JPH10279419A - Preparation for external use for skin - Google Patents

Abstract

PROBLEM TO BE SOLVED: To obtain the subject preparation improved in rough skin preventive and remedying effect by including a specific acetylated hyaluronic acid and an α-hydroxyacid (salt) in specified proportions. SOLUTION: This preparation is obtained by formulating (A) 0.0001-10 wt.% of an acetylated hyaluronic acid pref. 10,000-1,000,000 in molecular weight in terms of hyaluronic acid and 2-4 in the number of substitution of acetyl groups per hyaluronic acid constitutive unit, (B) 0.001-10 wt.% of an α-hydroxyacid (salt) so as to be (100:1) to (1:10,000) in the weight ratio A/B, and (C) as necessary, ultraviolet light absorber, oil, moisturizer, antioxidant, surfactant, activator, perfume, water, color, etc. The ingredient A is formed, for example, by dispersing powdery hyaluronic acid in acetic acid followed by reaction in the presence of trifluoroacetic anhydride as catalyst. The ingredient B is pref. lactic acid, tartaric acid, citric acid or glycolic acid.

Description

DETAILED DESCRIPTION OF THE INVENTION

[0001]

BACKGROUND OF THE INVENTION 1. Field of the Invention The present invention relates to an external preparation for skin, and more particularly, to an improvement in the function of preventing rough skin and improving rough skin.

[0002]

2. Description of the Related Art Conventionally, hyaluronic acid has been blended in an external preparation for skin for the purpose of imparting a moisturizing effect, and has also been used to obtain a feeling of use unique to polymers having affinity for skin. On the other hand, α-hydroxy acids (citric acid, lactic acid, etc.)
In recent years, has been used in many cosmetics for the purpose of improving rough skin.

[0003]

However, the effects of hyaluronic acid or α-hydroxy acid on preventing skin roughness and improving skin roughness have not been sufficient yet, and the effects have not been met. The present invention has been made in view of the above-mentioned problems of the related art, and an object of the present invention is to provide a novel external preparation for skin that has improved skin roughness prevention and skin roughness improvement effects.

[0004]

Means for Solving the Problems The present inventors have conducted intensive studies to solve the above-mentioned problems, and as a result, have found that acetylated hyaluronic acid and one or more selected from α-hydroxy acids and salts thereof are used. It has been found that this object can be achieved by blending, and the present invention has been completed.

That is, the external preparation for skin according to the present invention comprises:
When the number of substitution of acetyl groups per hyaluronic acid structural unit is 2
Acetylated hyaluronic acid of 0.001 to 10
% By weight, and 0.001 to 10% by weight of one or more selected from α-hydroxy acids and salts thereof, and the compounding weight ratio of acetylated hyaluronic acid to α-hydroxy acids and salts thereof is 100 / 1 to 1 / 10,000. Further, in the external preparation for skin according to the present invention, α-hydroxy acid is lactic acid, tartaric acid,
Citric acid and glycolic acid are preferred.

[0006]

Embodiments of the present invention will be described below in detail. The acetylated hyaluronic acid used in the present invention preferably has a molecular weight of about 10,000 to 1,000,000 in terms of hyaluronic acid.

The acetylated hyaluronic acid used in the present invention has 2 to 4 acetyl groups per hyaluronic acid structural unit. If the number of substitution of the acetyl group is less than 2, the effect of the present invention cannot be sufficiently obtained, and if the number of substitution of the acetyl group is more than 4, it is difficult in the production method. The method for producing the acetylated hyaluronic acid used in the present invention is as follows.

A method of dispersing hyaluronic acid in powder form in acetic acid and reacting by adding trifluoroacetic anhydride as a catalyst, a method of dispersing in acetic acid and adding p-toluenesulfonic acid and further adding acetic anhydride and reacting the same, A method of suspending in an acetic acid solvent and adding concentrated sulfuric acid to cause a reaction and the like are known (JP-A-6-9707, JP-A-8-53501).

In the present invention, when acetylated hyaluronic acid is added, the amount of the acetylated hyaluronic acid is 0.00
It is from 0.01 to 10% by weight, preferably from 0.001 to 5% by weight. If the amount is less than 0.0001% by weight, the effect may not be exhibited. If the amount is more than 10% by weight, no improvement in the roughening effect can be expected, and further, the usability may deteriorate, which is not preferable.

