TW201944991A - Composition for external application containing ascorbic acid and/or salt thereof - Google Patents

Abstract

The present invention provides a composition for external application, which has excellent stability and feeling of use. According to the present invention, a composition for external application is prepared to contain (A) 10% by mass or less of at least one compound that is selected from the group consisting of ascorbic acid and salts of ascorbic acid, (B) 30% by mass or more of a diol having three carbon atoms, and (C) 20% by mass or less of water, while having an ethoxydiglycol content of less than 30% by mass and a pH of 4.5 or less. Alternatively, a composition for external application according to the present invention is prepared to contain (A) 10-25% by mass of at least one compound that is selected from the group consisting of ascorbic acid and salts of ascorbic acid, (B) a diol having three carbon atoms in an amount of 30-90% by mass in the components other than the components (A) and (C), and (C) water, while having an ethoxydiglycol content of less than 30% by mass and a pH of 2.0 to 6.0 and satisfying (C)/(A) = 0.2-5.

Description

External composition containing ascorbic acid and / or its salt, and method for preventing coloring and / or crystallization of external composition

The present invention relates to an external composition containing ascorbic acid and / or a salt thereof.

It is known that ascorbic acid exerts anti-inflammatory effect, acne improvement effect, whitening effect, anti-aging effect, antioxidant effect, cell activation effect by promoting synthesis of biological components such as collagen, and inhibits epidermal keratinocytes caused by ultraviolet rays. Various effects such as cell damage and DNA (Deoxyribonucleic acid) damage are expected, and these effects are expected to be widely used as skin external preparations.

The industry is studying several methods for stably dissolving ascorbic acid in aqueous skin external preparations (for example, Patent Document 1: WO02 / 19972, Patent Document 2: WO00 / 78283, and Patent Document 3: Japanese Patent (Japanese Patent Application Laid-Open No. 2002-348228, Patent Document 4: Japanese Patent Application Laid-Open No. 2005-225865).
[Prior technical literature]
[Patent Literature]

Patent Document 1: WO02 / 19972.
Patent document 2: WO00 / 78283.
Patent Document 3: Japanese Patent Application Laid-Open No. 2002-348228.
Patent Document 4: Japanese Patent Application Laid-Open No. 2005-225865.

[Problems to be Solved by the Invention]

An object of the present invention is to provide an ascorbic acid-containing composition for external use having good properties.
[Means to solve the problem]

The present invention provides an external composition containing ascorbic acid and / or a salt thereof.

According to research by the present inventors, it has been found that if ascorbic acid and / or a salt thereof is blended, coloring may be seen from the time of manufacture, or coloring may be seen after a certain period of time. Furthermore, it turned out that the problem of precipitation of ascorbic acid at the time of low-temperature storage, or the problem of transdermal absorptivity may arise.

The inventors of the present invention have repeatedly conducted intensive research in order to solve the problem, and as a result, they have found that (A) at least one kind selected from the group consisting of ascorbic acid and a salt of ascorbic acid is 10% by mass or less, and (B) carbon 30% by mass or more of diols and 20% by mass or less of (C) water, and the content of ethoxydiglycol is set to less than 30% by mass, and the pH is set to 4.5 or less, or It contains (A) at least one 10% to 25% by mass selected from the group consisting of ascorbic acid and a salt of ascorbic acid, and (B) a diol having 3 carbon atoms in (A) and (C) 30% to 90% by mass of the other components, (C) water, and further set the content of ethoxyethylene glycol to less than 30% by mass, (C) / (A) = 0.2 to 5, and When the pH is set to 2.0 to 6.0, a composition for external use can be obtained, which can inhibit the coloring of ascorbic acid, and also has excellent transdermal absorption (skin permeability) of ascorbic acid, thereby completing the present invention.

That is, this invention provides the external use composition listed below.
Item 1.
A composition for external use, containing (A) at least one selected from the group consisting of ascorbic acid and a salt of ascorbic acid, at least 10% by mass, (B) 30% by mass of a diol having 3 carbons, and (C) The water is 20% by mass or less, the content of ethoxyethylene glycol is less than 30% by mass, and the pH is 4.5 or less.
Item 2.
The composition for external use according to item 1, wherein the content of the component (B) is 40% by mass or more.
Item 3.
The composition for external use according to item 1 or 2, wherein a content of the ascorbic acid or a salt thereof is 3% by mass to 10% by mass.
Item 4.
The composition for external use according to any one of items 1 to 3, wherein the content of (C) water is 10% by mass or less.
Item 5.
An external composition comprising (A) at least one 10% to 25% by mass selected from the group consisting of ascorbic acid and a salt of ascorbic acid, and (B) a diol having 3 carbon atoms in (A) and ( Among components other than C), it is 30% to 90% by mass, and (C) water, and the content of ethoxyethylene glycol is less than 30% by mass, (C) / (A) = 0.2 to 5, and pH It is 2.0 to 6.0.
Item 6.
The composition for external use according to any one of items 1 to 5, further comprising butanediol and / or a lower alcohol.
Item 7.
The composition for external use according to any one of items 1 to 6, wherein the component (B) is 1,3-propanediol and / or 1,2-propanediol.
Item 8.
The composition for external use according to any one of items 1 to 7, wherein the component (B) contains at least 1,3-propanediol.
Item 9.
The composition for external use according to any one of items 1 to 8, wherein the content of ethoxyethylene glycol is 10% by mass or less.
Item 10.
The external-use composition according to any one of items 1 to 9, wherein the external-use composition is a solubilized external-use composition having a transmittance of 85% to 100% at a wavelength of 700 nm.
Item 11.
The composition for external use according to any one of items 1 to 10, wherein the composition for external use is for promoting percutaneous absorption of ascorbic acid.
Item 12.
A method for preventing the coloring and / or crystal precipitation of a composition for external use, in which (A) at least one selected from the group consisting of ascorbic acid and a salt of ascorbic acid is used in the composition for external use in an amount of 10% by mass or less (B) 30% by mass or more of a diol having 3 carbon atoms, and (C) 20% by mass or less of water, and the content of ethoxyethylene glycol is set to less than 30% by mass, and the pH is set to 4.5 In the following, the coloring or crystal precipitation of at least one external-use composition containing (A) selected from the group consisting of ascorbic acid and a salt of ascorbic acid is prevented.
Item 13.
A method for preventing the coloring and / or the precipitation of crystals of a composition for external use, because the composition for external use contains (A) at least one 10% by mass of 25% by mass, (B) 3 diols having a carbon number of 30% to 90% by mass in components other than (A) and (C), and (C) water, and the content of ethoxyethylene glycol Less than 30% by mass, (C) / (A) = 0.2 to 5.0, and pH is set to 2.0 to 6.0 to prevent (A) at least one selected from the group consisting of ascorbic acid and a salt of ascorbic acid Coloring of external use composition or precipitation of crystals.
[Inventive effect]

According to the present invention, a composition for external use excellent in stability can be provided.

In this specification, the unit of content "mass%" has the same meaning as "g / 100g".

The first aspect of the present invention is a case where at least one selected from the group consisting of ascorbic acid and a salt of ascorbic acid is 10% by mass or less (hereinafter also referred to as the first invention).
The composition for external use of the first invention contains (A) at least one 10% by mass or less selected from the group consisting of ascorbic acid and a salt of ascorbic acid, (B) 30% by mass or more of a diol having 3 carbons, and (C) A composition for use other than 20% by mass of water, less than 30% by mass of ethoxyethylene glycol (diethylene glycol monoethyl ether), and having a pH of 4.5 or less.

The composition for external use of the first invention is (A) at least one selected from the group consisting of ascorbic acid and a salt of ascorbic acid, which is stable in a relatively low concentration region and has excellent transdermal absorbability.

[(A) at least one member selected from the group consisting of ascorbic acid and a salt of ascorbic acid]
In the present invention, ascorbic acid, which is commercially available as an ingredient for skin external use in the field of pharmaceuticals, quasi drugs, or cosmetics, can be used. These generally refer to L-forms.

Salts of ascorbic acid can also be used. Here, the ascorbic acid salt refers to a pharmaceutically acceptable salt. It is not limited, and examples thereof include salts with organic bases (e.g., trimethylamine salt, triethylamine salt, monoethanolamine salt, triethanolamine salt, pyridine salt, etc.) Basic ammonium salts such as amine acids, etc.), and salts with inorganic bases (for example, alkali metal salts such as ammonium, sodium, and potassium salts, alkaline earth metal salts such as calcium and magnesium salts, and aluminum salts). Particularly preferred salts of ascorbic acid are sodium and potassium salts. Specific examples include sodium ascorbate, sodium ascorbate monophosphate, sodium ascorbate diphosphate, sodium ascorbate triphosphate, and sodium ascorbate-2-sulfate.

