JPS61152613A - Skin cosmetic - Google Patents

Abstract

PURPOSE:A skin cosmetic showing chapped skin preventing effect, aging preventing effects, and beautifying effects, stable after long-period preservation, free from side effects and skin irritation unfavorable to the human body, containing a specifidc ascorbic acid derivative. CONSTITUTION:A skin cosmetic containing at least one 6-o-higher acylascorbic acidphosphoric ester salt selected from the group consisting of a 6-o-higher acylascorbic acid-2-phosphoric ester salt (e.g., 6-o-decanoylascorbic acid-2- phosphoric ester, etc.) and a 6-o-higher acylascrobic acid-3-phosphoric ester salt. The ascorbic acid derivative along or a mixture of the ascorbic acid derivatives may be blended with a cosmetic and the amount of the ascorbic acid derivative or its mixture blended is different depending upon the state of the skin cosmetic and preferably in a range of about 0.05-20wt% based on the total amounts of preparation components.

Description

Detailed Description of the Invention (Industrial Application Field) The present invention relates to a skin cosmetic containing a specific ascorbic acid derivative described below, and more specifically, it has no undesirable side effects or skin irritation on the human body, and has a long-term use. To provide a skin cosmetic that is stable even when stored and can simultaneously exhibit and impart excellent skin roughness prevention effects, skin anti-aging effects, and excellent skin whitening effects.

(Prior Art) Aging skin loses its flexibility and elasticity, wrinkles increase, the skin becomes dry and rough without smoothness, and a phenomenon of exfoliation of keratin follicles is observed.

Recently, a few cosmetics have been proposed for preventing skin aging, but none have been found to be sufficiently effective.

On the other hand, in order to restore sunburned skin to a healthy complexion, it is said that it is necessary to lighten the increasing amount of melanin pigment formed and inhibit tyrosinase activity during the melanin production process.

Applying these principles, as an active substance for nine whitening cosmetics,
Several ascorbic acid derivatives have been investigated, including the 8-mono-Ill fatty acid ester of ascorbic acid, 2.
6-di straight chain fatty acid esters have been proposed (Japanese Patent Publication No. 45-16 J1G1, Japanese Patent Publication No. 46-28684),
However, when applied to cosmetics, there are drawbacks such as problems with stability over time, discoloration and odor, and the inability to obtain excellent whitening effects.

On the other hand, the phosphoric acid ester of ascorbic acid proposed in Japanese Patent Publication No. 44-81287 has fairly good stability, but does not exhibit sufficient whitening effect when applied to cosmetics.

As described above, an excellent skin cosmetic that can simultaneously exhibit and provide skin roughness prevention effects, skin anti-aging effects, and skin whitening effects has not yet been found.

(Problems to be Solved by the Invention) The object of the present invention is to be stable even when stored for a long period of time, and to prevent discoloration and odor.
It beautifies the body, increases attractiveness, keeps the skin healthy, and can simultaneously express and impart skin anti-aging effects and whitening effects without causing a decrease in activity, while giving a good feel without harshness on the skin. Our goal is to provide excellent skin cosmetics.

(Means for Solving the Problems) The object of the present invention is to provide 6-0-higher acylascorbic acid-2-phosphate ester salts and 6-0-higher acylascorbic acid-8-phosphate ester salts. This is achieved by a skin cosmetic product characterized by containing.

The ascorbic acid derivative (6-0-higher acylascorbic acid phosphate ester salt) of the present invention is obtained by reacting 6-0-higher acylascorbic acid with a sulfur dioxide-trimethylamine complex, sulfuric anhydride, chlorosulfonic acid, etc. To the 6-0-higher acylascorbic acid phosphate ester produced by sulfuric acid esterification, sodium hydroxide,
It is obtained by reacting a base such as potassium hydroxide, magnesium hydroxide, calcium hydroxide, barium hydroxide, ammonium hydroxide, monoethanolamine, jetanolamine, triethanolamine, etc. (salt formation reaction).

