JP2001151660A - Skin preparation for external use - Google Patents

Abstract

PROBLEM TO BE SOLVED: To obtain a skin preparation for external use capable of stably formulating an acylated derivative of glycosyl-L-ascorbic acid being a bleaching ingredient into a system and preventing change in color against light rays and change of smell. SOLUTION: This skin preparation for external use is obtained by formulating the acylated derivative of glycosyl-L-ascorbic acid with an ultraviolet light absorber. The preparation is further formulated with (A) a sequestering agent, (2) a divalent and/or trivalent metal salt and (3) one of sulfurous acid, a sulfite, a hydrogensulfite, thiosulfuric acid, a thiosulfate, pyrosulfurous acid and a pyrosulfite.

Description

DETAILED DESCRIPTION OF THE INVENTION

[0001]

TECHNICAL FIELD The present invention relates to an external preparation for skin containing an acylated derivative of glycosyl-L-ascorbic acid, and more particularly, it can stably incorporate an acylated derivative of glycosyl-L-ascorbic acid. And an external preparation for skin that does not easily discolor to light.

[0002]

2. Description of the Related Art In recent years, as a stable and oil-soluble ascorbic acid derivative, glycosyl-L-, which is a substance in which a sugar and a fatty acid are coordinated at the 2- and 6-positions of ascorbic acid, respectively.
Acylated derivatives of ascorbic acid have been reported (Abstracts of the 118th Annual Meeting of the Pharmaceutical Society of Japan, 3, 77, 1998)
Issued March 5, 2009). The acylated derivative of glycosyl-L-ascorbic acid generates L-ascorbic acid by dissociating the fatty acid portion and the sugar portion by the esterase activity and glucosidase activity in the epidermis and dermis. L-ascorbic acid generally suppresses melanin production by reducing dopaquinone or dopachrome, which is a metabolic intermediate in the melanin production process, to dopa, and also converts the produced deep-color oxidized melanin into light-color reduced melanin. It is a compound that has a reversing action and is effective in treating and improving skin whitening, spots, freckles, melasma, plaques, and the like. Comparison of the acylated derivative of glycosyl-L-ascorbic acid with L-ascorbic acid shows that glycosyl-L
-The acylated derivative of ascorbic acid has no reducing group in the molecule, so it is stable against heat, light, oxygen, and metal ions. It is excellent in that the property is improved. In addition, as compared with conventionally used ascorbic acid and its derivatives, changes in color and odor with time and light are small.

[0003]

However, the above-mentioned whitening agent is not completely stable, and when it is added to an external preparation for skin, it is decomposed with time or by light, and is liable to cause coloring and odor. For this reason, it has been proposed to add an antioxidant or a reducing agent to the external preparation for skin, but none of them have been sufficiently satisfactory in terms of stability.

The present invention has been made to solve such a conventional problem, and an object of the present invention is to provide an external preparation for skin which contains an acylated derivative of glycosyl-L-ascorbic acid in a stable manner.

[0005]

The present inventors have conducted intensive studies to solve the above-mentioned problems, and as a result, the combined use of an acylated glycosyl-L-ascorbic acid derivative and an ultraviolet absorber has led to the use of the whitening agent. It has been found that decomposition by light can be suppressed and discoloration and odor of the external preparation for skin can be reduced, and the present invention has been completed.

[0006] That is, the present invention is an external preparation for skin characterized by comprising an acylated derivative of glycosyl-L-ascorbic acid and an ultraviolet absorber.

Hereinafter, the configuration of the present invention will be described in detail. Glycosyl-L-ascorbic acid as referred to in the present invention is all glycosyl-L whose oil solubility is improved by acylation.
-Ascorbic acid. Desirable glycosyl-L
As ascorbic acid, one or more glucosyl residues or galactosyl residues are bonded to the 2-position in L-ascorbic acid, for example, 2-O-α-D-
A series of 2-glucopyranosyl-L-ascorbic acids, including monoglucopyranosyl-L-ascorbic acid, and 2-O-β-D-monogalactopyranosyl-L
-A series of 2-galactopyranosyl-L-ascorbic acids, including ascorbic acid.

[0008] The term "acylation" as used in the present invention means the introduction of an acyl group RCO- into such glycosyl-L-ascorbic acid. Here, R represents a linear or branched saturated or unsaturated alkyl group having an integer of 2 to 19, preferably 4 to 17 carbon atoms. Therefore, the acylated derivative referred to in the present invention means one or more hydroxyl groups in glycosyl-L-ascorbic acid as described above, and preferably one or more hydroxyl groups in L-ascorbic acid residue in glycosyl-L-ascorbic acid. This means any compound in which an acyl group is bonded to a hydroxyl group, but is particularly preferably a monoacylated derivative.

[0009] Such acylated derivatives can be prepared by various methods. For example, a desired acylated derivative can be obtained by reacting glycosyl-L-ascorbic acid with an appropriate acylating agent. At this time, if necessary
A catalyst may coexist in the reaction system, and the catalyst may be an enzyme such as lipase. Glycosyl as raw material
L-ascorbic acid is described in, for example, Japanese Patent Application Laid-Open No. 3-13928.
No. 8, JP-A-3-135592 and JP-A-3-15992.
As described in JP-183492, an α-glucosyl compound such as cyclomaltodextrin or a starch hydrolyzate is reacted with L-ascorbic acid in the presence of a glycosyltransferase such as cyclomaltodextrin / glucanotransferase. Or JP-A-6-228
183 and JP-A-6-263790, by reacting a β-galactosyl compound such as lactose with 5,6-isopropylidene-L-ascorbic acid in the presence of β-galactosidase. Obtainable. Incidentally, commercially available 2-glucopyranosyl-L-ascorbic acid includes, for example, "AA-2G" (2-O-α-D per solid weight).
-Monoglucopyranosyl-L-ascorbic acid content 98
% Or more, sold by Hayashibara Shoji Co., Ltd.). In the present invention, depending on the use, glycosyl-L
-Ascorbic acid does not necessarily have to be highly purified, and may not be associated with other components that do not interfere with substantial acylation, even in analogs that are unique to the preparation method and in unseparated compositions from other components. It may be a mixture.

In the case of a chemical reaction, a general method for acylating a compound having a hydroxyl group may be applied. Examples of the individual method include an acid or an acid halide, an acid anhydride or an acid ester. And the like. As the acylating agent,
Usually, the carbon number is an integer selected from 3 to 20, preferably 4 to 18, for example, propionic acid, butyric acid,
Isobutyric acid, n-valeric acid, isovaleric acid, trimethylacetic acid, caproic acid, n-heptanoic acid, caprylic acid, pelargonic acid, capric acid, lauric acid, myristic acid, palmitic acid, palmitoleic acid, stearic acid, oleic acid, Carboxyls containing lower fatty acids and higher fatty acids such as ricinoleic acid, arachidic acid, petroselinic acid, vaccenic acid, linoleic acid, linolenic acid, eleostearic acid, ricanoic acid, parinaric acid, talilic acid, cadrainic acid and arachidonic acid as the basic skeleton. Acids and carboxylic acid halides, carboxylic anhydrides and carboxylic esters are used.