In the present invention, ascorbic acid or a salt thereof can be used singly or in combination of two or more kinds.

In the composition for external use of the first invention, the total content of the component (A) relative to the total amount of the composition for external use is appropriately set by balancing with other components. The total content of (A) component is not particularly limited as long as it is 10% by mass or less with respect to the total amount of the composition for external use, preferably 1% by mass or more, more preferably 2% by mass or more, and further preferably 3 Above mass%. The total content of the component (A) is 10% by mass or less, preferably 9% by mass or less, and further preferably 8% by mass or less with respect to the total amount of the composition for external use. The total content of the component (A) is preferably 1% to 10% by mass, more preferably 2% to 10% by mass, and still more preferably 3% to 8% by mass with respect to the total amount of the composition for external use.

[(B) 3 diols]
The diol having 3 carbon atoms used in the present invention is not particularly limited as long as it is a diol having 3 carbon atoms which is used as a component for external skin preparations in the fields of pharmaceuticals, quasi drugs or cosmetics. The diol having 3 carbon atoms is not limited, and preferably 1,3-propanediol (CAS number: 504-63-2, English name: 1,3-Dihydroxypropane or Trimethylene Glycol) or 1,2-propanediol (CAS number : 57-55-6, English name: 1,2-Dihydroxypropane, Japanese nickname: 1,2-propanediol). For example, any one or both of 1,3-propanediol or 1,2-propanediol may be used as the (B) component. Such a diol having 3 carbon atoms can also be used as it is. From the viewpoints of reducing skin irritation, improving the feeling of use, and suppressing coloration, it is preferable to combine 1,3-propanediol and 1,2-propanediol.

In the composition for external use of the first invention, the total content of the component (B) relative to the total amount of the composition for external use is 30% by mass or more, preferably 35% by mass or more, more preferably 40% by mass or more, and more It is preferably 45% by mass or more.
The total content of the (B) component with respect to the total amount of the composition for external use is preferably 90% by mass or less, more preferably 85% by mass or less, and even more preferably 80% by mass or less.

The total content of the component (B) with respect to the total amount of the composition for external use of the first invention is preferably 35% by mass to 90% by mass, more preferably 40% by mass to 85% by mass, and still more preferably 45% by mass to 80% by mass.

In the composition for external use according to the first invention, the ratio of the content of the component (B) to the component (A) is not particularly limited, but is preferably 1 part by mass to the total content of the component (A), preferably 3 parts by mass to 300 parts by mass, more preferably 3 to 30 parts by mass, and still more preferably 5 to 25 parts by mass.

[(C) Water]
The composition for external use according to the first invention is a liquid composition containing water. The proportion of water is not limited, and it is preferably 0.1% by mass or more, more preferably 1% by mass or more, and most preferably more than 1% by mass with respect to the composition for external use. The value exceeding 1% by mass is not limited, and may be, for example, a value of 1.01% by mass or more or 1.1% by mass or more. The proportion of water is 20% by mass or less based on the composition for external use. It is preferably 15% by mass or less, and more preferably 10% by mass or less.

The total content of the (C) component relative to the total amount of the composition for external use of the first invention is preferably 1% to 15% by mass, more preferably 1% to 10% by mass, and even more preferably 2% by mass. To 10% by mass.

In the composition for external use of the first invention, the ratio of the content of the component (C) to the component (A) is not particularly limited, but it is preferably 0.1 part by mass to 1 part by mass with respect to the total content of the component (A). 10 parts by mass, more preferably 0.125 parts by mass to 8 parts by mass, and still more preferably 0.2 parts by mass to 5 parts by mass.

In the present invention, even in a composition containing a small amount of water, precipitation of ascorbic acid or a salt thereof can be suppressed. Furthermore, a composition for external use which is also excellent in stability can be obtained. However, from the viewpoint of inhibiting the precipitation of ascorbic acid at a low temperature, a small amount is preferable.

[Ethoxyethylene glycol (diethylene glycol monoethyl ether)]
In the present invention, mainly from the viewpoint of improving stability, ethoxyethylene glycol is not contained, or even if it does not reach 30% by mass. As the ethoxyethylene glycol contained in the composition for external use, up to 30% by mass, as long as it is an ethoxyethylene glycol used as a skin external preparation in the field of pharmaceuticals, quasi drugs or cosmetics, There is no particular limitation.

In the composition for external use of the first invention, the content of ethoxyethylene glycol relative to the total amount of the composition for external use is less than 30% by mass, preferably 20% by mass or less, more preferably 10% by mass or less, and further It is preferably 5 mass% or less, and ethoxyethylene glycol may not be contained in the composition for external use.
The total content of ethoxyethylene glycol is 0 mass% or more and less than 30 mass%, preferably 0 mass% to 20 mass%, more preferably 0 mass% to 10 mass%, and even more preferably 0 mass% It is about 5 mass%.

In the composition for external use according to the first invention, the ratio of the content of the ethoxyethylene glycol component to the component (A) is 1 part by mass with respect to the total content of the (A) component, and preferably from 0 parts by mass to 10 parts by mass, more preferably 0 to 5 parts by mass. In addition, depending on the case, it may be 0.001 to 10 parts by mass or 0.01 to 5 parts by mass.

[pH]
From the viewpoints of the stability of the component (A), low irritation to the skin or mucous membrane, and good skin feeling, the first external composition of the present invention is more preferably pH 1.5 to 4.5, and more preferably It is an acidic region of pH 2 to 4.

The composition for external use according to the first invention contains a predetermined amount of (A) component, (B) component, and (C) component, and defines the content of ethoxyethylene glycol, and further sets the pH to 4.5 or less to obtain Good stability composition for external use.

[Glycol ether]
In the present invention, from the viewpoint of improving stability, it is preferable not to contain glycol ethers other than ethoxyethylene glycol, or to use it in combination with ethoxyethylene glycol even if it contains, and the glycol ether The total amount is less than 40% by mass. Herein, glycol ethers other than ethoxyethylene glycol are not particularly limited as long as they are glycol ethers used as components for external skin agents in the fields of pharmaceuticals, quasi-drugs, and cosmetics. What is necessary is just to dissolve 10 g or more of the glycol ether with respect to 100 g of water. Examples thereof include glycol ethers having a polymerization degree of 2 or less. Specific examples include diethylene glycol monomethyl ether, diethylene glycol monopropyl ether, diethylene glycol monobutyl ether, diethylene glycol monoisobutyl ether, diethylene glycol dimethyl ether, and ethylene glycol. Alcohol monobutyl ether, ethylene glycol monomethyl ether, ethylene glycol monoethyl ether, triethylene glycol monobutyl ether, tetraethylene glycol monobutyl ether, propylene glycol monomethyl ether, propylene glycol monoethyl ether, propylene glycol monopropyl ether, dipropylene glycol Monomethyl ether, dipropylene glycol monoethyl ether, dipropylene glycol monopropyl ether, and the like. Furthermore, diethylene glycol monomethyl ether, diethylene glycol monopropyl ether, diethylene glycol monobutyl ether, diethylene glycol monoisobutyl ether, diethylene glycol dimethyl ether, ethylene glycol monobutyl ether, Ethylene glycol monomethyl ether, ethylene glycol monoethyl ether, triethylene glycol monobutyl ether, tetraethylene glycol monobutyl ether, propylene glycol monomethyl ether, propylene glycol monoethyl ether, propylene glycol monopropyl ether, dipropylene glycol monomethyl ether, two Propylene glycol monoethyl ether and dipropylene glycol monopropyl ether are typical examples. In particular, diethylene glycol monomethyl ether, diethylene glycol monopropyl ether, ethylene glycol monobutyl ether, triethylene glycol monobutyl ether, tetraethylene glycol monobutyl ether, propylene glycol monomethyl ether, and propylene glycol monoethyl ether , Propylene glycol monopropyl ether, dipropylene glycol monomethyl ether, dipropylene glycol monoethyl ether, and dipropylene glycol monopropyl ether are typical examples.

These glycol ethers may be used singly or in combination of two or more kinds.

In the composition for external use of the first invention, the total content of glycol ether including ethoxyethylene glycol is preferably less than 40% by mass, and more preferably 30% by mass relative to the total amount of the composition for external use. Hereinafter, it is more preferably less than 10% by mass, more preferably 10% by mass or less, and the glycol ether may not be contained in the composition for external use.

The total content of the glycol ether including ethoxyethylene glycol is preferably 0% by mass or more and less than 40% by mass, more preferably 0% by mass or more and less than 30% by mass, and still more preferably 0% by mass. % Or more and about 10% by mass.

