TW202317091A - Water-in-oil composition for external use containing ascorbic acid and/or salt thereof - Google Patents

Abstract

Provided is a water-in-oil composition for external use that contains ascorbic acid or a salt thereof. This prepared water-in-oil composition for external use contains: (A) at least one selected from the group consisting of ascorbic acid and an ascorbic acid salt; (B) propanediol; (C) an oil component; and (D) a silicone-based surfactant. This water-in-oil composition for external use has good stability.

Description

Water-in-oil composition for external use containing ascorbic acid and/or its salt

The present invention relates to a water-in-oil external composition containing ascorbic acid and its salt.

Ascorbic acid is known to exhibit anti-inflammatory effects, acne-improving effects, whitening effects, anti-aging effects, antioxidant effects, cell activation effects by promoting the synthesis of collagen and other living components, and inhibition of epidermal keratinocytes caused by ultraviolet rays. Various effects such as cytotoxic effect and DNA (deoxyribonucleic acid; deoxyribonucleic acid) damage effect are expected, and these effects are widely used as skin external preparations.

Provided is an external composition containing ascorbic acid and having excellent stability and usability (for example, Patent Document 1: WO2018/003850 A). [Prior Art Literature] [Patent Document]

[Patent Document 1] WO2018/003850 publication.

[Problem to be Solved by the Invention]

The object of the present invention is to provide an excellent water-in-oil composition for external use containing ascorbic acid and a salt thereof. [Means to solve the problem]

Creams and emulsions are excellent in moisturizing properties and are widely used, for example, in the form of cosmetics. According to the study of the inventors of the present invention, it has been confirmed that preparations containing ascorbic acid and its salts sometimes have a problem of skin irritation depending on the condition of the skin. Furthermore, the inventors of the present invention noticed that the stability of preparations containing ascorbic acid and its salts may sometimes cause problems.

The inventors of the present invention have repeatedly conducted intensive studies to solve the present problem, and as a result, found that by containing (A) at least one selected from the group consisting of ascorbic acid and ascorbic acid salts, (B) propylene glycol, and (C ) oil component, an excellent water-in-oil type composition for external use can be obtained, thereby completing the present invention.

That is, the present invention provides the water-in-oil type external composition disclosed below. [1] A water-in-oil type composition for external use, comprising: (A) at least one selected from the group consisting of ascorbic acid and ascorbic acid salts; (B) propylene glycol; (C) oil; and (D) polysilicone Oxygen-based surfactants. [2] The water-in-oil composition for external use according to item 1, wherein the content of at least one selected from the group consisting of ascorbic acid and salts of ascorbic acid is 1% to 30% by mass. [3] The water-in-oil composition for external use according to item 1 or 2, wherein the content of the aforementioned (B) propylene glycol is 15% by mass or more. [4] The water-in-oil composition for external use according to any one of items 1 to 3, wherein the water content is 10% by mass or less. [5] The water-in-oil composition for external use according to any one of items 1 to 4, wherein the (C) oil component contains silicone oil. [6] The water-in-oil composition for external use according to any one of items 1 to 5, further comprising a lower alcohol. [7] A method for alleviating skin irritation of a water-in-oil type composition for external use, comprising (A) at least one selected from the group consisting of ascorbic acid and a salt of ascorbic acid, (B) propylene glycol, (C) Coexistence of oil and (D) polysiloxane-based surfactants relieves skin irritation of the water-in-oil type external composition containing (A) at least one selected from the group consisting of ascorbic acid and ascorbic acid salts. [Efficacy of the invention]

ADVANTAGE OF THE INVENTION According to this invention, the water-in-oil type external composition with little skin irritation can be provided. The present invention can also provide a stable water-in-oil type composition for external use.

In this specification, the unit "mass %" and "g/100g" of content are synonymous.

[Water-in-oil composition for external use] The water-in-oil type composition for external use of the present invention contains (A) at least one selected from the group consisting of ascorbic acid and ascorbic acid salts, (B) propylene glycol, (C) oil, and (D) polysiloxane Water-in-oil type external composition of surfactant.

[(A) At least one selected from the group consisting of ascorbic acid and a salt of ascorbic acid] Ascorbic acid used in the present invention can be used as ascorbic acid commercially available as a component of external skin preparations in the field of pharmaceuticals, quasi-drugs, or cosmetics, and these generally refer to L-form ascorbic acid.

In the present invention, a salt of ascorbic acid can also be used. Here, the salt of ascorbic acid means a pharmaceutically acceptable salt. It is not limited, for example: salts with organic bases (for example, trimethylamine salts, triethylamine salts, monoethanolamine salts, triethanolamine salts, pyridinium salts, etc.) and tertiary amine salts, arginine and other basic ammonium salts, etc.), salts with inorganic bases (for example, alkali metal salts such as ammonium salts, sodium salts, and potassium salts, alkaline earth metal salts such as calcium salts, and magnesium salts, aluminum salts, etc.), and the like. Preferred salts of ascorbic acid are sodium salt and potassium salt. Specifically, sodium ascorbate, sodium ascorbyl monophosphate, sodium ascorbyl diphosphate, sodium ascorbyl triphosphate, sodium ascorbyl-2-sulfate, and the like may, for example, be mentioned.

In the present invention, ascorbic acid or a salt thereof may be used alone or in combination of two or more.

In the water-in-oil type external use composition of this invention, the total content of (A) component with respect to the total amount of the water-in-oil type external use composition can be set suitably according to the balance with other components. The total content of the component (A) is preferably at least 1% by mass, more preferably at least 3% by mass, and still more preferably at least 5% by mass, based on the total amount of the water-in-oil type external use composition. The total content of the (A) component is preferably at most 30% by mass, more preferably at most 20% by mass, further preferably at most 15% by mass, based on the total amount of the water-in-oil type external composition. The total content of the component (A) is preferably from 1% by mass to 30% by mass, more preferably from 3% by mass to 20% by mass, further preferably from 5% by mass to the total amount of the water-in-oil type external composition. 15% by mass, and more preferably 5% to 10% by mass. In addition, 1 mass % to 10 mass %, 2 mass % to 7 mass %, 3 mass % to 5 mass %, etc. may be sufficient.