The reaction is usually carried out in a non-aqueous system in which the intrusion of water into the reaction system is blocked. For example, in an organic solvent such as pyridine, dimethylsulfoxide and dimethylformamide, if necessary, p-toluenesulfonic acid or the like can be used. The reaction of glycosyl-L-ascorbic acid with carboxylic acid anhydride in the presence of the above catalyst, or the reaction of glycosyl-L-ascorbic acid with carboxylic acid itself in the presence of a catalyst such as concentrated sulfuric acid. As the reaction conditions, a reaction generally used for acylation of L-ascorbic acid can be applied as it is, but the acylating agent is not more than 3 mol, preferably not more than 2 mol per mol of glycosyl-L-ascorbic acid. The reaction proceeds almost specifically,
An acyl group can be introduced at a specific site of an L-ascorbic acid residue in glycosyl-L-ascorbic acid. For example, in the case of 2-O-α-D-monoglucopyranosyl-L-ascorbic acid, when an acylating agent of 2 mol or less is reacted, the position at the 6-position in the L-ascorbic acid residue is substantially increased. Only the hydroxyl group of can be acylated. Also, after acylating only the hydroxyl group at the 6-position in L-ascorbic acid by a known method, an appropriate mixture of an organic solvent or an organic solvent and water is added.
For example, when an acylated L-ascorbic acid is reacted with an α-glucosyl compound such as cyclomaltodextrin or partially hydrolyzed starch in the presence of a glycosyltransferase such as cyclomaltodextrin glucanotransferase, A monoacylated derivative of 2-glucopyranosyl-L-ascorbic acid in which only the hydroxyl group at position 6 in the ascorbic acid residue is acylated can be obtained.

In the case of enzymatic reaction, glycosyl-L
-Ascorbic acid and an acylating agent are used as substrates, and an organic solvent appropriate for these substrates and enzymes is usually used. In some cases, a two-component system composed of water and an organic solvent having an appropriate distribution ratio is used. As the enzyme, lipase is generally used, and the enzyme agent may be immobilized. As the organic solvent, for example, hydrophilic organic solvents such as sec-butyl alcohol, t-butyl alcohol, t-amyl alcohol, dioxane, tetrahydrofuran, diethyl ether, dichloromethane and pyridine are used. The reaction conditions may be set in the same manner as in the case of the acylation of L-ascorbic acid by the enzymatic method, and the type of the enzyme is not particularly limited. Since glycosyl-L-ascorbic acid, particularly 2-glucopyranosyl-L-ascorbic acid, has remarkably high stability in an aqueous solution, it is necessary to set complicated conditions unlike the case of acylation of L-ascorbic acid. Absent.

The acylated derivative thus obtained is L-
It can be purified by applying a usual method for purifying a fatty acid ester of ascorbic acid. Individual purification methods include, for example, salting out, dialysis, filtration, concentration, fractional precipitation, separation extraction, gel chromatography, ion exchange chromatography, high performance liquid chromatography, gas chromatography, affinity chromatography, gel electrophoresis , Isoelectric focusing, crystallization, etc., and these are applied in an appropriate combination depending on the reaction conditions and the type and purity of the desired acylated derivative.

The acylated derivative of glycosyl-L-ascorbic acid used in the present invention has the following properties. (1) Oil solubility is higher than L-ascorbic acid and known inorganic acid esters. In addition, when the chain length of the alkyl group in the acylating agent is adjusted, oil solubility can be imparted and substantial water solubility can be maintained. (2) Unlike known fatty acid esters and inorganic acid esters, L-ascorbic acid is liberated in the living body.
Ascorbic acid's original physiological action can be expected and its safety is high. (3) Unlike L-ascorbic acid, it is extremely stable to heat, light, oxygen and metal ions. (4) Unlike L-ascorbic acid, it does not exhibit direct reducing properties, and thus does not cause a reaction such as the Maillard reaction. (5) Unlike L-ascorbic acid and known inorganic acid esters, it has high permeability to skin and mucous membranes. (6) Like L-ascorbic acid, it has a property of capturing radicals generated in a living body. (7) It is generally tasteless, odorless, and colorless, depending on the type of acylating agent and the degree of purification.

Due to these properties, the acylated derivative used in the present invention can stably and safely supply L-ascorbic acid in external preparations for skin including cosmetics and pharmaceuticals requiring L-ascorbic acid. It can be advantageously used as a source, and is expected to have a function of protecting the skin from free radicals caused by ultraviolet irradiation, a function of activating skin cells, a function of preventing light damage, a function of enhancing skin immunity, and the like, in addition to a whitening effect. Among the acylated derivatives used in the present invention, an acylated derivative having an acyl group having a relatively long chain length bonded thereto, particularly an acylated derivative having an acyl group having an integer of 8 or more carbon atoms is bonded to the skin or the like. It is particularly useful in the field of cosmetics and pharmaceuticals because of its extremely high permeability to mucous membranes.

Specific examples of the acylated derivative of glycosyl-L-ascorbic acid used in the present invention include, for example,
6-O-butyryl-2-O-α-D-monoglucopyranosyl-L-ascorbic acid, 2-O-α-D-monoglucopyranosyl-6-O-hexanoyl-L-ascorbic acid, 2-O-α-D-monoglucopyranosyl-6-O
-Octanoyl-L-ascorbic acid, 6-O-decanoyl-2-O-α-D-monoglucopyranosyl-L-ascorbic acid, 6-O-dodecanoyl-2-O-α-D
-Monoglucopyranosyl-L-ascorbic acid, 6-O
-Myristoyl-2-O-α-D-monoglucopyranosyl-L-ascorbic acid, 6-O-palmitoyl-2-
O-α-D-monoglucopyranosyl-L-ascorbic acid or 6-O-stearoyl-2-O-α-D-monoglucopyranosyl-L-ascorbic acid.

The amount of the glycosyl-L-ascorbic acid acylated derivative in the present invention is from 0.001 to 10.0.
% By weight, and 0.01 to 5.0% by weight in that it does not have an adverse effect such as whitening effect and stickiness as an external preparation for skin.
Is particularly preferred.