In the composition for external use of the first invention, the ratio of the content of the glycol ether component to the component (A) is 1 part by mass, and preferably 0 to 20 parts by mass relative to the total content of the (A) component. , More preferably 0 to 10 parts by mass. In addition, depending on the case, it may be 0.001 to 20 parts by mass or 0.01 to 10 parts by mass.

The composition for external use according to the first invention may be prepared by containing a predetermined amount of (A) component, (B) component, and (C) component, and defining the overall content of the glycol ether, and setting the pH to 4.5 or less. A composition having better stability for external use.

[Lower alcohol]
In the composition for external use according to the first invention, from the viewpoints of improvement in usability, stability, and promotion of percutaneous absorption, as long as the effects of the present invention are not hindered, the components (A), (B), and (C) In addition to the component, and glycol ethers such as ethoxyethylene glycol optionally contained, a lower alcohol may be contained. The lower alcohol used in the present invention is not particularly limited as long as it is a lower alcohol used as a component for external skin preparations in the fields of pharmaceuticals, quasi-drugs, or cosmetics. In this specification, when referred to as "lower alcohol" refers to C ₁ -C ₆ alcohols of. Among them, C ₁ -C ₃ alcohols can be particularly preferably used. As such an example, in addition to ethanol, methanol, n-propanol, isopropanol, and the like can be mentioned.

In the composition for external use of the first invention, the content of the lower alcohol relative to the total amount of the composition for external use, when contained, is preferably 0.01% by mass or more, more preferably 0.1% by mass or more, and even more preferably It is 0.25 mass% or more, more preferably 1 mass% or more, and most preferably 3 mass% or more. The content of ethanol is preferably 45% by mass or less, more preferably 40% by mass or less, still more preferably 35% by mass or less, and still more preferably 20% by mass or less.

The content of the lower alcohol contained in the composition for external use of the first invention is preferably 0.01% by mass to 45% by mass, more preferably 0.1% by mass to 40% by mass, still more preferably 0.25% by mass to 35% by mass, and furthermore It is more preferably 1 to 20% by mass, and most preferably 3 to 20% by mass.

[Butanediol]
In the composition for external use of the present invention, from the viewpoints of improvement in use feeling, stability, and promotion of percutaneous absorption, as long as the effects of the present invention are not hindered, the components (A), (B), and ( C) In addition to components and glycol ethers such as ethoxyethylene glycol, which may be contained, butanediol (1,3-butanediol) may be contained.

In the composition for external use of the first invention, the content of butanediol relative to the total amount of the composition for external use, when contained, is preferably 0.01% by mass or more, more preferably 0.1% by mass or more, It is preferably at least 0.25% by mass. The content of butanediol is preferably 55% by mass or less, more preferably 50% by mass or less, and still more preferably 45% by mass or less.

The content of butanediol in the composition for external use of the first invention is preferably 0.01% by mass to 55% by mass, more preferably 0.1% by mass to 50% by mass, and still more preferably 0.25% by mass to 45% by mass.

[pH adjuster]
In the composition for external use according to the first invention, from the viewpoints of improvement in usability, stability, and promotion of percutaneous absorption, as long as the effects of the first invention are not hindered, the components (A), (B), and In addition to (C) component, and glycol ethers, such as ethoxyethylene glycol, which may be contained, it may contain a pH adjuster.

As the pH adjusting agent used in the first invention, it can be used as a compound that is generally used as a component of external skin preparations in the fields of pharmaceuticals, quasi-drugs, and cosmetics. It is not particularly limited, and examples thereof include a pH adjusting agent having an amine (for example, aspartic acid or a salt thereof, ε-aminohexanoic acid or a salt thereof, glutamic acid or a salt thereof, and aminoethylsulfonic acid) Acid or its salt, monoethanolamine, triethanolamine, diisopropanolamine, triisopropanolamine, spermine, lysine, L-carnitine, low molecular betaine, preferably low molecular betaine, More preferred is trimethylglycine), organic acid salts (e.g. sodium lactate, sodium acetate, sodium citrate, sodium succinate, sodium oxalate, calcium gluconate, sodium pyrrolidone carboxylate, etc.), inorganic acid salts (e.g. For example, sodium metabisulfite, potassium metabisulfite, sodium phosphate, potassium nitrate, sodium borate, preferably sodium metabisulfite), basic amino acids and their salts (arginine, lysine, or histidine and the like) Salt), 3-O-ethyl ascorbic acid, or a salt thereof.

In the composition for external use of the first invention, the total content of the pH adjuster is not particularly limited with respect to the total amount of the composition for external use, but is preferably 0.01% by mass or more, and more preferably 0.05% by mass or more. The total content of the pH adjusting agent is preferably 10% by mass or less, and more preferably 5.0% by mass or less with respect to the total amount of the composition for external use. The content of the pH adjusting agent having an amine or an amine group is preferably 0.01% by mass to 10% by mass, and more preferably 0.05% by mass to 5.0% by mass with respect to the total amount of the composition for external use.

In the composition for external use of the first invention, the ratio of the content of the pH adjuster to the component (A) is not particularly limited, and it is preferably 0.00001 to 20 parts by mass relative to the total content of the (A) component. It is more preferably 0.0001 to 20 parts by mass, more preferably 0.0005 to 10 parts by mass, still more preferably 0.005 to 5 parts by mass, and most preferably 0.01 to 1 part by mass.

[Other ingredients]
In the composition for external use of the present invention, in addition to the components (A), (B), and (C), and optionally less than a certain amount of ethoxyethylene glycol, the composition is further enhanced or For the purpose of supplementing various effects of ascorbic acid, and in order to add other useful effects, whitening ingredients, anti-inflammatory ingredients, antibacterial ingredients, cell activating ingredients, astringent ingredients, antioxidant ingredients, acne improving ingredients, anti-aging ingredients, Various components such as collagen-promoting components such as collagen, blood circulation-promoting components, moisturizing components, and anti-aging components are prepared individually or in combination of two or more. One or two or more components of a whitening component, an anti-inflammatory component, an antibacterial component, a cell activating component, an astringent component, an antioxidant component, an anti-aging component, or a moisturizing component are preferred. Particularly preferred combinations of these ingredients include a combination with a whitening ingredient, a combination with a whitening ingredient and an antioxidant ingredient, a combination with an antioxidant ingredient, a combination with an antiaging ingredient, and a whitening ingredient and an antiaging ingredient. Of each combination. Each of these components is not particularly limited as long as it is a component that has been used as a component for external skin preparations in the pharmaceutical, quasi-drug, or cosmetic fields, and any component can be appropriately selected and used.

In the composition for external use of the present invention, in addition to the above components, a surfactant, a solubilizing component, a fat, a sugar, or a transdermal absorption-promoting component may be further formulated. In particular, the stability, effectiveness, and usability of ascorbic acid in an aqueous solvent can be further improved by blending a surfactant, a solubilizing component, or a fat.

In the composition for external use of the present invention, it is usually formulated for external use in the field of pharmaceuticals, quasi-drugs or cosmetics within the range of the amount and quality that does not impair the appearance stability or viscosity, and does not impair the effects of the present invention, as needed Various ingredients of the agent, such as amino acids, irritation reducing agents, tackifiers, preservatives, UV inhibitors, colorants, dispersants, additional pH adjusters, perfumes, etc. Moreover, these components can be mix | blended individually by 1 type, or 2 or more types can be mix | blended arbitrarily.

The composition for external use of the first invention contains (A) at least one kind of 10% by mass or less selected from the group consisting of ascorbic acid and a salt of ascorbic acid, (B) 30% by mass or more of a diol having three carbons, (C) 20% by mass or less of water, less than 30% by mass of ethoxyethylene glycol, and pH of 4.5 or less. If necessary, formulate and mix each of the above-mentioned components, and if necessary, formulate other solvents or use externally. The base of the agent can be prepared into various desired forms such as a paste, a mousse, a gel, a liquid, an emulsion, a cream, a sheet (supporting a substrate), an aerosol, and a spray. form. These can be manufactured by a common method in the industry.

The composition for external use of the present invention is particularly preferably a transparent or translucent composition obtained by dissolving ascorbic acid and / or a salt thereof. Here, "solubilization" is defined as follows. That is, for example, by the ultraviolet-visible absorbance measurement method, using a spectrophotometer or a photoelectric photometer UV-2450 (manufactured by Shimadzu Corporation), the transmittance at a wavelength of 700 nm is 80% to 100%, It is preferably in the range of 85% to 100%, more preferably 90% to 100%. Here, the water transmittance is set to 100%. The solubilized composition of the present invention has a transparent or translucent appearance. More specifically, the transmittance measurement method is based on the 16th revised Japanese Pharmacopoeia [B] General Test Method 2. Physical Test Method Optical Measurement Method 2.24 UV-Visible Absorptiometry.

