to 8.1 mass%. By using it within this range, it becomes particularly easy to obtain the desired effects such as good formation of α-gel and stabilization of the preparation.

[0034] When two or more kinds of components (B) are used in combination, the above content is the total amount of the two or more kinds. When two or more kinds of components (B) are combined, the mass ratio is not particularly limited.

[0035] <Component (C) α-monoalkyl glyceryl ether> The composition of the present invention contains an α-monoalkyl glyceryl ether as component (C). The α-monoalkyl glyceryl ether is not limited as long as it exhibits the effects of the present invention, and any α-monoalkyl glyceryl ether generally used in cosmetics, pharmaceuticals, etc. can be used.

[0036] The (C) α-monoalkyl glyceryl ether used in the present invention is not particularly limited, but is preferably one in which the alkyl group is a linear alkyl group having 8 to 24 carbon atoms or a branched alkyl group having 8 to 24 carbon atoms, such as chimyl alcohol (a monoether of glycerin and cetanol), batyl alcohol (a monoether of glycerin and stearyl alcohol), and selachyl alcohol (a monoether of glycerin and oleyl alcohol). Of these, batyl alcohol is preferred. (C) Commercially available α-monoalkyl glyceryl ethers can be used. One or a combination of two or more α-monoalkyl glyceryl ethers may be used in the present invention.

[0037] The content of component (C) in the composition of the present invention is not limited, and may be, for example, 4.0 mass% or more, 5.0 mass% or more, 5.5 mass% or more, or 6.0 mass% or more, and 20.0 mass% or less, 15.0 mass% or less, or 14.0 mass% or less, or any compatible combination thereof, relative to the total mass of the composition. Furthermore, the content of component (C) may be 6.3 to 13.25 mass%, 10.6 to 12.5 mass%, or 11.5 to 12.0 mass%. By using it within this range, it becomes particularly easy to obtain the desired effects such as good formation of α-gel and stabilization of the preparation.

[0038] When two or more kinds of components (C) are used in combination, the above content is the total amount of the two or more kinds. When two or more kinds of components (C) are combined, the mass ratio is not particularly limited.

[0039] In addition, the content ratio (mass ratio) of component (B) to component (C) in the present invention ((B) / (C)) is, for example, 0.1 to 2.5, 0.5 to 1.5, or 0.6 to 1, from the viewpoint of good formation of α-gel, stabilization of the preparation, etc. Similarly, the content ratio (mass ratio) of component (B) to component (C) in the present invention is, for example, 3.5:1.5 to 1:4, or 3:2 to 2:3.

[0040] <Oil-based ingredients other than (B) and (C) in ingredient (D)> The composition of the present invention contains, as component (D), an oily component other than (B) and (C). The oily component of component (D) is not limited as long as it exhibits the effects of the present invention, and any oily component commonly used in cosmetics, pharmaceuticals, etc. can be used. The oil component of component (D) is not particularly limited, but is preferably one or more selected from hydrocarbon oils, monoester oils, triglyceride oils, and silicone oils. Specific examples of preferred hydrocarbon oils include isododecane, isohexadecane, squalane, hydrogenated polyolefins, and hydrogenated polyisobutene, with hydrogenated poly(C6-14)olefins being particularly preferred. Specific preferred examples of monoester oils include cetyl 2-ethylhexanoate, isononyl isononanoate, isotridecyl isononanoate, isopropyl myristate, isopropyl palmitate, 2-ethylhexyl palmitate, 2-ethylhexyl stearate, and stearyl stearate, with 2-ethylhexyl palmitate being particularly preferred. Specific preferred examples of triglyceride oils include glyceryl tri(caprylic / capric acid), glyceryl tri(2-ethylhexanoate) (triethylhexanoin), glyceryl trimyristate, glyceride tri-2-heptylundecanoate, glyceryl trioctanoate, and glyceryl triisopalmitate, with triethylhexanoin being particularly preferred. Silicone oils include dimethylpolysiloxane (dimethicone), cyclopentasiloxane, decamethylcyclopentasiloxane, caprylyl methicone, trimethylsiloxysilicate, (dimethicone / vinyl dimethicone) crosspolymer, (dimethicone / phenyl vinyl dimethicone) crosspolymer, and the like.

[0041] As the oil component of component (D), commercially available products can be used. As the oil component of component (D), one type or a combination of two or more types may be used in the present invention.