The ultraviolet absorber used in the present invention includes para-aminobenzoic acid (hereinafter abbreviated as PABA),
PABA monoglycerin ester, N, N-dipropoxy PABA ethyl ester, N, N-diethoxy PAB
A ethyl ester, N, N-dimethyl PABA methyl ester, N, N-dimethyl PABA ethyl ester,
N, N-dimethylbutyl ester, N, N-dimethylP
Benzoic acid-based ultraviolet absorbers such as ABA2-ethylhexyl ester; anthranilic acid-based ultraviolet absorbers such as homomenthyl-N-acetylanthranilate: amyl salicylate, menthyl salicylate, homomenthyl salicylate, octyl salicylate, phenyl salicylate, benzyl salicylate, p Salicylic acid ultraviolet absorbers such as isopropanol phenyl salicylate; octyl cinnamate, ethyl-4-isopropyl cinnamate;
Methyl-2,5-diisopropylcinnamate, ethyl-2,4-diisopropylcinnamate, methyl-2,
4-diisopropylcinnamate, propyl-p-methoxycinnamate, isopropyl-p-methoxycinnamate, isoamyl-p-methoxycinnamate, octyl-p-methoxycinnamate (2-ethylhexyl-p-methoxycinnamate), 2 -Ethoxyethyl-
p-methoxycinnamate, cyclohexyl-p-methoxycinnamate, ethyl-α-cyano-β-phenylcinnamate, 2-ethylhexyl-α-cyano-β-
Cinnamic acid ultraviolet absorbers such as phenylcinnamate and glyceryl mono-2-ethylhexanoyl-diparamethoxycinnamate; 2,4-dihydroxybenzophenone;
2,2'-dihydroxy-4-methoxybenzophenone, 2,2'-dihydroxy-4,4'-dimethoxybenzophenone, 2,2'4,4'-tetrahydroxybenzophenone, 2-hydroxy-4-methoxybenzophenone, -Hydroxy-4-methoxy-4'-methylbenzophenone, 2-hydroxy-4-methoxybenzophenone-5-sulfonate, 4-phenylbenzophenone, 2-ethylhexyl-4-phenyl-benzophenone-2-carboxylate, 2- Hydroxy-4-n
Benzophenone-based ultraviolet absorbers such as octoxybenzophenone and 4-hydroxy-3-carboxybenzophenone; 3- (4-methylbenzylidene) -d, l-camphor, 3-benzylidene-d, l-camphor, urocanic acid ethyl ester , 2-phenyl-5-methylbenzoxazole, 2,2'-hydroxy-5-methylphenylbenzotriazole, 2- (2'-hydroxy-
5-methylphenylbenzotriazole, dibenzalasin, dianisoylmethane, 4-methoxy-4′-t-butyldibenzoylmethane, 5- (3,3′dimethyl-2)
-Norbornylidene) -3-pentan-2-one and the like can be used.

Further, among such ultraviolet absorbers, particularly, U
An ultraviolet absorber capable of absorbing UV light in the VA region, such as 4-methoxy-4'-t-butyldibenzoylmethane, and an ultraviolet absorber capable of absorbing UV light in the UV-B region; For example, N, N-dimethyl PABA2-
The effect of the present invention is further improved by combining with ethylhexyl ester and the like. Similarly, the effect can be improved by using 2-hydroxy-4-methoxybenzophenone-5-sulfonate or the like, which has absorptivity for ultraviolet rays in the UV-A and UV-B regions.

The amount of the ultraviolet absorber in the external preparation for skin is 0.01 to 10.0% by weight, more preferably 0.02 to 6.0% by weight, based on the total amount of the external preparation for skin. 0.01% by weight
If it is less than 10, the stabilizing effect is not recognized, and even if it exceeds 10.0% by weight, the effect is not improved.

In the present invention, (1) a sequestering agent, (2) a divalent and / or trivalent metal salt, (3) sulfurous acid and its salt, hydrogen sulfite and its salt, thiosulfuric acid and its salt, By further blending one or more selected from pyrosulfite and salts thereof, the effect of stabilizing the acylated derivative of glycosyl-L-ascorbic acid can be further enhanced. Further, by using (2) and (3) or (1) and (3) together, the stabilizing effect is further improved.

The sequestering agents used in the present invention include, for example, 1-hydroxyethane-1,1-diphosphonic acid, 1-hydroxyethane-1,1-diphosphonic acid tetrasodium salt, disodium edetate, edetic acid Examples include trisodium, tetrasodium edetate, sodium citrate, sodium polyphosphate, sodium metaphosphate, gluconic acid, phosphoric acid, citric acid, ascorbic acid, succinic acid, edetic acid, and the like.

The amount of the sequestering agent in the external preparation for skin is 0.001 to 1.0% by weight, more preferably 0.005 to 0.5% by weight, based on the total amount of the external preparation for skin. No improvement in the stabilizing effect is observed even when the amount exceeds 1.0% by weight.

Divalent and / or trivalent compounds used in the present invention
As the metal salt having a valency, any salts generally used in cosmetics and pharmaceuticals may be used, such as chlorides such as magnesium chloride, calcium chloride, and zinc chloride; and sulfuric acids such as ferrous sulfate, magnesium sulfate, and aluminum sulfate. Salts and the like can be mentioned.

The compounding amount of the polyvalent metal salt in the external preparation for skin is 0.0001 to 1.0% by weight based on the total amount of the external preparation for skin.
More preferably, the content is 0.001 to 0.1% by weight. 1.
No improvement in the stabilizing effect is observed even when the content exceeds 0% by weight.

The sulfite and its salt used in the present invention,
The blending amounts of hydrogen sulfite and its salts, thiosulfuric acid and its salts, pyrosulfite and its salts are 0.1% in the total amount of the external preparation for skin.
0001 to 1.0% by weight, more preferably 0.01% by weight.
0.01 to 0.1% by weight. No improvement in the stabilizing effect is observed even when the amount exceeds 1.0% by weight.

Further, in addition to the above essential components, the skin external preparations of the present invention include components used in ordinary skin external preparations, such as surfactants, aqueous media, oily components, higher alcohols, natural and synthetic water-soluble agents. Polymers, water-soluble and oil-soluble polymers, inorganic and organic pigments, inorganic and organic clay minerals, inorganic and organic pigments treated with metal soap or silicone, coloring agents such as organic dyes, preservatives, pigments, thickeners , PH
A regulator, a fragrance, various extracts, a moisturizer, a blood circulation promoter, a cooling agent, an antiperspirant, an antibacterial agent, a bactericide, etc. are blended within a qualitative and quantitative range that does not impair the object and effects of the present invention. be able to.

Here, for example, lipophilic nonionic surfactants include sorbitan monooleate, sorbitan monoisostearate, sorbitan monolaurate, sorbitan monopalmitate, sorbitan monostearate,
Sorbitan fatty acid esters such as sorbitan sesquioleate, sorbitan trioleate, diglycerol sorbitan penta-2-ethylhexylate, diglycerol sorbitan tetra-2-ethylhexylate, glycerin mono-cottonseed oil fatty acid, glycerin monoerucate, glycerin sesquioleate, mono Glycerin stearate,
Glycerin polyglycerin fatty acids such as diglycerin diisostearate, glycerin pyroglutamate α, α'-oleate, glyceryl monostearate, propylene glycol fatty acid esters such as propylene glycol monostearate, hydrogenated castor oil derivatives, glycerin alkyl Ether and the like.