[Viscosity]
The composition for external use of the present invention can be prepared as a composition having a moderate viscosity, which is particularly expected when used for application to a composition for external use on skin. The viscosity of the composition for external use of the present invention is not particularly limited. For example, the viscosity when measured at 25 ° C using an E-type viscometer is usually about 1 mPa · s to 300 mPa · s, preferably about 1 mPa · s to 200 mPa · s. , More preferably about 1 mPa · s to 100 mPa · s, and most preferably about 1 mPa · s to 50 mPa · s. More specifically, the viscosity measurement method is based on the 16th revised Japanese Pharmacopoeia [B] General test method 2. Physical test method Other physical test methods 2.53 Viscosity measurement method 2. Second method Rotary viscometer method 2.1.3 Cone-plate Rotary Viscometer (Cone Plate Viscometer).

[use]
The composition for external use of the present invention is particularly effective as a whitening agent, an anti-inflammatory agent, and an anti-aging agent, for example, it has the effects of preventing or treating acne and antioxidation. Furthermore, when applied to the skin, the effects of improving the transparency of the skin, keeping moist, adjusting the texture, and suppressing the roughness may be exerted. Furthermore, there are cases in which the effect of moisturizing the entire muscle that makes pores inconspicuous is exerted, and it can also be used for the prevention or treatment of spots.

The composition for external use of the present invention can be made into a basic cosmetic such as a cosmetic liquid, lotion, sun cream, lotion, cream, lotion, oil, and dressing; powder, lipstick, lipstick, mascara, eye shadow, eye liner , Eyebrow pencils, manicures, and other cosmetic materials; washing materials such as fabrics or facial cleansers, body cleansing materials; anti-underarm odorants, Hong Kong foot treatments, itching agents, wound healing agents, wipes, cleaning agents, Anti-inflammatory analgesics, acne treatments, hemorrhoids, bactericidal disinfectants, whitening agents, anti-ultraviolet agents, etc. are various external composition in the field of cosmetics, external medicines or quasi-drugs for external use. As far as the effect on the skin is concerned, the present invention is preferably a product applied to the outer skin, such as a skin external preparation (a preparation for the outer skin).

[Stabilization method]
The present invention also includes (A) at least one stabilization method selected from the group consisting of ascorbic acid and a salt of ascorbic acid. In the present invention, according to the method for stabilizing ascorbic acid, (A) at least one selected from the group consisting of ascorbic acid and a salt of ascorbic acid, at least 10% by mass or less, and (B) a diol having 3 carbon atoms 30% by mass or more and (C) 20% by mass or less of water, and the content of ethoxyethylene glycol is set to less than 30% by mass, and the pH is set to 4.5 or less, it can be made stable as long as it contains ascorbic acid preparation. That is, the present invention relates to a diol having at least one kind selected from the group consisting of (A) at least one selected from the group consisting of ascorbic acid and a salt of ascorbic acid, of 10% by mass or less, and 30% by mass of (B) a diol having 3 carbon atoms. And (C) 20% by mass or less of water, the content of ethoxyethylene glycol is set to less than 30% by mass, the pH is set to 4.5 or less, and the salt containing (A) is selected from the group consisting of ascorbic acid and ascorbic acid. A method for imparting stability to at least one external composition in the formed group. Here, the term "stabilization" is not limited, and means that, for example, stability is ensured even at high or low temperatures. Specifically, it means that ascorbic acid or a salt thereof can be inhibited at least when the composition for external use is stored at 4 ° C for one week, or the coloration is also inhibited after storage at 50 ° C or a certain period of time at 40 ° C. And other appearance changes.

In the method of the present invention, (A) at least one selected from the group consisting of ascorbic acid and a salt of ascorbic acid, (B) a diol having 3 carbons, and (C) water, and ethoxy The content of ethylene glycol, the ratio of each component, and the like are the same as those used in the external composition. Furthermore, the composition obtained by this method can be used once or several times a day according to the purpose and the like, and can be used in a known or customary usage and amount.

The second aspect of the present invention is a case where at least one selected from the group consisting of ascorbic acid and a salt of ascorbic acid is 10% by mass to 25% by mass (hereinafter also referred to as the second invention).
The composition for external use of the second invention contains (A) at least one 10% to 25% by mass selected from the group consisting of ascorbic acid and a salt of ascorbic acid, and (B) a diol having 3 carbon atoms in (A) ) And (C) are 30% to 90% by mass and (C) water, and the content of ethoxyethylene glycol is less than 30% by mass, (C) / (A) = 0.2 to 5 , And a composition other than pH 2.0 to 6.0.

The composition for external use of the second invention is (A) at least one selected from the group consisting of ascorbic acid and a salt of ascorbic acid, which is stable in a relatively high concentration region and has excellent transdermal absorbability.

[(A) at least one member selected from the group consisting of ascorbic acid and a salt of ascorbic acid]
In the present invention, ascorbic acid, which is commercially available as an ingredient for skin external use in the field of pharmaceuticals, quasi drugs, or cosmetics, can be used. These generally refer to L-forms.

Salts of ascorbic acid can also be used. Here, the salt of ascorbic acid is the same as the salt of ascorbic acid as defined in the case of the first invention. It is not limited, and examples thereof include salts with organic bases (e.g., trimethylamine salt, triethylamine salt, monoethanolamine salt, triethanolamine salt, pyridine salt, etc.) Basic ammonium salts such as amine acids, etc.), and salts with inorganic bases (for example, alkali metal salts such as ammonium, sodium, and potassium salts, alkaline earth metal salts such as calcium and magnesium salts, and aluminum salts). Particularly preferred salts of ascorbic acid are sodium and potassium salts. Specific examples include sodium ascorbate, sodium ascorbate monophosphate, sodium ascorbate diphosphate, sodium ascorbate triphosphate, and sodium ascorbate-2-sulfate.

In the present invention, ascorbic acid or a salt thereof can be used singly or in combination of two or more kinds.

In the composition for external use of the second invention, the total content of the component (A) relative to the total amount of the composition for external use is appropriately set by balancing with other components. It does not specifically limit if the total content of (A) component is 10 mass%-25 mass% with respect to the total amount of a composition for external use.

[(B) 3 diols]
As the diol having 3 carbon atoms used in the composition for external use in the second invention, as long as it is a diol having 3 carbon atoms which is used as a component of an external preparation for skin in the field of pharmaceuticals, quasi drugs or cosmetics, It is not particularly limited. It is the same as the diol having 3 carbon atoms as defined in the case of the first invention. The diol having 3 carbon atoms is not limited, but is preferably 1,3-propanediol or 1,2-propanediol. For example, any one or both of 1,3-propanediol and 1,2-propanediol may be used as the component (B). Such a diol having 3 carbon atoms can also be used as it is. From the viewpoints of reducing skin irritation, improving the feeling of use, and suppressing coloration, it is preferable to combine 1,3-propanediol and 1,2-propanediol.

In the composition for external use of the second invention, the total content of the component (B) relative to the total amount of the composition for external use is 10% by mass or more, preferably 15% by mass or more, more preferably 20% by mass or more, and more It is preferably at least 25% by mass.
The total content of the (B) component relative to the total amount of the external composition is preferably 90% by mass or less, more preferably 85% by mass or less, still more preferably 80% by mass or less, and still more preferably 70% by mass or less.

The total content of the (B) component relative to the total amount of the composition for external use is preferably 10% to 90% by mass, more preferably 15% to 85% by mass, and still more preferably 20% to 80% by mass, Furthermore, it is more preferably 25% by mass to 70% by mass.

In the composition for external use of the second invention, the ratio of the content of the component (B) to the component (A) is not particularly limited, but is preferably 0.5 parts by mass to 1 part by mass with respect to the total content of the component (A). 10 parts by mass, more preferably 0.75 to 8 parts by mass, and still more preferably 1 to 7 parts by mass.

In the composition for external use of the second invention, the content of the component (B) is preferably 30% to 95% by mass, and more preferably 40% by mass, with respect to the components other than the component (A) and the component (C) described later. It is 90% by mass, more preferably 50% by mass to 85% by mass.

[(C) Water]
The composition for external use of the second invention is a liquid composition containing water. The proportion of water is not limited, and it is preferably 0.01% by mass to 60% by mass, more preferably 1% by mass to 50% by mass, and even more preferably 3% by mass to 40% by mass, and even more preferably 5 mass% to 30 mass%.

