JP7294770B2 - Composition for external use on skin, composition for suppressing functional deterioration of ultraviolet absorber, and method for suppressing functional deterioration of ultraviolet absorbent - Google Patents

Description

TECHNICAL FIELD The present invention relates to a composition for external use on the skin, a composition for suppressing functional deterioration of an ultraviolet absorber, and a method for suppressing functional deterioration of an ultraviolet absorbent.

Excessive exposure to ultraviolet rays is known to cause skin erythema, acute inflammatory reaction, and subsequent blackening, which is one of the causes of skin cancer. It is also becoming clear that long-term exposure to ultraviolet light causes premature aging of the skin. Therefore, the demand for sunscreen cosmetics having a high UV-blocking effect is increasing year by year.

The above sunscreen cosmetics contain an ultraviolet absorber and an ultraviolet scattering agent in order to obtain a high SPF (Sun Protection Factor) value by blocking ultraviolet irradiation to the skin. Such sunscreen cosmetics absorb or scatter UVA and UVB by covering the skin with a coating film formed by these UV absorbers and UV scattering agents, thereby suppressing the amount of UV rays reaching the skin. It is a cosmetic intended to protect the skin from the harmful effects of ultraviolet rays.

The above ultraviolet absorbers block ultraviolet rays by absorbing light energy, but it is also known that the ultraviolet absorbers themselves decompose under the influence of ultraviolet rays. Therefore, there is a demand for a sunscreen cosmetic that maintains its sunscreen effect for a longer period of time by improving the photostability of the ultraviolet absorber. Therefore, as a method for improving the photostability of the ultraviolet absorber, there is a method of encapsulating the sunscreen (see Patent Document 1), and a method of dispersing the ultraviolet absorber in a specific resin to have a predetermined particle size. A method of forming composite particles (see Patent Document 2) and the like are known. However, these conventional methods still cannot sufficiently improve the photostability of the UV absorber.

U.S. Pat. No. 5,733,531 Japanese Patent Publication No. 2011-526271

The present invention has been made in view of such circumstances, and an object thereof is to provide a new type of composition for external use on the skin, which has an excellent UV-blocking effect and has a long-lasting effect.

The present inventors, as a result of intensive research to solve the above problems, along with the ultraviolet absorber,
By blending at least one component selected from the group consisting of polyamide-3, polyamide-8, ethyl cellulose and amino acid-based oil gelling agents, and a polyhydric alcohol, the light stability of the ultraviolet absorber is improved, Furthermore, the present inventors have found that a new type of composition for external use on the skin, which is excellent in water resistance and hardly causes secondary adhesion, can be obtained. That is, the gist of the present invention is as follows.

[1] (A) an ultraviolet absorber, (B) at least one component selected from the group consisting of polyamide-3, polyamide-8, ethyl cellulose and amino acid-based oil gelling agents, and (C) a polyhydric alcohol Skin external composition containing.
[2] The composition for external use on skin according to [1], wherein (A) the UV absorber is an oil-soluble UV absorber.
[3] (A) UV absorber is ethylhexyl methoxycinnamate, hexyl diethylaminohydroxybenzoylbenzoate, bisethylhexyloxyphenol methoxyphenyltriazine, ethylhexyltriazone, octocrylene, polysilicone-15, dimethoxybenzylidenedioxoimidazolidinepropion The external composition for skin according to [1] or [2], which is at least one selected from the group consisting of ethylhexyl acid and t-butylmethoxydibenzoylmethane.
[4] (C) polyhydric alcohol is propylene glycol, dipropylene glycol, glycerin, diglycerin, 1,2-pentanediol, 1,2-hexanediol, 1,3-propylene glycol, 1,3-butanediol The external skin composition according to any one of [1] to [3], which is at least one selected from the group consisting of:
[5] A composition for suppressing functional deterioration of an ultraviolet absorber, comprising at least one component selected from the group consisting of polyamide-3, polyamide-8, ethyl cellulose, and an amino acid-based oil gelling agent, and a polyhydric alcohol. .
[6] A method for suppressing functional deterioration of an ultraviolet absorber, using at least one component selected from the group consisting of polyamide-3, polyamide-8, ethyl cellulose and amino acid-based oil gelling agents, and a polyhydric alcohol.

According to the present invention, by blending at least one selected from the group consisting of polyamide-3, polyamide-8, ethyl cellulose and amino acid-based oil gelling agents, and a polyhydric alcohol together with an ultraviolet absorber, it is possible to block ultraviolet rays. It is possible to provide a new type of composition for external use on the skin, which is excellent in effect, maintains its effect for a long time, and does not cause white residue or whitening. Furthermore, the composition for external use on the skin of the present invention has the effect of being excellent in water resistance and less likely to cause a decrease in ultraviolet absorption capacity due to secondary adhesion.

The present invention will be described in detail below. In addition, the terms used in this specification are interpreted as meanings commonly used in the technical field unless otherwise specified.

[Composition for external use on the skin]
The composition for external use on the skin of the present invention comprises (A) an ultraviolet absorber, (B) at least one component selected from the group consisting of polyamide-3, polyamide-8, ethyl cellulose and an amino acid-based oil gelling agent, and ( C) Contains a polyhydric alcohol. Furthermore, the external composition for skin of the present invention may contain other ingredients as long as the effects of the present invention are not impaired. Each component will be described in detail below.