Examples of the hydrophilic nonionic surfactant include POE-sorbitan monooleate, POE-sorbitan monostearate, POE-sorbitan monooleate, POE-sorbitan fatty acid esters such as POE-sorbitan tetraoleate, and POE-sorbitan. Sorbit Monolaurate, POE-Sorbit Monooleate, POE-
POE sorbit fatty acid esters such as sorbit pentaoleate and POE-sorbit monostearate;
POE-monooleate, POE fatty acid esters such as ethylene glycol distearate, POE lauryl ether, POE oleyl ether, POE stearyl ether, POE behenyl ether, POE alkyl ethers such as POE-2-octyldodecyl ether, POE cholestanol ether; POE alkyl phenyl ethers such as POE octyl phenyl ethers, POE nonyl phenyl ether, POE dinonyl phenyl ether, Pluronics such as Pluronic, POE.
POP cetyl ether, POE / POP monobutyl ether, POE / POP-2-decyltetradecyl ether, POE / POP monobutyl ether, POE / PO
P hydrogenated lanolin, POE / POP alkyl ethers,
Tetraonic and other tetra POE / tetra POP ethylenediamine condensates, POE castor oil, POE hardened castor oil, POE hardened castor oil monoisostearate, POE
POE castor oil derivatives such as hardened castor oil triisostearate, POE hardened castor oil monopyroglutamic acid diester, POE hardened castor oil maleic acid, POE beeswax lanolin derivatives such as POE sorbit beeswax, coconut oil fatty acid diethanolamide, lauric acid monoester Ethanolamides, alkanolamides such as fatty acid isopropanolamide, POE fatty acid amide, sucrose fatty acid ester, POE nonylphenylformaldehyde condensate,
Alkyl ethoxydimethylamine oxide, trioleyl phosphoric acid and the like can be mentioned.

Examples of the anionic surfactant include soap bases, fatty acid soaps such as sodium laurate, sodium palmitate and sodium stearate; higher alkyl sulfates such as sodium lauryl sulfate and potassium lauryl sulfate; Alkyl ether sulfates such as POE lauryl sulfate triethanolamine and sodium POE lauryl sulfate; N-acyl sarcosine acids such as sodium lauroyl sarcosine;
-Higher fatty acid amide sulfonates such as sodium myristoyl-N-methyltaurine, sodium coconut fatty acid methyl tauride, sodium lauryl methyl tauride, POE sodium oleyl ether phosphate, POE
Phosphate salt such as stearyl ether phosphoric acid, di-
Sulfosuccinates such as sodium 2-ethylhexylsulfosuccinate and sodium monolauroylmonoethanolamide polyoxyethylene sulfosuccinate; alkylbenzenesulfonic acids such as sodium linear dodecylbenzenesulfonate, triethanolamine linear dodecylbenzenesulfonate, and linear dodecylbenzenesulfonate Salt, monosodium N-lauroylglutamate, N
N-acyl glutamates such as disodium stearoyl glutamate and monosodium N-myristoyl-L-glutamate; higher fatty acid ester sulfates such as hydrogenated castor oil fatty acid sodium glycerin sulfate; sulfated oils such as funnel oil; POE alkyl ether carboxylic acid Acid, PO
E alkyl ether carboxylate, α-olefin sulfonate, higher fatty acid alkylolamide sulfate, sodium lauroyl monoethanolamidosuccinate, N-palmitoyl aspartate ditriethanolamine, sodium caseinate and the like.

Examples of the cationic surfactant include alkyltrimethylammonium salts such as stearyltrimethylammonium chloride and lauryltrimethylammonium chloride, distearyldimethylammonium dialkyldimethylammonium chloride, and poly (N, N′-dimethyl-3, Alkylpyridinium salts such as 5-methylenepiperidinium), cetylpyridinium chloride, alkyl quaternary ammonium salts, alkyldimethylbenzylammonium salts, alkylisoquinolinium salts, dialkylmonophonium salts, POE alkylamines, alkylamine salts, Examples thereof include polyamine fatty acid derivatives, amyl alcohol fatty acid derivatives, benzalkonium chloride, benzethonium chloride and the like.

Examples of the amphoteric surfactant include 2-undecyl-N, N, N- (hydroxyethylcarboxymethyl) -2-imidazoline sodium and 2-cocoyl-2-imitazolinium hydroxide-1-carboxy. Imidazoline amphoteric surfactants such as ethyloxy disodium salt, 2-heptadecyl-N-carboxymethyl-N-hydroxyethylimidazolinium betaine,
Betaine-based surfactants such as betaine lauryldimethylaminoacetate, alkylbetaine, amidobetaine, and sulfobetaine are exemplified.

As the aqueous medium, water or water and ethanol, glycerin, polyethylene glycol, propylene glycol, dipropylene glycol, 1,3
-Butanediol, xylitol, sorbitol, maltitol, chondroitin sulfate, hyaluronic acid, mucoitin sulfate, caronic acid, atelocollagen, cholesteryl-12-hydroxystearate, sodium lactate,
Bile salts, dl-pyrrolidone carboxylate, short-chain soluble collagen, diglycerin (EO) PO adducts, and the like.

The oily components used in the present invention include the following. Liquid oils and fats include avocado oil, camellia oil, turtle oil, macadamia nut oil, corn oil, mink oil, olive oil, rapeseed oil, egg yolk oil, sesame oil, persic oil, wheat germ oil, sasanqua oil,
Castor oil, linseed oil, safflower oil, cottonseed oil, eno oil,
Soybean oil, peanut oil, teaseed oil, kaya oil, rice bran oil, sinagiri oil, Japanese kiri oil, jojoba oil, germ oil, triglycerin, trioctanoic acid glycerin, tetraoctanoic acid pentaerythritol, triisopalmitic acid glycerin, etc. is there. As solid oils and fats, cacao butter, coconut oil, horse fat, hardened coconut oil, palm oil, tallow, sheep butter, hardened tallow, palm kernel oil, lard, beef bone oil, mocro kernel oil, hardened oil, beef leg fat , Molle, hydrogenated castor oil and the like. The waxes include beeswax, candelilla wax, cotton wax, carnauba wax, bayberry wax, ibota wax, whale wax, montan wax, nuka wax, lanolin, kapok wax, lanolin acetate, liquid lanolin, sugar cane wax, isopropyl lanolin fatty acid, hexyl laurate, reduced lanolin , Jojoba wax, hard lanolin, shellac wax, POE lanolin alcohol ether, POE lanolin alcohol acetate, POE cholesterol ether, lanolin fatty acid polyethylene glycol, POE hydrogenated lanolin alcohol ether, and the like.

Examples of the hydrocarbon oil include liquid paraffin, ozokerite, squalene, pristane, paraffin, ceresin, squalene, petrolatum, microcrystalline wax and the like.