[0042] In the composition of the present invention, the content of component (D) is not limited, but may be, for example, 6.0 mass% or more, 7.0 mass% or more, or 8.0 mass% or more, and 20.0 mass% or less, 15.0 mass% or less, or 12.0 mass% or less, based on the total mass of the composition. Any compatible combination of these may be used. The content of component (D) may be 8.8 to 11.5 mass %, 9.00 to 10.5 mass %, or 9.5 to 10 mass % based on the total mass of the composition. By using it within this range, it becomes particularly easy to obtain the desired effects such as good formation of α-gel and stabilization of the preparation.

[0043] When two or more kinds of components (D) are used in combination, the above content is the total amount of the two or more kinds. When two or more kinds of components (D) are combined, the mass ratio is not particularly limited.

[0044] Furthermore, the total content of components (B, (C), and (D) in the present invention is, for example, 20.0 to 35.0% by mass, 25.0 to 35.0% by mass, or 26.0 to 32.0% by mass, from the viewpoint of good formation of α-gel, stabilization of the formulation, etc.

[0045] <Component (E) Glycerin and Component (F) Water> The composition of the present invention contains an aqueous phase component and an oil phase component. The formulation of the composition of the present invention is preferably an emulsion type, and more preferably an oil-in-water emulsion type. In the present invention, the dosage form is not particularly limited as long as the outermost phase is an aqueous phase, and may be an O / W type, a W / O / W type, an (O1+O2) / W type, or the like. The composition of the present invention contains water as the aqueous phase component, which is component (F). The aqueous phase component may also contain other components that dissolve in water at 25 to 90°C. Typically, glycerin, component (E), is also included in the aqueous phase. Commercially available glycerin products can be used.

[0046] The content of component (E) in the composition of the present invention is not limited, and may be, for example, 15.0 mass% or more, 20.0 mass% or more, or 22.0 mass% or more, and 70.0 mass% or less, 60.0 mass% or less, or 55.0 mass% or less, or any compatible combination thereof, relative to the total composition. The content of component (E) may be 23.2 to 53.1 mass%, 30.0 to 53.1 mass%, or 35.4 to 53.1 mass%, relative to the total composition. By using it within this range, it becomes particularly easy to obtain the desired effects such as good formation of α-gel and stabilization of the preparation.

[0047] The content of component (F) in the composition of the present invention is not limited, and may be, for example, 15.0 mass% or more, 17.0 mass% or more, or 19.0 mass% or more, and 70.0 mass% or less, 60.0 mass% or less, or 50.0 mass% or less, or any compatible combination thereof, relative to the total mass of the composition. Furthermore, the content of component (F) may be 19.5 to 44.2 mass%, 19.5 to 37.2 mass%, or 19.5 to 36.3 mass% relative to the total mass of the composition. By using it within this range, it becomes particularly easy to obtain the desired effects such as good formation of α-gel and stabilization of the preparation.

[0048] The oil phase component is not limited to oils but also includes powders and the like, and may be any component that undergoes phase separation from water after being suspended in water at 25 to 90°C and left to stand for 1 hour. In the emulsion composition of the present invention, the mass ratio of the contents of the aqueous phase component to the oil phase component is not particularly limited, but is preferably 99:1 to 50:50, more preferably 95:5 to 60:40.

[0049] The composition of the present invention can form an α-gel structure without using a surfactant, and also has excellent emulsion stability even after storage over time and temperature. Therefore, the composition of the present invention can be preferably applied to external skin preparations. The topical skin preparation is preferably in the form of a cosmetic preparation including a quasi-drug, and is suitable for skin care. More preferred examples include cosmetic preparations, sunscreen cosmetics, and makeup cosmetics.

[0050] The composition of the present invention can be produced according to a conventional method.

[0051] ≪Optional ingredients≫ The cosmetic of the present invention can optionally contain other ingredients commonly used in cosmetics, as long as the effects of the present invention are not impaired. Examples of such optional ingredients include oils, other alcohols, ethers, powders, clay minerals, moisturizers, other surfactants, sequestering agents, pearlescent agents, amino acids, organic amines, polymer emulsions, pH adjusters, vitamins, antioxidants, preservatives, water-soluble polymers, fragrances, and various active ingredients. The optional ingredients may be used alone or in combination of two or more.

[0052] Examples of oils include polar oils and natural oils.

