JP2011225487A - Cosmetic - Google Patents

Abstract

PROBLEM TO BE SOLVED: To provide a cosmetic comprising an ascorbic acid derivative that exhibits high stability with time of a preparation, is low irritating when applied to the skin and has functions inherent in ascorbic acid.SOLUTION: An ascorbic acid derivative having a specific structure formed by introducing a substituent group into a hydroxy group at 2- and 3-positions of ascorbic acid, and a thickening agent and/or a surfactant are incorporated into a cosmetic and is formed into a preparation such as gel, cream, milky lotion or the like to give a cosmetic that exhibits high stability with time and an excellent use feeling and has functions inherent in ascorbic acid.

Description

  The present invention relates to a cosmetic. More specifically, the present invention relates to a cosmetic that is excellent in stability and has a good feeling of use, containing a 2,3-substituted type ascorbic acid derivative and containing a thickener and / or a surfactant.

  Ascorbic acid is a safe and useful substance and is known as a compound having an antioxidant effect, a collagen production promoting effect, an excellent whitening effect, etc., and has an action of improving the skin condition and keeping it healthy. . However, ascorbic acid is very unstable with respect to light, heat and oxidation, and its use in cosmetics, foods, pharmaceuticals and the like has been hindered. Accordingly, ascorbic acid glucoside, ascorbic acid magnesium phosphate, ascorbic acid derivatives such as ethyl ascorbate or salts thereof have been proposed as those with improved temporal stability over ascorbic acid, and are incorporated into skin external preparations for whitening. For these purposes, it has been proposed to be incorporated into cosmetics. (Patent Document 1, Patent Document 2)

  However, ascorbic acid and the above ascorbic acid derivatives are ionic compounds and easily break the emulsification system. When blended in cosmetics such as creams, emulsions, gels, etc., the viscosity change over time, the water layer and the oil layer are 2 A change in appearance such as separation into layers occurs, which is a problem. Moreover, in order to prevent it, a large amount of surfactant, thickener, etc. were required. For this reason, the irritation | stimulation to the skin by surfactant, the deterioration of the usability | use_condition by a thickener, etc. became a problem, and ascorbic acid and an ascorbic acid derivative became difficult to use for cosmetics.

  In addition, the present inventors are well aware of the glyceryl ascorbic acid moisturizing effect, collagen production promoting effect, melanin production promoting effect, blending into cosmetics excellent in whitening effect, etc. (Patent Document 3). However, the stability of the preparation when the 2,3-position-substituted ascorbic acid derivative is blended in cosmetics, the feeling of use in cosmetics, etc. have not been sufficiently studied, and ascorbic acid and / or ascorbic acid derivatives The effect of using a combination of a surfactant and / or a thickener has not been elucidated.

JP 2005-60239 A JP 2005-120023 A WO2009 / 0253328

  The present invention solves the above-mentioned problems of the prior art, a cosmetic comprising an ascorbic acid derivative, having a high stability of the preparation, hardly changing the cosmetic system, and a function that ascorbic acid originally has It is an issue to provide.

  As a result of intensive studies in view of the above circumstances, the present inventors have found that ascorbic acid derivatives having a specific structure in which the hydrogen atoms at the 2-position and 3-position of ascorbic acid are substituted with substituents, and thickeners and / or interfaces. It was found that cosmetics such as gels, creams, and emulsions that are stable over time and have a good feeling of use can be obtained by blending the activator. The present invention has been completed based on these findings.

In the present invention, the component (A) is one or more selected from ascorbic acid derivatives represented by the following general formula (I), and the component (B) is a thickener and / or a surfactant. The cosmetic is characterized in that an agent is blended and the mass ratio of (A) :( B) is 1:50 to 50: 1.
[Wherein, R ¹ and R ² are each an alkyl group having 1 to 22 carbon atoms, an alkenyl group having ^{2 to} 22 carbon atoms, a benzyl group, R ³ —O—CH ₂ —CH (OH) —CH ₂ —, A group selected from the group consisting of R ⁴ —O—CH ₂ —CH (CH ₂ OH) —, R ⁵ —CH (CH ₂ OH) —, R ⁶ —CH (OH) —CH ₂ — and a hydroxycyclohexyl group; Wherein R ³ and R ⁴ are a hydrogen atom, an alkyl group having 1 to 22 carbon atoms, an alkenyl group having 2 to 22 carbon atoms, or a phenyl group, and R ⁵ and R ⁶ are a hydrogen atom, carbon number It is a 1-20 alkyl group, a C2-C20 alkenyl group, or a phenyl group. However, when R ¹ is an alkyl group having 1 to 22 carbon atoms, an alkenyl group having ^{2 to} 22 carbon atoms, or a benzyl group, R ² is a hydrogen atom, an alkyl group having 1 to 22 carbon atoms, or an alkenyl group having ^{2 to} 22 carbon atoms. Neither a group nor a benzyl group)

In this general formula (I), a carbon atom and a hydrogen atom bonded to the carbon atom are omitted. For example, the position of 1-4 in the formula is a carbon, the position of the 5 are CH groups, the position of 6 is CH ₂ group. The same applies to the following equations.