As synthetic ester oils, isopropyl myristate, cetyl octanoate, octyl dodecyl myristate, isopropyl palmitate, butyl stearate, hexyl laurate, myristyl myristate,
Decyl oleate, hexyl decyl dimethyl octoate, cetyl lactate, myristyl lactate, lanolin acetate, isocetyl stearate, isosetyl isostearate,
Cholesteryl 12-hydroxystearate, di-2-
Ethylene glycol ethylhexylate, fatty acid ester of dipentaerythritol, N-alkyl glycol monoisostearate, neopentyl glycol dicaprate, diisostearyl malate, glycerin di-2-heptylundecanoate, trimethylolpropane tri-2-ethylhexylate, Trimethylolpropane triisostearate, pentaerythritol tetra-2-ethylhexylate, glycerin tri-2-ethylhexylate, trimethylolpropane triisostearate, cetyl 2-ethylhexanoate, 2-ethylhexyl palmitate, glyceryl trimmyristate, Tri-2-
Heptylundecanoic acid glyceride, castor oil fatty acid methyl ester, oleyl oleate, cetostearyl alcohol, acetoglyceride, 2-heptylundecyl palmitate, diisobutyl adipate, N-lauroyl-L-glutamic acid-2-octyldodecyl ester, adipic acid Di-2-heptylundecyl, ethyl laurate, di-2-ethylhexyl sebacate, 2-hexyldecyl myristate, 2-hexyldecyl palmitate, 2-hexyldecyl adipate, diisopropyl sebacate, 2-ethylhexyl succinate , Ethyl acetate, butyl acetate, amyl acetate, triethyl citrate and the like.

Examples of the silicone include linear polysiloxanes such as dimethylpolysiloxane, methylphenylpolysiloxane and methylhydrogenpolysiloxane, and cyclic ones such as octamethylcyclotetrasiloxane, decamethylcyclopentasiloxane and dodecamethylcyclohexasiloxane. There is silicone and the like.

Examples of natural water-soluble polymers include gum arabic, tragacanth gum, galactan, guar gum, carob gum, karaya gum, carrageenan, pectin, agar, quince seed (quince), alge colloid (cassow extract), starch (rice, corn) , Potato, wheat), plant polymers such as glycyrrhizic acid, microbial polymers such as xanthan gum, dextran, succinoglucan, pullulan, collagen,
Animal-based polymers such as casein, albumin, and gelatin are exemplified.

As the semi-synthetic water-soluble polymer, for example,
Starch polymers such as carboxymethyl starch and methyl hydroxypropyl starch, methyl cellulose, nitrocellulose, ethyl cellulose, methyl hydroxypropyl cellulose, hydroxyethyl cellulose, sodium cellulose sulfate, hydroxypropyl cellulose, sodium carboxymethyl cellulose (CM
C), cellulosic polymers such as crystalline cellulose and cellulose powder, and alginic acid polymers such as sodium alginate and propylene glycol alginate.

Examples of the synthetic water-soluble polymer include vinyl polymers such as polyvinyl alcohol, polyvinyl methyl ether, polyvinylpyrrolidone, and carboxyvinyl polymer (Carbopol);
Polyoxyethylene polymers such as 000, 4,000 and 6,000, copolymer polymers such as polyoxyethylene polyoxypropylene copolymer, acrylic polymers such as sodium polyacrylate, polyethyl acrylate and polyacrylamide, polyethylene Examples include imines and cationic polymers.

Examples of the inorganic water-soluble polymer include bentonite, silicic acid A1Mg (Vegum), laponite,
Hectorite, silicic anhydride and the like.

As antibacterial agents, benzoic acid, salicylic acid,
Examples include carboxylate, sorbic acid, paraoxybenzoate, parachloromethcresol, chlorhexidine chloride, trichlorocarbanilide, and phenoxyethanol.

As various extracts, dokudami extract,
Oak extract, melilot extract, bonito extract, liquorice extract, peonies extract, bonsai extract, loofah extract, kina extract, saxifrage extract,
Clara extract, Kouhone extract, Fennel extract, Primrose extract, Rose extract, Jiao extract, Lemon extract, Sikon extract, Aloe extract, Shobu root extract, Eucalyptus extract, Japanese cedar extract, Sage extract, Thyme extract, Tea extract, Seaweed extract, Cucumber extract, Clove Extract, raspberry extract, melissa extract, carrot extract, carrot extract, marronie extract, peach extract, peach extract, mulberry extract, cornflower extract, hamamelis extract, placenta extract, chest wire extract, silk extract and the like.

Examples of the humectant include polyethylene glycol, propylene glycol, glycerin, 1,3-
Butylene glycol, xylitol, sorbitol, maltitol, chondroitin sulfate, hyaluronic acid, mucoitin sulfate, carolinic acid, atelocollagen, cholesteryl-12-hydroxystearate, sodium lactate, bile salts, dl-pyrrolidone carboxylate, short-chain soluble collagen , Diglycerin (EO) PO adducts, Izayobara extract, Achillea millefolium extract, melilot extract, trimethylglycine, tencha extract and the like.

The external preparation for skin of the present invention can be produced by a usual method, and can be applied, for example, as a basic cosmetic, a cosmeceutical, an external pharmaceutical base, and the like.

[0046]

Next, the present invention will be described in more detail with reference to examples and comparative examples, but the present invention is not limited to these examples. All amounts are by weight.

Examples 1 to 7 and Comparative Examples 1 to 8 Lotions were prepared by a conventional method according to the formulations shown in Tables 1 to 3, and the light stability was evaluated. The method for producing the acylated derivative of glycosyl-L-ascorbic acid used in Examples and the like is as described below. The light stability of each of the obtained samples was evaluated by the method described below. The results are also shown in Tables 1 to 3.

(1) Method for producing acylated derivative of glycosyl-L-ascorbic acid At room temperature, 2-glucopyranosyl-L-ascorbic acid (trade name "AA-2G", 2 wt.
-O-α-D-monoglucopyranosyl-L-ascorbic acid content of 98% or more;
1 g (8.0 mmol) was taken, 350 ml of pyridine was added under an argon stream, and the mixture was stirred until dissolved. Next, lauric anhydride (9.6 mm) dissolved in 50 ml of pyridine was used.
ol) was added dropwise to the reaction vessel over 2 minutes in an argon stream, and the mixture was reacted at room temperature for 165 minutes. afterwards,
Methanol was added to the reaction vessel, concentrated and dried to stop the reaction.

A solid of the obtained reaction mixture (4.65)
g) was subjected to silica gel for column chromatography (trade name “Wakogel”, manufactured by Wako Pure Chemical Industries, Ltd.)
Loaded on a 5 g column, 500 ml of ethyl acetate, 500 ml of an ethyl acetate / methanol mixture (volume ratio 9: 1), 500 ml of an ethyl acetate / methanol mixture (volume ratio 8: 2)
And a mixed solution of ethyl acetate / methanol (volume ratio 7: 3) 50
0 ml are passed in this order, while the eluate is
Each 100 ml was collected. A part of each eluted fraction is taken, and a small amount is dropped on a silica gel plate for thin layer chromatography (trade name “silica gel 60 F254”, manufactured by Merck), dried, and then mixed with an ethyl acetate / methanol mixture (volume ratio). 6: 4). After deployment,
The plate was dried, and the fraction eluted from the column containing the component that moved around Rf 0.42 when irradiated with ultraviolet light having a wavelength of 254 nm was collected, combined, concentrated and dried to dryness.

