JP2022080603A - Cosmetic containing ascorbic acid derivative - Google Patents

Abstract

To provide a cosmetic that contains ascorbic acid-2-phosphoric acid-6-fatty acid ester or a salt thereof as an ascorbic acid derivative, and has excellent stability, reduced unpleasant irritating sensation, and satisfactory use feeling.SOLUTION: A cosmetic contains ascorbic acid-2-phosphoric acid-6-fatty acid ester or a salt thereof and cyclohexyl glycerol.SELECTED DRAWING: None

Description

The present invention relates to a cosmetic containing ascorbic acid-2-phosphoric acid-6-fatty acid ester or a salt thereof as an ascorbic acid derivative, which is stable and has a good usability.

Ascorbic acid has a whitening effect, an antioxidant effect, a collagen synthesis promoting effect, etc., and is used as an active ingredient in pharmaceuticals, cosmetics, etc., and various derivatives having improved stability of ascorbic acid are known. ..
Among the ascorbic acid derivatives, compounds in which the hydroxyl group at the 2-position is phosphorically esterified and the hydroxyl group at the 6-position is fatty acid esterified and salts thereof are known as stable amphoteric derivatives that are difficult to be oxidized. The derivative has a high affinity for living organisms and is rapidly transferred to living tissues such as skin. However, when ascorbic acid-2-phosphoric acid-6-fatty acid ester or a salt thereof is formulated as an external preparation for skin, There is a problem that the ester is decomposed in the preparation, yellowing, turbidity, and precipitation occur over time, and the appearance is significantly impaired.

As a means for solving such a problem, a technique has been proposed in which a salt of ascorbic acid-2-phosphoric acid-6-fatty acid ester and a polyhydric alcohol, preferably a dihydric alcohol having 5 or 6 carbon atoms coexist. (Patent Document 1).
When a skin external preparation or cosmetic is prepared by the technique described in Patent Document 1, it is possible to prevent the occurrence of turbidity and precipitation over time in the preparation, and it is possible to improve the stability of the preparation. Although it does not cause skin irritation such as erythema and edema when using the agent, an unpleasant irritant feeling is felt, and a new problem has arisen that the feeling of use of external skin agents and cosmetics is impaired. rice field.

Therefore, in cosmetics containing ascorbic acid-2-phosphoric acid-6-fatty acid ester or salts thereof, there is a demand for cosmetics having excellent stability, reduced unpleasant irritation, and good usability. There is.

Japanese Unexamined Patent Publication No. 2005-336156

Therefore, according to the present invention, in a cosmetic containing ascorbic acid-2-phosphoric acid-6-fatty acid ester or a salt thereof as an ascorbic acid derivative, the stability is excellent and the unpleasant irritant feeling is reduced, so that the feeling of use is improved. The purpose is to provide good cosmetics.

As a result of diligent studies to solve the above problems, the present inventors have made a cosmetic containing ascorbic acid-2-phosphoric acid-6-fatty acid ester or a salt thereof and cyclohexylglycerin to obtain ascorbic acid-. We have found that the decomposition of 2-phosphoric acid-6-fatty acid ester or its salt is suppressed, it is stably maintained in cosmetics, unpleasant irritation is reduced, and the feeling of use is improved. The invention was completed.

That is, the present invention relates to the following.
[1] A cosmetic containing ascorbic acid-2-phosphoric acid-6-fatty acid ester or a salt thereof and cyclohexylglycerin.
[2] The cosmetic according to [1], wherein the content of ascorbic acid-2-phosphoric acid-6-fatty acid ester or a salt thereof is 0.2% by weight to 3% by weight.
[3] The cosmetic according to [1] or [2], wherein the content of cyclohexylglycerin is 1% by weight to 5% by weight.
[4] The content ratio of ascorbic acid-2-phosphate-6-fatty acid ester or its salt to cyclohexylglycerin (ascorbic acid-2-phosphate-6-fatty acid ester or its salt: cyclohexylglycerin) is the weight ratio. The cosmetic according to any one of [1] to [3], which is 1: 1 to 5.
[5] The cosmetic according to any one of [1] to [4], which is a skin cosmetic.