The 6-0-higher acylascorbic acid phosphate ester salt in the present invention includes, for example, 6-0-decanoyl ascorbic acid 2-phosphate, 6-O-
Decanoyl ascorbic acid-8-phosphate ester, 6-
0-dodecanoyl ascorbic acid-2-phosphate, 6-0-dodecanoyl ascorbic acid-8-phosphate, 6-0-tetradecanoyl ascorbic acid-2
-phosphoric acid ester, 6-o-tetradecanoyl ascorbic acid-8-phosphoric acid ester, 6-o-hexadecanoyl ascorbic acid-2-phosphoric acid ester, 6-0-hexadecanoyl ascorbic acid-8-phosphoric acid ester acid ester, 6
-o-octadecanoyl ascorbic acid-2-phosphate, 6-0-octadecanoyl ascorbic acid-8
- Phosphate, 6-0-eicosanoyl ascorbic acid-2-phosphate, sodium salt, potassium salt, magnesium salt, calcium salt, barium of 6-o-eicosanoyl ascorbic acid-8-phosphate Preferred are salts, ammonium salts, monoethanolamine salts, jetanolamine salts, triethanolamine salts, and the like.

In the present invention, each of the ascorbic acid derivatives of the present invention is incorporated into a skin cosmetic base either alone or as a mixture of two or more. Although its amount varies depending on the form (type) of skin cosmetics, the overall amount is as follows:
Based on the total amount of prescription ingredients of the cosmetic concerned (the same applies hereinafter),
It is usually within the range of 0.06 to 20% by weight.

More specifically, the blending amount range is 0.05 to 10% (preferably 1 to 1%) for creamy (emulsified) cosmetics.
5% by weight), and 0.05-10% by weight for emulsion cosmetics (
Preferably 1 to 5% by weight), and 0.05 to 2.0% by weight for aqueous transparent liquid cosmetics (preferably o, i to 1.0% by weight).
weight%), 0.05 to 20% by weight (preferably 1 to 15% by weight) for oily cosmetics, and 0.06% for cake-like cosmetics.
~17% by weight (preferably 8-10% by weight), 1-20% by weight (preferably 5-15% by weight) for powdered cosmetics
, 0.1 to 8% by weight in pack agents (preferably 0.6 to 8% by weight)
2% by weight).

The cream or emulsion cosmetic of the present invention is a base of known cream or emulsion skin cosmetics such as pine surge cream, cleansing cream, skin cream, foundation cream, and milky lotion. The ascorbic acid derivative of the present invention is blended into the agent in the required amount. A known method can be used for the blending method.

Base emulsifiers that can be used in the base of the cosmetic include:
For example, synthetic emulsifiers such as ordinary nonionic surfactants, anionic surfactants, amphoteric surfactants, lecithin,
Shi! ! Sugar fatty acid ester, higher acyl glutamate,
Natural surfactants such as pectin, karaya gum, locust bean gum, glycyrrhizin (18α monolithic or 18β monolithic) acid or its alkali gold IA4, ammonium salts, water-soluble collagen (polypeptide), sodium bentonite, etc. Known emulsifiers may be mentioned. The amount of emulsifier added is usually 0.05% of the total amount of prescription ingredients.
-5% by weight.

In addition, the oily substance for the base material is an oily substance for skin cosmetics, such as vegetable oil, animal oil, higher fatty acid, higher alcohol, synthetic ester oil, waxes, silicone oil, and the like.

What is the blending amount of such an oily substance as a base material?

It is usually 5 to 60% by weight based on the total amount of prescription ingredients.

Other ingredients that may be blended include fragrances, preservatives, pigments, etc., as well as skin nutrients, moisturizers, UV inhibitors,
pH adjusting agents may be applied.

The ascorbic acid derivative of the present invention has good stability, compatibility with oily bases, emulsifying properties, etc., so it is easy to design formulations for emulsifying cosmetics, and it also has anti-aging effects, whitening effects, and emulsifying properties. Products with good stability, storage stability, viscosity (hardness) stability, appearance (texture, gloss), spreadability and feel during use can be easily obtained.

The aqueous transparent liquid cosmetic composition of the present invention can be obtained by blending a required amount of the ascorbic acid derivative of the present invention into a base such as a usual skin care product or a film-type pack agent. In this case, the ascorbic acid derivative of the present invention may contain water or water-
Because it is easily solubilized in alcohol and has high secondary properties, it is extremely easy to design formulations, and it stably maintains skin anti-aging and whitening effects, making it easy to create transparent low-scene and transparent film-type whitening packs. You can get it.