The obtained solid (2.09 g) was purified again by column chromatography in the same manner as described above, and the fraction eluted from the column containing the component shifted to around Rf 0.42 in thin layer chromatography was collected. And unite,
After concentration and drying, 6-O-dodecanoyl-2-
1.93 g of O-α-D-monoglucopyranosyl-L-ascorbic acid was obtained as tasteless and odorless white fine particles (yield 46.4%).

6-O-myristoyl-2-O-α-D-
Monoglucopyranosyl-L-ascorbic acid and 6-
O-palmitoyl-2-O-α-D-monoglucopyranosyl-L-ascorbic acid was also produced in the same manner as described above.

(2) Light stability test Each sample was subjected to a sun exposure test for 10 days, and changes in color and odor with respect to a product stored at 0 ° C. were evaluated as follows.

(Evaluation for Color Change) A: No change. ：: Very slight discoloration. Δ: slightly discolored. X: Strong discoloration.

(Evaluation for change in odor) A: No change. ：: Very slight odor. Δ: Slight odor. X: Strong odor.

[0055]

[Table 1] ─────────────────────────────────── Example Comparative example ────── ─ １ 1 2 3 1 2 3 ─────────────────────────────────── 6− O-Dodecanoyl-2-O-α-D-monoglucopyranosyl-L-ascorbic acid 2.0 2.0 2.0 2.0 2.0 2.0 2-hydroxy-4-methoxybenzophenone-5-sulfonate 0.05 0.05 0.05---Trisodium edetate 0.05 − − 0.05 − − Ferrous sulfate − 0.0005 − − 0.0005 − Butylhydroxytoluene 0.01 0.01 0.01 0.01 0.01 0.01 1,3-butylene glycol 5.0 5.0 5.0 5.0 5.0 5.0 Ethanol 5.0 5.0 5.0 5.0 5.0 5.0 Citric acid 0.02 0.02 0.02 2.0 2.0 2.0 Sodium citrate 0.08 0.08 0.08 0.08 0.08 0.08 Preservative 0.1 0.1 0.1 0.1 0.1 0.1 Distilled water Residue Residue Residue Residual Residual ─────────────────────────────────── Color ○ ○ ○ × △ × Smell ◎ ◎ ○ △ △ × ───────────────────────────────────

[0056]

[Table 2] {Example 4 5 6 7} ────────────────────────────── 6-O-myristoyl-2-O-α-D-monoglucopyranosyl-L-ascorbin Acid 0.5 0.5 0.5 0.5 2-Hydroxy-4-methoxy benzophenone-5-sulfonate 0.05 0.05 0.05 0.05 Trisodium edetate--0.02 0.02 Ferrous sulfate 0.0005 0.0005--Sodium pyrosulfite 0.01-0.01-Butylhydroxytoluene 0.01 0.01 0.01 0.01 1,3-butylene glycol 5.0 5.0 5.0 5.0 ethanol 5.0 5.0 5.0 5.0 POE (15) oleyl alcohol ether 0.5 0.5 0.5 0.5 citric acid 0.02 0.02 0.02 0.02 sodium citrate 0.08 0.08 0.08 0.08 preservative 0.1 0.1 0.1 0.1 distilled water Remainder Remainder Remainder Remainder ───── ───────────────────────────── Color ◎ ○ ◎ ○ Smell ◎ ◎ ◎ ◎ ─────────── ────────────────────────

[0057]

[Table 3] {Comparative Example 4 5 6 7 8} ─────────────────────────────── 6-O-palmitoyl-2-O-α-D-monoglucopyranosyl-L- Ascorbic acid 0.5 0.5 0.5 0.5 0.5 2-hydroxy-4-methoxybenzophenone-5-sulfonate-----Trisodium edetate--0.02 0.02-Ferrous sulfate 0.0005 0.0005---Sodium pyrosulfite 0.01-0.01 − − Butylhydroxytoluene 0.01 0.01 0.01 0.01 0.01 1,3-butylene glycol 5.0 5.0 5.0 5.0 5.0 Ethanol 5.0 5.0 5.0 5.0 5.0 POE (15) Oleyl alcohol ether 0.5 0.5 0.5 0.5 0.5 Citric acid 0.02 0.02 0.02 0.02 0.02 Sodium citrate 0.08 0.08 0.08 0.08 0.08 Preservative 0.1 0.1 0.1 0.1 0.1 Distillation Residue Residue Residue Residue Residue ─────────────────────────────────── Color △ △ △ × × Smell ○ △ △ △ × ───────────────────────────────────

As described above, the external preparation of the present invention is excellent in light stability.

Next, in order to make the external preparation for skin of the present invention more concrete, examples will be further shown. In addition, the blending amount is% by weight.
Is shown. Evaluation was performed according to Example 1. As a result, the external preparation for skin of each Example showed excellent light stability similar to that of Example 1.

Example 8 Emulsion A. Vaseline 1.0% by weight Liquid paraffin 2.0 POE (20) Oleic acid 1.0 Glycerin monooleate 1.0 Octyl methoxycinnamate 0.05 4-Methoxy-4'-t-butyl dibenzoylmethane 0.05 butyl Hydroxytoluene 0.01 Preservative 0.2 Fragrance 0.1 B. Propylene glycol 1.0 2-O-α-D-monoglucopyranosyl-6-O-octanoyl-L-ascorbic acid 1.0 Hibiswako 105 0.2 Potassium hydroxide 0.4 Trisodium edetate 0. 05 2-Hydroxy-4-methoxy benzophenone-5-sulfonate 0.3 Distilled water residue (Preparation method) The raw material of the oil phase part belonging to A and the raw material of the water phase part belonging to B were each heated to 70 ° C. After dissolution, the oil phase is mixed with the aqueous phase and emulsified by an emulsifier. The emulsion is cooled to a final temperature of 30 ° C. in a heat exchanger.

