JPS62129212A - Cosmetic - Google Patents

Abstract

PURPOSE:To provide a cosmetic containing esterified vitamin C and/or its salt and a 2-hydroxybenzophenone compound and remarkably effective in beautifying the skin and improving chapped skin. CONSTITUTION:The objective cosmetic contains (A) 0.01-15wt% esterified vitamin C (e.g. ascorbyl palminate, L-ascorbyl stearate, L-ascorbic acid 2-phosphate, etc.) and (B) 0.01-25wt% one or more compounds of formula (A, B, C, D and E are H, 1-8C acyl, 1-18C alkyl, 1-2C alkoxy, OH, sulfonic acid group, etc.) (e.g. 2-hydroxy-4-methoxybenzophenone). It is essential that the compound of formula is soluble in water or oil, has a benzophenone skeleton and contains one or more phenolic hydroxyl groups in a molecule. It is used in the form of cream, milky lotion, powder, etc.

Description

DETAILED DESCRIPTION OF THE INVENTION The present invention provides chemical compound 111 which has excellent whitening effect and rough skin improvement effect.
More specifically, it relates to cosmetics and whitening cosmetics that are stably blended with an esterified product of vitamin C.

Conventionally, vitamin C has been added to cosmetics for purposes such as skin whitening. However, since vitamin C itself is chemically unstable, when it is added to cosmetics, it may deteriorate over time or when exposed to sunlight or other rays.
In some cases, vitamin C was decomposed or altered, resulting in deterioration in quality and coloration.

As a preventive measure against these problems, there are a method of adding urocanic acid (Japanese Patent Publication No. 57-49550) and a method of adding a foamy water compound (
There have also been attempts to stabilize vitamin C by derivatizing it. That is, alkyl esterification (Japanese Patent Publication No. 38-2136
No. 5), phosphoric acid esterification (Special Publication No. 43-9218@,
Special Publication No. 44-31237, Special Publication No. 45-4497)
As disclosed in et al., this whitening cosmetic uses an esterified product of vitamin C. Although these attempts have achieved some results, they are unable to prevent the yellowing phenomenon caused by exposure to sunlight and other light rays. Furthermore, there is no other whitening ingredient that satisfactorily combines efficacy, safety, and stability, and a new whitening cosmetic has been needed.

In view of the above-mentioned current situation, the present inventors have conducted extensive research in order to solve these problems, and have first examined many substances such as anti-fading agents and ultraviolet absorbers. For example, even when BHT, BHA, tocopherols, etc. are blended into cosmetics together with vitamin C esters, favorable results have not been achieved. next,
When considering ultraviolet absorbers, we found that urocanin 1
1. Similarly, favorable results were not obtained with benzoic acid derivatives, cinnamic acid derivatives, etc., but we discovered a benzophenone compound that had favorable effects, and as a result of extensive research, we obtained the following general formula. It has been found that a compound containing a 2-hydroxybenzophenone compound represented by (1) and an esterified product of vitamin C can solve the above-mentioned problems. The present invention is based on this knowledge.

The present invention will be explained in detail below.

The present invention relates to a cosmetic containing an esterified product of vitamin C and/or a salt thereof and one or more 2-hydroxybenzophenone compounds represented by the following general formula (1). .