[0053] Polar oils include synthetic ester oils such as isopropyl myristate, cetyl octanoate, octyldodecyl myristate, isopropyl palmitate, butyl stearate, hexyl laurate, myristyl myristate, decyl oleate, hexyldecyl dimethyloctanoate, cetyl lactate, myristyl lactate, lanolin acetate, isocetyl stearate, isocetyl isostearate, cholesteryl 12-hydroxystearate, ethylene glycol di-2-ethylhexylate, dipentaerythritol fatty acid ester, N-alkyl glycol monoisostearate, neopentyl glycol dicaprate, diisostearyl malate, glyceryl di-2-heptylundecanoate, trimethylolpropane tri-2-ethylhexylate, trimethylolpropane triisostearate, pentaerythritol tetra-2-ethylhexylate, erythritol, trimethylolpropane triisostearate, cetyl 2-ethylhexanoate, 2-ethylhexyl palmitate, castor oil fatty acid methyl ester, oleic acid oil, acetoglyceride, 2-heptylundecyl palmitate, diisobutyl adipate, N-lauroyl-L-glutamic acid-2-octyldodecyl ester, di-2-heptylundecyl adipate, ethyl laurate, di-2-ethylhexyl sebacate, 2-hexyldecyl myristate, 2-hexyldecyl palmitate, 2-hexyldecyl adipate, diisopropyl sebacate, 2-ethylhexyl succinate, ethyl acetate, butyl acetate, amyl acetate, triethyl citrate, octyl methoxycinnamate, 2-ethylhexyl paramethoxycinnamate, diethylamino hydroxybenzoyl hexyl benzoate, and the like.

[0054] Examples of natural oils include avocado oil, camellia oil, turtle oil, macadamia nut oil, corn oil, mink oil, olive oil, rapeseed oil, egg yolk oil, sesame oil, persic oil, wheat germ oil, camellia oil, castor oil, linseed oil, safflower oil, cottonseed oil, perilla oil, soybean oil, peanut oil, tea seed oil, kaya oil, rice bran oil, Chinese tung oil, Japanese tung oil, jojoba oil, germ oil, sunflower oil, and triglycerin.

[0055] Other alcohols include, for example, monohydric alcohols such as ethanol; dihydric alcohols such as ethylene glycol, 1,3-butylene glycol, trimethylene glycol, 1,2-butylene glycol, propylene glycol, dipropylene glycol, propanediol, 1,2-pentanediol, 3-methyl-1,3-butanediol, tetramethylene glycol, 2,3-butylene glycol, pentamethylene glycol, 2-butene-1,4-diol, hexylene glycol, and octylene glycol; trihydric alcohols such as trimethylolpropane; tetrahydric alcohols such as pentaerythritol; pentahydric alcohols such as xylitol; polyhydric alcohol polymers such as triglycerin, tetraglycerin, and polyglycerin; and sugar alcohols such as starch hydrolysis sugar reduction alcohols. Ethylene glycol monomethyl ether, ethylene glycol monoethyl ether, alcohol alkyl ethers such as ethylene glycol monobutyl ether, ethylene glycol monophenyl ether, ethylene glycol monohexyl ether, ethylene glycol mono-2-methylhexyl ether, ethylene glycol isoamyl ether, ethylene glycol benzyl ether, and ethylene glycol isopropyl ether; alcohol alkyl ethers such as diethylene glycol monomethyl ether, diethylene glycol monoethyl ether, diethylene glycol monobutyl ether, triethylene glycol monomethyl ether, triethylene glycol monoethyl ether, propylene glycol monomethyl ether, propylene glycol monoethyl ether, propylene glycol monobutyl ether, propylene glycol isopropyl ether, dipropylene glycol methyl ether, dipropylene glycol ethyl ether, and dipropylene glycol butyl ether; Alcohol polymers such as diethylene glycol, triethylene glycol, polypropylene glycol, tetraethylene glycol, and polyethylene glycol; Examples include glycerol; tetrahydrofurfuryl alcohol; POE-tetrahydrofurfuryl alcohol; POP-butyl ether; POP·POE-butyl ether; tripolyoxypropylene glycerin ether; POP-glycerin ether; POP-glycerin ether phosphate; POP·POE-pentaneerythritol ether, etc.

[0056] In addition to the above alcohols, ethers include: Examples of the ethylene glycol dimethyl ether include ethylene glycol diethyl ether, ethylene glycol dibutyl ether, diethylene glycol dimethyl ether, diethylene glycol diethyl ether, diethylene glycol methyl ethyl ether, ethylene glycol monomethyl ether acetate, ethylene glycol monoethyl ether acetate, ethylene glycol monobutyl ether acetate, ethylene glycol monophenyl ether acetate, ethylene glycol diadipate, ethylene glycol disuccinate, diethylene glycol monoethyl ether acetate, diethylene glycol monobutyl ether acetate, propylene glycol monomethyl ether acetate, propylene glycol monoethyl ether acetate, propylene glycol monopropyl ether acetate, and propylene glycol monophenyl ether acetate.