In the invention of claim 2, the component of (A) is the above general formula (I), wherein R ¹ is —CH ₂ —CH (OH) —CH ₂ OH or —CH (CH ₂ OH) —CH ₂ OH. And R ² is one or more selected from ascorbic acid derivatives of —CH ₂ —CH (OH) —CH ₂ OH or —CH (CH ₂ OH) —CH ₂ OH, and (B) 2. The cosmetic composition according to claim 1, wherein the component is a carboxyvinyl polymer and / or an alkyl-modified carboxyvinyl polymer. By using an ascorbic acid derivative having a glyceryl group, moisture retention is achieved. Excellent cosmetics can be obtained. Furthermore, by using a carboxyvinyl polymer and / or an alkyl-modified carboxyvinyl polymer, a cosmetic material that is more stable over time can be produced. Claim 2 corresponds to this particularly preferable embodiment.

The invention of claim 3 is that the component of (A) is the above general formula (I), wherein R ¹ is —CH ₂ —CH (OH) —CH ₂ OH or —CH (CH ₂ OH) —CH ₂ OH. And R ² is one or more selected from ascorbic acid derivatives of —CH ₂ —CH (OH) —CH ₂ OH or —CH (CH ₂ OH) —CH ₂ OH, and (B) 2. The cosmetic according to claim 1, wherein the component is an ionic surfactant, and by using an ionic surfactant as the component of (B), 2 of a cream, a milky lotion, etc. Separation into layers can be suppressed, and a cosmetic that is more stable over time can be produced. Claim 3 corresponds to this particularly preferable aspect.

  The amount of one or more selected from the 2,3-position-substituted ascorbic acid derivatives of the above general formula (I) of the component (A) in the cosmetic according to the present invention varies depending on the use and is particularly limited. However, the total of the component (A) is usually preferably in the range of 0.01% by mass to 20.0% by mass of the entire cosmetic. When the content is less than 0.01%, the effects inherent to ascorbic acid such as collagen production promotion effect and whitening effect are often low. When the content exceeds 20.0% by mass, collagen production promotion effect commensurate with the blending amount is obtained. In many cases, effects such as whitening and whitening cannot be expected.

  Further, the blending amount of the thickener and / or surfactant of the component (B) varies depending on the use and is not particularly limited, but the total of the component (B) is usually 0.01% by mass to the total cosmetics. It is preferable to blend in the range of 20.0% by mass. When the amount is less than 0.01%, the appearance of the preparation is often changed and the viscosity is decreased. When the amount exceeds 20.0% by mass, the irritation is increased and the feeling of use is often deteriorated.

  Moreover, when mixing the said component of (A) and the component of (B) with cosmetics, it is 1: 50-50: 1 by mass ratio from reasons, such as manufacture of cosmetics, stability of a formulation, and a usability | use_condition. It is preferable to mix in a ratio range.

  A cosmetic comprising the component (A) and the component (B) of the present invention has functions that ascorbic acid originally has, such as a whitening effect and a collagen production promoting effect, and is therefore suitable as a cosmetic for skin. Used. Further, the agent system is not particularly limited, but cosmetics such as gels, creams, and emulsions are suitable in that the cosmetics do not easily flow when applied to the skin and the feeling of use is good.

  Unlike cosmetics containing ionic ascorbic acid derivatives such as ascorbic acid glucoside, magnesium ascorbate phosphate, ethyl ascorbate, and 2-glyceryl ascorbic acid, the cosmetics of the present invention have different cosmetic agent systems. It is a cosmetic compounded with an ascorbic acid derivative that is difficult and excellent in stability of the preparation, is less irritating and excellent in feeling of use, and has functions such as whitening effect and collagen production promotion effect inherent in ascorbic acid.

  Specific examples of the ascorbic acid derivative of the general formula (I) of the component (A) and the thickener and surfactant of the component (B) of the present invention include the compounds shown below.

Specific examples of the ascorbic acid derivative represented by the general formula (I) are shown below. In the following examples,
The glyceryl group represents HOCH ₂ —CH (OH) —CH ₂ — or HOCH ₂ —CH (CH ₂ OH) —,
The alkyl glyceryl group refers to R—O—CH ₂ —CH (OH) CH ₂ — or R—O—CH ₂ —CH (CH ₂ OH) — (R represents an alkyl group).
The alkyl group is a methyl group, ethyl group, propyl group, isopropyl group, butyl group, pentyl group, hexyl group, heptyl group, octyl group, nonyl group, decyl group, undecyl group, dodecyl group, tridecyl group, tetradecyl group, A pentadecyl group, a hexadecyl group, a heptadecyl group, an octadecyl group, a nonadecyl group, an eicosyl group, a behenyl group, etc .;
An alkenyl group refers to a vinyl group, an allyl group, a butenyl group, an isobutenyl group, a crotyl group, an octenyl group, a decenyl group, a dodecenyl group, etc.
The hydroxyalkyl group represents R—CH ₂ —CH (OH) — or R—CH (OH) —CH ₂ — (R represents an alkyl group), and examples thereof include a hydroxyethyl group, a hydroxypropyl group, a hydroxy group. Butyl, hydroxypentyl, hydroxyhexyl, hydroxyheptyl, hydroxyoctyl, hydroxynonyl, hydroxydecyl, hydroxyundecyl, hydroxydodecyl, hydroxytridecyl, hydroxytetradecyl, hydroxypentadecyl , Hydroxyhexadecyl group, hydroxyheptadecyl group, hydroxyoctadecyl group, hydroxynonadecyl group, hydroxyeicosyl group, hydroxybehenyl group and the like.