<(A) UV absorber>
(A) Ultraviolet absorber refers to a compound that absorbs ultraviolet rays and converts them into heat, vibration, fluorescence, radicals, etc., and has the function of protecting the skin. Examples include cinnamic acid derivatives and benzalmalonate derivatives. , triazine derivatives, dibenzoylmethane derivatives, benzoic acid derivatives, salicylic acid derivatives, benzophenone derivatives, benzylidene camphor derivatives, phenylbenzoylimidazole derivatives, anthranyl derivatives, imidazolidine derivatives and the like. A ultraviolet absorber can be used individually by 1 type or in combination of 2 or more types.

Examples of cinnamic acid derivatives include ethylhexyl methoxycinnamate (Ubinal MC80, Ubinal MC80N, BASF Japan; Parsol MCX, DSM Nutrition Japan, etc.), isoamyl methoxycinnamate (Neohelipan TS, Harman Andreimer, etc.), 2-ethylhexyl α-cyano-β-phenylcinnamate (alias: Octocrylene, Parsol 340, DSM Nutrition Japan, etc.), isopropyl methoxycinnamate, cinoxate, DEA methoxycinnamate, diisopropyl methylcinnamate, trimethoxycinnamate bis(trimethylsimexy)silylisopentyl acid, methyl 2,5-diisopropylcinnamate, glyceryl mono-2-ethylhexanoate di-paramethoxycinnamate, and the like.

Benzalmalonate derivatives include, for example, polysilicone-15 (also known as Dimethicodiethylbenzalmalonate, Parsol SLX, DSM Nutrition Japan, etc.).

Examples of triazine derivatives include bisethylhexyloxyphenolmethoxyphenyltriazine (2,4-bis-[{4-(2-ethylhexyloxy)-2-hydroxy}-phenyl]-6-(4-methoxyphenyl)-1, 3,5-triazine) (Tinosolv S, BASF Japan, etc.), 2,2′-methylenebis(6-(2H-benzotriazol-2-yl)-4-(1,1,3,3-tetramethylbutyl ) Phenol (Tinosolv M, BASF Japan, etc.), Ethylhexyltriazone (2,4,6-tris [4-(2-ethylhexyloxycarbonyl)anilino]-1,3,5-triazine) (Ubinal T150, BASF Japan Co., Ltd.), diethylhexylbutamide triazoline (Yubasorb HEB, Sigma 3V Co., etc.), and the like.

Examples of dibenzoylmethane derivatives include t-butylmethoxydibenzoylmethane (alias: 4-tert-butyl-4′-methoxydibenzoylmethane, Parsol 1789, DSM Nutrition Japan, etc.), 4-isopropyldibenzoylmethane (U. Solex 8020, Merck Co., etc.) and the like.

Benzoic acid derivatives include, for example, hexyl diethylaminohydroxybenzoylbenzoate (Uvinal A Plus, BASF Japan, etc.), amyl paradimethylaminobenzoate, 2-ethylhexyl paradimethylaminobenzoate, paraaminobenzoic acid (PABA), glyceryl PABA, Ethyl PABA, ethyl-dihydroxypropyl PABA, ethylhexyl-dimethyl PABA and the like.

Examples of salicylic acid derivatives include homomenthyl salicylate (Parsol HMS, DSM Nutrition Japan, etc.), ethylhexyl salicylate (Neoheliopan OS, Harman Andreimer, etc.), dipropylene glycol salicylate (Dipisal, Skell), TEA salicylate ( Neoheliopan TS, Harman Andreimer Co., etc.), ethylene glycol salicylate, and the like.

Examples of benzophenone derivatives include benzophenone-1 (Uvinal 400, BASF Japan, etc.), benzophenone-2 (Uvinal D50, BASF Japan, etc.), benzophenone-3 (Uvinal M40, BASF Japan, etc.), benzophenone-4 (Uvinal MS40, BASF Japan Co., etc.), benzophenone-5 (Helisorb 11, Norquai Co., etc.), benzophenone-8 (Spectrasorb, American Cyanamid Co., etc.), benzophenone-9 (Ubinal DS49, BASF Japan Co., etc.) and the like. .

Examples of benzylidene camphor derivatives include 3-benzylidene camphor (Megizolyl SD, Simex Co., etc.), benzylidene camphor sulfonic acid (Megizolyl SL, Simex Co., etc.), camphor benzalkonium methosulfate (Megizolyl SO, Simex Co., etc.), terephthalate lylidene camphor sulfonic acid (Megizolyl SX, Simex Co., etc.), polyacrylamide methyl benzylidene camphor (Megizolyl SW, Simex Co., etc.), and the like.

Examples of phenylbenzoylimidazole derivatives include phenylbenzimidazole sulfonic acid (Parsol HS, DSM Nutrition Japan, etc.), disodium phenyldibenzimidazole tetrasulfonate (Neoheliopan AP, Harman Andreimer, etc.), and the like.

Anthranyl derivatives include, for example, menthyl anthranilate.

Examples of imidazolidine derivatives include ethylhexyl dimethoxybenzylidenedioxoimidazolidinepropionate (also known as 2-ethylhexyl dimethoxybenzylideneoxoimidazolidinepropionate).

(A) As the ultraviolet absorber, cinnamic acid derivatives, benzalmalonate derivatives, and triazine derivatives are used from the viewpoint that the photostability is remarkably improved by blending the components (B) and (C), which will be described later. , dibenzoylmethane derivatives, and benzoic acid derivatives are preferred, and among them, oil-soluble ultraviolet absorbers are more preferred, ethylhexyl methoxycinnamate, hexyl diethylaminohydroxybenzoylbenzoate, bisethylhexyloxyphenol methoxyphenyltriazine, ethylhexyltriazone, octocrylene, More preferred are Polysilicone-15, ethylhexyl dimethoxybenzylidenedioxoimidazolidinepropionate, and t-butyl methoxydibenzoylmethane, with ethylhexyl methoxycinnamate being particularly preferred.