[(B) Propylene Glycol] The propylene glycol used in the present invention is not particularly limited as long as it is used as a component of external skin preparations in the field of pharmaceuticals, quasi-drugs, or cosmetics. In addition, a commercially available product can be used as it is. Propylene glycol refers to 1,3-propanediol (CAS number: 504-63-2, English name: 1,3-Dihydroxypropane or Trimethylene Glycol). The component (B) contributes to the stability of the water-in-oil composition for external use of the present invention.

In the water-in-oil type external use composition of the present invention, the total content of (B) component is not particularly limited relative to the total amount of the water-in-oil type external use composition, but is preferably 15% by mass or more, more preferably 20% by mass % or more, more preferably 30% by mass or more, and more preferably 40% by mass or more. The total content of the (B) component is preferably at most 80% by mass, more preferably at most 70% by mass, further preferably at most 60% by mass, based on the total amount of the water-in-oil type external use composition. From the viewpoint of improving the stability of the water-in-oil composition for external use of the present invention, the total content of component (B) relative to the total amount of the water-in-oil composition for external use is not particularly limited, but is preferably 15 mass % to 80 mass%, more preferably 20 mass% to 75 mass%, and more preferably 40 mass% to 70 mass%. In addition, it may be in the range of 20 mass % to 80 mass %, 20 mass % to 60 mass %, 30 mass % to 75 mass %, 30 mass % to 60 mass %, or 40 mass % to 60 mass %.

In the water-in-oil type composition for external use of the present invention, the ratio of the compounded amount of (B) component to (A) component is not particularly limited, but is preferably 0.5 per part by mass of the total content of (A) component Parts by mass to 80 parts by mass, more preferably 1 part by mass to 30 parts by mass, further preferably 4 parts by mass to 12 parts by mass. Moreover, 2 mass parts - 80 mass parts, 4 mass parts - 35 mass parts, 8 mass parts - 20 mass parts, etc. may be sufficient.

[(C) oil content] The (C) oil used in the present invention is not limited, and examples thereof include natural animal and vegetable oils, hydrocarbon oils, ester oils, silicone oils, higher fatty acids, animals and plants, and synthetic essential oils.

Examples of natural animal and vegetable oils include avocado oil, linseed oil, almond oil, olive oil, cocoa butter, butter, tung oil, wheat germ oil, sesame oil, rice germ oil, rice bran oil, safflower oil, Soybean Oil, Evening Primrose Oil, Camellia Oil, Corn Oil, Rapeseed Oil, Horse Oil, Peach Kernel Oil, Palm Oil, Palm Kernel Oil, Castor Oil, Sunflower Oil, Lard Oil, Grape Oil, Jojoba Oil, Macadamia Oil, Mink oil, cottonseed oil, wood wax, beeswax, white beeswax, coconut oil, hydrogenated oils (non-limiting examples are hydrogenated jojoba oil, hydrogenated castor oil, hydrogenated soybean oil, hydrogenated rice oil, hydrogenated coconut oil, etc.), Peanut Oil, Lanolin, Egg Butter, Rosehip Oil, Peppermint Oil, Lemon Oil, Eucalyptus Oil, Lavender Oil, Roman Chamomile Oil, Orange Oil, Coix Oil, Passiflora Edulis Seed Oil, Rosa Rosa Oil , tea tree oil, grapefruit oil, miscellaneous lavender oil, cistus oil, fennel oil, or orange peel oil (Orange Roughy Oil).

As the hydrocarbon oil, for example, paraffinic hydrocarbons and olefinic hydrocarbons can be used, and more specifically, for example, squalane, squalene, ceresin, paraffin, pristane, microcrystalline wax, liquid Paraffin wax, vaseline, olefin oligomer, hydrogenated polyisobutylene, isoparaffin, polyethylene wax, ozokerite, etc.

As the ester oil, for example, synthetic esters, esters of higher alcohols and higher fatty acids can be used, for example, diisobutyl adipate, 2-hexyldecyl adipate, di-2-heptyl adipate Undecyl Isostearate, Isostearyl Isostearate, Trimethylolpropane Triisostearate, Cetyl 2-Ethylhexanoate, Neopentyl Glycol Di-2-Ethylhexanoate Esters, trimethylolpropane tri-2-ethylhexanoate, pentaerythritol tetra-2-ethylhexanoate, cetyl caprylate, oleyl oleate, octyldodecyl oleate, decyl oleate Esters, Neopentyl Glycol Dicaprate, 2-Ethylhexyl Succinate, Isocetyl Stearate, Butyl Stearate, Diisopropyl Sebacate, Cetyl Lactate, Myristyl Lactate Alkyl esters, Isopropyl myristate, Octyldodecyl myristate, Cetyl myristate, Myristyl myristate, Octyl palmitate, 2-Ethylhexyl palmitate, Palmitic acid 2-Hexyldecyl Ester, 2-Heptyl Undecyl Palmitate, Cholesterol 12-Hydroxystearate, Phytosteryl Oleate, Diisostearyl Malate, P-Methoxycinnamate, Pentaerythritol tetrarosinate, or triglyceride (caprylic acid/capric acid) ester, etc.

The so-called polysiloxane oil typically refers to an oil containing at least one silicon atom, especially at least one Si-O group. Oils having 2 to 7 silicon atoms, optionally containing alkyl or alkoxy groups containing 1 to 10 carbon atoms, may also be used. Examples of silicone oils include: dimethylpolysiloxane, methylpolysiloxane (including high-polymerization methylpolysiloxane, cross-linked methylpolysiloxane), methylbenzene Polysiloxane, Methylhydropolysiloxane, Cyclohexasiloxane, Octamethylcyclotetrasiloxane, Octamethylcyclopentasiloxane, Decamethylcyclohexasiloxane, Octylmethyl Polysiloxane, Decamethylcyclopentasiloxane, Dodecamethylcyclohexasiloxane, Heptamethylhexyltrisiloxane, Heptamethyloctyltrisiloxane, Hexamethyldisiloxane , octamethyltrisiloxane, decamethyltetrasiloxane and dodecamethylpentasiloxane, stearoxy polysiloxane and other advanced alkoxy modified polysiloxane, alkyl modified polysiloxane Oxygen, higher fatty acid ester modified polysiloxane, etc. or a mixture of these.