Example 9 Emulsion A. Vaseline 1.0% by weight Liquid paraffin 2.0 POE (20) Oleic acid 1.0 Glycerin monooleate 1.0 Behenic acid 0.3 Stearic acid 0.5 Isostearic acid 0.4 Licorice extract 0.1 Butylhydroxytoluene 0 .01 preservative 0.2 perfume 0.1 B. Propylene glycol 1.0 6-O-decanoyl-2-O-α-D-monoglucopyranosyl-L-ascorbic acid 1.0 Trisodium edetate 0.05 2-Hydroxy-4-methoxybenzophenone-5 Sulfonate 0.3 Hibiswako 105 0.1 Potassium hydroxide 0.05 Distilled water Residue (Preparation method) Same as in Example 8

Example 10 Daytime Emulsion A. Vaseline 1.0% by weight Tetra-2-ethylhexyl pentaerythritol 5.0 Liquid paraffin 2.0 POE (20) oleic acid 1.0 Glycerin monooleate 1.0 Behenic acid 0.7 Stearic acid 0.1 Isostearic acid 0 0.2 Octyl methoxycinnamate 5.0 4-Methoxy-4'-t-butyldibenzoylmethane 3.0 2-Hydroxy-4-methoxybenzophenone 0.5 Di-paramethoxycinnamic acid-mono-Glyceryl ethylhexanoate 1.0 butylhydroxytoluene 0.01 preservative 0.2 fragrance 0.1 B. Propylene glycol 1.0 6-O-dodecanoyl-2-O-α-D-monoglucopyranosyl-L-ascorbic acid 1.0 Trisodium edetate 0.05 Hibiswako 105 0.2 Potassium hydroxide 0. 45 2-Hydroxy-4-methoxybenzophenone-5-sulfonate 0.3 Distilled water residue (Preparation method) The raw material of the oil phase part belonging to A and the raw material of the water phase part belonging to B were each heated to 70 ° C. After dissolution, the oil phase is mixed with the aqueous phase and emulsified by an emulsifier. The emulsion is cooled to a final temperature of 30 ° C. in a heat exchanger.

Example 11 Cream A. Cetanol 2.0 wt% Vaseline 2.0 Squalane 20.0 Glycerin monofatty acid ester 2.0 Tween 60 3.0 (POE (20) sorbitan monostearate) Isopropyl myristate 6.0 Stearyl glycyrrhetinate 0.5 Glyceryl mono- 2-ethylhexanoyl-diparamethoxycinnamate 0.05 4-methoxy-4'-t-butyldibenzoylmethane 0.05 butylhydroxytoluene 0.01 preservative 0.3 perfume 0.2 B. Glycerin 10.0 Propylene glycol 5.0 2-O-α-D-monoglucopyranosyl-6-O-hexanoyl-L-ascorbic acid 5.0 Trisodium edetate 0.1 Potassium hydroxide 1.0 Distillation Water residue (Preparation method) The raw material of the oil phase part belonging to A and the raw material of the water phase part belonging to B are heated to 70 ° C. and completely dissolved, and then the oil phase part is mixed with the water phase part. Emulsify. The emulsion is cooled to a final temperature of 30 ° C. in a heat exchanger.

Example 12 Pack 2-O-α-D-monoglucopyranosyl-6-O-hexanoyl-L-ascorbic acid 10.0% by weight 2-hydroxy-4-methoxybenzophenone-5-sulfonate 0.5 butylhydroxytoluene 0.01 polyvinyl alcohol 10.0 polyethylene glycol 3.0 propylene glycol 7.0 ethanol 10.0 POE (15) oleyl alcohol ether 0.5 preservative 0.05 trisodium edetate 0.2 Perfume 0.05 Distilled water Residue (Preparation method) In distilled water, add 2-O-α-D-monoglucopyranosyl-6-O-hexanoyl-L-ascorbic acid, polyethylene glycol, 2-hydroxy-4-methoxybenzophenone A -5-sulfonic acid salt and a preservative were added and dissolved by stirring. Next, polyvinyl alcohol was added and dissolved by heating. Further, propylene glycol to which butylhydroxytoluene and POE (15) oleyl alcohol ether were added and dissolved by heating was mixed. Finally, ethanol in which the fragrance was dissolved was added, and the mixture was stirred and dissolved to obtain a pack.

Example 13 Emulsion A. Vaseline 1.0% by weight Liquid paraffin 2.0 POE (20) Oleic acid 1.0 Jojoba oil 1.0 Glycerin monooleate 1.0 Octyl-p-methoxycinnamate 0.05 4-Methoxy-4'-t- B. butyldibenzoylmethane 0.05 butylhydroxytoluene 0.01 preservative 0.2 perfume 0.1 Propylene glycol 1.0 Glycerin 2.0 6-O-dodecanoyl-2-O-α-D-monoglucopyranosyl-L-ascorbic acid 1.0 Magnesium chloride 0.01 Placenta extract 0.3 Sodium hyaluronate 0 .01 Carboxyvinyl polymer 0.15 Caustic potassium 0.05 Distilled water Residue (Preparation method) The raw material of the oil phase part belonging to A and the raw material of the water phase part belonging to B were heated to 70 ° C. and completely dissolved, and then the oil phase was dissolved. Part is mixed with the aqueous phase part and emulsified by an emulsifier. The emulsion is cooled to a final temperature of 30 ° C. in a heat exchanger.

Example 14 Cream A. Cetanol 2.0 wt% Vaseline 2.0 Squalane 20.0 Glycerin monofatty acid ester 2.0 Tween 60 3.0 (POE (20) sorbitan monostearate) Isopropyl myristate 6.0 Stearyl glycyrrhetinate 0.5 Glyceryl mono- 2-ethylhexanoyl-diparamethoxycinnamate 0.05 4-methoxy-4'-t-butyldibenzoylmethane 0.05 butylhydroxytoluene 0.01 preservative 0.3 perfume 0.2 B. Glycerin 10.0 Propylene glycol 5.0 2-O-α-D-monoglucopyranosyl-6-O-octanoyl-L-ascorbic acid 5.0 Dipotassium glycyrrhizinate 0.1 Calcium chloride 0.005 Distilled water Residue (Preparation method) The raw material of the oil phase part belonging to A and the raw material of the water phase part belonging to B were each heated to 70 ° C. and completely dissolved, and then the oil phase was mixed with the water phase and emulsified by an emulsifier. I do. The emulsion is cooled to a final temperature of 30 ° C. in a heat exchanger.

Example 15 pack 6-O-dodecanoyl-2-O-α-D-monoglucopyranosyl-L-ascorbic acid 1.0% by weight 2-hydroxy-4-methoxybenzophenone 0.05 butylhydroxytoluene 0.01 Polyvinyl alcohol 10.0 Polyethylene glycol 3.0 Propylene glycol 7.0 Calcium hydroxide 0.1 Ethanol 10.0 POE (15) Oleyl alcohol ether 0.5 Preservative 0.05 Perfume 0.05 Distilled water Residue (Preparation method) 6-O-dodecanoyl-2-O-α-
D-monoglucopyranosyl-L-ascorbic acid, polyethylene glycol, 2-hydroxy-4-methoxybenzophenone-5-sulfonate, and a preservative were added and dissolved by stirring. Next, polyvinyl alcohol was added and dissolved by heating. Further, propylene glycol, butylhydroxytoluene, POE (15) oleyl alcohol ether, and calcium hydroxide were added and dissolved by heating. Finally, ethanol in which the fragrance was dissolved was added, and the mixture was stirred and dissolved to obtain a pack.