INDUSTRIAL APPLICABILITY According to the present invention, a cosmetic that stably contains ascorbic acid-2-phosphoric acid-6-fatty acid ester or a salt thereof, has excellent formulation stability, reduces unpleasant irritation, and has a good usability is provided. be able to.
Therefore, according to the present invention, it is possible to provide a cosmetic having a stable whitening effect, an antioxidant effect, a collagen synthesis promoting effect, and the like, and also has a good usability.

The present invention provides a cosmetic containing ascorbic acid-2-phosphoric acid-6-fatty acid ester or a salt thereof and cyclohexylglycerin (hereinafter, also referred to as "cosmetics of the present invention" in the present invention).

In the ascorbic acid-2-phosphoric acid-6-fatty acid ester contained in the cosmetic of the present invention, the hydroxyl group at the 2-position of ascorbic acid is phosphoric acid esterified, and the hydroxyl group at the 6-position is esterified with the fatty acid. It is an ascorbic acid derivative.
Examples of the fatty acid forming an ester with the hydroxyl group at the 6-position of the ascorbic acid-2-phosphate ester include saturated or unsaturated fatty acids having about 8 to 20 carbon atoms, and the number of carbon atoms is high from the viewpoint of oxidative stability and the like. Saturated fatty acids of 10 to 20 are preferable, and saturated fatty acids having 12 to 18 carbon atoms are more preferable.
The fatty acid may be either a linear fatty acid or a branched chain fatty acid, and lauric acid, myristic acid, palmitic acid, stearic acid, 2-hexyldecanoic acid, isostearic acid and the like are exemplified as preferable fatty acids.

The salt of ascorbic acid-2-phosphate-6-fatty acid ester contained in the cosmetic of the present invention is preferably formed by a phosphate residue bonded to the hydroxyl group at the 2-position of ascorbic acid and a base. Examples of the salt include alkali metal salts such as sodium salt and potassium salt; alkaline earth metal salts such as calcium salt and magnesium salt; and transition metal salts such as zinc salt, and sodium salts are preferably used.

The cosmetic of the present invention is one of the group consisting of ascorbic acid-2-phosphoric acid-6-fatty acid ester or a salt thereof as described above as ascorbic acid-2-phosphoric acid-6-fatty acid ester or a salt thereof. Can be used alone or in combination of two or more.
In the present invention, the ascorbic acid-2-phosphoric acid-6-fatty acid ester and its salt can be produced and used by a production method known per se, for example, the method described in JP-A No. 10-298174. , Commercial products manufactured and sold by Showa Denko KK, etc. can also be used.

The content of ascorbic acid-2-phosphoric acid-6-fatty acid ester or a salt thereof in the cosmetic of the present invention is usually 0.01% by weight to 10% by weight, preferably 0.1% by weight to 5% by weight. It is more preferably 0.2% by weight to 3% by weight.

The cyclohexylglycerin (3- (cyclohexyloxy) -1,2-propanediol) contained in the cosmetic of the present invention is a dihydric alcohol having a structure in which one hydroxyl group of glycerin is substituted with a cyclohexyloxy group. ..
The content of cyclohexylglycerin in the cosmetic of the present invention is usually 0.5% by weight to 10% by weight, preferably 0.7% by weight to 7.5% by weight, and more preferably 1% by weight to 5% by weight. It is% by weight.
Further, in the cosmetic of the present invention, cyclohexylglycerin is a content ratio of ascorbic acid-2-phosphoric acid-6-fatty acid ester or a salt thereof (ascorbic acid-2-phosphoric acid-6-fatty acid ester or a salt thereof: cyclohexyl). Glycerin) is preferably contained in a weight ratio of 1: 0.5 to 10, and more preferably 1: 1 to 5.