In addition to conventional bases such as ethanol and film agents, the aqueous transparent liquid whitening cosmetic base contains fragrances, colorants, preservatives, and if necessary, skin nutrients, moisturizers, pH1JII agents, etc. It is possible.

The oily whitening cosmetic composition of the present invention can be obtained by adding an appropriate amount of the ascorbic acid derivative of the present invention to a liquid oily base material as described below and uniformly dissolving it. Examples of the liquid oil base include almond oil, olive oil,
Examples include sesame oil, safflower oil, mink oil, avocado oil, jojoba oil, isopropyl palmitate, isopropyl myristate, oleyl alcohol, isostearyl alcohol, octyldodecanol, and the like.

Among these, oily substances that are easily soluble in sebum are particularly preferred.

The oily whitening cosmetic composition of the present invention has a substantially transparent highly fluid oily state and is non-aqueous. As mentioned above, the ascorbic acid derivative of the present invention has excellent solubility and stability, so it is completely dissolved in the liquid oily base, and does not cause a decrease in activity even after long-term storage. However, it can exhibit good skin anti-aging effects and whitening effects.

The cake-like cosmetic composition of the present invention is produced by a known process using a pigment as the main constituents and the ascorbic acid derivative of the present invention or a conventional oily substance for cosmetics.

The powdered whitening cosmetic of the present invention is produced by adding the ascorbic acid derivative of the present invention to a conventional powder base material such as starch, lactose, mannitol, precipitated calcium carbonate, etc., and uniformly kneading the mixture.

(Function) The ascorbic acid derivative in the present invention has appropriate hydrophilicity and lipophilicity, and has high stability in cosmetic systems, compatibility with cosmetic base materials, emulsifying properties, and safety for the human body. This makes it easy to design formulations for skin cosmetics, and it is possible to provide cosmetics that have good stability over time and give a good feeling without causing irritation to the skin.

When the skin cosmetic of the present invention is applied to the skin, the ascorbic acid derivative of the present invention quickly dissolves and diffuses into the sebum and easily penetrates the sebum, promoting the activity and metabolism of the skin tissue, and as a result. In addition to exhibiting the above-mentioned skin aging prevention effect, it can inhibit the activity of tyrosinase in skin tissues to a moderate degree and exhibit an excellent skin whitening effect.

(!l!Example) Hereinafter, the present invention will be explained in more detail with reference to Examples.

In addition, parts shown in Examples are parts by weight, and % is weight %.

Test methods for improving rough skin, keratin improving effect, sensory effect, whitening effect, storage stability, etc. are as follows.

(1) Test method for measuring the effect of improving rough skin The effect of continuous application over 4J\I was investigated on 20 middle-aged and elderly subjects who had rough skin on their lower legs. 2 per day to the subject's left lower leg test site.
About 1 time! Apply the cosmetic sample (i) and judge the condition of the skin before and after the test according to the criteria in Table 1.9.

No sample was applied to the right lower leg and it was used as a control.

Table 1 Judgment criteria for skin dryness m: Normal ±: Slight dryness, no flaking +: Slight dryness, flaking ++: Moderate dryness, flaking +++: Significant dryness, flaking Judgment results of the test site and control site before and after the test If the skin dryness has improved by two or more levels (e.g. +→-1)
++→±) was considered "effective," one level of improvement was considered "slightly effective," and no change was considered "ineffective." There were no cases of skin dryness progressing during the test period.

(2) Test method for measuring the effect of improving keratin (increasing the anti-exfoliation properties of keratinocytes) A Scotch tape (Tiban mending tape) was adhered to the test area skin before and after the start of the rough skin improvement measurement test described above. The condition of the keratinocytes that adhered to the tape when it was peeled off was examined in detail using a scanning electron microscope, and the anti-removal properties of skin keratinocytes were determined according to the criteria shown in Table 2, and the keratin improving effect was determined.