As the ascorbic acid derivative of the component (A), (1) 2,3-di-O-glyceryl ascorbic acid, 2,3-di-O-alkyl glyceryl ascorbic acid, 2,3-di-O-alkenyl glyceryl Ascorbic acid, 2,3-di-O-phenylglyceryl ascorbic acid, 2,3-di-O-hydroxyalkyl ascorbic acid, 2,3-di-O-hydroxyalkenyl ascorbic acid, 2,3-di-O- Hydroxyphenyl ethyl ascorbic acid (2) 3-O-glyceryl-2-O-alkyl glyceryl ascorbic acid, 3-O-glyceryl-2-O-alkenyl glyceryl ascorbic acid, 3-O-glyceryl-2-O-phenyl glyceryl Ascorbic acid, 3-O-glyceryl-2-O-hydroxyalkylglyceryl ascorbic acid, -O-glyceryl-2-O-alkylascorbic acid, 3-O-glyceryl-2-O-alkenylascorbic acid, 3-O-glyceryl-2-O-phenylglyceryl ascorbic acid (3) 2-O-glyceryl- 3-O-alkylglyceryl ascorbic acid, 2-O-glyceryl-3-O-alkenyl glyceryl ascorbic acid, 2-O-glyceryl-3-O-phenylglyceryl ascorbic acid, 2-O-glyceryl-3-O-hydroxy Alkyl glyceryl ascorbic acid, 2-O-glyceryl-3-O-alkyl ascorbic acid, 2-O-glyceryl-3-O-alkenyl ascorbic acid, 2-O-glyceryl-3-O-phenylglyceryl ascorbic acid (4) 3-O-alkylglyceryl-2-O-alkylglyceryl ascor Acid (provided that 3-O-alkyl and 2-O-alkyl are different), 3-O-alkylglyceryl-2-O-alkenylglyceryl ascorbic acid, 3-O-alkylglyceryl-2-O- Phenylglyceryl ascorbic acid, 3-O-alkyl glyceryl-2-O-hydroxyalkyl glyceryl ascorbic acid, 3-O-alkyl glyceryl-2-O-alkyl ascorbic acid, 3-O-alkyl glyceryl-2-O-alkenyl ascorbic acid Acid, 3-O-alkyl glyceryl-2-O-phenylglyceryl ascorbic acid (5) 2-O-alkyl glyceryl-3-O-alkenyl glyceryl ascorbic acid, 2-O-alkyl glyceryl-3-O-phenyl glyceryl ascorbine Acid, 2-O-alkylglyceryl-3-O-hydride Roxyalkyl glyceryl ascorbic acid, 2-O-alkyl glyceryl-3-O-alkyl ascorbic acid, 2-O-alkyl glyceryl-3-O-alkenyl ascorbic acid, 2-O-alkyl glyceryl-3-O-phenyl glyceryl ascorbine An acid etc. can be mentioned.

  As the thickener of component (B), gum arabic, gum tragacanth, cablo gum, guar gum, pectin, agar, quince seed, starch, alge colloid, xanthan gum, dextran, succinoglucan, collagen, gelatin, casein, albumin, carboxy Methyl starch, methyl cellulose, ethyl cellulose, methyl hydroxypropyl cellulose, carboxymethyl cellulose, hydroxymethyl cellulose, hydroxypropyl cellulose, nitrocellulose, sodium cellulose sulfate, sodium carboxymethyl cellulose, sodium alginate, polyvinyl methyl ether, carboxyvinyl polymer, alkyl-modified carboxyvinyl polymer, Sodium polyacrylate, polyethylene acrylate Polyacrylamide, cationic polymers, dimethylpolysiloxane polymer.

  As the surfactant of the component (B), anionic surfactants such as higher fatty acid soaps, polyoxyethylene alkyl ether sulfates, acyl-N-methyl taurate salts, N-acyl amino acid salts, alkyl phosphate ester salts, etc. , Cationic surfactants such as alkyltrimethylammonium chloride, dialkyldimethylammonium chloride, amphoteric surfactants such as alkyldimethylaminoacetic acid betaine, alkylamidoaminoacetic acid betaine, 2-alkyl-N-carboxy-N-hydroxyimidazolinium betaine And nonionic surfactants such as agents, alkyl glucosides, polyoxyethylene alkyl ethers, polyethylene glycol fatty acid esters, polyhydric alcohol fatty acid esters, and polyether-modified silicones.

  In addition to the above components (A) and (B), the cosmetics of the present invention include components usually used in cosmetics, such as oily raw materials, moisturizers, antioxidants, whitening agents, drugs, and UV absorbers. Further, a sequestering agent or the like can be appropriately blended.