The content of (A) the ultraviolet absorber in the composition for external use on skin of the present invention is preferably 0.01% by weight or more and 30% by weight or less, and 0.05% by weight or more and 25% by weight, based on the total amount of the composition for external use on skin. % by weight or less is more preferable, and 0.1% by weight or more and 20% by weight or less is even more preferable. (A) If the content of the ultraviolet absorber is within the above numerical range, the composition for external use on the skin can sufficiently provide an ultraviolet shielding effect.

<(B) At least one component selected from the group consisting of polyamide-3, polyamide-8, ethyl cellulose and amino acid-based oil gelling agents>
Component (B) can significantly improve the photostability of UV absorber (A) by blending it with component (C), which will be described later, in an external composition for skin containing (A) UV absorber. is an ingredient. The component (B) is generally used as a thickener, film-forming agent, and the like. (B) component can be used individually by 1 type or in combination of 2 or more types.

(Polyamide-3; Polyamide-3)
Polyamide-3 is a copolymer obtained by condensing dilinoleic acid, ethylenediamine and polypropyleneglycoldiamine and blocking both ends with PEG/PPG-32/10 aminopropyl methyl ether. Examples of these commercially available products include OleoCraft MP-30, OleoCraft HP-31, and OleoCraft MP-32 (manufactured by CRODA).

(Polyamide-8; Polyamide-8)
Polyamide-8 is a copolymer of ethylenediamine, neopentyl glycol and hydrogenated dimer dilinoleic acid whose ends are blocked with stearyl alcohol. Commercially available products thereof include, for example, OleoCraft LP-20 (manufactured by CRODA).

(ethyl cellulose)
Ethyl cellulose is obtained by replacing some or all of the hydroxyl groups of glucose units of cellulose obtained by condensation polymerization of β-glucose with ethyl ether. Examples of these commercially available products include ETHOCEL Standard 7 Premium, ETHOCEL Standard 10 Premium, ETHOCEL Standard 45 Premium, ETHOCEL Standard 100 Premium (manufactured by The Dow Chemical Company made) and the like.

(Amino acid-based oil gelling agent)
Amino acid-based oil gelling agents are derivatives of N-acyl amino acids such as amides, esters and amine salts, such as dibutyl lauroyl glutamide, dibutyl ethylhexanoyl glutamide, lauroyl glutamic acid stearylamide, dicaproyl lysine laurylamide. , dicaproyllysine laurylamine salt, dicaproyllysine lauryl ester, lauroylphenylalanine laurylamide, and the like. Among these, dibutyl lauroyl glutamide and dibutylethylhexanoyl glutamide are preferred from the viewpoint of the effects of the present invention. Commercially available products thereof include, for example, GP-1 and EB-21 (manufactured by Ajinomoto Healthy Supply Co., Ltd.).

As the component (B) contained in the composition for external use on the skin of the present invention, polyamide-3, polyamide-8, ethyl cellulose, dibutyl lauroyl glutamide are more preferred, polyamide-3, polyamide-8 and ethyl cellulose are more preferred, and polyamide- 8 is particularly preferred.

The content of component (B) in the external composition for skin of the present invention is preferably 0.01% by weight or more and 30% by weight or less, more preferably 0.05% by weight or more and 25% by weight, based on the total amount of the external composition for skin. The following are more preferable, and 0.1% by weight or more and 20% by weight or less are even more preferable. When the content of the component (B) is within the above numerical range, the effect of significantly improving the photostability of the UV absorber (A) in the composition for external use on the skin can be obtained together with the component (C) described later.

The ratio of the (A) ultraviolet absorber and the (B) component contained in the composition for external use on the skin of the present invention is such that the ratio of the (B) component (% by weight) to the (A) ultraviolet absorber (% by weight) is 1 /50 to 10, preferably 1/20 to 5, more preferably 1/10 to 3, even more preferably 1/5 to 1.5.

<(C) Polyhydric alcohol>
(C) The polyhydric alcohol can improve the photostability of (A) the UV absorber by blending it with the above-described component (B) in the composition for external use on the skin containing (A) the UV absorber. is an ingredient. (C) A polyhydric alcohol can be used individually by 1 type or in combination of 2 or more types.

(C) Polyhydric alcohols preferably have 2 to 10 carbon atoms, such as glycerin, diglycerin, triglycerin, propylene glycol, 1,3-propylene glycol, dipropylene glycol, 1,3-butanediol ( 1,3-butylene glycol), ethylene glycol, diethylene glycol, isoprene glycol, sorbitol, xylitol, erythritol, mannitol, 1,2-pentanediol, 1,2-hexanediol, octanediol, decanediol, neopentyl glycol, and the like. be done.

Among these, glycerin, diglycerin, triglycerin, propylene glycol, 1,3-propylene glycol, dipropylene glycol, 1,3-butanediol, ethylene glycol, diethylene glycol, isoprene glycol, and sorbitol are preferred from the viewpoint of the effects of the present invention. , xylitol, erythritol, mannitol, 1,2-pentanediol, 1,2-hexanediol and octanediol are preferred, and glycerin, propylene glycol, 1,3-propylene glycol, dipropylene glycol and 1,2-hexanediol are more preferred. preferable.