[0057] The powder may be spherical, needle-like, plate-like, or any other suitable shape, and examples thereof include inorganic powders (e.g., talc, kaolin, mica, sericite, muscovite, phlogopite, synthetic mica, lepidolite, biotite, vermiculite, magnesium carbonate, calcium carbonate, aluminum silicate, barium silicate, calcium silicate, magnesium silicate, strontium silicate, tungstate metal salts, magnesium, silica, alumina, zeolite, barium sulfate, calcined calcium sulfate (calcined gypsum), calcium phosphate, fluorapatite, hydroxyapatite, ceramic powder, boron nitride, etc.); organic powders (e.g., polyamide resin powder (nylon powder), polyethylene powder, polymethyl (meth)acrylate powder, polystyrene powder, styrene-acrylic acid copolymer resin powder, silicone resin powder, benzoguanamine resin powder, polytetrafluoroethylene powder, cellulose powder, etc.); metal soaps (e.g., mica, silica, alumina, zeolite, barium sulfate, calcined calcium sulfate (calcined gypsum), calcium phosphate, fluorapatite, hydroxyapatite, ceramic powder, boron nitride, etc.); Zinc stearate, calcium palmitate, aluminum stearate); inorganic white pigment (e.g., titanium dioxide, zinc oxide, etc.); inorganic red pigments (e.g., iron oxide (red iron), iron titanate, etc.); inorganic brown pigments (e.g., γ-iron oxide, etc.); inorganic yellow pigments (e.g., yellow iron oxide, ochre, etc.); inorganic black pigments (e.g., black iron oxide, low-order titanium oxide, etc.); inorganic purple pigments (e.g., mango violet, cobalt violet, etc.); inorganic green pigments (e.g., chromium oxide, chromium hydroxide, cobalt titanate, etc.); inorganic blue pigments (e.g., ultramarine, iron blue, etc.); pearl pigments (e.g., titanium oxide-coated mica, titanium oxide-coated metal powder pigments (e.g., aluminum powder, copper powder, etc.); organic pigments such as zirconium, barium, or aluminum lakes (e.g., organic pigments such as Red No. 201, Red No. 202, Red No. 204, Red No. 205, Red No. 220, Red No. 226, Red No. 228, Red No. 405, Orange No. 203, Orange No. 204, Yellow No. 205, Yellow No. 401, and Blue No. 404, Red No. 3, Red No. 104, Red No. 106, Red No. 227, Red No. 230, Red No. 401, Red No. 505, Orange No. 205, Yellow No. 4, Yellow No. 5, Yellow No. 202, Yellow No. 203, Green No. 3, and Blue No. 1); natural pigments (e.g., chlorophyll, beta-carotene, etc.); and organically modified clay minerals.

[0058] Examples of organically modified clay minerals include hectorite, montmorillonite, saponite, hectorite, bentonite, smectite, etc. Organically modified clay minerals obtained by treating these with organic cations may also be used, such as dimethyl distearyl ammonium hectorite (quaternium-18 hectorite, etc.), dimethyl distearyl ammonium bentonite (quaternium-18 bentonite, quaternium-90 bentonite, etc.), benzyl dimethyl stearyl ammonium hectorite, dioctadecyl dimethyl ammonium salt-modified montmorillonite, octadecyl dimethyl benzyl ammonium salt-modified montmorillonite, dihexadecyl dimethyl ammonium salt-modified montmorillonite, dimethyl distearyl ammonium smectite, etc.

[0059] Examples of moisturizing agents include chondroitin sulfate, hyaluronic acid, mucoitin sulfate, caronic acid, atelocollagen, cholesteryl-12-hydroxystearate, sodium lactate, dl-pyrrolidone carboxylate, short-chain soluble collagen, diglycerin (EO)PO adduct, Rosa robur extract, yarrow extract, and melilot extract.

[0060] When a surfactant is used in combination with the composition of the present invention, examples of the surfactant include anionic surfactants, cationic surfactants, amphoteric surfactants, and nonionic surfactants.