The α-hydroxy acid used in the present invention is
An organic compound having a carboxyl group and an alcoholic hydroxyl group in one molecule, wherein the hydroxyl group is bonded to the carbon atom (α carbon) to which the carboxyl group is bonded. Specific examples include lactic acid, tartaric acid, citric acid, glycolic acid and salts thereof.

The amount of the α-hydroxy acid and its salt in the present invention is not particularly limited, but is preferably 0.001 to 10% by weight, more preferably 0.01 to 5% by weight, based on the total amount of the external preparation for skin. %. When the amount of the α-hydroxy acid and its salt is less than 0.001% by weight, a remarkable skin roughness improving effect may not be obtained.
If the amount is more than 0% by weight, no improvement in skin roughness improvement effect can be expected, and further, the usability may be deteriorated, which is not preferable.

In the present invention, the compounding weight ratio in which synergistic action of both acetylated hyaluronic acid and α-hydroxy acid and a salt thereof is remarkably recognized is approximately 100/1 to 1 after satisfying both effective compounding amounts. It is 1/10000. If the ratio is out of this range, one of the agents is added more than necessary, and there is no problem in the effect of improving skin roughness, but it is disadvantageous in terms of cost.

[0013] In addition to the above essential components, the skin external preparation of the present invention also contains other ingredients usually used in skin external preparations such as cosmetics and pharmaceuticals, such as avocado oil, palm oil, peanut oil, tallow, rice bran oil, jojoba oil. Oil, carnauba wax, lanolin, liquid paraffin, oxystearic acid, oil such as isostearyl palmitate, isostearyl alcohol, glycerin, sorbitol, polyethylene glycol, pyrrolidone carboxylic acid and salts thereof, collagen,
Moisturizers such as hyaluronic acid and its salts, chondroitin sulfate and its salts, ultraviolet absorbers such as amyl paradimethylaminobenzoate, urocanic acid, ethyl diisopropylcinnamate, and antioxidants such as sodium erythorbate, sage extract, and parahydroxyanisole Agent, sodium stearyl sulfate, diethanolamine cetyl sulfate,
Surfactants such as cetyltrimethylammonium saccharin, polyethylene glycol isostearate, and glyceryl arachiate; preservatives such as ethylparaben and butylparaben; extracts such as oak, orange, sicon, peonies, assembly, birch and loquat; Inflammatory agents such as glycyrrhetinic acid derivatives, salicylic acid derivatives, hinokitiol, zinc oxide, allantoin, placenta extracts, glutathione, yukinoshita extracts, ascorbic acid derivatives, etc. , Extract such as lily, royal jelly, photosensitizer, cholesterol derivative, activator such as various amino acids, saffron, senkyu, ginger, hypericum, ononis, rosemary, garlic, etc. Exudates, blood circulation promoters such as γ-oryzanol, dextran sodium sulfate, etc., antiseborrheic agents such as sulfur and thiantole, fragrances, water, alcohols, thickeners such as carboxyvinyl polymer, titanium yellow, carsamine, safflower red, etc. The coloring agent and the like can be appropriately compounded as needed.

The dosage form of the external preparation for skin of the present invention is arbitrary,
Any dosage form, such as a solution type, a solubilizing type, an emulsifying type, a powder dispersing type, a water-oil two-layer system, a water-oil-powder three-layer system, may be used. In addition, the use of the external preparation for skin of the present invention is also optional. Facial cosmetics such as lotions, emulsions, creams, packs and the like, makeup cosmetics such as foundations, lipsticks, eye shadows, etc., body cosmetics, aromatic cosmetics, cleaning Paints, ointments and the like.

[0015]

EXAMPLES Next, the present invention will be specifically described with reference to Examples, Comparative Examples and Test Examples. The present invention is not limited by this. In addition, the compounding amount is weight%. The acetylation degree indicates the number of acetyl groups substituted per hyaluronic acid constituent unit of acetylated hyaluronic acid. First, the present inventors conducted the following tests in the process of studying a skin external preparation containing acetylated hyaluronic acid.

Comparison between the present invention and the prior art [Example 1 and Comparative Example] Creams having the compositions shown in Table 1 were prepared and used as Example 1 and Comparative Example.