As higher fatty acids, saturated or unsaturated linear or branched fatty acids with 12 to 22 carbon atoms can be used, for example, isostearic acid, oxystearic acid, oleic acid, stearic acid, palmitic acid, Yushu acid, myristic acid, lauric acid, lanolic acid, linoleic acid, sublinolenic acid, etc.

As (C)component, these components can be used 1 type or in combination of 2 or more types. It is not limited, but as (C)component, it is preferable to contain silicone oil at least.

These oils can be prepared using natural products or by synthesis, and commercial products can also be used as they are.

In the water-in-oil type external use composition of the present invention, the total content of (C) component equivalent to the total amount of the water-in-oil type external use composition is not particularly limited, but is preferably at least 1% by mass, more preferably 3% by mass % or more, and more preferably 5% by mass or more. The total content of the component (C) is preferably at most 40% by mass, more preferably at most 30% by mass, further preferably at most 20% by mass, based on the total amount of the water-in-oil type external use composition. The content of component (C) is preferably from 1% by mass to 40% by mass, more preferably from 3% by mass to 30% by mass, further preferably from 5% by mass to 20% by mass, based on the total amount of the water-in-oil type external composition. quality%.

In the water-in-oil type external composition of the present invention, the ratio of the compounded amount of (C) component to (A) component is not particularly limited, but is preferably 0.01 per part by mass of the total content of (A) component Parts by mass to 40 parts by mass, more preferably 0.1 parts by mass to 10 parts by mass, further preferably 0.5 parts by mass to 4 parts by mass. In addition, 0.1 to 40 parts by mass, 0.4 to 15 parts by mass, 1 to 7 parts by mass, etc. may be used.

[(D) Polysiloxane Surfactant] The (D) polysiloxane-based surfactant used in the present invention is not limited, and from the viewpoint of improving the stability of the oil-in-water type composition for external use of the present invention, for example: (Dimethicone Oxane/(PEG-10/15)) Crosspolymer, PEG-11 Methyl Ether Dimethicone, PEG/PPG-20/22 Butyl Ether Dimethicone, PEG-3 Dimethicone Silicone, PEG-10 Dimethicone, PEG-32 Methyl Ether Dimethicone, Cetyl PEG/PPG-10/1 Dimethicone, PEG-9 Dimethicone Siloxyethyl Dimethicone, Lauryl PEG-9 Polydimethylsiloxyethyl Dimethicone, Cetyl Diglyceryl Tris(trimethylsiloxy)silyl Ethyl dimethyl polysiloxane, or polyoxyethylene-methyl polysiloxane copolymer, etc. The HLB (Hydrophilic Lipophilic Balance) of the preferred active agent is preferably 1-10, more preferably 2-8, and more preferably 3-5.

As (D)component, these components can be used 1 type or in combination of 2 or more types.

In the water-in-oil composition for external use of the present invention, the total content of component (D) relative to the total amount of the water-in-oil composition for external use is not particularly limited. From the viewpoint of stability, it is preferably at least 1% by mass, more preferably at least 3% by mass, and still more preferably at least 5% by mass. The total content of the component (D) is preferably at most 30% by mass, more preferably at most 20% by mass, and still more preferably at most 10% by mass, based on the total amount of the water-in-oil type external use composition. The total content of (D) components is preferably from 1% by mass to 30% by mass, more preferably from 3% by mass to 20% by mass, further preferably from 5% by mass to 10% by mass.

In the water-in-oil type composition for external use of the present invention, the ratio of component (D) to component (A) is preferably 0.01 to 30 parts by mass, more preferably 0.01 to 30 parts by mass, based on 1 part by mass of the total content of component (A). Preferably, it is 0.1 mass part - 7 mass parts, More preferably, it is 0.5 mass part - 2 mass parts. In addition, 0.1 to 30 parts by mass, 0.4 to 10 parts by mass, 1 to 4 parts by mass, etc. may be used.

[water] The water-in-oil composition for external use of the present invention may be a liquid composition containing water, or a composition containing no water. The ratio of the water to be formulated is not limited, but is preferably at most 15% by mass, more preferably at most 10% by mass, and still more preferably at most 7% by mass, relative to the water-in-oil type external use composition. When water is contained, it is preferably 1% by mass to 15% by mass, more preferably 1% by mass to 10% by mass, further preferably 1% by mass to 7% by mass. Even when the water-in-oil type external composition of the present invention does not contain water, the water phase in the water-in-oil type is formed by the component (B) or any aqueous component.

In the water-in-oil type external composition of the present invention, the ratio of water to component (A) is preferably 0.01 to 10 parts by mass, more preferably 0.01 to 10 parts by mass, based on 1 part by mass of the total content of component (A) 0.05 to 3 parts by mass, and more preferably 0.1 to 1 part by mass. Moreover, 0.1-10 mass parts, 0.1-3.5 mass parts, 0.2-2 mass parts, etc. may be sufficient.

[(E) lower alcohol] In the water-in-oil type composition for external use of the present invention, from the viewpoint of improvement of the feeling of use, higher stability, and promotion of percutaneous absorption, as long as the effect of the present invention is not hindered, in addition to the above-mentioned (A) component, In addition to (B) component, (C) component, and (D) component, (E) lower alcohol may be included arbitrarily. The lower alcohol used in the present invention is not particularly limited as long as it is used as a component of external skin preparations in the field of pharmaceuticals, quasi-drugs, or cosmetics. In this specification, when described as "lower alcohol", it means C1-C6 alcohol. Among them, C1-C3 alcohols can be particularly preferably used. As such an example, methanol, ethanol, n-propanol, isopropanol, etc. are mentioned.

In one aspect of the present invention, the total content of the (E) component is preferably 1% by mass to 30% by mass, more preferably 3% by mass to 20% by mass relative to the total amount of the water-in-oil type external composition , and more preferably 5% by mass to 10% by mass.

In the water-in-oil type external composition of the present invention, the ratio of the compounded amount of (E) component to (A) component is preferably 0.01 mass part to 1 mass part of the total content of (A) component 30 parts by mass, more preferably 0.1 to 7 parts by mass, further preferably 0.5 to 2 parts by mass. In addition, 0.1 to 30 parts by mass, 0.2 to 15 parts by mass, 0.4 to 10 parts by mass, 1 to 4 parts by mass, etc. may be used.