In the composition for external use of the second invention, the ratio of the content of the component (C) to the component (A) is not particularly limited, but is preferably 0.2 parts by mass to 1 part by mass with respect to the total content of the component (A). 5 parts by mass, more preferably 0.5 to 2 parts by mass, and still more preferably 0.6 to 1.8 parts by mass.

[Ethoxyethylene glycol (diethylene glycol monoethyl ether)]
In the second invention, from the viewpoint of improving stability, it is considered that it does not contain ethoxyethylene glycol or does not reach 30% by mass even if it is contained. As the ethoxyethylene glycol contained in the composition for external use, up to 30% by mass, as long as it is an ethoxyethylene glycol used as a skin external preparation in the field of pharmaceuticals, quasi drugs or cosmetics, There is no particular limitation.

In the composition for external use of the second invention, the content of ethoxyethylene glycol relative to the total amount of the composition for external use is less than 30% by mass, preferably 20% by mass or less, more preferably 10% by mass or less, and further It is preferably 5 mass% or less, and ethoxyethylene glycol may not be contained in the composition for external use.
The total content of ethoxyethylene glycol is 0 mass% or more and less than 30 mass%, preferably 0 mass% to 20 mass%, more preferably 0 mass% to 10 mass%, and even more preferably 0 mass% It is about 5 mass%.

In the composition for external use of the second invention, the ratio of the content of the ethoxyethylene glycol component to the component (A) is 1 part by mass with respect to the total content of the (A) component, and preferably from 0 parts by mass to 10 parts by mass, more preferably 0 to 5 parts by mass. In addition, depending on the case, it may be 0.001 to 10 parts by mass or 0.01 to 5 parts by mass.

[pH]
The composition for external use of the present invention generally only needs to have a liquidity of pH 1 to 8. From the viewpoints of ascorbic acid stability, low irritation to the skin or mucous membrane, and good skin feel, it is more preferably pH 2 To 7, more preferably pH 2 to 6, even more preferably pH 2 to 5, and even more preferably an acidic region of pH 2 to 4.5.

[Glycol ether]
In the present invention, from the viewpoint of improving stability, it is preferable not to contain glycol ethers other than ethoxyethylene glycol, or to use it in combination with ethoxyethylene glycol even if it contains, and the glycol ether The total amount is less than 40% by mass. Herein, glycol ethers other than ethoxyethylene glycol are not particularly limited as long as they are glycol ethers used as components for external skin agents in the fields of pharmaceuticals, quasi-drugs, and cosmetics. What is necessary is just to dissolve 10 g or more of the glycol ether with respect to 100 g of water. Examples thereof include glycol ethers having a polymerization degree of 2 or less. Specific examples include diethylene glycol monomethyl ether, diethylene glycol monopropyl ether, diethylene glycol monobutyl ether, diethylene glycol monoisobutyl ether, diethylene glycol dimethyl ether, and ethylene glycol. Alcohol monobutyl ether, ethylene glycol monomethyl ether, ethylene glycol monoethyl ether, triethylene glycol monobutyl ether, tetraethylene glycol monobutyl ether, propylene glycol monomethyl ether, propylene glycol monoethyl ether, propylene glycol monopropyl ether, dipropylene glycol Monomethyl ether, dipropylene glycol monoethyl ether, dipropylene glycol monopropyl ether, and the like. Furthermore, diethylene glycol monomethyl ether, diethylene glycol monopropyl ether, diethylene glycol monobutyl ether, diethylene glycol monoisobutyl ether, diethylene glycol dimethyl ether, ethylene glycol monobutyl ether, Ethylene glycol monomethyl ether, ethylene glycol monoethyl ether, triethylene glycol monobutyl ether, tetraethylene glycol monobutyl ether, propylene glycol monomethyl ether, propylene glycol monoethyl ether, propylene glycol monopropyl ether, dipropylene glycol monomethyl ether, two Propylene glycol monoethyl ether and dipropylene glycol monopropyl ether are typical examples. In particular, diethylene glycol monomethyl ether, diethylene glycol monopropyl ether, ethylene glycol monobutyl ether, triethylene glycol monobutyl ether, tetraethylene glycol monobutyl ether, propylene glycol monomethyl ether, and propylene glycol monoethyl ether , Propylene glycol monopropyl ether, dipropylene glycol monomethyl ether, dipropylene glycol monoethyl ether, and dipropylene glycol monopropyl ether are typical examples.

These glycol ethers may be used singly or in combination of two or more kinds.

In the composition for external use of the second invention, the total content of glycol ether including ethoxyethylene glycol is preferably less than 40% by mass, and more preferably 30% by mass relative to the total amount of the composition for external use. Hereinafter, it is more preferably less than 10% by mass, more preferably 10% by mass or less, and the glycol ether may not be contained in the composition for external use.

The total content of the glycol ether including ethoxyethylene glycol is preferably 0% by mass or more and less than 40% by mass, more preferably 0% by mass or more and less than 30% by mass, and still more preferably 0% by mass. % Or more and about 10% by mass.

In the composition for external use of the second invention, the ratio of the content of the glycol ether component to the component (A) is 1 part by mass, and preferably 0 to 20 parts by mass relative to the total content of the (A) component. , More preferably 0 to 10 parts by mass. In addition, depending on the case, it may be 0.001 to 20 parts by mass or 0.01 to 10 parts by mass.

The composition for external use according to the second invention contains a predetermined amount of (A) component, (B) component, and (C) component, and the overall content of the glycol ether is regulated, and the pH is preferably 1.5 to 4.5 or less. The pH is 2 to 4.5 or less, and a composition for external use with better stability can also be prepared.

[Lower alcohol]
In the composition for external use according to the second invention, from the viewpoints of improvement in feeling of use, stability, and promotion of percutaneous absorption, as long as the effects of the present invention are not hindered, the components (A), (B), and (C) In addition to the component, and glycol ethers such as ethoxyethylene glycol optionally contained, a lower alcohol may be contained. The lower alcohol used in the present invention is not particularly limited as long as it is a lower alcohol used as a component for external skin preparations in the fields of pharmaceuticals, quasi-drugs, or cosmetics. In this specification, when referred to as "lower alcohol" refers to C ₁ -C ₆ alcohols of. Among them, C ₁ -C ₃ alcohols can be particularly preferably used. As such an example, in addition to ethanol, methanol, n-propanol, isopropanol, and the like can be mentioned.

In the composition for external use of the second invention, the content of the lower alcohol relative to the total amount of the composition for external use, when contained, is preferably 0.01% by mass or more, more preferably 0.1% by mass or more, and even more preferably It is 0.25 mass% or more, more preferably 1 mass% or more, and most preferably 3 mass% or more. The content of ethanol is preferably 45% by mass or less, more preferably 40% by mass or less, still more preferably 35% by mass or less, and still more preferably 20% by mass or less.

The content of the lower alcohol contained in the composition for external use of the second invention is preferably 0.01% to 45% by mass, more preferably 0.1% to 40% by mass, still more preferably 0.25% to 35% by mass, and furthermore It is more preferably 1 to 20% by mass, and most preferably 3 to 20% by mass.

[Butanediol]
In the composition for external use of the present invention, from the viewpoints of improvement in use feeling, stability, and promotion of percutaneous absorption, as long as the effects of the present invention are not hindered, the components (A), (B), and ( C) In addition to components and glycol ethers such as ethoxyethylene glycol when contained, butanediol (1,3-butanediol) may be contained.

In the composition for external use of the second invention, the content of butanediol relative to the total amount of the composition for external use, when contained, is preferably 0.01% by mass or more, more preferably 0.1% by mass or more, and more preferably It is preferably at least 0.25% by mass. The content of butanediol is preferably 40% by mass or less, more preferably 35% by mass or less, and further preferably 30% by mass or less.

The content of butanediol in the composition for external use of the second invention is preferably 0.01% by mass to 40% by mass, more preferably 0.1% by mass to 35% by mass, and still more preferably 0.25% by mass to 30% by mass.

[pH adjuster]
In the composition for external use according to the second invention, from the viewpoints of improvement in usability, stability, and promotion of percutaneous absorption, as long as the effects of the second invention are not hindered, the components (A), (B), and In addition to (C) component, and glycol ethers, such as ethoxyethylene glycol, which may be contained, it may contain a pH adjuster.