[0061] Examples of anionic surfactants include fatty acid soaps (e.g., sodium laurate, sodium palmitate, etc.); higher alkyl sulfates (e.g., sodium lauryl sulfate, potassium lauryl sulfate, etc.); alkyl ether sulfates (e.g., POE triethanolamine lauryl sulfate, POE sodium lauryl sulfate, etc.); N-acyl sarcosinates (e.g., sodium lauroyl sarcosinate, etc.); higher fatty acid amide sulfonates (e.g., sodium N-myristoyl-N-methyl taurate, sodium coconut oil fatty acid methyl tauride, sodium lauryl methyl tauride, etc.); phosphate salts (sodium POE oleyl ether phosphate, sodium POE stearyl ether phosphate, etc.); sulfosuccinates (e.g., sodium di-2-ethylhexyl sulfosuccinate, sodium monolauroyl monoethanolamide polyoxyethylene sulfosuccinate, sodium lauryl methyl tauride, etc.); sodium polypropylene glycol sulfosuccinate, etc.); alkylbenzene sulfonates (e.g., sodium linear dodecylbenzene sulfonate, triethanolamine linear dodecylbenzene sulfonate, linear dodecylbenzene sulfonic acid, etc.); higher fatty acid ester sulfates (e.g., sodium hydrogenated coconut oil fatty acid glycerin sulfate, etc.); N-acyl glutamates (e.g., monosodium N-lauroyl glutamate, disodium N-stearoyl glutamate, monosodium N-myristoyl-L-glutamate, etc.); sulfated oils (e.g., turmeric oil, etc.); POE alkyl ether carboxylic acids; POE alkyl allyl ether carboxylates; α-olefin sulfonates; higher fatty acid ester sulfonates; secondary alcohol sulfates; higher fatty acid alkylolamide sulfates; sodium lauroyl monoethanolamide succinate; N-palmitoyl glutamate ditriethanolamine dispartate; sodium caseinate; and the like.

[0062] Examples of cationic surfactants include alkyltrimethylammonium salts (e.g., stearyltrimethylammonium chloride, lauryltrimethylammonium chloride, etc.); alkylpyridinium salts (e.g., cetylpyridinium chloride, etc.); distearyldimethylammonium chloride, dialkyldimethylammonium salts; poly(N,N'-dimethyl- 3,5-Methylenepiperidinium; Alkyl quaternary ammonium salts; Alkyl dimethyl benzoates Examples of the alkylamine salt include benzylammonium salts; alkylisoquinolinium salts; dialkylmorphonium salts; POE alkylamines; alkylamine salts; polyamine fatty acid derivatives; amyl alcohol fatty acid derivatives; benzalkonium chloride; and benzethonium chloride.

[0063] Examples of amphoteric surfactants include imidazoline-based amphoteric surfactants (e.g., 2-undecyl-N,N,N-(hydroxyethylcarboxymethyl)-2-imidazoline sodium, 2-cocoyl-2-imidazolinium hydroxide-1-carboxyethyloxy disodium salt, etc.); betaine-based surfactants (e.g., 2-heptadecyl-N-carboxymethyl-N-hydroxyethylimidazolinium betaine, lauryldimethylaminoacetic acid betaine, alkyl betaine, amido betaine, sulfobetaine, etc.).