[Polyol] In the water-in-oil type external composition of the present invention, as long as the effects of the present invention are not hindered, in addition to the above-mentioned (A) component, (B) component, (C) component, and (D) component, (B) component may also be included. Polyols other than ingredients.

The polyol used in the present invention is not particularly limited as long as it is used as a component of external skin preparations in the field of pharmaceuticals, quasi-drugs, or cosmetics. The polyhydric alcohol is not limited, and may be added for moisturizing or as a solubilizing agent. Specifically, glycerin, diglycerin, dipropylene glycol, propylene glycol, 1,3-butanediol, 3-methyl-1,3-butanediol, hexanediol, pentylene glycol, sorbitol, or maltitol etc.

In one aspect of the present invention, when polyhydric alcohols other than component (B) are contained, the total content of polyhydric alcohols other than component (B) is preferably 0.1% by mass to 30% by mass, more preferably 0.5% by mass to 20% by mass, further preferably about 1% by mass to 10% by mass.

In one aspect of the present invention, the ratio of component (B) to the total polyol in the water-in-oil type composition for external use is preferably 30% by mass or more, more preferably 40% by mass or more. In one aspect of this invention, the aspect which contains only (B) component as a polyhydric alcohol in a water-in-oil type composition for external use may be sufficient.

In one aspect of the present invention, the ratio of the polyhydric alcohols other than the (B) component to the (B) component is relatively low relative to 1 part by mass of the content of the (B) component from the viewpoint of improving stability. Preferably, it is 0 mass part - 3 mass parts, More preferably, it is 0.001 mass part - 2 mass parts, More preferably, it is 0.005 mass part - 1.5 mass parts. In addition, the ratio of polyhydric alcohols other than component (B) may be 0 to 1 part by mass, 0 to 0.5 parts by mass, or 0 to 0.35 parts by mass with respect to 1 part by mass of the content of component (B). wait.

In one aspect of the present invention, from the viewpoint of improving stability, for example, 1,3-butanediol is preferably 0 to 3 parts by mass relative to 1 part by mass of the content of component (B), More preferably, it may be 0.001 to 2 parts by mass, and still more preferably, it may be 0.005 to 1 part by mass.

[3-O-Ethyl Ascorbic Acid] In the water-in-oil type external composition of the present invention, as long as the effect of the present invention is not hindered, in addition to the above-mentioned (A) component, (B) component, (C) component and (D) component, 3-O - Ethyl ascorbic acid or a salt thereof. 3-O-Ethyl ascorbic acid can be synthesized by ethoxylating the hydroxyl group at the 3-position of ascorbic acid (for example, according to a known method described in JP-A-8-134055). 3-O-Ethyl ascorbic acid can also use a commercial item as it is. The commercially available product is not limited, and for example, "VC diethyl ether" manufactured by Nippon Seika Co., Ltd., and products manufactured by Junsei Chemical Co., Ltd. are also illustrated.

3-O-ethyl ascorbic acid contributes to the stability of the water-in-oil topical composition of the present invention.

3-O-Ethyl ascorbic acid can also be used in the form of a salt. Here, the salt of 3-O-ethyl ascorbic acid refers to a pharmaceutically acceptable salt. It is not limited, for example: salts with organic bases (for example, trimethylamine salts, triethylamine salts, monoethanolamine salts, triethanolamine salts, pyridinium salts, etc.) and tertiary amine salts, arginine and other basic ammonium salts, etc.), salts with inorganic bases (for example, alkali metal salts such as ammonium salts, sodium salts, and potassium salts, alkaline earth metal salts such as calcium salts, and magnesium salts, aluminum salts, etc.), and the like. Particularly preferred salts of 3-O-ethyl ascorbic acid are sodium salts and potassium salts.

In the present invention, 3-O-ethylascorbic acid or a salt thereof may be used alone or in combination of two or more.

In one aspect of the present invention, the total content of 3-O-ethyl ascorbic acid or its salt relative to the total amount of the water-in-oil composition for external use can be appropriately set based on the balance with other components. The total content of 3-O-ethyl ascorbic acid or its salt is preferably from 0.0001% by mass to 10% by mass, more preferably from 0.001% by mass to 5% by mass, relative to the total amount of the water-in-oil type external composition, and further preferably Preferably, it is 0.005 mass % to 3 mass %, More preferably, it is 0.01 mass % to 3 mass %.

In one aspect of the present invention, regarding the ratio of the compounded amount of 3-O-ethyl ascorbic acid or its salt to (A) component, 3-O- The total content of ethyl ascorbic acid or its salts is preferably 0.000003 to 10 parts by mass, more preferably 0.00025 to 1 part by mass, further preferably 0.001 to 0.6 parts by mass.

[Surfactant other than (D) component] The water-in-oil type external composition of the present invention may contain a surfactant as long as the effects of the present invention are not hindered. Surfactants can aid in the stabilization of ingredients. As the surfactant, for example, polyoxyethylene hydrogenated castor oil 40, polyoxyethylene hydrogenated castor oil 60, polyoxyethylene hydrogenated castor oil 80, polyoxyethylene polyoxypropylene decyl tetradecyl ether, polyoxyethylene ( 20) Polyoxypropylene (4) cetyl ether, PEG-8 glyceryl isostearate, polyoxyethylene sorbitan monolaurate (20E.O.), polyoxyethylene sorbitan isostearate (20E.O.), Polyoxyethylene Sorbitan Stearate (20E.O.), Polyglyceryl-10 Coconut Fatty Acid Ester, Polyglyceryl-3 Coconut Fatty Acid Ester, PEG-7 Glyceryl Coconut Oil Fatty acid ester, polyglyceryl-10 dioleate, polyglyceryl-10 diisostearate, PEG-40 glyceryl triisostearate, PEG-40 glyceryl isostearate, polyglyceryl-10 triisostearate Laurate, hexaglyceryl tricaprylate, polyglyceryl laurate, polyglyceryl myristate, polyoxyethylene lauryl ether, etc., especially, polyoxyethylene polyoxypropylene decyl tetradecyl ether, Polyoxyethylene hydrogenated castor oil 40, polyoxyethylene hydrogenated castor oil 60, polyoxyethylene hydrogenated castor oil 80, polyoxyethylene sorbitan isostearate (20E.O.), polyoxyethylene sorbitan monolauric Ester (20E.O.), polyglyceryl laurate, etc.