As the pH adjusting agent used in the second invention, it can be used as a compound that is generally used as a component of external skin preparations in the fields of pharmaceuticals, quasi-drugs, and cosmetics. It is not particularly limited, and examples thereof include a pH adjusting agent having an amine (for example, aspartic acid or a salt thereof, ε-aminohexanoic acid or a salt thereof, glutamic acid or a salt thereof, and aminoethylsulfonic acid) Acid or its salt, monoethanolamine, triethanolamine, diisopropanolamine, triisopropanolamine, spermine, lysine, L-carnitine, low molecular betaine, preferably low molecular betaine, More preferred is trimethylglycine), organic acid salts (e.g. sodium lactate, sodium acetate, sodium citrate, sodium succinate, sodium oxalate, calcium gluconate, sodium pyrrolidone carboxylate, etc.), inorganic acid salts (e.g. For example, sodium metabisulfite, potassium metabisulfite, sodium phosphate, potassium nitrate, sodium borate, preferably sodium metabisulfite), basic amino acids and their salts (arginine, lysine, or histidine and the like) Salt), 3-O-ethyl ascorbic acid, or a salt thereof.

In the composition for external use of the second invention, the total content of the pH adjuster is not particularly limited with respect to the total amount of the composition for external use, but is preferably 0.01% by mass or more, and more preferably 0.05% by mass or more. The total content of the pH adjusting agent is preferably 20% by mass or less, and more preferably 10% by mass or less with respect to the total amount of the composition for external use. The content of the pH adjusting agent having an amine or an amine group is preferably 0.01% by mass to 20% by mass, and more preferably 0.05% by mass to 10% by mass with respect to the total amount of the composition for external use.

In the composition for external use of the second invention, the ratio of the content of the pH adjuster to the component (A) is not particularly limited, but is preferably 0.00001 to 20 parts by mass relative to the total content of the (A) component. It is more preferably 0.0001 to 20 parts by mass, more preferably 0.0005 to 10 parts by mass, still more preferably 0.005 to 5 parts by mass, and most preferably 0.01 to 1 part by mass.

[Other ingredients]
In the composition for use other than the second invention, in addition to the components (A), (B), and (C), and optionally less than a certain amount of ethoxyethylene glycol, the composition is further enhanced or For the purpose of supplementing various effects of ascorbic acid, and in order to add other useful effects, whitening ingredients, anti-inflammatory ingredients, antibacterial ingredients, cell activating ingredients, astringent ingredients, antioxidant ingredients, acne improving ingredients, anti-aging ingredients, Various components such as collagen-promoting components such as collagen, blood circulation-promoting components, moisturizing components, and anti-aging components are prepared individually or in combination of two or more. One or two or more components of a whitening component, an anti-inflammatory component, an antibacterial component, a cell activating component, an astringent component, an antioxidant component, an anti-aging component, or a moisturizing component are preferred. Particularly preferred combinations of these ingredients include a combination with a whitening ingredient, a combination with a whitening ingredient and an antioxidant ingredient, a combination with an antioxidant ingredient, a combination with an antiaging ingredient, and a whitening ingredient and an antiaging ingredient. Of each combination. Each of these components is not particularly limited as long as it is a component that has been previously used as a component for external skin preparations in the pharmaceutical, quasi-drug, or cosmetic fields, and any component can be appropriately selected and used.

In the composition for external use of the present invention, in addition to the above components, a surfactant, a solubilizing component, a fat, a sugar, or a transdermal absorption-promoting component may be further formulated. In particular, the stability, effectiveness, and usability of ascorbic acid in an aqueous solvent can be further improved by blending a surfactant, a solubilizing component, or oils and fats.

In the composition for external use of the present invention, it can be formulated into pharmaceuticals, quasi-drugs, or cosmetics, if necessary, in a range that does not impair the appearance stability or viscosity, and the amount and quality of the effects of the present invention. Various components of the ingredients for external use, such as amino acids, irritation reducing agents, tackifiers, preservatives, UV protection agents, colorants, dispersants, additional pH adjusters, perfumes, etc. Moreover, these components can be mix | blended individually by 1 type, or 2 or more types can be mix | blended arbitrarily.

The composition for external use of the second invention contains (A) at least one 10% to 25% by mass selected from the group consisting of ascorbic acid and a salt of ascorbic acid, and (B) a diol having 3 carbon atoms in ( Among components other than A) and (C), it is 30% to 90% by mass, and (C) water, and the content of ethoxyethylene glycol is less than 30% by mass, (C) / (A) = 0.2 to 5, and the pH is 2.0 to 6.0, if necessary, mix and mix each of the above components, and then if necessary, other solvents or bases for external use, etc., can be prepared into a paste, mousse, gel, liquid It can be in various desirable forms such as a state, an emulsion state, a cream state, a sheet state (supporting a substrate), an aerosol state, and a spray state. These can be manufactured by a common method in the industry.

The composition for external use of the present invention is particularly preferably a transparent or translucent composition obtained by dissolving ascorbic acid and / or a salt thereof. Here, "solubilization" is defined as follows. That is, for example, by the ultraviolet-visible absorbance measurement method, using a spectrophotometer or a photoelectric photometer UV-2450 (manufactured by Shimadzu Corporation), the transmittance at a wavelength of 700 nm is 80% to 100%, It is preferably in the range of 85% to 100%, more preferably 90% to 100%. Here, the water transmittance is set to 100%. The solubilized composition of the present invention has a transparent or translucent appearance. More specifically, the transmission measurement method is based on the 16th revised Japanese Pharmacopoeia [B] General Test Method 2. Physical Test Method Optical Measurement Method 2.24 The method described in the UV-Visible Absorptiometry.

[Viscosity]
The composition for external use of the present invention can be prepared into a composition having a moderate viscosity, which is particularly expected when used for application to a composition for external use on skin. The viscosity of the composition for external use of the present invention is not particularly limited. For example, the viscosity when measured at 25 ° C using an E-type viscometer is usually about 1 mPa · s to 300 mPa · s, preferably about 1 mPa · s to 200 mPa · s. , More preferably about 1 mPa · s to 100 mPa · s, and most preferably about 1 mPa · s to 50 mPa · s. More specifically, the viscosity measurement method is based on the 16th revised Japanese Pharmacopoeia [B] General test method 2. Physical test method Other physical test methods 2.53 Viscosity measurement method 2. Second method Rotary viscometer method 2.1.3 Conical-plate type Rotary viscometer (cone plate viscometer).

[use]
The composition for external use of the present invention is particularly effective as a whitening agent, an anti-inflammatory agent, and an anti-aging agent, for example, it has the effects of preventing or treating acne and antioxidation. Furthermore, when applied to the skin, the effects of improving the transparency of the skin, keeping moist, adjusting the texture, and suppressing the roughness may be exerted. Furthermore, there are cases in which the effect of moisturizing the entire muscle that makes pores inconspicuous is exerted, and it can also be used for the prevention or treatment of spots.

The composition for external use of the present invention can be made into a basic cosmetic such as a cosmetic liquid, lotion, sun cream, lotion, cream, lotion, oil, and dressing; powder, lipstick, lipstick, mascara, eye shadow, eyeliner , Eyebrow pencils, manicures, and other cosmetic materials; washing materials such as fabrics or facial cleansers, body cleansing materials; anti-underarm odorants, Hong Kong foot treatments, itching agents, wound healing agents, wipes, cleaning agents, Anti-inflammatory analgesics, acne treatments, hemorrhoids, bactericidal disinfectants, whitening agents, anti-ultraviolet agents, etc. are various external composition in the field of cosmetics, external medicines or quasi-drugs for external use. As far as the effect on the skin is concerned, the present invention is preferably a product applied to the outer skin, such as a skin external preparation (a preparation for the outer skin).

[Stabilization method]
The present invention also includes (A) at least one stabilization method selected from the group consisting of ascorbic acid and a salt of ascorbic acid. In the present invention, according to a method for stabilizing ascorbic acid, by containing (A) at least one kind selected from the group consisting of ascorbic acid and a salt of ascorbic acid, 10% to 25% by mass, and (B) three carbons The diol is 30% to 90% by mass in components other than (A) and (C), and (C) water, and the content of ethoxyethylene glycol is less than 30% by mass, (C) / ( A) = 0.2 to 5, and a pH of 2.0 to 6.0 can be used to prepare a stable formulation containing ascorbic acid. That is, the present invention relates to a diol containing (A) at least one 10% to 25% by mass selected from the group consisting of ascorbic acid and a salt of ascorbic acid, and (B) a diol having 3 carbon atoms. (A) and (C) components are 30% to 90% by mass, and (C) water, and the content of ethoxyethylene glycol is less than 30% by mass, (C) / (A) = 0.2 To 5, and a pH of 2.0 to 6.0, and a method for imparting stability to a composition for external use containing (A) at least one selected from the group consisting of ascorbic acid and a salt of ascorbic acid. Here, the term "stabilization" is not limited, and means, for example, that stability is ensured even at high or low temperatures. Specifically, it means that ascorbic acid or a salt thereof can be inhibited at least when the composition for external use is stored at 4 ° C for one week, or the coloration is also inhibited after storage at 50 ° C or a certain period of time at 40 ° C. And other appearance changes.