General formula (1) %Formula% (In the formula, A to E are each the same or different and represent hydrogen, an acyl group having 1 to 8 carbon atoms, an alkyl group having 1 to 18 carbon atoms, and an alkoxy group having 1 to 2 carbon atoms. , represents a group selected from a hydroxyl group, a sulfonic acid group, a sulfonate, and a carboxylic acid group.) The esterified product of vitamin C (hereinafter abbreviated as VC ester) applied to the present invention is vitamin c 71', It is an esterified derivative of L-ascorbic acid, and includes L-ascorbic acid alkyl ester, L-ascorbic acid phosphate ester, L-ascorbic acid sulfate ester, etc. Specific examples include palmitic acid-ascorbyl, Isopalmitin ILL-ascorbyl, Dipalmitin Shun L-ascorbyl, Diisopalmitin IL-ascorbyl, Stearin ML-ascorbyl,
Isostearin ML - Ascorbyl, Distearin Kura L
- Ascorbyl, diisostearate L - Ascorbyl, myristic IL - Ascorbyl, isomyristic acid - Ascorbyl, dimyristine L - Ascorbyl, diisomyristic IL - Ascorbyl, 2-ethylhexane IL - Ascorbyl, di2-ethylhexanoate L - Ascorbyl, oleic acid 1IaL - Ascorbyl, dioleic acid - L-ascorbic acid alkyl esters such as ascorbyl, L-ascorbic acid phosphorus such as L-ascorbic acid-2-phosphate, L-ascorbic acid-3-phosphate, etc. Acid ester, L-ascorbic acid-2
Examples include L-ascorbic acid IA acid esters such as -sulfuric acid ester and L-ascorbic acid -3-sulfuric ester, and these are used alone or by kneading 21Φ or more. In the present invention, these salts can also be used, and alkali metal salts such as sodium salts and potassium salts, alkaline earth metal salts such as calcium salts and magnesium salts, and the like are preferably used.

Among the above-mentioned VC esters or salts thereof, L-ascorbic acid phosphate esters or salts thereof are represented by the above-mentioned general formula (1).
Particularly favorable results are obtained when it is blended into cosmetics together with a 2-hydroxybenzophenone compound represented by the following formula, and it is preferably used in the present invention.

The above-mentioned VC ester is mainly obtained by known synthetic methods, but it can also be obtained by other methods (47), and commercially available vitamin C esters and Its salt can be used.

Moreover, the stabilizing effect of the VC ester brought about by the present invention is related to vitamin C esterified products and salts thereof.
Although a stabilizing effect is observed for vitamin C itself, that is, L-ascorbic acid or its salts, it is insufficient in terms of preventing yellowing when exposed to sunlight or other light rays. Therefore, L-ascorbic acid and its salts are not normally used in the cosmetics provided by the present invention. However, the presence of these substances itself does not essentially impede the effects of the present invention, so it is okay to blend them in small amounts to the extent that yellowing does not occur.

Furthermore, the 2-hydroxybenzophenone compound (hereinafter abbreviated as benzophenone compound 2) represented by the above-mentioned general formula (1) applied to the present invention is soluble in water or oil, and has a benzoenone skeleton. It is essential that the molecule contains one or more phenolic hydroxyl groups. As long as this condition is satisfied, almost all penzophenone compounds can be used. Specific examples include 2-hydroxybenzophenone, 2,4-dihydroxybenzophenone, 2,4-dihydroxybenzophenone-5-sulfonic acid, and 2.2=.

4-trihydroxybenzophenone, 2.2-.

4.4'-tetrahydroxybenzophenone, 2゜2'
-dihydroxy-4,4'-dimethoxybenzophenone, 2,2'-dihydroxy-4,-methoxybenzophenone, 2,2'-dihydroxy-4,4'-dimethoxy-5-sulfobenzophenone sodium salt, 2.2'
, 4-trihydroxy-4'-methoxybenzophenone, 2-hydroxy-4methoxybenzophenone, 2-
Examples include hydroxy-4methoxy-4'-methylbenzophenone, and these may be used alone or in combination of two or more. Among the above benzophenone compounds (1), those having 1 to 4 phenolic hydroxyl groups in the molecule and 1 to 2 methoxy groups in the molecule, or those having 2 phenolic hydroxyl groups in the molecule. Particularly preferred are those having at least one.

In the present invention, it is important to contain both the above-mentioned VC ester and the benzophenone compound, and cosmetics containing only one of them will not have the intended effects of the present invention, that is, whitening and skin beautifying effects. It is not possible to achieve excellent safety and stability. The above-mentioned effects unique to the present invention are primarily clear from the fact that known ultraviolet absorbers other than benzophenone compound (1) have almost no effect on stabilizing VC ester.