[0064] Examples of nonionic surfactants include polyether-modified silicones (e.g., polyethylene glycol-10 dimethicone, polyethylene glycol-12 dimethicone, PEG-9 polydimethylsiloxyethyl dimethicone, PEG-9 polydimethylsiloxyethyl dimethicone, etc.); polyglycerin-modified silicones (e.g., polyglyceryl-3 disiloxane dimethicone, polyglyceryl-3 polydimethylsiloxyethyl dimethicone, etc.); sorbitan fatty acid esters (e.g., sorbitan monooleate, sorbitan monostearate, sorbitan monoisostearate, sorbitan monolaurate, sorbitan monopalmitate, sorbitan monostearate, sorbitan sesquioleate, sorbitan trioleate, diglycerol sorbitan penta-2-ethylhexylate, diglycerol sorbitan tetra-2-ethylhexylate, etc.); glycerin fatty acids (e.g., monocottonseed oil fatty acid glycerin, monoerucate glycerin, sesquioleate glycerin, monostearate glycerin, α,α'-oleic acid pyroglutamic acid glycerin, monostearate malate, etc.); propylene glycol fatty acid esters (e.g., propylene glycol monostearate, etc.); POE castor oil / hydrogenated castor oil derivatives (POE castor oil, POE hydrogenated castor oil, etc.); non-hydrophilic nonionic surfactants such as glycerin alkyl ethers.Also, polyglycerol fatty acid esters (e.g., polyglyceryl monooleate, polyglyceryl monostearate, etc.); POE sorbitan fatty acid esters (e.g., POE sorbitan monooleate, POE sorbitan monostearate, POE sorbitan tetraoleate, etc.); POE sorbit fatty acid esters (e.g., POE sorbit monolaurate, POE sorbit monooleate, POE sorbit pentaoleate, POE sorbit monostearate, etc.); POE glycerin fatty acid esters (e.g., POE monooleates such as POE glycerin monostearate, POE glycerin monoisostearate, POE glycerin triisostearate, etc.); POE fatty acid esters (e.g., POE distearate, POE monodioleate, ethylene glycol distearate, etc.); POE alkyl ethers (e.g., POE lauryl ether, POE oleyl ether, POE stearyl ether, POE-behenyl ether, POE-2-octyldodecyl ether, POE cholestanol ether, etc.); POE alkyl phenyl ethers (e.g., POE nonylphenyl ether, etc.); Pluronic types (e.g., Pluronic (registered trademark), etc.); POE·POP alkyl ethers (e.g., POE·POP cetyl ether, POE·POP-2-decyltetradecyl ether, POE·POP monobutyl ether, POE·POP hydrogenated lanolin, POE·POP glycerin ether, etc.); tetra POE·tetraPOP ethylene diamine. Other examples of hydrophilic nonionic surfactants include amine condensates (e.g., Tetronic); POE castor oil hydrogenated castor oil derivatives (e.g., POE castor oil, POE hydrogenated castor oil, POE hydrogenated castor oil monoisostearate, POE hydrogenated castor oil triisostearate, POE hydrogenated castor oil monopyroglutamic acid monoisostearate diester, POE hydrogenated castor oil maleic acid, etc.); POE beeswax / lanolin derivatives (e.g., POE sorbitol beeswax, etc.); alkanolamides (e.g., coconut oil fatty acid diethanolamide, lauric acid monoethanolamide, fatty acid isopropanolamide, etc.); POE propylene glycol fatty acid esters; POE alkylamines; POE fatty acid amides; sucrose fatty acid esters; alkyl glucosides; alkylethoxydimethylamine oxide; and trioleyl phosphate.

[0065] Examples of sequestering agents include 1-hydroxyethane-1,1-diphosphonic acid, 1-hydroxyethane-1,1-diphosphonic acid tetrasodium salt, edetate disodium, edetate trisodium, edetate tetrasodium, sodium citrate, sodium polyphosphate, sodium metaphosphate, gluconic acid, phosphoric acid, citric acid, ascorbic acid, succinic acid, edetic acid, and ethylenediaminehydroxyethyltriacetate trisodium salt.

[0066] Examples of pearlescent agents include glycol distearate and titanium mica.

[0067] Examples of the amino acid include neutral amino acids (e.g., threonine, cysteine, etc.); basic amino acids (e.g., hydroxylysine, etc.); and the amino acid derivatives include, for example, acyl sarcosine sodium (sodium lauroyl sarcosine), acyl sarcosine sodium (sodium lauroyl sarcosine), Examples of the anti-inflammatory agent include glutamic acid salts, acyl β-alanine sodium, glutathione, and pyrrolidone carboxylic acid.

[0068] Examples of organic amines include monoethanolamine, diethanolamine, triethanolamine, morpholine, triisopropanolamine, 2-amino-2-methyl-1,3-propanediol, and 2-amino-2-methyl-1-propanol.

[0069] Examples of polymer emulsions include acrylic resin emulsion, polyethyl acrylate emulsion, acrylic resin liquid, polyacrylic alkyl ester emulsion, polyvinyl acetate resin emulsion, and natural rubber latex.

[0070] Examples of pH adjusters include buffers such as lactic acid-sodium lactate, citric acid-sodium citrate, and succinic acid-sodium succinate, and are usually used to adjust the pH of the internal phase (aqueous component).

[0071] Vitamins include, for example, vitamins A, B1, B2, B6, C, E and their derivatives. Examples of such substances include pantothenic acid and its derivatives, biotin, etc.

[0072] Examples of antioxidants include tocopherols, dibutylhydroxytoluene (BHT), butylhydroxyanisole, pyrosulfite, gallic acid ester, phosphoric acid, citric acid, ascorbic acid, maleic acid, malonic acid, succinic acid, fumaric acid, cephalin, hexametaphosphate, phytic acid, and ethylenediaminetetraacetic acid.

[0073] Examples of preservatives include parabens and phenoxyethanol.