The cosmetic of the present invention comprises water, a hydrophilic solvent such as lower alcohol (ethanol, isopropanol, etc.), polyhydric alcohol (propylene glycol, dipropylene glycol, etc.), a hydrophilic base such as gelatin, polyethylene glycol, and ascorbic acid. -2-phosphate-6-fatty acid ester or a salt thereof, and cyclohexylglycerin are added, and if necessary, general cosmetic additives are added as long as the characteristics of the present invention are not impaired. , Milky lotion, beauty liquid, gel, oil-in-water or water-in-oil cream, skin cosmetics such as packs; makeup bases, milky liquid foundations, creamy foundations and other makeup cosmetics; body lotions, body creams and the like It can be provided as a cosmetic for use, and preferably as a skin cosmetic.

Additives for cosmetics include oily bases, suspending agents, surfactants, emulsifiers, viscous agents, moisturizers, astringents, antioxidants, whitening agents, stabilizers, and UV absorbers. , Antioxidants, preservatives, pH adjusters, pigments, pigments, fragrances and the like.

Oil-based bases include animal and vegetable fats and oils such as olive oil, soybean oil, camellia oil, sesame oil, peanut oil, cacao butter, beef fat, and pork fat; waxes such as carnauba wax, honeydew, and jojoba oil; Fatal alcohols such as alcohols; fatty acids such as oleic acid, palmitic acid, and stearic acid; hydrocarbons such as squalane, white vaseline, liquid paraffin, selecin, and microcrystallin wax can be mentioned.
Examples of the suspending agent include propylene glycol alginate, sodium dioctylsulfosuccinate, soybean lecithin, povidone and the like.
Examples of the surfactant or emulsifier include lecithin, hydrogenated lecithin, polyoxyethylene hydrogenated castor oil, polyoxyethylene alkylail (polyoxyethylene oleyl ether, etc.), polyoxyethylene sorbitan fatty acid ester (polyoxyethylene sorbitan monolaurate, etc.). Polyoxyethylene sorbitan monostearate, polyoxyethylene sorbitan monooleate, etc.), fatty acid glyceryl (glyceryl monostearate, etc.), fatty acid polyglyceryl (diglyceryl distearate, decaglyceryl isostearate, etc.), sucrose fatty acid ester, N- Examples thereof include acyl amino acid esters (such as hexyldecyl N-myristylmethylaminopropionate).
Examples of the viscous agent include carboxyvinyl polymer, sodium polyacrylate, carboxymethyl cellulose, hydroxypropyl cellulose, xanthan gum and the like.
Examples of the moisturizer include 1,3-butanediol, glycerin, polyglycerin (triglycerin, decaglycerin, etc.), DL-pyrrolidone sodium carboxylate, sodium hyaluronate, and the like.
Examples of the astringent include arnica extract, hamamelis extract, rosemary extract and the like.
Examples of the anti-inflammatory agent include dipotassium glycyrrhizinate, chamomile extract, sage extract and the like.
Examples of the whitening agent include arbutin, kojic acid, chamomile extract and the like.
Examples of the stabilizer include sodium edetate, sorbitol, thymol, polyoxyethylene polyoxypropylene glycol and the like.
Examples of the ultraviolet absorber include 2-ethylhexyl methoxycinnamate, 2-ethylhexyl paradimethylaminobenzoate, t-butylmethoxydibenzoylmethane and the like.
Examples of the antioxidant include sodium erythorbate, tocopherol acetate, dibutylhydroxytoluene and the like.
Examples of the preservative include sorbic acid, sodium dehydroacetate, methyl paraoxybenzoate, propyl paraoxybenzoate, butyl paraoxybenzoate, phenoxyethanol and the like.
Examples of the pH adjuster include hydrochloric acid, citric acid, sodium citrate, acetic acid, sodium acetate, potassium hydroxide, sodium hydroxide, sodium hydrogenphosphate and the like.
Examples of the dye include tar dyes (red No. 2, blue No. 1, yellow No. 4, etc.), natural dyes (safrole yellow, riboflavin, turmeric dye, etc.) and the like.
Examples of pigments include extender pigments (talc, calcium carbonate, etc.), white pigments (zinc oxide, titanium oxide, etc.), coloring pigments (bengala, yellow iron oxide, black iron oxide, etc.), pearl pigments (mica titanium, etc.), etc. Be done.
Examples of the fragrance include natural fragrances (lavender oil, orange oil, rose oil, etc.), synthetic fragrances (geraniol, l-menthol, vanillin, etc.) and the like.