The content of component (C) in the external composition for skin of the present invention is preferably 0.01% by weight or more and 30% by weight or less, more preferably 0.05% by weight or more and 20% by weight, based on the total amount of the external composition for skin. The following are more preferable, and 0.1% by weight or more and 15% by weight or less are even more preferable. If the content of the component (C) is within the above numerical range, the effect of improving the photostability of the ultraviolet absorber (A) in the composition for external use on skin can be obtained together with the component (B) described above.

The ratio of the (A) ultraviolet absorber to the (C) component contained in the composition for external use on the skin of the present invention is such that the ratio of the (C) component (% by weight) to the (A) ultraviolet absorber (% by weight) is 1 /50 to 20, preferably 1/20 to 10, more preferably 1/15 to 5, even more preferably 1/10 to 1.

The ratio of component (B) to component (C) contained in the external composition for skin of the present invention is such that the ratio of component (C) (% by weight) to component (B) (% by weight) is 1/50 to 20. , preferably 1/20 to 10, more preferably 1/15 to 5, even more preferably 1/5 to 2.5.

<Other ingredients>
Optional ingredients contained in the composition for external use on the skin of the present invention include, for example, active whitening ingredients, turnover accelerators, anti-glycation ingredients, antioxidant ingredients, anti-aging ingredients, anti-inflammatory agents, cooling agents, bactericides, and vitamins. , organic acids, moisturizing ingredients, scrubbing agents, ultraviolet scattering ingredients, astringent ingredients, peptides or derivatives thereof, amino acids or derivatives thereof, cleansing ingredients, keratin softening ingredients, cell activating ingredients, blood circulation promoting ingredients, and the like. In the composition for external use on the skin of the present invention, each of these components may be used alone, or two or more of them may be used in combination.

Examples of the whitening active ingredient include tocopherol, vitamin C and its derivatives, arbutin, kojic acid, placenta, ellagic acid, nicotinamide, tranexamic acid and its derivatives, hydroquinone, rucinol (registered trademark), and potassium 4-methoxysalicylate. salts, linoleic acid and its derivatives, and the like.

Examples of the turnover accelerator include vitamins, keratin softening components, cell activating components, and blood circulation promoting components, which will be described later.

Examples of the anti-glycation component include plant extracts such as Budreja axillaris leaf extract, evening primrose oil, amla fruit, fruit juice or extracts thereof, L-arginine, L-lysine, hydrolyzed casein, and hydrolyzable tannins. , carnosine and the like.

Examples of the antioxidant components include components derived from plants (e.g., grapes, panax ginseng, comfrey, etc.); sodium hydride, erythorbic acid and its salts, flavonoids, glutathione and the like.

Examples of the anti-aging ingredients include hydrolyzed soy protein, retinoids (retinol and its derivatives, retinoic acid, retinal, etc.), pangamic acid, kinetin, ursolic acid, turmeric extract, sphingosine derivatives, silicon, silicic acid, N- methyl-L-serine, mevalonolactone and the like.

Examples of the anti-inflammatory agent include allantoin and its derivatives, glycyrrhetinic acid and its derivatives, glycyrrhizic acid and its derivatives, salicylic acid derivatives, aminocaproic acid, azulene and its derivatives, zinc oxide, and tocopherol acetate.

Examples of the cooling agent include terpenes such as menthol, camphor, and geraniol (these may be d-, l-, or dl-forms); eucalyptus oil, bergamot oil, peppermint oil, coolmint oil, spearmint Oil, essential oils such as peppermint oil, and the like.

Examples of the disinfectant include isopropylmethylphenol, salicylic acid, benzalkonium chloride, ethanol, benzethonium chloride, gluconic acid and its derivatives, photosensitizer No. 101, photosensitizer No. 201, paraben, phenoxyethanol, pyroctoolamine, miconazole, and the like. mentioned.

The above-mentioned vitamins may be either water-soluble vitamins or oil-soluble vitamins. water-soluble vitamin Cs, oil-soluble vitamins C, vitamin Ks; vitamin-like acting factors such as ferulic acid;

Examples of the organic acid include gluconic acid, aspartic acid, aminoethylsulfonic acid, citric acid, glutamic acid, succinic acid, oxalic acid, fumaric acid, propionic acid, malic acid, salicylic acid, glycolic acid, phytic acid, tartaric acid, and acetic acid. , lactic acid, and salts thereof. Salts include, for example, salts of mineral acids such as sulfuric acid, hydrochloric acid or phosphoric acid, salts of organic acids such as maleic acid or methanesulfonic acid, alkali metal salts such as sodium or potassium, alkaline earth metal salts, ammonium salts and the like. is mentioned.

Examples of the moisturizing ingredients include sodium hyaluronate, heparin analogs, sodium chondroitin sulfate, collagen, elastin, keratin, chitin, chitosan, and other high-molecular compounds; glycine, aspartic acid, arginine, and other amino acids; sodium lactate, urea, natural moisturizing factors such as sodium pyrrolidonecarboxylate; lipids such as ceramide, cholesterol and phospholipids; and plant extracts such as chamomile extract, hamamelis extract, tea extract and perilla extract.

Examples of the scrubbing agent include apricot kernel powder, almond shell powder, apricot kernel powder, sodium chloride grains, olive kernel powder, seawater dried grains, candelilla wax, walnut shell powder, cherry kernel powder, coral powder, and charcoal powder. , husk powder, polyethylene powder, silicic anhydride, and the like.