Table 2 Judgment criteria for keratin improvement effect (increased anti-desquamation property of keratinocytes) Evaluation points 1 Two scales not observed # 2: Small scales dotted # 8: Small scales are noticeable 4: Large scales are noticeable Table 2 shows 4 consecutive weeks When the difference between the evaluation score of the test site after application and that of the control site was 2 or more points, it was considered "effective," when it was 1 point, "somewhat effective," and when it was 0 points, "ineffective."

In addition, there are no cases where the evaluation score of the test site is higher than that of the control site.

The exfoliation properties of these corneocytes serve as an index for determining the structural properties of the stratum corneum, and in general, in dry skin and aging skin, the amount of intercellular bonds is weak and the density of the structure is poor. It has been confirmed that the index is high because the index is also low.

(3) Sensory effect panel test 8 (lt7) A sample was applied to the face of a middle-aged (80-60 years old) female panelist twice a day for two months, and each panelist tested the test before and after the test. The condition of the skin was evaluated for ``wrinkle smoothing effect,'' ``effect on firmness, and ``effect on moisturizing feeling.''

(4) Panel test of skin whitening effect The sample was applied to a panel of 20 female subjects suffering from dark skin, age spots, and freckles every morning for two months, and was found to be effective.
, Panela itself will judge whether it is ``slightly effective'' or ``ineffective.''

(5) Storage stability test (stability of cosmetics after 6 months at 40°C) Changes in appearance (presence or absence of separation, coloring, etc.) of cosmetics samples after storing them in a constant temperature room at 40°C for 6 months, Eight specialized concave inspectors inspected the containers for the presence or absence of strange odors.

Example 1 Prescription ■ 4.0 parts of 6-0-hexadecanoyl ascorbic acid-2-phosphate magnesium salt ■ Squalane
25.0 ■Microcrystalline wax 5.00 Olive oil
a, O■xanthan gum
1.0 ■ Monoammonium glycyrrhizinate
0.80 Methylparaben
0.2 ■ Purified water 61
．． 5. Perfume Appropriate amount A cream cosmetic in the form of an O/W emulsion was obtained using the above formulation in a conventional manner. The test results for this cosmetic are shown in Table 8 below.

The structural formula of the compound of summer component (■) is as follows.

Comparative Example 1 Ascorbic acid-2 instead of 6-0-hexadecanoyl ascorbic acid-2-phosphate magnesium salt
-A comparative cream cosmetic was obtained in the same manner as in Example 1, except that the magnesium phosphate ester salt was used.

The test results for this cosmetic are shown in Table 8 below.

Comparative Example 2 Example 2 except that 5,6-0-isopropylidene ascorbic acid-2-phosphate magnesium salt was used instead of 6-0-hexadecanoyl ascorbic acid-2-phosphate magnesium salt. A comparative creamy cosmetic was obtained in the same manner as in Example 1. The test results of this cosmetic are shown in Table 8 below. Table 48 Example 2 6-0-hexadecanoyl ascorbic acid-2-phosphate ester magnesium salt was replaced with 6-0-tetradecanoyl ascorbic acid-2-phosphate. A cream cosmetic was obtained in the same manner as in Example 1, except that 8-phosphoric acid ester heptanoethanolamine salt was used.

The stability of the obtained creamy cosmetic after 6 months at 40°C was good, with no coloration or odor.

In addition, the results of sensory tests such as wrinkle smoothing effect, firmness effect, and whitening effect were similarly good.

Example 8 Instead of 6-0-hexadecanoyl ascorbic acid-2-phosphate magnesium salt, the following structure 6-0
A cream cosmetic was obtained in the same manner as in Example 1, except that -decanoyl ascorbic acid-2-phosphate heptanosodium salt [Co., Ltd.] was used.

The stability of the obtained creamy cosmetic after 6 months at 40°C was good, with no coloration or odor.

The results of sensory tests such as eyelids, wrinkle smoothing effect, firmness effect, and whitening effect were similarly good.

[Phase] ON! HO-P=0 Example 4 6-0-octadecanoyl ascorbic acid-2-phosphate triethanolamine salt is used instead of 6-0-hexadecanoyl ascorbic acid-2-phosphate magnesium salt A cream cosmetic was obtained in the same manner as in Example 1 except for the following steps.

The stability of the obtained creamy cosmetic after 6 months at 40°C was good, with no coloration or odor.