[0017]

[Table 1] ──────────────────────────── Composition (cream) Example 1 Comparative Example ク リ ー ム──────────────────── A. Cetanol 0.5 0.5 Vaseline 2.0 2.0 Squalane 7.0 7.0 Self-emulsifying glyceryl monostearate 2.5 2.5 POE (20) sorbitan monostearate 1.5 1.5 Punt Tenyl ethyl ether 0.5 0.5 Jojoba oil 5.0 5.0 B. Propylene glycol 5.0 5.0 Glycerin 5.0 5.0 Vegum (montmorillonite) 5.0 5.0 Aceylated hyaluronic acid ^{* 1} 0.1 Hyaluronic acid-0.1 Glycolic acid 1.0 1.0 KOH 0 0.3 0.3 water residue residue ──────────────────────────── * 1: acetylation degree 3.7, molecular weight 100,000 − Production method-A (oil phase) and B (aqueous phase) are each heated to 70 ° C and completely dissolved. Add A to B and emulsify with an emulsifier. The emulsion was cooled using a heat exchanger to obtain a cream.

<Surface Roughness Improving Effect Test> The cream having the formulation shown in Table 1 above was subjected to a skin roughness improving effect test on a human body panel.
First, when selecting a panel, the skin surface morphology of a healthy female person (face) was sampled using a replica method with myristin resin, and a replica of the skin was taken and observed with a microscope (17 ×). Based on the criteria shown in Table 2, 20 panelists (rough skin panels) judged to have rough skin evaluations 1 and 2 from the state were used as panels. The cream of Example 1 and the cream of Comparative Example were applied to the left and right half of the face of each panel twice a day. Two weeks later, a replica was again taken to observe the condition of the skin, and evaluated according to the criteria shown in Table 2. Table 3 shows the evaluation results.
Shown in

[0019]

[Table 2]

[0020]

[Table 3] As is clear from the results in Table 3, the cream containing acetylated hyaluronic acid and α-hydroxy acid (glycolic acid) (Example 1) is a cream containing normal hyaluronic acid and α-hydroxy acid (Comparative Example). ), A remarkable skin roughness improving effect was observed. From this, the present invention can be expected to have a remarkable effect in preventing rough skin. In addition, no side effects were observed in the test subjects (skin rough panel).

Acetylated hyaluronic acid and α-hydroxy
Mixing of acids and salts thereof [Test Examples 1 to 4] A cream with various formulations shown in Table 4 below was subjected to a test for improving the rough skin by 30 rough skin panels, and the results are shown in Table 5. The method for producing the cream and the method for testing the effect of improving skin roughness were performed in accordance with Example 1 and Comparative Example, and the evaluation criteria were as shown in Table 2.

[0022]

[Table 4] ───────────────────────────── Composition (cream) Test example No. 1 2 3 4 ────────────────────────── A. Cetanol 0.5 0.5 0.5 0.5 Vaseline 2.0 2.0 2.0 2.0 Squalane 7.0 7.0 7.0 7.0 Self-emulsifying glycerin monostearate 2.5 2.5 2.5 2.5 POE (20) sorbitan monostearate 1.5 1.5 1.5 1.5 Pantothenyl ethyl ether 0.5 0.5 0.5 0.5 Jojoba oil 5.0 5.0 5.0 5.0 B. Propylene glycol 5.0 5.0 5.0 5.0 Glycerin 5.0 5.0 5.0 5.0 Podium (montmorillonite) 5.0 5.0 5.0 5.0 Aceylated hyaluronic acid ^{* 1} 0.1 1.1 Glycolic acid 1.0 1.1 KOH 0.3 0.3 0.3 0.3 Water Residual Residual Residual ────────────────────────── ───

[0023]

[Table 5]

As is clear from the results shown in Table 5, a cream containing both acetylated hyaluronic acid and α-hydroxy acid (glycolic acid) (Test Example 1) was used on the face portion without using both creams (Test Example 1). As compared with the facial part using Test Examples 2 to 4, a remarkable skin roughness improving effect was observed. Therefore, it can be seen that the effect of preventing skin roughness and improving skin roughness is drastically improved by blending acetylated hyaluronic acid, α-hydroxy acid and a salt thereof.

Placement of acetyl group on acetylated hyaluronic acid
Permutation [Test Examples 5 to 8] A rough skin improving effect test of creams of various formulations containing different acetylated hyaluronic acids having different degrees of acetylation in Table 6 below was performed by 20 rough skin panels.
Table 7 shows the results. In addition, the production method of cream,
The method of the skin roughness improvement effect test is performed according to Example 1 and Comparative Example, and the evaluation criteria are as shown in Table 2.