Examples of the ultraviolet scattering component include inorganic compounds such as hydrous silicic acid, zinc silicate, cerium silicate, titanium silicate, zirconium oxide, cerium oxide, titanium oxide, iron oxide, zinc oxide, and silicic anhydride; Inorganic compounds coated with inorganic powders such as hydrous silicic acid, aluminum hydroxide, mica and talc, composited with resin powders such as polyamide, polyethylene, polyester, polystyrene, nylon, silicone oil and fatty acid aluminum Examples include those treated with salt or the like.

Examples of the astringent component include alum, zinc sulfate, aluminum chloride, zinc sulfocarbate, and tannic acid.

Examples of the peptides or derivatives thereof include keratin-degrading peptides, hydrolyzed keratin, collagen, fish-derived collagen, atelocollagen, gelatin, elastin, elastin-degrading peptides, collagen-degrading peptides, hydrolyzed collagen, hydroxypropylammonium chloride hydrolyzed collagen, Elastin-degrading peptide, conchiolin-degrading peptide, hydrolyzed conchiolin, silk proteolytic peptide, hydrolyzed silk, lauroyl hydrolyzed silk sodium, soybean proteolytic peptide, hydrolyzed soybean protein, wheat protein, wheat proteolytic peptide, hydrolyzed wheat protein, Examples include casein-degraded peptides, acylated peptides (palmitoyl oligopeptide, palmitoyl pentapeptide, palmitoyl tetrapeptide, etc.).

Examples of the above amino acids or derivatives thereof include betaine (trimethylglycine), proline, hydroxyproline, arginine, lysine, serine, glycine, alanine, phenylalanine, β-alanine, threonine, glutamic acid, glutamine, asparagine, aspartic acid, cysteine, Cystine, methionine, leucine, isoleucine, valine, histidine, taurine, γ-aminobutyric acid, γ-amino-β-hydroxybutyric acid, carnitine, carnosine, creatine and the like.

Examples of the cleaning component include soaps selected from alkaline metal salts such as potassium laurate, potassium myristate, potassium palmitate or potassium stearate, alkanolamide salts or amino acid salts; sodium cocoyl glutamate, sodium cocoyl methyltaurate. Amino acid-based surfactants such as amino acid-based surfactants; ether sulfate salts such as sodium laureth sulfate; ether carboxylates such as sodium lauryl ether acetate; sulfosuccinate salts such as alkyl sulfosuccinate Na; coconut oil fatty acid monoethanolamide, coconut oil Fatty acid alkanolamides such as fatty acid diethanolamide; monoalkyl phosphate ester salts such as sodium lauryl phosphate and sodium polyoxyethylene lauryl ether phosphate; coconut oil fatty acid amidopropyl dimethylamino acetate betaine, lauryl dimethylamino acetate betaine, 2-alkyl -N-carboxymethyl-N-hydroxyethylimidazolinium betaine, lauryl hydroxysulfobetaine and lauroylamidoethyl hydroxyethyl carboxymethyl betaine betaine-type amphoteric surfactants such as sodium hydroxypropyl phosphate; amino acids such as sodium laurylaminopropionate type amphoteric surfactants, and the like.

Examples of the keratin softening component include lactic acid, salicylic acid, glycolic acid, citric acid, malic acid, fruit acid, phytic acid, urea, and sulfur.

Examples of the cell activating components include amino acids such as γ-aminobutyric acid; vitamins such as retinol, thiamine, riboflavin, pyridoxine hydrochloride, and pantothenic acids; α-hydroxy acids such as glycolic acid and lactic acid; tannins, flavonoids, saponin, photosensitizer No. 301, and the like.

Examples of the blood circulation-promoting ingredients include plants (e.g., Panax ginseng, Angelica keiskei, Arnica, Ginkgo biloba, Fennel, Trichophyllum japonicum, Holland oak, Chamomile, Roman chamomile, Carrot, Gentian, Burdock, Rice, Hawthorn, Shiitake mushroom, Ginger, Hawthorn, Juniperus juniper). , Cnidium, Senburi, Thyme, Clove, Chimp, Chili Pepper, Angelica, Tonin, Spruce, Carrot, Garlic, Butcher Bloom, Grape, Button, Horse Chestnut, Melissa, Yuzu, Yokuinin, Ryokucha, Rosemary, Rosehip, Chimp, Angelica, spruce, peach, apricot, walnut, corn, etc.); acetylcholine, ictamol, cantharis tincture, gamma oryzanol, cepharanthine, tolazoline, tocopherol nicotinate, glucosyl hesperidin, and the like.

<Method for producing composition for external use on skin>
The method for producing the composition for external use on the skin of the present invention is not particularly limited. components, bases or carriers described later, additives, etc.) can be appropriately selected and blended, and can be produced by a conventional method. In the composition for external use on the skin of the present invention, the (A) ultraviolet absorber, the (B) component and the (C) component are uniformly dispersed.

<Uses of the composition for external use on the skin>
The composition for external use on skin of the present invention is used in expectation of its UV blocking effect and sunscreen effect. The composition for external use on the skin of the present invention has excellent photostability, so that its effect lasts for a long time. Furthermore, it has excellent water resistance and is resistant to secondary adhesion, so it can be used effectively in all environments. The external composition for skin of the present invention used for such purposes is suitable as, for example, a sunscreen, a beauty essence, a lotion, an emulsion, a cream, a gel cream, a makeup base, a foundation, a lip care agent, a cleansing agent, a cleanser, and the like. It can be used, and more preferably, it can be used as skin care products such as sunscreens, serums, lotions, milky lotions, creams and gel creams.