[0074] Examples of water-soluble polymers include plant-based polymers (e.g., gum arabic, tragacanth, etc.). Gum, galactan, guar gum, carob gum, karaya gum, carrageenan, pectin, agar, quince seed (quince), algae colloid (cassow extract), starch (co (corn, potato, wheat), glycyrrhizic acid); microbial polymers (e.g. natural water-soluble polymers such as xanthan gum, dextran, succinoglucan, pullulan, etc.; animal polymers (e.g., collagen, casein, albumin, gelatin, etc.); semi-synthetic water-soluble polymers such as starch-based polymers (e.g., carboxymethyl starch, methylhydroxypropyl starch, etc.); cellulose-based polymers (hydroxypropylmethylcellulose, hydroxyethylcellulose, hydroxypropylcellulose, methylcellulose, ethylcellulose, hydroxypropylmethylcellulose stearoxy ether, sodium cellulose sulfate, carboxymethylcellulose, sodium carboxymethylcellulose, crystalline cellulose, cellulose powder, etc.); alginic acid-based polymers (e.g., sodium alginate, propylene glycol alginate, etc.), etc. Examples include synthetic water-soluble polymers such as vinyl polymers (e.g., polyvinyl alcohol, polyvinyl methyl ether, polyvinylpyrrolidone, carboxyvinyl polymer, etc.); polyoxyethylene polymers (e.g., polyethylene glycol 20,000, 40,000, 60,000, etc.); acrylic polymers (e.g., sodium polyacrylate, polyethyl acrylate, polyacrylamide, etc.); polyethyleneimine; and cationic polymers.

[0075] Examples of various active ingredients include anti-inflammatory agents (e.g., glycyrrhizinic acid derivatives, glycyrrhetinic acid derivatives, salicylic acid derivatives, hinokitiol, zinc oxide, allantoin, etc.); whitening agents (e.g., placenta extract, saxifrage extract, arbutin, resorcinol derivatives, etc.); various extracts (e.g., Phellodendron bark, Coptis chinensis, Lithospermum root, Peony, Swertia japonica, Birch, sage, Loquat, Carrot, Aloe, Mallow, Iris, Grape, Job's tears, Luffa, Lily, Saffron, Cnidium rhizome, Angelica acutiloba, Garlic, Chili pepper, Citrus fruit, Angelica acutiloba, Seaweed, etc.), activators (e.g., Rhododendron rhizome, jelly, photosensitizers, cholesterol derivatives, etc.); blood circulation promoters (e.g., nonylic acid valenylamide, nicotinic acid benzyl ester, nicotinic acid β-butoxyethyl ester, capsaicin, zingerone, cantharides tincture, ichthammol, tannic acid, α-borneol, tocopherol nicotinate, inositol hexanicotinate, cyclandelate, cinnarizine, tolazoline, acetylcholine, verapamil, cepharanthine, γ-oryzanol, etc.); antiseborrheic agents (e.g., sulfur, thianthol, etc.); anti-inflammatory agents (e.g., tranexamic acid, thiotaurine, hypotaurine, etc.), etc. [Example]

[0076] The present invention will be specifically described below with reference to examples, but these are merely examples of the present invention and the scope of the present invention is not limited to these examples.

[0077] <Preparation of emulsion composition> The emulsion compositions of the present invention were prepared according to the formulations in Table 1. Specifically, the phase A components were mixed while heated to 65°C and dissolved uniformly. Next, the phase B components, which had been heated to 65°C, were mixed with stirring, and the mixture of phases A and B was then forcibly stirred using a homomixer to complete the emulsification. The emulsions were cooled to room temperature to obtain the emulsion compositions (creams) of the Examples and Comparative Examples. Each of the resulting emulsion compositions was evaluated for the following items.

[0078] <Evaluation> (Wide-angle X-ray diffraction (WAXD)) The resulting emulsion composition was subjected to WAXD measurement using an XRD measurement device MiniFlex600 (X-ray source: CuKα) (manufactured by Rigaku Co., Ltd.). This can be confirmed by the disappearance of the peak around Bragg angle = 24°, which is also seen in 65 single material (for example, when the peak area becomes 1% or less of the single material's peak area), and the presence or absence of a single diffraction peak that appears around Bragg angle = 21.4°, which is characteristic of α-gel.

[0079] The X-ray diffraction charts of Comparative Examples 2 and 3 and Examples 1 to 3 are shown in FIG. The results of confirming the formation of α-gel (disappearance of the peak around 24° and appearance of a single diffraction peak around 21.4°: ○, ×) are shown in Table 1.

[0080] (Microscopic observation) The α-gel formation and emulsification state of the resulting emulsion composition were observed using an all-in-one fluorescence microscope BZ-X800 (Keyence Corporation) at 400x bright field magnification. The α-gel structure can be confirmed by the formation of a maltase cross image when observed under crossed Nicols with a polarizing filter setting.