[0026]

[Table 6] ───────────────────────────── Composition (cream) Test example No. 56678 ─── ────────────────────────── A. Cetanol 0.5 0.5 0.5 0.5 Vaseline 2.0 2.0 2.0 2.0 Squalane 7.0 7.0 7.0 7.0 Self-emulsifying glycerin monostearate 2.5 2.5 2.5 2.5 POE (20) sorbitan monostearate 1.5 1.5 1.5 1.5 Pantothenyl ethyl ether 0.5 0.5 0.5 0.5 Jojoba oil 5.0 5.0 5.0 5.0 B. Propylene glycol 5.0 5.0 5.0 5.0 Glycerin 5.0 5.0 5.0 5.0 Podium (montmorillonite) 5.0 5.0 5.0 5.0 Acetylation degree of hyaluronic acid acetylation 1 0.1 Degree of acetylation 1.5 0.1 Degree of acetylation 2 0.1 Degree of acetylation 4 0.1 Glycolic acid 1.0 1.0 1.0 1.0 KOH 0.3 0.3 0.3 0.3 Water Residue Residue Residue ──────── ────── ──────────────

[0027]

[Table 7]

As is clear from the results shown in Table 7, the creams containing acetylated hyaluronic acid having 2 to 4 acetyl groups per hyaluronic acid structural unit (Test Examples 8 to 9) were prepared. Cream containing acetylated hyaluronic acid having less than 2 substitutions (Test Examples 5 and 6)
It can be seen that the skin roughness improvement effect is superior to that of Comparative Example 1.

Formulation of α-hydroxy acids and salts thereof [Test Examples 9 to 14] The cream roughening improving effect test of creams of various formulas containing α-hydroxy acids or other skin roughening inhibitors shown in Table 8 below was performed. The results are shown in Table 9. The method for producing the cream and the method for testing the effect of improving skin roughness were performed in accordance with Example 1 and Comparative Example, and the evaluation criteria were as shown in Table 2.

[0030]

[Table 8] ──────────────────────────────────── Composition example number of cream 9 10 11 12 13 14 A. Cetanol 0.5 0.5 0.5 0.5 0.5 0.5 Vaseline 2.0 2.0 2.0 2.0 2.0 2.0 Squalane 7.0 7.0 7.0 7.0 7.0 7.0 Self-emulsifying glycerin monostearate 2.5 2.5 2.5 2.5 2.5 2.5 POE (20) sorbitan monostearate 1.5 1.5 1.5 1.5 1.5 1.5 Pantothenyl ethyl ether 0.5 0.5 0.5 0.5 0.5 0.5 Jojoba oil 5.0 5.0 5.0 5.0 5.0 5.0 B. propylene glycol 5.0 5.0 5.0 5.0 5.0 5.0 glycerin 5.0 5.0 5.0 5.0 5.0 5.0 pericamu (montmorillonite) 5.0 5.0 5.0 5.0 5.0 5.0 acetylated hyaluronic acid ^{* 1} 0.1 0.1 0.1 0.1 0.1 0.1 Glycolic acid 1.0 Lactic acid 1.0 Tartaric acid 1.0 Citric acid 1.0 Tanni Acid 1.0 pantothenic acid 1.0 KOH 0.3 0.3 0.3 0.3 0.3 0.3 water residue residue residue residue residue residue residue ────────────────────────────── ──────

[0031]

[Table 9] レ プ リ カ Replica test example number Evaluation 910 11 12 13 14 ──────────────────────────────────── 1 point 0 people 0 people 0 people 0 people 0 people 0 people 2 0 0 0 0 2 3 3 0 1 0 1 1 5 6 4 3 4 1 ... 4 3 1 5 7 8 6 5 0 5 0 ────────────────── Panel total 10 people 10 people 10 people 10 people 10 people 10 people ────────────────── ──────────────────

As is clear from the results shown in Table 9, the creams containing acetylated hyaluronic acid and α-hydroxy acid (Test Examples 9 to 12) have excellent skin roughness improving effects. On the other hand, tannic acid which is not an α-hydroxy acid but has both a hydroxyl group and a carboxyl group and is used for preventing rough skin (Test Example 1)
3) It can be seen that a cream containing pantothenic acid (Test Example 14) cannot achieve a remarkable synergistic effect of improving skin roughness as in the present invention.

Amount of acetylated hyaluronic acid [Test Examples 15 to 20] A test for improving the rough skin of creams of various formulations having different amounts of acetylated hyaluronic acid shown in Table 10 below was conducted by 30 rough skin panels. The results are shown in Table 11. The method for producing the cream and the method for testing the effect of improving skin roughness were performed in accordance with Example 1 and Comparative Example, and the evaluation criteria were as shown in Table 2.