In one aspect of the present invention, the total content of the surfactant with respect to the total amount of the water-in-oil composition for external use can be appropriately set according to the balance with other components. The total content of the surfactant including component (D) is preferably from 1% by mass to 30% by mass, more preferably from 3% by mass to 20% by mass, based on the total amount of the water-in-oil type external composition, and further Preferably it is 5 mass % to 10 mass %.

[other ingredients] In the water-in-oil type external composition of the present invention, in addition to the above-mentioned (A) component, (B) component, (C) component, and (D) component, the various components of ascorbic acid and or its salts are further enhanced or supplemented. For the purpose of action, and in order to add other useful effects, the following ingredients can be used alone or in combination of two or more: whitening ingredients, anti-inflammatory ingredients, antibacterial ingredients, cell activation ingredients, astringent ingredients, antioxidant ingredients, acne improvement ingredients , Collagen and other biological ingredients synthesis promoting ingredients, blood flow promoting ingredients, moisturizing ingredients, anti-aging ingredients and other ingredients. Preferably, it is one or more of whitening ingredients, anti-inflammatory ingredients, antibacterial ingredients, cell activation ingredients, astringent ingredients, antioxidant ingredients, anti-aging ingredients or moisturizing ingredients. Examples of a particularly preferable combination of these ingredients include: a combination with a whitening ingredient, a combination of a whitening ingredient and an antioxidant ingredient, a combination with an antioxidant ingredient, a combination with an antiaging ingredient, and each of a whitening ingredient and an antiaging ingredient. combination. These components are not particularly limited as long as they are previously used in the field of pharmaceuticals, quasi-drugs, or cosmetics and will be used as components of external skin preparations in the future, and arbitrary components can be selected and used as appropriate.

[base or carrier] In the water-in-oil type composition for external use of the present invention, in terms of the improvement of the feeling of use and the improvement of stability, as long as the effects of the present invention are not hindered, except for the above-mentioned (A) component, (B) component, and ( In addition to the component C), a base or a carrier may also be included. As the base or carrier, for example, cellulose derivatives such as ethyl cellulose, hydroxypropyl cellulose, and hydroxypropylmethyl cellulose; polyvinylpyrrolidone; carrageenan; polyvinylpyrrolidone; Vinyl butyral; polyethylene glycol; such as ethylene glycol monomethyl ether, ethylene glycol monoethyl ether, ethylene glycol monopropyl ether, diethylene glycol monomethyl ether, diethylene glycol monoethyl ether, diethylene glycol Glycol ethers such as alcohol monopropyl ether, diethylene glycol monobutyl ether, propylene glycol monoethyl ether, propylene glycol monopropyl ether, dipropylene glycol monoethyl ether, and dipropylene glycol monopropyl ether; or lithium dimethyldistearyl ammonium Organic modified clay minerals such as bentonite. One type or two or more types of bases or carriers can be used.

[additive] In the water-in-oil type composition for external use of the present invention, it can be formulated for general use in the field of pharmaceuticals, quasi-drugs, or cosmetics as needed within the range of quantity and quality that does not impair the appearance, stability, viscosity, etc., and does not impair the effects of the present invention. Various components used as components of external preparations, such as amino acids, irritation reducing agents, thickening agents, preservatives, ultraviolet absorbers, ultraviolet protection agents, colorants, dispersants, additional pH adjusters, fragrances, etc. In addition, these components can be compounded individually by 1 type or arbitrarily compounded 2 or more types.

[Manufacturing method] The production method of the water-in-oil type composition for external use of the present invention is not particularly limited, and the stirring method during emulsification, the emulsification temperature, the order of adding the oil phase and the water phase, and the speed of adding can be appropriately set.

Specifically, if necessary, the oil phase and the water phase which are mixed after heating and dissolving are prepared separately, the water phase is slowly added to the oil phase at room temperature, and the method of emulsifying with a mechanical stirring force such as a homogenizer, etc. can be mentioned. However, it is not particularly limited to these methods.

[Preparation form] The water-in-oil type composition for external use of the present invention can be mixed with bases or carriers commonly used in pharmaceuticals, quasi-drugs, or cosmetics, and additives as needed to make pharmaceuticals, quasi-drugs, or cosmetics A water-in-oil composition for external use.

The form of the water-in-oil type composition for pharmaceuticals is not particularly limited, for example, liquid, suspension, emulsion, cream, ointment, gel, liniment, lotion, patch Agents and aerosol agents, etc. These preparations can be produced in accordance with the methods described in the fifteenth revision of the Japanese Pharmacopoeia General Rules for Preparations, etc. Among them, solutions, suspensions, emulsions, creams, ointments, gels, lotions, and patches are preferred, and creams, emulsions, ointments, lotions, and gels are more preferred.

When it is made into a water-in-oil type external composition for quasi-drugs or cosmetics, it can also be made into the same form as the above-mentioned medicines. Moreover, in addition to this, the tablet which impregnated the liquid medicine in a stick, and a nonwoven fabric, etc. are also mentioned. Among them, liquid preparations, suspension preparations, emulsions, creams, ointments, gels, lotions, sticks and tablets are preferred, and creams, emulsions, ointments, gels or washes are more preferred. agent.

The water-in-oil composition for external use of the present invention includes an oil phase and a water phase, which will be emulsified, and typically take the form of a cream or emulsion.

As the use when it is prepared as a water-in-oil type external composition for quasi-drugs or cosmetics, specific examples include lotion, lotion, gel, cream, beauty essence, sunscreen cosmetics, Basic cosmetics such as compresses, facial masks, hand creams, and body lotions; and cosmetics for face makeup such as powders and primers, lip cosmetics such as lipsticks, lip balms, lip glosses, and lip liners.

The mass ratio of the oil phase and the water phase in the present invention can be appropriately set without limitation. In terms of obtaining better stability and feeling of use, the oil phase:water phase=1:9 to 6: 4.