[0081] Microscopic images of Comparative Examples 2 and 3 and Examples 1 to 3 are shown in FIG. In addition, expert evaluators evaluated the emulsification state using the following three-point scale. ○: Fine and uniform emulsified particles are observed △: Coarse emulsified particles and aggregates are observed in some areas ×: Coarse emulsified particles and aggregates are observed throughout

[0082] (Stability over time) After storing for one month at 5°C, 20°C, 40°C, and cycle conditions (-5∞45°C), the hardness was measured using a hardness tester, Card Meter MAX ME-500 (manufactured by I.technoEngineering), and the measured values ​​were compared. 〇: No change in hardness, stable ×: Hardness fluctuates greatly and is unstable The results are shown in Table 1.

[0083] [Table 1]

[0084] <Result> The emulsion compositions of the examples were confirmed to have formed α-gel, and the emulsion state was found to be good. Furthermore, it also had excellent stability over time. On the other hand, in Comparative Example 1, which did not contain component (C), and Comparative Examples 2 and 3, in which the content ratio of component (B) to component (C) did not satisfy the specific numerical range, α-gel formation was not confirmed, and after one month of storage under cycle conditions, an extreme increase in hardness was observed, and the stability over time was also insufficient. In Comparative Example 4, in which the contents of components (B), (C), and (D) did not satisfy the specific numerical ranges, the emulsion state was not uniform, and after one month of storage under cycle conditions, the hardness increased significantly, and the stability over time was also insufficient. [Industrial Applicability]

[0085] The present invention can be applied to external skin preparations, pharmaceuticals, cosmetics including quasi-drugs, and the like.

Claims

1. The following components (A) to (F): (A) a modified hyaluronic acid or a salt thereof containing a glycerin skeleton-containing group; (B) higher alcohol; (C) α-monoalkyl glyceryl ether; (D) an oily component other than (B) and (C); (E) glycerin; and (F) Water; Including, the content ratio (mass ratio) of (B) to (C) ((B) / (C)) is 0.1 to 2.5, A composition in which the total content of (B), (C), and (D) is 20.0 to 35.0 mass% based on the total content of the composition, The (A) to (F) form an α-gel. composition.

2. The composition according to claim 1, wherein (A) is a modified hyaluronic acid or a salt thereof containing a glycerin skeleton-containing group represented by the following general formula (1): -O-CH ２ -CHOH-CH ２ -OR １ ・・・(1) (In the formula, R １ represents a linear or branched alkyl or alkenyl group.

3. The composition according to claim 1, wherein (A) is hydrolyzed alkyl (C12-13) glyceryl hyaluronate.

4. 2. The composition according to claim 1, wherein (B) is a higher alcohol having 16 to 22 carbon atoms.

5. The composition according to claim 1, wherein (B) is cetanol or behenyl alcohol.

6. 2. The composition according to claim 1, wherein (C) is an α-monoalkyl glyceryl ether having an alkyl group with 8 to 24 carbon atoms.

7. The composition of claim 1 , wherein (C) is batyl alcohol.

8. The composition according to claim 1, wherein (D) is at least one selected from the group consisting of hydrocarbon oils, monoester oils, triglyceride oils, and silicone oils.

9. 2. The composition according to claim 1, wherein (D) is at least one selected from the group consisting of hydrogenated polyolefins, 2-ethylhexyl palmitate, triethylhexanoin, and dimethicone.

10. The composition according to claim 1, wherein the content of (A) is 0.9 to 1.8 mass% based on the total mass of the composition.

11. The composition according to claim 1, wherein the content of (B) is 3.0 to 14.7 mass% based on the total mass of the composition.

12. The composition according to claim 1, wherein the content of (C) is 5.5 to 13.25 mass% based on the total mass of the composition.

13. The composition according to claim 1, wherein the content of (D) is 8.8 to 11.5 mass% based on the total mass of the composition.

14. The composition according to claim 1, wherein the content of (E) is 23.2 to 53.1 mass% based on the total mass of the composition.

15. The composition according to claim 1, wherein the content of (F) is 19.5 to 44.2 mass% based on the total mass of the composition.

16. 2. The composition according to claim 1, wherein the mass ratio of the content of (B) to the content of (C) is 3.5:1.5 to 1:

4.

17. 10. The composition of claim 1, which is in the form of an oil-in-water emulsion.

18. The composition according to any one of claims 1 to 17, which is an external preparation for skin.

19. The composition according to claim 18, which is a cosmetic.

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