The cosmetic of the present invention is used in a well-known pharmaceutical means in the field of pharmaceuticals, for example, the method described in the 17th revised Japanese Pharmacopoeia General Provisions [3] Pharmaceutical Articles "11. It can be manufactured according to the above.
For example, when the cosmetic of the present invention is provided as a lotion or beauty essence, ascorbic acid-2-phosphoric acid-6-fatty acid ester or a salt thereof and cyclohexylglycerin are added to purified water or the like as appropriate. It can be produced by adding it to a hydrophilic solvent and mixing it uniformly.
When the cosmetic of the present invention is provided as an oil-in-water emulsion or cream, an oil-based additive is dissolved in an oil-based base to prepare an oil phase component, while ascorbic acid-2-lin. The acid-6-fatty acid ester or a salt thereof and cyclohexylglycerin are dissolved in a hydrophilic solvent such as purified water together with a surfactant and other additives to prepare an aqueous phase component, which is heated to 75 ° C to 85 ° C, respectively. The oil phase component can be prepared by gradually adding the oil phase component to the aqueous phase component while stirring and emulsifying.
When the cosmetic of the present invention is prepared as a water-in-oil cream, purified water or the like of ascorbic acid-2-phosphoric acid-6-fatty acid ester or a salt thereof and cyclohexylglycerin together with other additives as necessary. The aqueous phase component is prepared by dissolving it in the hydrophilic solvent of the above, while the oil phase component is prepared by dissolving the surfactant and the lipophilic additive in the oily base and heated to 75 ° C to 85 ° C, respectively. Then, it can be prepared by gradually adding the aqueous phase component to the oil phase component while stirring and emulsifying.
When the cosmetic of the present invention is provided as a pack, ascorbic acid-2-phosphoric acid-6-fatty acid ester or a salt thereof and cyclohexylglycerin are appropriately heated together with additives such as a moisturizing agent, a film forming agent and a thickener. It can be prepared by dissolving it in a hydrophilic solvent such as purified water or lower alcohol and making it uniform.

In the cosmetic of the present invention, the stability of the ascorbic acid-2-phosphoric acid-6-fatty acid ester or a salt thereof is improved, the decomposition of the ester bond is suppressed, and the generation of turbidity and precipitation is suppressed.
In addition, when the cosmetic of the present invention is used, an unpleasant irritant feeling is reduced and a good feeling of use is exhibited.

Hereinafter, the present invention will be described in more detail with reference to Examples and Test Examples.

[Test Example 1] Examination of stabilizing effect of cyclohexylglycerin on a salt of ascorbic acid-2-phosphate-6-fatty acid ester (1) Preparation of sample As a salt of ascorbic acid-2-phosphate-6-fatty acid ester, Dissolve 1% by weight of ascorbic acid-2-phosphate-6-trisodium palmitate (hereinafter abbreviated as "APPS"), 0.2% by weight of sodium citrate, and 0.1% by weight of citric acid in purified water. did. Hexanediol, pentanediol, and cyclohexylglycerin were each added to the solution to the concentrations shown in Table 1 and dissolved, and the pH was adjusted to 7.0 (25 ° C.) with sodium hydroxide, and each sample was prepared. And said.