  Examples of the oily raw material include oils and fats such as olive oil, coconut oil, macadamia nut oil, tea seed oil, castor oil, and tri (caprin / capryl) glyceryl, jojoba oil, carnauba wax, candelilla wax, lanolin, beeswax and other waxes, Hydrocarbons such as liquid paraffin, paraffin, petrolatum, ceresin, microcrystalline wax, squalane, fatty acids such as lauric acid, myristic acid, palmitic acid, stearic acid, behenic acid, isostearic acid, cetyl alcohol, stearyl alcohol, isostearyl Higher alcohols such as alcohol, isopropyl myristate, 2-octyldodecyl myristate, cetyl 2-ethylhexanoate, diisostearyl malate, tri-2-ethylhexanoin, methylpolysiloxa , Methyl phenyl polysiloxanes, silicones such as decamethylcyclopentasiloxane or the like.

  Examples of the humectant include glycerin, propylene glycol, maltitol, sorbitol, 1,3-butylene glycol, sodium lactate, polyethylene glycol, sodium pyrrolidone carboxylate, and sodium hyaluronate.

  Examples of the antioxidant include vitamin E, tannin, BHT (butylhydroxytoluene) and the like.

  Examples of whitening agents include ellagic acid, chamomile extract, licorice extract, lucinol, rosemary extract, arbutin, tranexamic acid, and 4-methoxysalicylic acid potassium salt.

  Examples of other drugs include rough skin prevention agents and anti-inflammatory agents. Examples of the rough skin preventive agent or anti-inflammatory agent include dipotassium glycyrrhizinate, stearyl glycyrrhetinate, methyl salicylate, pyridoxine hydrochloride, allantoin, sea salt, persimmon extract, aloe extract, gardenia extract, chamomile extract, licorice extract, mukuroji extract, Kyounin extract, Ogon extract, strawberry tea extract, loquat extract, ginkgo biloba extract, hypericum extract, sorghum extract, safflower extract, spruce extract, salvia extract, birch extract, chimpi extract, tonin extract, gayo extract, altea extract, arnica extract, carrot extract, peony extract , Cucumber extract, gentian extract, cordyceps extract, duckweed extract, ginseng extract, ginseng extract, peach leaf Kiss, kumazasa extract, Yokuininekisu, horse chestnut extract, hawthorn extract, Coptis extract, litchi extract, Toukinsenkaekisu, peppermint extract, comfrey extract, Butcher bloom extract, mortar Beni mallow extract, YAG Rumaru Saw extract, Togenashiekisu, and the like. In addition, other agents such as hair-growth agents, acne agents, dandruff and itching agents, and odor-preventing agents can also be mentioned.

  Examples of protein hydrolysates include protein hydrolysates such as milk protein, silk protein, wheat protein, rice protein, pea protein, collagen, keratin, soybean, sesame, conchiolin, marine collagen, and derivatives thereof.

  Examples of amino acids or derivatives thereof include glycine, valine, leucine, isoleucine, serine, threonine, phenylalanine, arginine, lysine, asparagine, aspartic acid, glutamine, glutamic acid, cystine, cysteine, methionine, tryptophan, proline, histidine and the like. Examples include amino acids and their derivatives.

  Examples of the pH adjuster include lactic acid, citric acid, glycolic acid, succinic acid, tartaric acid, malic acid, potassium carbonate, sodium hydrogen carbonate, ammonium hydrogen carbonate and the like.

  Examples of the preservative include paraoxybenzoic acid alkyl ester, benzoic acid, sodium benzoate, sorbic acid, potassium sorbate, and phenoxyethanol.

  Examples of the dye include tar dyes, natural dyes, inorganic pigments, and polymer powders. Examples of the fragrances include natural fragrances, synthetic fragrances, and blended fragrances.

  The agent system of the cosmetic of the present invention is arbitrary, and any of a solution system, a solubilization system, an emulsification system, a gel system, a powder dispersion system, etc. is possible, and the above (A) and (B ) And the above-described optional compounding components.

  As a method of mixing the component (A) and the component (B) into the cosmetic, the water phase part and the oil phase part (non-aqueous phase part) are prepared as in the case of preparing the skin lotion, cream, emulsion, etc. Examples thereof include a method of dissolving and mixing each. At that time, the component (A) is often dissolved and blended in the water phase part, and the component (B) is often blended in addition to the oil phase part (non-aqueous phase part). The method is not particularly limited.

  Next, specific modes for carrying out the present invention will be described by way of examples. However, the scope of the present invention is not limited by the following examples. Prior to the examples, production examples of ascorbic acid derivatives used in the examples are shown.

Production Example 1 Synthesis of 2,3-di-O-glyceryl ascorbic acid L-ascorbic acid (100 g) and sodium hydrogen carbonate (14.4 g) were added to water in an argon atmosphere, and the mixture was stirred at room temperature for 30 minutes to give glycidol. (42.0 g) was added. The mixture was heated to 50 ° C. and stirred for 5 hours. Thereafter, glycidol (57.5 g) was added, heated to 80 ° C., stirred for 4 hours, and then concentrated under reduced pressure. 232 g of the obtained residue was subjected to alumina column chromatography, eluted with a mixture of chloroform / methanol / water = 6/4/1, concentrated under reduced pressure, and 2,3-diglyceryl represented by Chemical Formula 2 Ascorbic acid (23.0 g) was obtained.