[container] The water-in-oil type composition for external use of the present invention can be accommodated in a container of a shape and material appropriately selected according to the purpose and application. Specific examples of containers include spray type, bottle type, tube type, can type, dropper type, dispenser type, stick type, pouch, and penguin pack (CHEER PACK).

In addition, examples of the material of the container include polyethylene terephthalate, polypropylene, polyethylene (HDPE (High Density Polyethylene; high-density polyethylene), LDPE (Low Density Polyethylene; low-density polyethylene), LLDPE (Linear Low Density Polyethylene; linear low density polyethylene), etc.), ABS (Acrylonitrile Butadiene Styrene; acrylonitrile-butadiene-styrene) resin, ethylene vinyl alcohol resin, polystyrene, glass, and metal (aluminum, etc.) wait. In addition, these materials can be used as container materials by performing various coating treatments in consideration of strength, flexibility, weather resistance, or component stability, or by combining or laminating these materials, for example, by mixing.

[How to relieve skin irritation] In addition, the present invention also includes a method for alleviating skin irritation of a water-in-oil type external composition containing (A) ascorbic acid and a salt thereof. According to the present invention, by preparing (A) at least one selected from the group consisting of ascorbic acid and ascorbic acid salts, (B) propylene glycol, (C) oil, and (D) polysiloxane-based surfactants The water-in-oil type composition for external use can alleviate the skin irritation of the water-in-oil type composition for external use, so it can be made into a water-in-oil type composition for external use with low irritation. Here, conditions such as the content, ratio, and other components of each component in the skin irritation suppression method are based on the content described in [water-in-oil type composition for external use].

[How to improve stability] In addition, the present invention also includes a method for improving the stability of the water-in-oil composition for external use containing (A) ascorbic acid and its salt. According to the present invention, the water-in-oil type external application containing (A) at least one selected from the group consisting of ascorbic acid and ascorbic acid salts, (C) oil, and (D) polysiloxane-based surfactant The coexistence of the composition and (B) propylene glycol can improve the stability of the water-in-oil composition for external use. Here, the content, ratio, and other conditions of each component in the method of improving stability are based on the content described in [Water-in-Oil Type Composition for External Use].

[use] The water-in-oil type external composition of the present invention is especially effective as a whitening agent, anti-inflammatory agent, and anti-aging agent, for example, it has the effect of preventing or treating acne and anti-oxidation. Furthermore, it can be used in products aimed at whitening, anti-wrinkle, and anti-aging. When applied to the skin, it can sometimes exert the effects of improving the transparency of the skin, maintaining moisture, smoothing the texture, and suppressing roughness. Furthermore, sometimes it also exerts effects such as making pores less conspicuous, regulating skin moisture, etc. In addition, it can also be used for the prevention or treatment of chloasma.

In terms of effects on the skin, the present invention is preferably a product used as an external preparation for the skin (preparation for the skin). The water-in-oil composition of the present invention can be divided into several times a day according to the application, etc., and used in known or customary usage and dosage.

The present invention relates to: (1) a water-in-oil composition for external use, containing: (A) at least one selected from the group consisting of ascorbic acid and ascorbic acid salts; (B) propylene glycol; (C) oil; and (D) Polysiloxane-based surfactant. Here, the following aspects can be exemplified.

(2) The water-in-oil type external composition according to (1) above, wherein the content of at least one selected from the group consisting of ascorbic acid and salts of ascorbic acid is 5% to 15% by mass. (3) The water-in-oil composition for external use as described in (1) or (2), wherein the content of the aforementioned (B) propylene glycol is 15% by mass to 80% by mass. (4) The water-in-oil composition for external use as described in any one of (1) to (3), wherein the content of the aforementioned (C) oil component is 1% by mass to 40% by mass. (5) The water-in-oil type external composition as described in any one of (1)-(4) whose content of the said (D) component is 1 mass % - 30 mass %. (6) The water-in-oil type external use composition as described in (5) whose content of the said (D) component is 1 mass % - 5 mass %. (7) The water-in-oil composition for external use as described in any one of (1) to (6), which further contains ethanol. (8) The water-in-oil composition for external use as described in any one of (1) to (7), which further contains a polyhydric alcohol other than the (B) component. (9) The water-in-oil composition for external use as described in (8), wherein the ratio of the component (B) to all the polyols in the water-in-oil composition for external use is 30% by mass or more. (10) The water-in-oil composition for external use as described in any one of (1) to (9), which is a cream or an emulsion. (11) The water-in-oil composition as described in any one of (1) to (10), wherein water is 0.05 to 3 parts by mass relative to 1 part by mass of the total content of the component (A). (12) The water-in-oil composition as described in any one of (1) to (10), wherein the component (B) is 4 to 35 parts by mass relative to 1 part by mass of the total content of the component (A) share. [Example]

Next, although an Example demonstrates this invention concretely, this invention is not limited to a following Example. In addition, the unit of each component quantity in a table|surface is mass %.

Compositions with the compositions shown in Table 1 to Table 4 were prepared according to conventional methods. In the table, unless otherwise specified, the numerical values represent % by mass.

[Cytotoxicity test] After preparing the compositions of Comparative Examples and Examples, a cytotoxicity test was carried out using three-dimensional cultured skin. Add 0.5mL to each well of the special detection medium attached to the lower part of the transwell (transwell) (transwell for 24-well plate) of human three-dimensional culture epidermis LabCyte EPI-MODEL24 (Japan Tissue Engineering company), Pre-incubate at 37°C (5% to 10% CO2) for 18 hours to 22 hours.

Then, the special detection medium was replaced with 0.5mL PBS (phosphate buffered saline, phosphate buffered saline), and pre-incubated on a constant temperature bath at 37°C for 30 minutes. Furthermore, the PBS was replaced with an equivalent amount of fresh PBS, 0.1 mL of each composition was added directly on top of the cells, and the cells were left to stand for 30 minutes.