In the method of the present invention, (A) at least one selected from the group consisting of ascorbic acid and a salt of ascorbic acid, (B) a diol having 3 carbons, and (C) water, and ethoxy The content of ethylene glycol, the ratio of each component, and the like are the same as those used in the external composition. Furthermore, the composition obtained by this method can be used once or several times a day according to the purpose and the like, and can be used in a known or customary usage and amount.
[Example]

Next, the present invention will be specifically described by examples, but the present invention is not limited to the following examples. The unit of the amount of each component in the table is mass%.

The external composition having the composition shown in Tables 1 to 6 was prepared according to a conventional method. These compositions were then tested for each test item.

[Confirmation test for inhibition of ascorbic acid staining]
The visual inspection and the color difference meter were used to evaluate whether or not the external-use compositions of some examples and comparative examples of the present invention were inhibited in coloration after being stored at 40 ° C or 50 ° C. Specifically, ascorbic acid was added to a mixed solution of various ingredients according to the formula (mass%) described in various formula tables, and the mixture was heated at 60 ° C. and mixed for 10 minutes to dissolve the composition, thereby preparing a composition. The prepared composition was filled into a transparent glass bottle, and left to stand for 1 week (indicated as 1W) or 4 weeks (indicated as 4W) in each constant temperature and humidity machine at 40 ° C or 50 ° C. The container was taken out of the thermostat during each measurement period, and the temperature was evaluated at 25 ° C. The presence or degree of coloring of each test solution was determined by visual observation and measurement by a colorimeter.

The measurement with a color difference meter was performed by adding 1 mL of a test solution to a glass tank (CM-A97, thickness 2 mm), and measuring the b value of the color difference with a spectrophotometer CM-5 (manufactured by Konica Minolta Co., Ltd.). The measurement value was Δb * when purified water was used as a blank sample. The change in color difference is calculated by the following calculation formula.
(Amount of change in color difference (Δb value)) = (Measured value of test solution after holding (b value after accelerated test))-(Measured value of test solution before holding (b value before accelerated test))
The b value is used as an index indicating the sense of transparency. Therefore, the smaller the Δb value, the less the coloration. In addition, if the ratio of Δb between the two is 1.4 or less, the difference in coloring is not clearly felt. On the other hand, if it exceeds 1.4, the difference in coloring can be visually recognized, and it can be seen that a defect may occur in quality. Therefore, the presence or absence of coloring is judged based on whether or not the ratio when the value of Δb of the sample in which no change in coloring is seen at all is set to 1.4 or less.

[Confirmation test for inhibition of ascorbic acid precipitation]
The external composition of some examples and comparative examples of the present invention was visually evaluated for the presence or absence of ascorbic acid when the preparation was stored at a low temperature. Specifically, ascorbic acid was added to a mixed solution of various ingredients according to the formula (mass%) described in various formula tables, and the mixture was heated at 60 ° C. and mixed for 10 minutes to dissolve the composition, thereby preparing a composition. The prepared composition was filled in a transparent glass bottle, and left to stand at 4 ° C. under light-shielding conditions, and stored for 1 week or 4 weeks, and each test solution was visually inspected to determine whether crystals were precipitated.

> Evaluation Criteria>
(Circle): The state of the precipitate cannot be confirmed visually.
×: The state of the precipitate can be confirmed visually.

[Percutaneous absorption test of ascorbic acid]
The transdermal absorptivity of the external-use compositions of some examples and comparative examples of the present invention was verified. As the transdermal absorption is improved, ascorbic acid penetrates into the skin, and as a composition, a higher anti-aging effect can be expected. That is, depending on the circumstances, the effect of ascorbic acid can be reached to the depth of the stratum corneum.

The percutaneous absorption of the ascorbic acid with respect to the composition for external use prepared in the Example and the comparative example was measured by the measurement by the evaluation using the peeling of a stratum corneum.

Specifically, first, the amount of ascorbic acid in the stratum corneum of components that penetrated into the skin of the upper arm and forearm of a healthy person was confirmed by peeling off the tape. Two healthy male subjects who voluntarily agreed to participate in the trial were set as subjects. 750 μL of cotton impregnated with the external use composition of the embodiment or the comparative example was stuck to the inner side of the upper arm of the subject at 1.5 cm × 1.5 cm, and left to stand for 5 minutes. After the cotton is removed, the sample remaining on the skin surface is removed with fresh cotton and left for 30 minutes. Let this time be the penetration time of a sample. Then, using adhesive tape (manufactured by Sumitomo 3M Co., Ltd.), 7 consecutive strips of tape were peeled from the application site to remove keratinocytes, and the entire layer of the obtained tape was used as a measurement specimen. The number of times the tape is peeled off is determined by a preliminary test to confirm that a necessary amount of keratinocytes are peeled off each time the tape is peeled off, and no inflammation or pain is generated after the tape is peeled off.

The obtained measurement sample was extracted with 1 mL of an extraction solvent of a mixed solution (1: 1: 1000) of Tritonx-100 (manufactured by MP Biomedicals), mercaptoethanol (manufactured by Wako Pure Chemical Industries, Ltd.), and purified water. The amount of ascorbic acid permeation (μg / cm ² ) was measured using an HPLC (High Performance Liquid Chromatography) method with an extraction solution from which foreign matter was removed by a 0.45 μm syringe filter (manufactured by GL Sciences). Attached to an HPLC (mobile phase: acetonitrile / 0.02M phosphoric acid solution (pH3.0) (1: 9), absorbance detection wavelength: 270nm) manufactured by Agilent with a reverse column (CAPCELL PAK C18 SG120, manufactured by Shiseido) ) To measure the amount of L-ascorbic acid contained in the solution. The results were compared using the value obtained by averaging the measured values of the measurement specimens taken from each of the three parts of the two arms of the subject as the amount of penetration (μg / cm ² ).

In addition, the detection of ascorbic acid by HPLC was performed using a UV absorbance photometer at a wavelength of 270 nm using a reverse column (CAPCELL PAK C18 SG120, manufactured by Shiseido Co., Ltd.), and the content was calculated according to the calibration curve.

(Example 1-1 to Example 1-6, Comparative Example 1-1 to Comparative Example 1-3)
The compositions for external use of Examples and Comparative Examples having the compositions shown in Table 1 were prepared according to a conventional method. In the evaluation items, the ratio of Δb is the ratio of the value of the comparison based on the color difference value of the composition for external use in Example 1-1 as the reference (1). That is, the ratio of stability indicates the ratio of Δb.

The results of the ascorbic acid coloration suppression confirmation tests of the compositions of the examples and comparative examples are shown in Tables 1 and 2.

[Table 1]

[Table 2]

The composition of the example has a color-suppressing effect even when stored in a high temperature state, and exhibits excellent stability for a long period of time. On the other hand, the composition of the comparative example showed coloration under test storage conditions.

(Example 2-1 to Example 2-2, Comparative Example 2-1)
The compositions for external use of Examples and Comparative Examples having the composition shown in Table 3 were prepared according to a conventional method. In the evaluation items, the ratio of Δb is the ratio of the value of the comparison based on the color difference value of the composition for external use in Example 2-1 as a reference (1). That is, the stability ratio indicates a ratio when the value of Δb in Example 2-1 is set to 1.

Table 3 shows the results of the ascorbic acid coloration suppression confirmation test and the results of the ascorbic acid precipitation suppression confirmation test of the compositions of the examples and comparative examples.

[table 3]

That is, it can be seen that the composition shown in the examples achieves both properties of suppressing the precipitation of ascorbic acid and suppressing the coloration of the composition.

(Example 3-1 to Example 3-3, Comparative Example 3-1 to Comparative Example 3-2)
The compositions for external use of Examples and Comparative Examples having the compositions shown in Table 4 were prepared according to a conventional method.

The results of the ascorbic acid coloration suppression confirmation test and the results of the ascorbic acid precipitation suppression confirmation test of the compositions of the examples and comparative examples are shown in Table 4.

[Table 4]

(Example 4-1 to Example 4-3, Comparative Example 4-1 to Comparative Example 4-2)
The compositions for external use of Examples and Comparative Examples having the compositions shown in Table 5 were prepared according to a conventional method.

The results of the ascorbic acid coloration suppression confirmation test and the results of the ascorbic acid precipitation suppression confirmation test of the compositions of the examples and comparative examples are shown in Table 4. In the evaluation items, the ratio of Δb is the ratio of the value of the comparison based on the color difference value of the composition for external use in Example 4-1 as the reference (1). That is, the stability ratio indicates a ratio when the value of Δb in Example 4-1 is set to 1.