About the obtained product, < ¹ > H-NMR and < ¹³ > C-NMR measurement are performed, and it is confirmed from this measurement result that this product is 2,3-diglyceryl ascorbic acid represented by the following structural formula. It was done.

The analysis results by NMR (nuclear magnetic resonance spectroscopy) were as follows.
¹ H-NMR (400 MHz, CD ₃ OD):
δ ppm 3.58 (2H, m), 3.61 (2H, m), 3.65 (2H, m), 3.88 (1H, m), 3.91 (1H, m), 3.93 (1H, m), 3.99 (1H, m), 4.16 (1H, m), 4.53 (1H, m), 4.65 (1H, dd), 4.88 (1H, m)
¹³ C-NMR (100 MHz, CD ₃ OD):
δ ppm 63.22, 63.60, 63.63, 63.95, 63.98, 64.44, 70.57, 70.60, 71.68, 71.94, 71.98, 73.87, 74.27, 74.33, 75.06, 76.83, 123.02, 159.48, 172.29

In addition, also in the manufacture example shown below, about the obtained product, < ¹ > H-NMR and < ¹³ > C-NMR measurement are performed and the measurement result is shown.

Production Example 2 Synthesis of 3-O-glyceryl ascorbic acid In an argon atmosphere, L-ascorbic acid (300 g) and sodium bicarbonate (42.9 g) were added to water, and the mixture was stirred at room temperature for 30 minutes, and then glycidol (126 g). Was added. Thereafter, the mixture was heated to 50 ° C. and stirred for 5 hours. Methanol was added and filtered, the filtrate was concentrated under reduced pressure, and 457 g of the resulting residue was subjected to silica gel column chromatography. Elution was performed with chloroform / methanol / water = 65/35/5, and concentration was performed under reduced pressure to obtain 3-O-glyceryl ascorbic acid (296 g) represented by Chemical formula 3.

The analysis results by NMR (nuclear magnetic resonance spectroscopy) were as follows.
¹ H-NMR (600 MHz, CD ₃ OD):
δ ppm 3.59 (2H, m), 3.66 (2H, m), 3.89 (1H, m), 3.92 (1H, m), 4.45 / 4.49 (1H, dd) , 4.59 / 4.62 (1H, dd), 4.82 (1H, d)
¹³ C-NMR (150 MHz, CD ₃ OD):
δ ppm 63.4, 63.7, 70.56, 70.61, 71.79, 71.89, 73.4, 73.6, 76.9, 121.17, 121.24, 151.84 151.88, 173.04, 173.07

Production Example 3 Synthesis of 3-O-glyceryl-2-O-octylascorbic acid Under argon atmosphere, 3-O-glyceryl ascorbic acid (54.1 g) obtained in Production Example 2 was stirred in DMSO (200 mL). Further, sodium hydrogen carbonate (18.5 g) was added, and the mixture was stirred at room temperature for 30 minutes. Thereafter, octyl bromide (63.7 g) was added, the mixture was heated to 100 ° C., stirred for 3 hours, and extracted with ethyl acetate. The extract was dried over anhydrous sodium sulfate and concentrated under reduced pressure. 131 g of the obtained residue was subjected to silica gel column chromatography. Elution was performed with a mixed solution of chloroform / methanol / water = 10/3 / 0.4, followed by concentration under reduced pressure, and 3-O-glyceryl-2-O-octylascorbic acid represented by the chemical formula (48.0 g). Got.

The analysis results by NMR (nuclear magnetic resonance spectroscopy) were as follows.
¹ H-NMR (600 MHz, CD ₃ OD):
δ ppm 0.90 (3H, t), 1.32 (8H, m), 1.42 (2H, m), 1.70 (2H, m), 3.60 (2H, brd), 3.65 (2H, m), 3.89 (1H, m), 3.91 (1H, m), 4.02 (1H, m), 4.47 (1H, dd), 4.48 (1H, dd) , 4.57 (1H, dd), 4.59 (1H, dd), 4.86 (1H, d)
¹³ C-NMR (150 MHz, CD ₃ OD):
δ ppm 14.4, 23.7, 26.9, 30.37, 30.44, 30.8, 33.0, 63.2, 63.56, 63.59, 70.5, 70.6, 71.5, 71.6, 74.01, 74.04, 74.1, 76.7, 123.27, 123.30, 159.2, 159.3, 172.2

Production Example 4 Synthesis of 3-O-glyceryl-2-O-benzylascorbic acid Under argon atmosphere, 3-O-glyceryl ascorbic acid (2.93 g) obtained in Production Example 2 was added to water and sodium bicarbonate (1 .42 g) was added and stirred at room temperature for 30 minutes, benzyl bromide (2.61 g) was added, and the mixture was heated to 50 ° C. and stirred for 2 hours. Then, it concentrated under pressure reduction and melt | dissolved in methanol. The resulting solution was dried over anhydrous magnesium sulfate and concentrated under reduced pressure, and 6.13 g of the resulting residue was subjected to silica gel column chromatography. Elution was performed with chloroform / methanol / water = 10/3 / 0.4 mixed solution, followed by concentration under reduced pressure, and 3-O-glyceryl-2-O-benzylascorbic acid represented by the chemical formula 5 (2.47 g). Got.