Next, after carefully washing the permeated porous membrane with PBS, the PBS at the lower part of the permeated porous membrane was replaced with 0.5 mL of (3-(4,5-dimethylthiazol-2-yl)-2,5 -diphenyltetrazolium bromide solution (MTT solution). Then, cultivated at 37° C. for 3 hours and cultivated under light-shielding. The MTT solution was prepared by dissolving 0.5 mg of MTT in 1 mL of PBS. Then, the Transfer the human three-dimensional cultured epidermis peeled through the porous membrane to a microtube, add 0.3mL of isopropanol, and incubate in a cool place for more than 15 hours for pigment extraction. For the extracted pigment, use Corona Electric Co., Ltd. Measure the absorbance (measurement wavelength: 570nm, 650nm) with a microdisk reader. Based on the measured value, use the following formula to calculate the cell survival rate and evaluate the cytotoxicity of the composition. Measured value=[(each composition treatment group for Absorbance at 570nm) - (Absorbance at 650nm of each composition treatment group)] - [(Absorbance of isopropanol at 570nm) - (Absorbance of isopropanol at 650nm)] Cell survival rate (%) = 100 × (each The measured value of the composition treatment group) / (the measured value of the PBS treatment group) the improvement rate of the cell survival rate (%) = 100 × {(the survival rate based on each composition/the survival rate based on the reference composition)-1}

The evaluation results of the compositions of Examples, Reference Examples, and Comparative Examples are shown in Tables 1 to 3.

[Table 1] [% represents mass%] Comparative example 1-1 Example 1-1 ingredient name Deployment volume (%) Deployment volume (%) 1,3-Propanediol - 50 Diethylene glycol monoethyl ether 50 - ascorbic acid 10 10 ethanol 15 15.5 Mixture of decamethylcyclopentasiloxane and cross-linked methylpolysiloxane 1.5 1.5 Mixture of cross-linked polyether modified polysiloxane and methylpolysiloxane 3 3 Cetyl PEG/PPG-10/1 Dimethicone 3 3 Methylpolysiloxane 17 17 purified water 10 10 total 100 100 Survival improvement rate based on Comparative Example 1 (%) / 55.8

In Table 1, Comparative Example 1-1 and Example 1-1 are water-in-oil compositions. As shown in Table 1, compared with Comparative Example 1-1 using diethylene glycol monoethyl ether, the cell viability was improved in Example 1-1 using 1,3-propanediol.

[Table 2] [% represents mass%] Comparative example 2-1 Comparative example 2-2 Example 2-1 Example 2-2 ingredient name Deployment volume (%) Deployment volume (%) Deployment volume (%) Deployment volume (%) 1,3-Propanediol 50 50 50 50 ascorbic acid 10 10 10 10 ethanol 5 5 5 5 glycerin 5.5 5.5 5.5 5.5 1,3-Butanediol 19.5 29.5 - 10 Mixture of decamethylcyclopentasiloxane and cross-linked methylpolysiloxane - - 1.5 1.5 Mixture of cross-linked polyether modified polysiloxane and methylpolysiloxane - - 3 3 Cetyl PEG/PPG-10/1 Dimethicone - - 3 3 Methylpolysiloxane - - 12 12 purified water 10 - 10 - total 100 100 100 100 Improvement rate of cell viability based on comparative example 2-1 (%) / -7.4 9.2 10.3 The improvement rate of cell viability based on Comparative Example 2-2 (%) / / 17.9 19.1

In Table 2, Comparative Example 2-1 and Comparative Example 2-2 are beauty lotions composed of water-based ingredients, and Example 2-1 and Example 2-2 are water-in-oil compositions. As shown in Table 2, when 1,3-propanediol was used, the cell survival rate decreased, especially in the cosmetic serum without water. Cell viability was improved when 1,3-propanediol was used to make water-in-oil creams. Furthermore, the cream formulation without water showed further improved cell viability.

[Table 3] [% represents mass%] Comparative example 3-1 Example 3-1 ingredient name Deployment volume (%) Deployment volume (%) 3-O-ethyl ascorbic acid 0.5 0.5 1,3-Propanediol - 60 1,2-propanediol 60 - ascorbic acid 10 10 ethanol 5 5 Mixture of decamethylcyclopentasiloxane and cross-linked methylpolysiloxane 1.5 1.5 Mixture of cross-linked polyether modified polysiloxane and methylpolysiloxane 3 3 Cetyl PEG/PPG-10/1 Dimethicone 3 3 Methylpolysiloxane 17 17 purified water - - total 100 100 Survival rate improvement rate based on Comparative Example 3-1 / 29.2

According to the results in Table 3, it can be seen that compared with the cream formulated with 1,2-propanediol water-in-oil composition, cells can be seen in the cream formulated with 1,3-propanediol water-in-oil composition Improvement in survival rate. From the above, it can be seen that the skin irritation of the composition was relieved by preparing a cream containing a water-in-oil composition containing 1,3-propanediol.

[Stability test] After preparing the compositions of Comparative Examples and Examples, they were left at room temperature for one day to confirm the initial properties. Then, it was left still in a 60 degreeC thermostat, and the state of the formulation after 2 weeks and 3 weeks was confirmed. The state of the preparation after storage at 60°C was taken out from the constant temperature tank at 60°C, and then was thermostated at 25°C to observe the properties from the appearance of the preparation.

Table 4 shows the evaluation results of the compositions of Examples, Reference Examples, and Comparative Examples. [Table 4] [% represents mass%] Example 4-1 Example 4-2 Example 4-3 Comparative example 4-1 Comparative example 4-2 ingredient name Deployment volume (%) Deployment volume (%) Deployment volume (%) Deployment volume (%) Deployment volume (%) 1,3-Propanediol 50 20 50 - - 1,2-propanediol - - - 50 - Dipropylene glycol - - - - 50 1,3-Butanediol - 30 - - - ascorbic acid 5 5 3 5 3 ethanol 5 5 5 5 5 Mixture of decamethylcyclopentasiloxane and cross-linked methylpolysiloxane 2 2 2 2 2 Mixture of (Dimethicone/(PEG-10/15)) Crosslinked Polymer and Dimethicone 2 2 2 2 2 Dimethyldistearyl ammonium lithium bentonite mixture with decamethylcyclopentasiloxane and polyoxyethylene-methylpolysiloxane copolymer 8 8 8 8 8 Methylpolysiloxane 18 18 20 18 20 purified water 10 10 10 10 10 total 100 100 100 100 100 character Prepare the next day not separated not separated not separated not separated separate After 1 week at 60°C not separated not separated not separated not separated - After 3 weeks at 60°C not separated not separated not separated separate -

As shown in Table 4, when 1,3-propanediol was formulated, a stable water-in-oil type external composition was obtained. On the other hand, as shown in Comparative Example 1, separation was confirmed after storage at 60° C. for 3 weeks in a composition containing only 1,2-propanediol without 1,3-propanediol. Furthermore, in the composition of Comparative Example 1, a separation tendency was observed after storage at 60° C. for 2 weeks. As shown in Comparative Example 2, in the composition containing only dipropylene glycol, separation was confirmed on the second day of preparation.