Next, the cosmetics provided by the present invention include creams, emulsions, lotions, powders, lip balms, lip colors, under make-up, sun care, and many other cosmetics. The blending amount is arbitrarily selected depending on the properties of the cosmetic, but usually (1,; for the cosmetic IFI weight d, VC
Preferably, the ester is used in an amount of about 0.01 to 15% by weight, and the benzophenone compound (1) is used in an amount of about 0.01 to 25% by weight. If the blending ω is less than 0.01%, the preferred results of the present invention cannot be obtained, and although there is no particular restriction on the upper limit, if a large amount is blended, a sticky feeling will result, making it difficult to use as a cosmetic. may not be desirable.

Next, the method of compounding is to use the above VC ester and benzophenone compound crab as is or with water, alcohol,
i It can be dissolved in alcohol, oil, etc. and incorporated into cosmetics in the same manner as conventional medicinal ingredients.

In addition to the above-mentioned VC ester and benzophenone compound, the cosmetics according to the present invention also contain additives commonly used in cosmetics, such as oils and fats, surfactants, antioxidants, fragrances, pigments, alcohols, and polyvalents. Alcohol, preservatives, sunscreen agents, water, humectants, etc. can be added.

Next, in order to prove the superiority of the present invention, a photostability test was conducted using L-ascorbic acid-2-phosphate magnesium salt (hereinafter abbreviated as AP2MQ) as a VC ester, and a color change test was conducted. The results are shown in Table 1, and the results of the residual rate test are shown in Table 2.

The test method is as follows.

<Specimen> (hereinafter referred to as weighted parts) A (product of the present invention) 5 parts of AP2MC1O and 0.5 parts of 2-hydroxy-4-methoxybenzophenone were dissolved in 99 parts of an ethanol-water isomer mixture.

B (product of the present invention) AP2MC] 0', 5 parts and 2.24
．． A product obtained by dissolving 0.5 part of 4'-tetrahydroxybenzophenone in 99 parts of an ethanol-water isostatic mixture.

C (product of the present invention) 0.5 part of AP2MCI and 0.5 part of 2-hydroxy-4-methoxybenzophenone-5-sulfonic acid were dissolved in 99 parts of an ethanol-water mixture.

D (reference product) 0.5 parts of ascorbic acid-2-phosphate magnesium salt and 0.5 parts of 2-ethylhexyl-paradimethylaminobenzoate were dissolved in 99 parts of the old mixture of ethanol and water.

E (control product) 0.5 part of AP2Mg was added to ethanol.
Dissolved in 99.5 parts of an equal mixture of water.

Discoloration test: 10 g of each of the above specimens A to E were separately weighed into a 20 m screw tube, three specimens were each, and the specimens were irradiated with xenon lamp light at 25° C. for 16 hours. The xenon lamp is Shimadzu xenon tester XF-603.
Using a mold, at a lamp output of 5 -, the light energy a received at the sample surface is about 1200 μW/s 2 /sec, and its wavelength is close to that of sunlight. Next, the color density of each sample after light irradiation was measured using the Gardner method, and the degree of color change was examined by comparing it with the sample after light irradiation.The average field of each three sample items is shown in Table 1. . The numbers in the table are Gardner numbers, and the higher the number, the darker the yellow.

Residual rate test: For each of the same three specimens (light-irradiated and light-irradiated products) used in the above discoloration test, 1 g of each was added to methanol-
Add an equal amount of water mixture to make 10ml1 and HPLC
AP as a specimen for use by high-performance liquid chromatography.
2MCI was quantified and the residual rate was calculated using the following formula, and each sample 3
Table 2 shows the average values of the products. The higher the residual rate of AP2MO, the better the stability. The column is made of aminopropyl silica gel and the detection wavelength is UV258n.
It is m.