The analysis results by NMR (nuclear magnetic resonance spectroscopy) were as follows.
¹ H-NMR (500 MHz, CD ₃ OD):
δ ppm 3.49 (2H, m), 3.65 (2H, m), 3.81 (1H, m), 3.88 (1H, m), 4.47 (1H, dd), 4.28 (1H, dd), 4.36 (1H, dd), 4.37 (1H, dd), 4.85 (1H, brs), 5.05 (2H, m), 7.35 (3H, m) , 7.43 (2H, m)
¹³ C-NMR (175 MHz, CD ₃ OD):
δ ppm 63.21, 63.51, 63.54, 70.54, 70.57, 71.42, 71.49, 74.12, 74.20, 75.25, 75.28, 76.80, 76.82, 122.27, 122.31, 129.60, 129.95, 130.11, 137.61, 159.90, 159.94, 172.17

Production Example 5 Synthesis of 3-O-butylglyceryl ascorbic acid L-ascorbic acid (100 g) and sodium hydrogen carbonate (14.3 g) were added to water under an argon atmosphere, and the mixture was stirred at room temperature for 30 minutes, and butyl glycidyl ether. (73.8 g) was added. The mixture was heated to 80 ° C. and stirred for 12 hours. Then, it extracted with n-butanol. The extract was dried over anhydrous sodium sulfate and concentrated under reduced pressure. 96.8 g of the obtained residue was subjected to silica gel column chromatography. Elution was performed with a mixed solution of chloroform / methanol / water = 20/3 / 0.3, and concentration was performed under reduced pressure to obtain 3-O-butylglyceryl ascorbic acid (74.2 g) represented by Chemical formula 6.

¹ H-NMR (500 MHz, CD ₃ OD):
δ ppm 0.93 (3H, m), 1.38 (2H, m), 1.56 (2H, m), 3.49 (2H, m), 3.50 (2H, m), 3.66 (2H, m), 3.88 (1H, m), 4.03 (1H, m), 4.44 (1H, dd), 4.46 (1H, dd), 4.59 (1H, dd) 4.62 (1H, dd), 4.81 (1H, d)
¹³ C-NMR (125 MHz, CD ₃ OD):
δ ppm 14.2, 20.3, 32.8, 63.36, 63.39, 70.2, 70.4, 70.56, 70.61, 72.4, 72.5, 72.6 73.8, 73.9, 76.8, 121.1, 121.2, 151.7, 151.8, 172.9, 173.0

Production Example 6 Synthesis of 3-O-butylglyceryl-2-O-allyl ascorbic acid Under argon atmosphere, 3-O-butylglyceryl ascorbic acid (3.56 g) obtained in Production Example 5 was mixed with water and sodium hydrogen carbonate. (0.98 g) was added and stirred at room temperature for 30 minutes. Thereafter, allyl bromide (1.68 g) was added, and the mixture was heated to 60 ° C. and stirred for 5 hours, followed by extraction with ethyl acetate. The extract was dried over anhydrous sodium sulfate and then concentrated under reduced pressure, and 3.53 g of the resulting residue was subjected to silica gel column chromatography. Elution was performed with chloroform / methanol / water = 30/3 / 0.3 mixed solution, followed by concentration under reduced pressure, and 3-O-butylglyceryl-2-O-allyl ascorbic acid (3.00 g) represented by Chemical formula 7 )

The analysis results by NMR (nuclear magnetic resonance spectroscopy) were as follows.
¹ H-NMR (500 MHz, CD ₃ OD):
δ ppm 0.93 (3H, t), 1.39 (2H, m), 1.55 (2H, m), 3.48 (4H, m), 3.65 (2H, m), 3.89 (1H, m), 4.01 (1H, m), 4.457 / 4.464 (1H, dd), 4.54 (2H, m), 4.586 / 4.594 (1H, dd), 4.87 (1H, 1d), 5.25 (1H, m), 5.35 (1H, m), 6.04 (1H, m)
¹³ C-NMR (175 MHz, CD ₃ OD):
δ ppm 14.24, 20.33, 32.83, 63.19, 70.00, 70.10, 70.50, 70.54, 72.42, 72.45, 72.50, 74.14, 74.63, 74.63, 76.77, 76.79, 119.25, 122.50, 122.54, 134.52, 159.67, 159.72, 172.08