Example 16 Emulsion A. Vaseline 1.0% by weight Liquid paraffin 2.0 POE (20) Oleic acid 1.0 Jojoba oil 1.0 Glycerin monooleate 1.0 Octyl-p-methoxycinnamate 0.05 4-Methoxy-4'-t- B. butyl dibenzoylmethane 0.05 butylhydroxytoluene 0.01 preservative 0.2 perfume 0.1 Propylene glycol 1.0 Glycerin 2.0 6-O-dodecanoyl-2-O-α-D-monoglucopyranosyl-L-ascorbic acid 1.0 Sodium bisulfite 0.1 Sodium hyaluronate 0.01 Carboxyvinyl Polymer 0.15 Caustic potash 0.05 Distilled water Residue (Preparation method) The raw material of the oil phase belonging to A and the raw material of the aqueous phase belonging to B are heated to 70 ° C. and completely dissolved, and then the oil phase is dissolved in the aqueous phase. And emulsify with an emulsifier. The emulsion is cooled to a final temperature of 30 ° C. in a heat exchanger.

Example 17 Cream A. Cetanol 2.0% by weight Vaseline 2.0 Squalane 20.0 Glycerin mono fatty acid ester 2.0 POE (25) cetyl ether 3.0 Isopropyl myristate 6.0 Stearyl glycyrrhetinate 0.5 Glyceryl mono-2-ethylhexanoyl -Diparamethoxycinnamate 0.05 4-methoxy-4'-t-butyl dibenzoylmethane 0.05 butylhydroxytoluene 0.01 preservative 0.3 perfume 0.2 B. Glycerin 10.0 Propylene glycol 5.0 2-O-α-D-monoglucopyranosyl-6-O-octanoyl-L-ascorbic acid 5.0 Dipotassium glycyrrhizinate 0.1 Sodium sulfite 0.005 Distilled water Residue (Preparation method) The raw material of the oil phase part belonging to A and the raw material of the water phase part belonging to B were each heated to 70 ° C. and completely dissolved, and then the oil phase was mixed with the water phase and emulsified by an emulsifier. I do. The emulsion is cooled to a final temperature of 30 ° C. in a heat exchanger.

Example 18 Pack 6-O-palmitoyl-2-O-α-D-monoglucopyranosyl-L-ascorbic acid 0.1% by weight Sodium 2-hydroxy-4-methoxybenzophenonesulfonate 0.05 Butylhydroxytoluene 0.01 Polyvinyl alcohol 10.0 Polyethylene glycol 3.0 Propylene glycol 7.0 Sodium pyrosulfite 0.001 Ethanol 10.0 POE (15) Oleyl alcohol ether 0.5 Preservative 0.05 Perfume 0.05 Distilled water residue (Production method) 6-O-palmitoyl-2-O-α-
D-monoglucopyranosyl-L-ascorbic acid, polyethylene glycol, sodium 2-hydroxy-4-methoxybenzophenonesulfonate, and a preservative were added and dissolved by stirring. Next, polyvinyl alcohol was added and dissolved by heating. Further, propylene glycol, butylhydroxytoluene, POE (15) oleyl alcohol ether, and sodium pyrosulfite were added and dissolved by heating. Finally, ethanol in which the fragrance was dissolved was added, and the mixture was stirred and dissolved to obtain a pack.

The skin external preparations of Examples 8 to 18 were all excellent in light stability.

[0072]

As described above, according to the present invention, an acylated derivative of glycosyl-L-ascorbic acid, which is a whitening agent, can be stably compounded in a system, and discoloration and odor to light can be suppressed. It can be prevented.

 ──────────────────────────────────────────────────続 き Continuing from the front page (72) Inventor Seitaka Hasegawa 1050 Nippa-cho, Kohoku-ku, Yokohama, Kanagawa Prefecture Inside Shiseido Daiichi Research Center Co., Ltd. (72) Inventor Eiji Ifuku Nippa-cho, Kohoku-ku, Yokohama, Kanagawa No. 1050 Shiseido Daiichi Research Center Co., Ltd. (72) Inventor Tadashi Yamamoto 1-102 Hanajiri Kikyocho, Okayama City, Okayama Prefecture F-term (reference) AC262 AC302 AC342 AC392 AC402 AC422 AC442 AC472 AC532 AC792 AD042 AD092 AD112 AD332 AD532 AD641 AD642 BB45 BB46 CC02 CC05 CC07 DD31 EE01 EE16

Claims (13)

[Claims] 1. An external preparation for skin, comprising an acylated derivative of glycosyl-L-ascorbic acid and an ultraviolet absorber. 2. The method according to claim 1, wherein the glycosyl-L-ascorbic acid of the acylated glycosyl-L-ascorbic acid derivative is 2-glucopyranosyl-L-ascorbic acid or 2-galactopyranosyl-L-ascorbic acid. External preparation for skin. 3. The external preparation for skin according to claim 1, wherein the acyl group in the acylated glycosyl-L-ascorbic acid derivative has a lower fatty acid or a higher fatty acid as a basic skeleton. 4. The external preparation for skin according to claim 1, wherein the acyl group in the glycosyl-L-ascorbic acid acylated derivative has an integer of 3 to 20 carbon atoms. 5. The external preparation for skin according to any one of claims 1 to 4, wherein the acylated glycosyl-L-ascorbic acid derivative is a monoacylated derivative. 6. A hydroxyl group at the 6-position of a glycosyl-L-ascorbic acid residue of an acylated glycosyl-L-ascorbic acid derivative is acylated.
6. The external preparation for skin according to any one of items 1 to 5. 7. The compounding amount of the glycosyl-L-ascorbic acid acylated derivative is 0.001 to 1 in the total amount of the external preparation for skin.
The skin external preparation according to claim 1, wherein the amount is 0.0% by weight, and the blending amount of the ultraviolet absorber is 0.01 to 10.0% by weight based on the total amount of the skin external preparation. 8. The external preparation for skin according to claim 1, further comprising a sequestering agent. 9. The compounding amount of the sequestering agent is 0.001.
The external preparation for skin according to claim 8, wherein the amount is from 1.0 to 1.0% by weight. 10. The external preparation for skin according to claim 1, further comprising a divalent and / or trivalent metal salt. 11. The external preparation for skin according to claim 10, wherein the compounding amount of the divalent and / or trivalent metal salt is 0.0001 to 1.0% by weight. 12. The method according to claim 1, further comprising one or more selected from sulfurous acid and a salt thereof, hydrogen sulfite and a salt thereof, thiosulfuric acid and a salt thereof, and pyrosulfite and a salt thereof. External preparation for skin. 13. One or more compounds selected from the group consisting of sulfurous acid and its salts, hydrogen sulfite and its salts, thiosulfuric acid and its salts, pyrosulfite and its salts, in an amount of 0.0
The external preparation for skin according to claim 12, wherein the amount is 001 to 1.0% by weight.