<Formulation>
The composition for external use on the skin of the present invention contains the essential ingredients and other ingredients described above, etc., as a base or carrier commonly used in cosmetics, pharmaceuticals, and quasi-drugs, and if necessary, additives described later. It can be mixed with agents according to a conventional method and, if necessary, emulsified or solubilized to prepare external skin compositions in various formulation forms.

Examples of the base or carrier include liquid paraffin, paraffin wax, squalane, petrolatum, gelling hydrocarbons (plastibase, etc.), ozokerite, mineral oil, α-olefin oligomers, hydrocarbons such as light liquid paraffin; (dimethicone), cyclic silicone (cyclopentasiloxane), modified silicone (diphenyldiphenylsiloxyphenyltrimethicone, etc.), silicone oils such as silicone resin; oils and fats such as coconut oil, olive oil, rice bran oil, shea butter; Waxes such as candelilla wax and lanolin; higher alcohols such as cetanol, cetostearyl alcohol, stearyl alcohol, behenyl alcohol, octyldodecanol, isostearyl alcohol, phytosterol and cholesterol; methylcellulose, hydroxypropylcellulose, hydroxypropylmethylcellulose polyvinylpyrrolidone, carrageenan , polyethylene glycol, isopropyl myristate, octyldodecyl myristate, isopropyl palmitate, cetyl palmitate, cetyl ethylhexanoate, alkyl benzoate, isononyl isononanoate, isotridecyl isononanoate, neopentyl glycol dicaprate, diethylhexyl succinate, apple Esters such as diisostearyl acid, tri(caprylic/capric)glyceryl, triethylhexanoin, triethylhexyl trimellitate, pentaerythrityl tetraethylhexanoate (tetra-2-ethylhexanoate pentaerythrityl); dextrin, maltodextrin lower alcohols such as ethanol; glycol ethers such as diethylene glycol monoethyl ether; and water.

One of the bases or carriers described above may be used alone, or two or more thereof may be used in combination. In addition, the amount of these to be used is appropriately selected from the range known to those skilled in the art.

<Additive>
The external composition for skin of the present invention may contain known additives added to cosmetics, pharmaceuticals, and quasi-drugs, such as surfactants, antioxidants, coloring agents, as long as they do not impair the effects of the present invention. A pearl luster imparting agent, a chelating agent, a pH adjuster, a preservative, a thickening agent (excluding the component (B)), a feel-improving agent and the like can be added. These additives may be used singly or in combination of two or more.

Examples of the surfactant include nonionic surfactants, cationic surfactants, anionic surfactants, amphoteric surfactants, and the like. Examples include sorbitan monoisostearate and sorbitan monolaurate. , sorbitan monopalmitate, sorbitan monostearate, diglycerol sorbitan penta-2-ethylhexylate, and diglycerol sorbitan tetra-2-ethylhexylate; propylene glycol fatty acid esters such as propylene glycol monostearate; Polyoxyethylene hydrogenated castor oil 40 (HCO-40), polyoxyethylene hydrogenated castor oil 50 (HCO-50), polyoxyethylene hydrogenated castor oil 60 (HCO-60), polyoxyethylene hydrogenated castor oil 80 (HCO80), etc. Hydrogenated Castor Oil Derivatives of; , polyoxyethylene sorbitan fatty acid esters such as polyoxyethylene (20) sorbitan isostearate; polyoxyethylene monococonut oil fatty acid glyceryl; glycerin alkyl ether; alkyl glucoside; polyoxyalkylene alkyl ether such as polyoxyethylene cetyl ether; Amines such as amine and oleylamine; sucrose caprylate, sucrose caprate, sucrose laurate, sucrose myristate, sucrose palmitate, sucrose stearate, sucrose isostearate, etc. sucrose fatty acid esters; silicone surfactants such as polyoxyethylene/methylpolysiloxane copolymer, lauryl PEG-9 polydimethylsiloxyethyl dimethicone, PEG-9 polydimethylsiloxyethyl dimethicone, PEG-12 dimethicone, etc. mentioned.

Examples of the antioxidant include tocopherols and derivatives thereof or salts thereof (α-tocopherol, δ-tocopherol, acetate-α-tocopherol, tocotrienol, etc.), pyrroloquinoline quinone and derivatives thereof or salts thereof, ubiquinones and derivatives thereof or salts thereof, retinols and derivatives thereof or salts thereof, pantothenic acids and derivatives thereof or salts thereof, ascorbic acids and derivatives thereof or salts thereof, vitamins such as erythorbic acids and derivatives thereof or salts thereof antioxidants, sulfur-containing antioxidants such as cysteine, homocysteine, acetylcysteine, thiotaurine, methionine, thioglycerol, sodium sulfite, dibutylhydroxytoluene, butylhydroxyanisole, bisethylhexylhydroxydimethoxybenzyl malonate, dimethoxybenzyl malonate Phenolic antioxidants such as ethylhexylsyringylidene, chlorogenic acids and their derivatives or their salts, gallic acids and their derivatives or their salts, proanthocyanidins derived from plants (grape, Panax ginseng, comfrey etc.), hesperidin, Examples include polyphenol antioxidants such as glucosyl hesperidin and flavonoids.

Examples of the coloring agent include inorganic pigments and natural pigments.

Examples of the chelating agent include EDTA.disodium salt (sodium edetate), hydroxyethanediphosphonic acid.calcium.disodium salt, and the like.