Production Example 7 Synthesis of 3-O-octylglyceryl-2-O-hexadecylascorbic acid Under an argon atmosphere, sodium hydrogen carbonate (14.3 g) and 200 ml of DMSO were added to L-ascorbic acid (100 g), and octylglycidyl ether was further added. (127 g) was added. The mixture was heated to 80 ° C. and stirred for 24 hours, and then extracted with ethyl acetate. The extract was dried over anhydrous sodium sulfate and concentrated under reduced pressure, and 150 g of the resulting residue was subjected to silica gel column chromatography. Thereafter, elution was performed with a chloroform / methanol / water = 30/3 / 0.3 mixed solution, followed by concentration under reduced pressure to obtain 3-O-octylglyceryl ascorbic acid (36 g). The obtained 3-O-octylglyceryl ascorbic acid (5.17 g) was stirred in DMSO (10 mL) under an argon atmosphere, sodium hydrogen carbonate (1.20 g) and hexadecyl bromide (5.22 g) were added, The mixture was heated to 100 ° C. and stirred for 3 hours. Then, it extracted with ethyl acetate. The extract was dried over anhydrous sodium sulfate and concentrated under reduced pressure, and 9.06 g of the residue was subjected to silica gel column chromatography, eluting with chloroform / methanol / water = 50/3 / 0.3 mixed solution. Then, concentration was performed under reduced pressure to obtain 3-O-octylglyceryl-2-O-hexadecylascorbic acid (3.41 g) represented by Chemical Formula 8.

The analysis results by NMR (nuclear magnetic resonance spectroscopy) were as follows.
¹ H-NMR (600 MHz, d ₆ -DMSO):
δ ppm 0.90 (6H, m), 1.24 (34H, brs), 1.34 (2H, m), 1.48 (2H, m), 1.60 (2H, m), 3.38 (4H, m), 3.46 (2H, m), 3.72 (1H, m), 3.87 (1H, m), 3.94 (2H, m), 4.25 (1H, dd) , 4.31 (1H, dd), 4.42 (1H, dd), 4.45 (1H, dd), 4.82 (1H, d)
¹³ C-NMR (150 MHz, d ₆ -DMSO, 40 ° C.):
δ ppm 13.95, 22.13, 25.40, 25.42, 25.63, 25.71, 28.74, 28.78, 28.87, 28.97, 29.09, 29.20, 29.28, 29.30, 31.34, 61.72, 68.04, 68.09, 68.81, 70.88, 71.48, 71.52, 72.14, 73.24, 73. 43, 74.55, 121.29, 157.71, 157.85, 169.42.

Example 1 (Gel)
2,3 position substitution type ascorbic acid derivative, ascorbic acid and ascorbic acid derivative (ascorbic acid glucoside, ascorbic acid magnesium phosphate, ascorbic acid ethyl, 2-O-glyceryl ascorbic acid) is mixed 3.0% Gels prepared by blending 0.05%, 0.5%, and 2.0% of carboxyvinyl polymer as a viscosity agent and adjusting the pH to around 5 were prepared with the compositions shown in Table 1. In addition, the numerical value in a table | surface represents the mass%, and the remainder means the quantity required in order to make a compounding quantity total 100 weight part.

  Ten panelists evaluated the appearance immediately after the prepared gel, the appearance when stored at 50 ° C. for 24 hours, the feeling of use, and the twist according to the following criteria.

Appearance (immediately after):
3: It is in a yogurt shape.
2: Although it is in yogurt form, it is fluid.
1: It is liquid.
Appearance (24h):
3: It is in a yogurt shape.
2: Although it is in yogurt form, it is fluid.
1: It is liquid.
Feeling of use:
3: Stickiness, almost no weight, very good.
2: Sticky and a little heavy, but good.
1: Sticky, heavy weight felt strong, bad.
Shake:
3: Almost no kinking was confirmed after 1 hour of application.
2: A little twisting is confirmed 1 hour after application | coating.
1: A twist is confirmed 1 hour after application | coating.

Based on the evaluation results, classification was made as follows. The results are shown in Tables 2-4.
○: Total score of 10 people is 25 or more △: Total score of 10 people is 15-24
×: Total score of 10 people is 14 or less

  From the results of Tables 2 to 4, the cosmetics of the present invention can prepare gel even when 0.05% of carboxyvinyl polymer is blended as a thickener, and 0.5% When 0.0% was blended, a stable gel was obtained over time. In addition, the cosmetic of the present invention was excellent in use feeling and twist. However, in the comparative example, the gel could not be prepared with 0.05% and 0.5% carboxyvinyl polymer. Further, when 2.0% of carboxyvinyl polymer was blended, an appearance like a gel could be obtained, but it was unstable over time, the feeling of use was bad, and kinking was confirmed.

  Furthermore, when the same test was conducted using the alkyl-modified carboxyvinyl polymer, xanthan gum and methylcellulose as a thickener instead of the carboxyvinyl polymer described in Table 1, the same components were used, and the same test was performed. Results similar to those shown in -4 were obtained.

Example 2 (Cream)
2,3 position substitution type ascorbic acid derivative, ascorbic acid and ascorbic acid derivative (ascorbic acid glucoside, ascorbic acid magnesium phosphate, ascorbic acid ethyl, 2-O-glyceryl ascorbic acid) 3.0% as a comparison, various A cream with 5.0% or 10.0% surfactant (prepared for 5.0% cream that cannot be prepared) and pH adjusted to around 5 was prepared with the composition shown in Table 5. In addition, the numerical value in a table | surface represents the mass%, and the remainder means the quantity required in order to make a compounding quantity total 100 weight part.

  Ten panelists evaluated the appearance immediately after the prepared cream, the appearance when stored at 50 ° C. for 24 hours, and the feeling of use.