[table 5]

It can be seen that the composition shown in the examples achieves both properties of suppressing the precipitation of ascorbic acid at a low temperature and suppressing the coloration of the composition. For example, when the ethoxyethylene glycol has a high concentration of 40% by mass or more, it can be seen that precipitation occurs particularly at low temperatures when the pH is low. It can be seen that in a formulation with a slightly higher pH, no precipitation at low temperature is observed even with a high concentration of ethoxyethylene glycol, but if it is 30% by mass or more, the degree of coloring is significantly high. Therefore, it is preferable to set it to less than 30 mass% even if ethoxyethylene glycol is mix | blended.

Furthermore, the results of the ascorbic acid coloration suppression confirmation test, the ascorbic acid precipitation suppression confirmation test, and the percutaneous absorption test of the compositions of the other examples and comparative examples are shown in Table 6. In the evaluation items, the ratio of Δb is the ratio of the value of the comparison based on the color difference value of the composition for external use in Example 5-1 as the reference (1). That is, the stability ratio indicates a ratio when the value of Δb in Example 5-1 is set to 1.

[TABLE 6]

It can be seen that the compositions of the examples have a balance between the properties of the compositions of the comparative examples, which can suppress the precipitation of ascorbic acid even under low-temperature storage, and further suppress the coloration of the composition due to storage. Furthermore, it turns out that the composition of this invention is also excellent in percutaneous absorption.

The results of the transdermal absorption of the compositions of Examples 5-1 to 5-2 and Comparative Examples 5-1 to 5-2 are shown in FIG. 1.

Next, a composition for external use having the composition shown in Tables 7 to 9 was prepared according to a conventional method. These compositions were then tested for each test item.

[Confirmation test for inhibition of ascorbic acid staining]
The presence or absence of coloration inhibition of the composition for external use having the composition shown in Tables 7 to 9 after storage at 40 ° C or 50 ° C was evaluated visually and with a color difference meter. Specifically, the confirmation test was performed by a method exactly the same as that performed in Examples 1 to 5, and Comparative Examples 1 to 5.

[Confirmation test for inhibition of ascorbic acid precipitation]
The external composition having the composition shown in Tables 7 to 9 was visually evaluated for the presence or absence of ascorbic acid when the preparation was stored at a low temperature. Specifically, the confirmation test was performed by a method exactly the same as that performed in Examples 1 to 5, and Comparative Examples 1 to 5.

[Percutaneous absorption test of ascorbic acid]
The transdermal absorptivity of the external-use compositions of some examples and comparative examples of the second invention was verified. As the transdermal absorption is improved, ascorbic acid penetrates into the skin, and as a composition, a higher anti-aging effect can be expected. That is, depending on the circumstances, the effect of ascorbic acid can be reached to the depth of the stratum corneum.

The percutaneous absorption of the ascorbic acid with respect to the composition for external use prepared in the Example and the comparative example was measured by the measurement by the evaluation using the peeling of a stratum corneum. Specifically, the confirmation test was performed by a method exactly the same as that performed in Examples 1 to 5, and Comparative Examples 1 to 5.

(Example 6-1 to Example 8-1, Comparative Example 6-2 to Comparative Example 8-3)
The compositions for external use of Examples and Comparative Examples having the compositions shown in Table 7 were prepared according to a conventional method. In the evaluation items in this table, the ratio of Δb is the ratio of the value of the comparison based on the color difference value of the composition for external use in Example 1 as the reference (1). That is, the ratio of stability indicates the ratio of Δb. In addition, the ratios listed in the results of the transdermal absorption test of the external composition of the examples and comparative examples are those of Comparative Example 5-1 (formulation 40) to be formulated based on 1,3-butanediol. The transdermal absorption amount is set to 1 and is a value determined from the ratio.
Ratio = (percutaneous absorption amount of any of the examples and comparative examples (μg / cm ² ) / (percutaneous absorption amount of the composition of comparative example 5-1 (μg / cm ² )

The test results of the compositions of the examples and comparative examples are shown in Tables 7 to 9 together.

[TABLE 7]

[TABLE 8]

[TABLE 9]

The composition of the example has a color-suppressing effect even when stored in a high temperature state, and exhibits excellent stability for a long period of time. On the other hand, the composition of the comparative example showed coloration under test storage conditions. In addition, in the composition of the example, the precipitation at a low temperature was suppressed compared with the composition of the comparative example.

[Formula example]
Formulation examples are shown in Tables 10 to 12 below. The formulation examples can be preferably used for lotions, beauty liquids, and the like. The contents in the formulation examples are all mass%.

[TABLE 10]

[TABLE 11]

[TABLE 12]

no.

FIG. 1 is a graph showing the results of a transdermal absorption test of the external composition of Examples and Comparative Examples.

Claims (15)

A composition for external use, containing: (A) 10% by mass or less of at least one selected from the group consisting of ascorbic acid and a salt of ascorbic acid; (B) 30% by mass or more of a diol having 3 carbons; and (C) Less than 20% by mass of water; The content of ethoxyethylene glycol is less than 30% by mass, and the pH is 4.5 or less. The composition for external use according to claim 1, wherein the content of the component (B) is 40% by mass or more. The composition for external use according to claim 1 or 2, wherein the content of the ascorbic acid or a salt thereof is 3% by mass to 10% by mass. The composition for external use as described in claim 1 or 2, wherein the content of (C) water is 10% by mass or less. A composition for external use, containing: (A) 10% to 25% by weight of at least one selected from the group consisting of ascorbic acid and a salt of ascorbic acid; (B) a diol having 3 carbon atoms is 30% to 90% by mass in components other than (A) and (C); and (C) water; The content of ethoxyethylene glycol is less than 30% by mass, (C) / (A) = 0.2 to 5, and pH is 2.0 to 6.0. The composition for external use according to 2 or 5, further comprising butanediol and / or a lower alcohol. The composition for external use according to 2 or 5, wherein the component (B) is 1,3-propanediol and / or 1,2-propanediol. The composition for external use according to 2 or 5, wherein the component (B) contains at least 1,3-propanediol. The composition for external use according to 2 or 5, wherein the content of ethoxyethylene glycol is 10% by mass or less. The external-use composition according to 2 or 5, wherein the external-use composition is a solubilizing external-use composition having a transmittance of 85% to 100% at a wavelength of 700 nm. The composition for external use according to 2 or 5, wherein the composition for external use is for promoting percutaneous absorption of ascorbic acid. A method for preventing the coloring of a composition for external use by using (A) at least one selected from the group consisting of ascorbic acid and a salt of ascorbic acid in an amount of 10% by mass or less, and (B) the carbon number of 3 30% by mass of diols and 20% by mass of (C) water, and the content of ethoxyethylene glycol is set to less than 30% by mass, and the pH is set to 4.5 or less to prevent (A ) Coloring of at least one composition for external use selected from the group consisting of ascorbic acid and a salt of ascorbic acid. A method for preventing the precipitation of crystals of a composition for external use, in which (A) at least one kind selected from the group consisting of ascorbic acid and a salt of ascorbic acid is used in the composition for external use in combination with at least 10% by mass and (B) carbon 30% by mass of diols and 20% by mass of (C) water, and the content of ethoxyethylene glycol is set to less than 30% by mass, and the pH is set to 4.5 or less to prevent the (A) Precipitation of crystals of at least one external-use composition selected from the group consisting of ascorbic acid and a salt of ascorbic acid. A method for preventing the coloring of a composition for external use is because the composition for external use contains (A) at least one selected from the group consisting of ascorbic acid and a salt of ascorbic acid at 10% to 25% by mass, (B) The diol having 3 carbon atoms is 30% to 90% by mass in components other than (A) and (C), and (C) water, and the content of ethoxyethylene glycol is less than 30% by mass, and (C) / (A) = 0.2 to 5.0, and the pH is set to 2.0 to 6.0 to prevent the coloring of (A) at least one external-use composition selected from the group consisting of ascorbic acid and a salt of ascorbic acid. A method for preventing the precipitation of crystals of a composition for external use, because the composition for external use contains (A) at least one selected from the group consisting of ascorbic acid and a salt of ascorbic acid at 10% to 25% by mass, ( B) The diol having 3 carbon atoms is 30% to 90% by mass in components other than (A) and (C), and (C) water, and the content of ethoxyethylene glycol is less than 30% by mass And (C) / (A) = 0.2 to 5.0, and the pH is set to 2.0 to 6.0 to prevent (A) at least one external-use composition selected from the group consisting of ascorbic acid and a salt of ascorbic acid. Precipitation of crystals.