[Recipe Example] Formulation examples (formulation example 1 to formulation example 10) are shown in following Table 5 and Table 6. The formulation examples are all creams, and the contents in the formulation examples are all mass %. Furthermore, Table 6 is a continuation of Table 5.

[table 5] Preparation Example 1 Preparation example 2 Preparation example 3 Preparation Example 4 Preparation Example 5 Preparation example 6 Preparation Example 7 Preparation Example 8 Preparation Example 9 Preparation Example 10 cream cream cream cream cream cream cream cream sunscreen sunscreen ascorbic acid 5 5 7 10 3 10 12 15 5 15 1,3-Propanediol 30 50 40 30 50 60 30 30 30 50 squalane 5 8 3 Glyceryl tri(caprylic/capric) ester 1.5 3 1 Mangosteen Seed Oil 3 5 2 2 hydrogenated oil 0.5 1 Cetyl 2-Ethylhexanoate 4 5 Methylpolysiloxane 5 8 4 10 5 3 15 20 vaseline 2 2 1 shea butter 3 1 Glyceryl Tri(caprylic/capric/myristic/stearic acid) 0.5 1 stearic acid 1 0.3 cetyl alcohol 0.5 eucalyptus 0.5 0.5 Isononyl isononanoate 1 2 liquid paraffin 2 5 Decamethylcyclopentasiloxane 1 3 2 Cross-linked methylpolysiloxane 2 1 4 Cross-linked polyether modified polysiloxane mixture 3 2 0.5 Cetyl PEG/PPG-10/1 Dimethicone 3 3 2.5 Highly Polymerized Methylpolysiloxane (1) 5 2 Lauryl PEG-9 Polydimethylsiloxyethyl Dimethicone 2 1 PEG/PPG-20/22 Butyl ether dimethicone 2 (Dimethicone/(PEG-10/15)) Crosspolymer 1 3 Methylphenyl polysiloxane 0.5 2 0.8 Dimethyldistearyl ammonium lithium bentonite 2 3 1 Polyoxyethylene-methyl polysiloxane copolymer 3 6 4 Absolute ethanol 5 7 10 10 12 5 3 5 10 7 3-O-ethyl ascorbic acid 0.5 1 0.5 0.3 0.5 0.5 glycerin 17.52 29.7 1,3-Butanediol 34.3 6.75 0.2 1,2-propanediol 8.04 13.23 Pentylene glycol 3 Hexylene glycol 2 Dipropylene glycol 6.35 1.69 26.7 Methylparaben 0.2 0.25 Sodium metabisulfite 0.02 0.03 Phenoxyethanol 0.3 0.3 0.2 Chlorphenesin 0.1 Glycerol mono-2-ethylhexyl ether 0.05 0.1 carboxy vinyl polymer 0.2 0.15 Hydroxypropyl Methyl Cellulose 0.05 0.1 Polyoxyethylene Sorbitan Isostearate (20E.O.) 2 1.5 Diglyceryl Triisostearate 0.5 3 2 Soy Protein Hydrolyzate 0.01 0.1 Hydrolyzed Collagen 0.02 0.05 Ceramide 2 0.005 0.05 Ceramide 3 0.01 0.05 glycerol glucoside 1 Coix Seed Extract 0.02 [Table 6] Artichoke Extract 0.05 Chrysanthemum Extract 0.01 thorn extract 0.04 rosemary extract 0.01 lemon extract 0.02 grapefruit extract 0.04 0.01 yeast extract 0.01 0.01 d-delta-tocopherol 0.05 0.1 0.1 Royal Jelly Extract 0.06 citric acid Appropriate amount Appropriate amount Appropriate amount Sodium citrate Appropriate amount Appropriate amount Appropriate amount Disodium edetate 0.1 0.05 0.1 0.05 0.1 0.05 0.1 2-Ethylhexyl p-methoxycinnamate 2 2-Ethylhexyl Salicylate 0.5 4-tert-butyl-4'-methoxydibenzoylmethane 1.5 Phenylbenzimidazole sulfonic acid 0.2 Diethylamino hydroxybenzoyl hexyl benzoate 2 Bisethylhexyloxyphenylmethoxyphenyltriazine 2 purified water 5 3 10 5 3 10 5 3 8 10 total 100 100 100 100 100 100 100 100 100 100

Claims (7)

A water-in-oil composition for external use, comprising: (A) At least one selected from the group consisting of ascorbic acid and salts of ascorbic acid; (B) propylene glycol; (C) oil content; and (D) Polysiloxane-based surfactant. The water-in-oil composition for external use as described in Claim 1, wherein the content of at least one selected from the group consisting of ascorbic acid and ascorbic acid salts is 1% to 30% by mass. The water-in-oil type composition for external use as described in claim 1, wherein the content of the aforementioned (B) propylene glycol is 15% by mass or more. The water-in-oil composition for external use as described in claim 1, wherein the water content is 10% by mass or less. The water-in-oil type composition for external use as described in claim 1, wherein the aforementioned (C) oil component contains polysiloxane oil. The water-in-oil type composition for external use as described in Claim 1 further contains lower alcohols. A method for relieving skin irritation of a water-in-oil type composition for external use, by making (A) at least one selected from the group consisting of ascorbic acid and a salt of ascorbic acid, (B) propylene glycol, and (C) an oil component coexist , to alleviate the skin irritation of the water-in-oil type external composition containing (A) at least one selected from the group consisting of ascorbic acid and ascorbic acid salts.