(2) Evaluation of APPS stability (i) Measurement of residual amount of APPS After storing each sample prepared in (1) at 5 ° C and 40 ° C for 1 month and then at 40 ° C for 1 month. The residual amount of APPS was quantified by high performance liquid chromatography (HPLC), and the residual amount (%) with respect to the added amount was shown for each sample.
In the measurement by HPLC, each sample is dispersed by ultrasonic treatment in the solution used as the mobile phase shown below, the volume is made constant by the solution, and then the sample is filtered through a 0.45 μm membrane filter under the conditions shown below. Measured below.
<HPLC measurement conditions>
Equipment used: "Liquid chromatograph LC-10A series" (Shimadzu Corporation)
Pump; "LC-10ADvp" (Shimadzu Corporation)
Autosampler; "SIL-10ADvp" (Shimadzu Corporation)
Column oven; "CTO-10Avp" (Shimadzu Corporation)
Detector; "SPD-M10Avp" (Shimadzu Corporation)
Column; Octadecylsilylated silica gel (average particle size = 5 μm) Column (inner diameter = 4.6 mm, length = 15 cm)
Mobile phase; mixed solution of acetonitrile / 0.03M potassium dihydrogen phosphate aqueous solution (volume ratio = 3: 2)
Flow rate; 1.0 mL / min Measurement wavelength: 265 nm
Spectral measurement range; 200 nm to 400 nm
Column temperature; about 40 ° C
Sample injection volume; 5 μL

(Ii) Observation of changes in appearance Changes in appearance (presence or absence of precipitates, changes in color tone) after storage at 5 ° C and 40 ° C for 1 month were visually observed. The presence or absence of precipitate was evaluated according to the following evaluation criteria.
<Evaluation criteria>
++; Slight precipitation is observed ++; Precipitation is clearly observed ++++; Precipitation is observed in a considerable amount ++++; Precipitation is noticeably observed

(3) Evaluation results The evaluation results for the stability of APPS are summarized in Table 1.

As shown in Table 1, in the aqueous solution to which the polyhydric alcohol was not added, the residual rate of APPS after storage at 40 ° C. for 1 month was 87%, and the formation of a precipitate was remarkable.
The addition of hexanediol improves the residual rate of APPS after storage at 40 ° C. for 1 month, and the addition of 1.0% by weight to 5.0% by weight with respect to 1% by weight of APPS suppresses the formation of precipitates. The aqueous solution had a transparent appearance. However, with the addition of 10.0% by weight of hexanediol, yellowing of the aqueous solution was observed after storage at 5 ° C and 40 ° C for 1 month.
The stabilizing effect of APPS by pentanediol was inferior to that of hexanediol, and even when 2.0% by weight of pentanediol was added, the formation of a precipitate was confirmed after storage at 40 ° C. for 1 month. However, when 10.0% by weight of pentanediol was added, yellowing as in the case of adding hexanediol was not observed.
When cyclohexylglycerin was added, almost the same APPS stabilizing effect as when hexanediol was added was observed, and 1.0% by weight to 5.0% by weight of cyclohexylglycerin was added to 1% by weight of APPS. Therefore, it was confirmed that the decrease in the residual rate due to the decomposition of APPS and the change in the appearance of the aqueous solution were well suppressed.

[Test Example 2] Evaluation of irritation of cosmetic water containing a salt of ascorbic acid-2-phosphoric acid-6-fatty acid ester The polyhydric alcohol and APPS shown in Table 2 were added to purified water and dissolved in Examples. The lotion waters of No. 1 and Comparative Examples 1 and 2 were prepared. The pH of the cosmetic was 7.8 at 20 ° C.
Each of the lotions of Examples and Comparative Examples was used on the face by five panelists with sensitive skin, and the unpleasant irritation felt at that time was evaluated according to the following evaluation criteria and scored.
<Evaluation criteria>
No stimulus: 1 point Almost no stimulus: 2 points Slight stimulus: 3 points Clear stimulus: 4 points Strong stimulus: 5 points The evaluation results are based on the number of panelists with each evaluation point. It is shown in Table 3.