Examples of the pH adjuster include inorganic acids (hydrochloric acid, sulfuric acid, etc.), organic acids (lactic acid, sodium lactate, citric acid, sodium citrate, succinic acid, sodium succinate, etc.), inorganic bases (potassium hydroxide, hydroxide sodium, etc.), organic bases (triethanolamine, diisopropanolamine, triisopropanolamine, etc.), and the like.

Examples of the preservative include benzoic acid, sodium benzoate, dehydroacetic acid, sodium dehydroacetate, ethyl parahydroxybenzoate, propyl parahydroxybenzoate, methyl parahydroxybenzoate, sorbic acid, phenoxyethanol and the like.

Examples of the thickener include vinyl thickeners such as polyvinyl alcohol, polyvinylpyrrolidone and carboxyvinyl polymer; cellulose thickeners such as methylcellulose, hydroxymethylcellulose, hydroxypropylcellulose, hydroxypropylmethylcellulose and carboxymethylcellulose; and guar gum. , pectin, pullulan, gelatin, locust bean gum, carrageenan, agar, xanthan gum, alkyl acrylate methacrylate copolymer, polyethylene glycol, bentonite, alginic acid, propylene glycol alginate, macrogol, sodium chondroitin sulfate, hyaluronic acid, sodium hyaluronate , (hydroxyethyl acrylate/acryloyldimethyltaurate Na) copolymer, (acryloyldimethyltaurate ammonium/vinylpyrrolidone) copolymer, and the like.

Examples of the feel-improving agents include polystyrene, polymethyl methacrylate, acrylates copolymer, acrylates crosspolymer, (butyl acrylate/glycol dimethacrylate) crosspolymer, methyl methacrylate crosspolymer, (methyl methacrylate/ glycol dimethacrylate) crosspolymer, (styrene/divinylbenzene) crosspolymer, lauroyllysine, nylon-12, polymethylsilsesquioxane and the like.

<Formulation form>
The formulation form of the composition for external use on the skin of the present invention is not particularly limited. Examples include sherbet formulations, aerosol formulations, foam formulations, spray formulations, stick formulations, other ointments, solid formulations, and the like. These formulations can be produced according to a conventional method, for example, the method described in the Japanese Pharmacopoeia General Rules for Pharmaceutical Preparations, 17th Edition. In consideration of the desired stability, feeling of use, etc., the dosage form such as W/O, O/W, W/O/W and O/W/O emulsions can be selected as appropriate.

<pH>
The pH of the external composition for skin of the present invention is generally pH 3.0 to 8.0, preferably pH 3.5 to 7.5. In addition, this pH can be adjusted, for example, by using a pH adjuster to be described later. However, this does not apply to formulation forms for which pH measurement is impossible or difficult.

[Composition for suppressing functional deterioration of ultraviolet absorber]
The present invention comprises at least one component (component (B) above) selected from the group consisting of polyamide-3, polyamide-8, ethyl cellulose and amino acid-based oil gelling agents, and a polyhydric alcohol (component (C) above). ) and a composition for suppressing functional deterioration of the ultraviolet absorber (component (A) above). As detailed in the section of the external skin composition of the present invention, in the external skin composition containing an ultraviolet absorber, at least selected from the group consisting of polyamide-3, polyamide-8, ethyl cellulose and amino acid-based oil gelling agents By blending one type of component (the above component (B)) and a polyhydric alcohol (the above component (C)), the photostability of the ultraviolet absorber can be improved. That is, at least one component (component (B) above) selected from the group consisting of polyamide-3, polyamide-8, ethyl cellulose and amino acid-based oil gelling agents, and a polyhydric alcohol (component (C) above) By adding a composition containing to an external skin composition containing an ultraviolet absorber, it is possible to suppress deterioration of the function of the ultraviolet absorber due to ultraviolet rays. A detailed description of each component, the ratio of the component (B) to the component (C), the ratio of adding each component to the component (A), etc. are described in the section of the composition for external use on the skin of the present invention described above. Explanation is applicable.

[Method for Suppressing Functional Decline of Ultraviolet Absorber]
The present invention also includes a method for suppressing functional deterioration of an ultraviolet absorber using at least one selected from the group consisting of polyamide-3, polyamide-8, ethyl cellulose and amino acid-based oil gelling agents, and a polyhydric alcohol. According to the method for suppressing functional deterioration of an ultraviolet absorber of the present invention, it is possible to easily improve the photostability of an ultraviolet absorber in a composition for external use such as a sunscreen simply by blending the above components, and moreover, , the resulting external composition for skin is excellent in safety and feeling of use. The detailed description of each component, the ratio between component (B) and component (C) when used, the ratio of adding each component to component (A), etc. are described above in the composition for external use on skin of the present invention. The descriptions in the item section apply.

EXAMPLES The present invention will be described in more detail below with reference to examples, but the present invention is not limited by these examples.

<Preparation of composition for external use on skin>
According to the formulations shown in Tables 1 to 5 below, uniformly dispersed compositions for external use on the skin (sunscreen cosmetics) were prepared.

[Test 1] Photostability evaluation test A composition for external use on the skin (sunscreen cosmetic) having the composition shown in Table 1 below was prepared by a conventional method. Each of the obtained compositions for external use on the skin was uniformly applied to a plate made of polymethyl methacrylate (PMMA) with a length of 50 mm and a width of 50 mm so as to be 2 mg/cm ² , and a commercially available in vitro SPF evaluation device was used to A spectral transmission spectrum was measured at wavelengths from 290 to 400 nm. At this time, the wavelength step was 1 nm, the spectral transmission spectrum was measured at one point, and the number of measurements was seven. From the obtained spectrum, the absorbance at λmax (310 nm) of ethylhexyl methoxycinnamate was calculated, and the ratio (%) of the absorbance at the 7th measurement when the absorbance at the 1st measurement was taken as 100% was shown. The results are shown in Tables 1 to 5 below.