(Left below) AP2Mg residual rate (%) Amount of AP2MQ in unirradiated specimen (Left below) Table 2 As described above, in the present invention, AP2Mg is stabilized, and it is not irradiated with light such as sunlight or fluorescent light. Even under conditions of exposure to light, a sufficient amount of AP2MCl remains without being decomposed or altered.Also, as shown in Table 1 above, AP2MCl remains
The invented product is also highly effective in preventing yellowing of chemical additives using Mg. However, compared to the light-irradiated specimens of the reference and control products, the light-irradiated specimens had a much more obvious yellow coloration, and the makeup t...
'l is at a level that will significantly damage the prices of goods (Western prices).

On the other hand, in the present invention, this yellowing is significantly suppressed and is at a level that poses no problem in practical use.

Next, after a clinical test with continuous use for 30 days, a sensory evaluation was conducted on Chemical T 14, which is applied to the invention, and the results are shown in the table below.
Shown in 3. At this time, as a product of the present invention, Example-2 described later
As a control amount, the emulsion of Example 2 from which the above-mentioned AP2MC] and benzophenone compound (1) were removed was used.

The test method is as follows.

Clinical test: A panel of 20 mixed male and female needle users applied a control amount to the inside of the left upper arm and the present invention to the inside of the right upper arm twice a day in the same manner as in normal use, and applied this for 30 days. After continuing,
The four sensory evaluation items of skin firmness, luster, smoothness, and dullness were evaluated using the following criteria.
The average value of 20 people was used as the evaluation score.

Skin's shine 1 No ← - Always always
Nara Niitomo Table 3 As shown in several items with sensory evaluation points or higher, the cosmetics applied to the present invention exert favorable effects on skin firmness, luster, smoothness, dullness, etc. when used continuously on the skin. In particular, it has a remarkable effect on maintaining good skin firmness and improving skin dullness.

7 Examples” Next, examples of the present invention will be shown. The amounts listed below are based on weight.

Example-1 Emollient Cream (A>Cetanol 2.0 Gy
Row
5.0 Liquid paraffin 7.0 Olive oil 18.0 Stearic acid 7.0 Sorbitan monostearate 4.0 Polyoxyethylene monostear
4.0 Sorbitan phosphate (20EO) 2.2-. 4.4'-tetra 0.5 hydroxybenzophenone vitamin C dipalmitate 2.0(B)L-
Ascorbic acid-2-phosphoric acid 3.0 ester propylene glycol 10.0 ethylparaben 01 purified ice
36.0(C) Fragrance
Mix and heat the above formulation (A) to 80''C.

The above formulation (B) was mixed and heated in the same manner, and 80'
Add C and homogeneously emulsify with a homomixer, add the above (C) and cool to obtain a product.

Example-2 Emulsion (A>Milow)
1.0 cetanol
1. .

La) Lin
3.0 stearic acid
2.0 liquid paraffin 7.
0 Olive oil 3.0 Polyoxyethylene monoolein 2.0 Acid ester
(10E, 0.) 2-Hydroxy-4-methoxy 0.7 Penzophenone scent 4'to

Suitable bte(B) L-ascorbic acid-2-phosphate ester magnesium salt 0.9 Hyaluronic acid
0.7 glycerin
4.0 Propylene glycol 4. Q Triethanolamine 1.0 Methylparaben
0.3 Purified water
69.0 Mix and heat the above formulation (B) to 70'C.

The above formulation (A>) was mixed and heated in the same manner, and the mixture was heated for 70'
Add C, homogeneously emulsify with a homomixer, and cool to obtain a product.

Example-3 Stain removal lotion (A) 95% ethanol/L, 30.
01.3 Butylene glycol 4.0 Ethyl adipate 2.0 2-hydroxy-4methoxy O,0S-4'-methylbenzophenone jojoba oil 1.0 Polyoxyethylene hydrogenated castor oil (50E, 0.) 1.0
fragrance
0.2.8) L-Ascorbic acid-2-0,1 sulfate ester magnesium salt 2.2'-dihydroxy-4,0,0541-dimethoxy-5-sulfobenzophenone sodium salt Citric acid 0.1 Sodium citrate 0 .1 Purified water
60.6 Stir and dissolve the above formulation (A>, add the above formulation (B) to it,
By mixing, a transparent liquid stain removal lotion was obtained.