In addition, the results of sensory tests such as wrinkle smoothing effect, firmness effect, and whitening effect were similarly good.

Example 6 Example 1 except that 6-0-hexadecanoyl ascorbic acid-2-phosphate dipotassium salt was used instead of 6-0-hexadecanoyl ascorbic acid-2-phosphate magnesium salt. A creamy cosmetic was obtained in the same manner as above.

The stability of the obtained nine creamy cosmetics after 6 months at 40°C was good with no discoloration or odor.

In addition, the results of sensory tests such as wrinkle smoothing effect, firmness effect, and whitening effect were similarly good.

Example 6 Example 6 except that 6-0-octadecanoyl ascorbic acid 2-phosphate disodium salt was used instead of 6-0-hexadecanoyl ascorbic acid 2-phosphate magnesium salt. A creamy cosmetic was obtained in the same manner as in 1.

The stability of the obtained creamy cosmetic after 6 months at 40°C was good, with no coloration or odor.

In addition, the results of sensory tests such as wrinkle smoothing effect, firmness effect, whitening effect, etc. were also good.

Example 7 ■ 6-0-Dodecanoyl ascorbic acid-2-phosphate magnesium salt 4.0 parts ■ Stearic acid 2.5 ■ Liquid paraffin 6.00 Behenyl alcohol
0.9■Vaseline
0.6 ■ Sorbitan monolaurate 0.5
07nostearate polyoxyethylene sorbitan (2
0E, O,) 0.5 ■ Glycerin 8.0 ■ Sodium N-acylglutamate 0.7 [Phase] Methyl paraben
0.2@purified water 8
8.20 Examination Applicability By using the above formulation, a milky lotion cosmetic of an O/W type emulsion was obtained by a conventional method. The test results for this cosmetic are ′”″“′″°′°
i1・h・)1, Moxibustion1. l! Table 4 Example 8 6-0-)' 6-0-octadecanoyl ascorbic acid-2-phosphate magnesium salt was used instead of decanoyl ascorbic acid-2-phosphate magnesium salt. A milky lotion cosmetic was obtained in the same manner as in Example 7.

The stability of the obtained liquid cosmetic after 6 months at 40°C is as follows:
A container that is much better against coloring, odor, etc. In addition, the results of sensory tests such as wrinkle smoothing effect, firmness effect, and whitening effect were also good.

Example 9 6-0-dodecanoyl ascorbic acid-2-phosphate instead of monoethanolamine salt.

A milky lotion cosmetic was prepared in the same manner as in Example 5, except that 6-0-octadecanoyl ascorbic acid-2-phosphate monopotassium salt was used.

? The stability of the emulsion cosmetic after 6 months at 40°C was good with no discoloration or odor. In addition, the results of sensory tests such as wrinkle smoothing effect, firmness effect, and whitening effect were similarly good.

Example 10 0.7 parts of 6-0-decanoyl ascorbic acid ester barium salt, 0.7 parts of 6-0-eicosanoyl ascorbic acid ester ammonium salt
1 part ethanol, 1 part glycerin S, 2 parts polyoxyethylene hydrogenated castor oil.

A pack agent of the present invention having a formulation (composition) of 71.6 parts of water and 9 parts of polyvinyl alcohol was prepared by a conventional method. The stability of the obtained pack agent after 6 months at 40°C was good, with no discoloration, odor, etc. It also has good results in sensory tests such as wrinkle smoothing effect, firmness effect, moisturizing effect, and whitening effect.

Example 11 12 parts of 6-0-tetradecanoyl ascorbic acid-8-phosphate calcium salt, 80 parts of starch, 5 parts of lactose
5 parts and an appropriate amount of perfume were mixed uniformly to obtain the powdered cosmetic of the present invention.

This powdered cosmetic was uniformly kneaded into a 10-fold amount of emulsion and applied to the face. When used twice a day for two months, sensory tests such as wrinkle smoothing effect, firmness effect, moisturizing effect, whitening effect, etc. were also positive.

Claims (1)

[Claims] 6-0-higher acylascorbic acid-phosphate ester selected from the group consisting of 6-0-higher acylascorbic acid-2-phosphate ester salt and 6-0-higher acylascorbic acid-3-phosphate ester salt A skin cosmetic containing at least one salt.