As shown in Table 3, with respect to the cosmetic solution of Comparative Example 1 containing APPS and 1,2-hexanediol, 4 out of 5 panelists evaluated that they felt a slight irritation or a clear irritation. did. Regarding the lotion of Comparative Example 2 containing APPS and 1,2-pentanediol, two panelists evaluated that they did not feel irritation, and one evaluated that they felt a little irritation.
On the other hand, regarding the cosmetic solution of Example 1 containing APPS and cyclohexylglycerin, 4 out of 5 panelists evaluated that they did not feel irritation, and the remaining 1 panelist also evaluated that they felt almost no irritation.

From the results of Test Examples 1 and 2 above, in the cosmetic of the present invention containing a salt of ascorbic acid-2-phosphate-6-fatty acid ester and cyclohexylglycerin, the ascorbic acid-2-phosphate-6-fatty acid ester was used. The salt is stabilized to the same extent as when a polyhydric alcohol having 5 or 6 carbon atoms such as 1,2-pentanediol and 1,2-hexanediol is added, and further, the salt has 5 or 6 carbon atoms. It was suggested that the unpleasant irritation caused by the valent alcohol was reduced.

[Example 2] Beauty essence The components (1) to (9) shown in Table 4 were sequentially added to (10), stirred, and uniformly dissolved to prepare the beauty essence of Example 2. In addition, 1,2-hexanediol was added instead of cyclohexylglycerin of (2) and prepared in the same manner to prepare the beauty essence of Comparative Example 3. The pH of each of the beauty essences of Example 2 and Comparative Example 3 was 7.5 at 20 ° C.
The beauty essences of Example 2 and Comparative Example 3 were stored at 40 ° C. for 1 month, and the residual rate of APPS was measured in the same manner as in the case of Test Example 1. As a result, the residual rate was 80% in any of the beauty essences. there were.
Sodium dl-α-tocopheryl phosphate is known to promote the decomposition of APPS in a cosmetic preparation, but the beauty essence of Example 2 of the present invention is the same as the beauty essence of Comparative Example 3. The APPS residual rate was observed.
From the above results, according to the present invention, 1,2-hexanediol can be obtained even when it is provided as a beauty essence containing an additive that affects the stability of APPS, such as sodium dl-α-tocopheryl phosphate. It was suggested that APPS was stabilized to the same extent as when used.

As described in detail above, according to the present invention, ascorbic acid-2-phosphoric acid-6-fatty acid ester or a salt thereof is stably contained, the formulation stability is excellent, the unpleasant irritant feeling is reduced, and the usability is also improved. Good cosmetics can be provided.
The cosmetic of the present invention can exhibit a stable whitening effect, an antioxidant effect, a collagen synthesis promoting effect and the like, and can be provided as a cosmetic having a good usability.

Claims (5)

A cosmetic containing ascorbic acid-2-phosphoric acid-6-fatty acid ester or a salt thereof and cyclohexylglycerin. The cosmetic according to claim 1, wherein the content of the ascorbic acid-2-phosphoric acid-6-fatty acid ester or a salt thereof is 0.2% by weight to 3% by weight. The cosmetic according to claim 1 or 2, wherein the content of cyclohexylglycerin is 1% by weight to 5% by weight. The content ratio of ascorbic acid-2-phosphate-6-fatty acid ester or its salt to cyclohexylglycerin (ascorbic acid-2-phosphate-6-fatty acid ester or its salt: cyclohexylglycerin) is 1: The cosmetic according to any one of claims 1 to 3, which is 1 to 5. The cosmetic according to any one of claims 1 to 4, which is a skin cosmetic.