Example-4 Lotion (A) Ethanol 12.0 Glycerin 2. O B-Menthol 0.02 Polyoxyethylene 0.5 Hydrogenated castor oil (50
E, O,) 2-Hydroxy-4-methoxy 0.3 Benzophenone Fragrance Appropriate amount (B) L-Ascorbic acid-2-0,02 phosphate ester sodium salt Hydrolyzed collagen 0.05 Riene @
0.1 Sodium citrate 0
．． 2 Methylparaben 0.1 Allantoin 0.1 Purification
Water 84.5 Dissolve the above formulation (A> and (B) by heating, and dissolve (A) in (, B).
and solubilize it to make a product.

Example-5 Whitening Powder D-Mannit 63. OL-ascorbic acid-2-phosphate potassium salt, 5. .

Squalene 1.0 Vitamin C dipalmitate 1,02-hydroxy-4
-Methoxy 20.0 Benzophenone-5-sulfonic acid fragrance Gimme [Appropriate amount Mix and stir the above formulation to make it homogeneous and use it as a product.

Claims (6)

[Claims] (1) A cosmetic comprising an esterified product of vitamin C and/or a salt thereof and one or more 2-hydroxybenzophenone compounds represented by the following general formula (1). General Formula (1) ▲ Numerical formulas, chemical formulas, tables, etc. group, an alkoxy group having 1 to 2 carbon atoms, a hydroxyl group, a sulfonic acid group, a sulfonate, and a carboxylic acid group.) (2) The 2-hydroxybenzophenone compound represented by the above general formula (1) is 2-hydroxy-4-methoxybenzophenone, 2,2',4,4'-tetrahydroxybenzophenone, 2,2'-dihydroxy-4, 4'-
dimethoxy-5-sulfobenzophenone sodium salt,
Claim 1 selected from 2-hydroxy-4-methoxybenzophenone-5-sulfonic acid
Cosmetics listed in section. (3) Esterified products of vitamin C include L-ascorbyl palmitate, L-ascorbyl isopalmitate, L-ascorbyl dipalmitate, L-diisopalmitate
Ascorbyl, L-ascorbyl stearate, L-ascorbyl isostearate, L-ascorbyl distearate, L-ascorbyl diisostearate, L-ascorbyl myristate, L-ascorbyl isomyristate, L-ascorbyl dimyristate, diisomyristic acid L-ascorbyl, 2-ethylhexanoate L
-Ascorbyl, L-ascorbyl di-2-ethylhexanoate, L-ascorbyl oleate, L- dioleate
L-ascorbic acid alkyl ester such as ascorbyl, L-ascorbic acid 2-phosphate ester, L-ascorbic acid phosphate ester such as L-ascorbic acid 3-phosphate, L-ascorbic acid 2-sulfuric acid ester , L-ascorbic acid-3-sulfate, etc.
The cosmetic according to claim 1, which is one or a mixture of two or more selected from ascorbic acid sulfate esters. (4) Esterified products of vitamin C include L-ascorbic acid phosphate esters such as L-ascorbic acid-2-phosphate ester and L-ascorbic acid-3-phosphate ester;
- L-ascorbic acid-2-phosphate ester magnesium salt, L-ascorbic acid-3-phosphate ester magnesium salt, L-ascorbic acid phosphate ester sodium salt, L-ascorbic acid-2-phosphate ester dipotassium salt, etc. - The cosmetic according to claim 1, which is one or a mixture of two or more selected from ascorbic acid phosphate ester salts. (5) A 2-hydroxybenzophenone compound having a total content of esterified products of vitamin C and salts thereof of 0.01 to 15% by weight in the total weight of the cosmetic, and represented by the above general formula (1). Claim 1, wherein the total content of one or more of the following is 0.01 to 25% by weight.
Cosmetics listed in section. (6) The cosmetic according to claim 1, wherein the cosmetic is a whitening cosmetic.