Appearance (immediately after):
3: It is a uniform layer.
2: Water or oil particles are observed.
1: Separated into two layers.
Appearance (24h):
3: It is a uniform layer.
2: Water or oil particles are observed.
1: Separated into two layers.
Feeling of use:
3: Very good when applied to the skin without any foreign body sensation.
2: There is almost no foreign material feeling when applied to the skin.
1: When applied to the skin, there is a feeling of foreign matter, which is bad.

Based on the evaluation results, classification was made as follows. The results are shown in Tables 6-9.
○: Total score of 10 people is 25 or more △: Total score of 10 people is 15-24
×: Total score of 10 people is 14 or less

  From the results of Tables 6 to 9, the creams of the examples containing the ascorbic acid derivative represented by the above general formula (I) and a surfactant were stable over time and good in usability. However, when the ascorbic acid derivative of the comparative example was blended, creams were not obtained with various surfactants, and the water layer and the oil layer were separated, resulting in poor usability. Further, even when the surfactant was blended at a high concentration, after 24 hours, the product was separated into two layers, and a cream was not obtained.

Example 3 (Emulsion)
2,3 position substitution type ascorbic acid derivative, ascorbic acid and ascorbic acid derivative (ascorbic acid glucoside, ascorbic acid magnesium phosphate, ethyl ascorbate, 2-O-glyceryl ascorbic acid) 0.5% as a comparison, interface An emulsion containing 5.0% diglycerol dioleate as an activator and 15.0% quince seed as a thickener and adjusting the pH to around 5 was prepared with the composition shown in Table 10. In addition, the numerical value in a table | surface represents the mass%, and the remainder means the quantity required in order to make a compounding quantity total 100 weight part.

  Ten panelists evaluated the appearance immediately after the prepared emulsion, the appearance when stored at 50 ° C. for 24 hours, and the feeling of use.

Appearance (immediately after):
3: It is a uniform layer.
2: Water or oil particles are observed.
1: Separated into two layers.
Appearance (24h):
3: It is a uniform layer.
2: Water or oil particles are observed.
1: Separated into two layers.
Feeling of use:
3: Very good when applied to the skin without any foreign body sensation.
2: There is almost no foreign material feeling when applied to the skin.
1: When applied to the skin, there is a feeling of foreign matter, which is bad.

Based on the evaluation results, classification was made as follows. The results are shown in Table 11.
○: Total score of 10 people is 25 or more △: Total score of 10 people is 15-24
×: Total score of 10 people is 14 or less

From the results of Table 11, the emulsions of the examples containing the ascorbic acid derivative represented by the above general formula (I), the surfactant and the thickener were stable over time and good in usability. . However, when the ascorbic acid derivative of the comparative example was blended, the water layer and the oil layer were separated, and a stable emulsion was not obtained, resulting in poor usability.

Claims (3)

As a component of (A), one or more selected from ascorbic acid derivatives represented by the following general formula (I), a thickener and / or a surfactant as a component of (B), The cosmetics characterized by the mass ratio of (A) :( B) being 1:50 to 50: 1.
[Wherein, R ¹ and R ² are each an alkyl group having 1 to 22 carbon atoms, an alkenyl group having ^{2 to} 22 carbon atoms, a benzyl group, R ³ —O—CH ₂ —CH (OH) —CH ₂ —, A group selected from the group consisting of R ⁴ —O—CH ₂ —CH (CH ₂ OH) —, R ⁵ —CH (CH ₂ OH) —, R ⁶ —CH (OH) —CH ₂ — and a hydroxycyclohexyl group; Wherein R ³ and R ⁴ are a hydrogen atom, an alkyl group having 1 to 22 carbon atoms, an alkenyl group having 2 to 22 carbon atoms, or a phenyl group, and R ⁵ and R ⁶ are a hydrogen atom, carbon number It is a 1-20 alkyl group, a C2-C20 alkenyl group, or a phenyl group. However, when R ¹ is an alkyl group having 1 to 22 carbon atoms, an alkenyl group having ^{2 to} 22 carbon atoms, or a benzyl group, R ² is a hydrogen atom, an alkyl group having 1 to 22 carbon atoms, or an alkenyl group having ^{2 to} 22 carbon atoms. Neither a group nor a benzyl group) The component of (A) is the above general formula (I), wherein R ¹ is —CH ₂ —CH (OH) —CH ₂ OH or —CH (CH ₂ OH) —CH ₂ OH, and R ² is — It is one or more selected from ascorbic acid derivatives that are CH ₂ —CH (OH) —CH ₂ OH or —CH (CH ₂ OH) —CH ₂ OH, and the component (B) is a carboxyvinyl polymer. And / or an alkyl-modified carboxyvinyl polymer. The component of (A) is the above general formula (I), wherein R ¹ is —CH ₂ —CH (OH) —CH ₂ OH or —CH (CH ₂ OH) —CH ₂ OH, and R ² is — It is one or more selected from ascorbic acid derivatives that are CH ₂ —CH (OH) —CH ₂ OH or —CH (CH ₂ OH) —CH ₂ OH, and the component (B) is an ionic interface. The cosmetic according to claim 1, wherein the cosmetic is one or more active agents.