[Test 2] Water resistance evaluation test (residual test after water treatment)
Each composition for external use on the skin was uniformly applied to a plate made of PMMA so as to be 1.3 mg/cm ² and dried. After drying the sample, the absorbance at λmax (310 nm) of ethylhexyl methoxycinnamate on each PMMA plate was calculated using a UV-visible spectrophotometer (UV-2450: manufactured by Shimadzu Corporation). Thereafter, water treatment was performed, and the absorbance at 310 nm was measured again by the same method, and the residual ratio was calculated by comparing the absorbances before and after the water treatment. The calculation formula is as follows. In this test example, the water treatment means that the PMMA plate coated with the composition is attached to one end of the stirring blade of a water bath, and the stirring blade is immersed in a water bath (tap water) at 20 to 25 ° C. for 5 minutes. After that, the PMMA plate is slowly removed and left to dry in a dark place for 30 minutes. In addition, the UV absorption spectrum was measured at 5 different points within the same PMMA plate, and the average value thereof was taken. The results are shown in Tables 1 to 4 below.

Residual rate after water treatment (%)
= [(absorbance after water treatment) / (absorbance before water treatment)] × 100 (%)

[Test 3] Secondary Adhesion Evaluation Test Each composition for external use on the skin was uniformly applied to a PMMA plate at a sample level of 2 mg/cm ² and dried. After drying the sample, the absorbance at λmax (310 nm) of ethylhexyl methoxycinnamate on each PMMA plate was calculated using a UV-visible spectrophotometer (UV-2450; manufactured by Shimadzu Corporation). After that, put the coated surface of the PMMA plate down on the tissue paper, apply a load of 500 g from the top of the PMMA plate for 10 minutes, attach it to the tissue paper, and then calculate the absorbance at 310 nm again. The residual ratio was calculated by comparing the absorbance. The smaller the difference in absorbance before and after adhesion, the lower the secondary adhesion was evaluated. The calculation formula is as follows. The ultraviolet absorption spectrum was measured at 5 different points on the same PMMA plate, and the average value thereof was taken. The results are shown in Tables 1 to 4 below.

Residual rate of UV absorbency (%)
= [(absorbance after attachment)/(absorbance before attachment)] x 100 (%)

[Test 4] Evaluation of white residue 50 µL of each external composition for skin was applied to a 5 cm square black artificial leather, and the color was visually observed. The results are shown in Tables 1 to 5 below.

Evaluation criteria -: No white residue +: White residue present

As shown in Tables 1 to 5, it was found that the external skin compositions of Examples had a higher residual rate of absorbance at the 7th measurement and excellent photostability compared to Comparative Examples. In addition, it was found that the decrease in absorbance due to water treatment was suppressed, and the water resistance was excellent. In addition, since secondary adhesion is less likely to occur, the reduction in UV absorbency caused by secondary adhesion is suppressed, so that the composition for external use on skin of the present invention maintains its UV blocking effect for a long period of time. have understood.

Below, formulation examples of the composition for external use on the skin of the present invention are shown.

According to the present invention, by blending at least one selected from the group consisting of polyamide-3, polyamide-8, ethyl cellulose and amino acid-based oil gelling agents, and a polyhydric alcohol together with an ultraviolet absorber, it is possible to block ultraviolet rays. It is possible to provide a new type of composition for external use on the skin, which is excellent in effect, maintains its effect for a long time, and does not cause white residue or whitening. Furthermore, the composition for external use on the skin of the present invention exhibits the effect of being excellent in water resistance and less likely to cause a decrease in ultraviolet absorption capacity due to secondary adhesion.

Claims (3)

(A) selected from the group consisting of ethylhexyl methoxycinnamate, diethylaminohydroxybenzoylhexylbenzoate, bisethylhexyloxyphenol methoxyphenyltriazine, ethylhexyltriazone, polysilicone-15, and ethylhexyl dimethoxybenzylidenedioxoimidazolidinepropionate; at least one UV absorber,
(B ) contains polyamide - 8, and (C) a polyhydric alcohol ,
The content of component (C) is 0.1% by weight or more and 15% by weight or less with respect to the total amount of the composition for external use on the skin, and
A composition for external use on skin in which the ratio of component (C) (% by weight) to component (B) (% by weight) contained in the composition for external use on skin is 1/50 to 20 (provided that the refractive index is 1.45 to 1 0.55 silica powder, composite particles formed by components (A) and (B), and linoleic acid). (C) polyhydric alcohol group consisting of propylene glycol, dipropylene glycol, glycerin, diglycerin, 1,2-pentanediol, 1,2-hexanediol, 1,3-propylene glycol and 1,3-butanediol 2. The composition for external use on skin according to claim 1 , which is at least one selected from the above. Ethylhexyl methoxycinnamate, hexyl diethylaminohydroxybenzoylbenzoate, bisethylhexyloxyphenol methoxyphenyltriazine, ethylhexyltriazone, polysilicone-15, and dimethoxybenzylidenedioxoimidazolidine, including polyamide-8 and polyhydric alcohols A composition for suppressing functional deterioration of at least one ultraviolet absorber selected from the group consisting of ethylhexyl propionate (provided that silica having a refractive index in the range of 1.45 to 1.55 is blended as powder, containing UV absorbers and composite particles formed by polyamide -8, except those containing linoleic acid).