[0034]

[Table 10] ──────────────────────────────────── Composition (Cream) Test Example No. 15 16 17 18 19 20 ──────────────────────────────────── A. Cetanol 0.5 0.5 0.5 0.5 0.5 0.5 Vaseline 2.0 2.0 2.0 2.0 2.0 2.0 Squalane 7.0 7.0 7.0 7.0 7.0 7.0 Self-emulsifying glycerin monostearate 2.5 2.5 2.5 2.5 2.5 2.5 POE (20) sorbitan monostearate 1.5 1.5 1.5 1.5 1.5 1.5 Pantothenyl ethyl ether 0.5 0.5 0.5 0.5 0.5 0.5 Jojoba oil 5.0 5.0 5.0 5.0 5.0 5.0 B. propylene glycol 5.0 5.0 5.0 5.0 5.0 5.0 glycerin 5.0 5.0 5.0 5.0 5.0 5.0 pericamu (montmorillonite) 5.0 5.0 5.0 5.0 5.0 5.0 acetylated hyaluronic acid ^{* 1} 0.00005 0.0001 0.001 5 10 15 Glycolic acid 1.0 1.0 1.0 1.0 1.0 1.0 KOH 0. 3 0.3 0.3 0.3 0.3 0.3 Water Residue Residue Residue Residue Residue ────────────────────────────────────

[0035]

[Table 11] レ プ リ カ Replica test example number Evaluation 15 16 17 18 19 20 ──────────────────────────────────── 1 point 0 people 0 people 0 people 0 people 0 people 0 people 2 2 0 0 0 0 0 3 6 3 1 2 1 0 1 2 4 3 3 4 2 3 2 5 0 4 5 6 7 7 7 ────────────────── Panel total 10 people 10 people 10 people 10 people 10 people 10 people ────────────────── ──────────────────

As is clear from the results in Table 11, the content of acetylated hyaluronic acid was 0.0001 to 10% by weight.
It can be seen that the creams (Test Examples 16 to 19) have excellent skin roughness improving effects.

On the other hand, the cream (Test Example 20) in which the blending amount of acetylated hyaluronic acid exceeds 10% by weight is excellent in the effect of improving rough skin, but it is understood that the effect is not improved. Also, from Table 11, the compounding amount of the acetylated hyaluronic acid used in the present invention is 0.0001% by weight.
It is understood that the effect of the present invention is hardly obtained when the amount is smaller than the above (Test Example 16). Therefore, in the skin external preparation of the present invention, the blending amount of acetylated hyaluronic acid is 0.000.
It is found that the content is preferably 1 to 10% by weight.

Amounts of α-Hydroxy Acid and Salts [Test Examples 21 to 26] Tests for improving skin roughness of creams of various formulas with different amounts of α-hydroxy acid shown in Table 12 below were carried out by 30 rough skin panels. Table 1
3 is shown. The method for producing the cream and the method for testing the effect of improving skin roughness were performed according to Example 1 and Comparative Example.
The evaluation criteria are as shown in Table 2.

[0039]

[Table 12] 組 Composition (Cream) Test Example No. 21 22 23 24 25 26 A. Cetanol 0.5 0.5 0.5 0.5 0.5 0.5 Vaseline 2.0 2.0 2.0 2.0 2.0 2.0 Squalane 7.0 7.0 7.0 7.0 7.0 7.0 Self-emulsifying glycerin monostearate 2.5 2.5 2.5 2.5 2.5 2.5 POE (20) sorbitan monostearate 1.5 1.5 1.5 1.5 1.5 1.5 Pantothenyl ethyl ether 0.5 0.5 0.5 0.5 0.5 0.5 Jojoba oil 5.0 5.0 5.0 5.0 5.0 5.0 B. propylene glycol 5.0 5.0 5.0 5.0 5.0 5.0 glycerin 5.0 5.0 5.0 5.0 5.0 5.0 pericamu (montmorillonite) 5.0 5.0 5.0 5.0 5.0 5.0 acetylated hyaluronic acid ^{* 1} 0.1 0.1 0.1 0.1 0.1 0.1 Glycolic acid 0.0005 0.001 0.01 5 10 15 KOH 0.3 0. 3 0.3 0.3 0.3 0.3 Water Residue Residue Residue Residue Residue ────────────────────────────────────

[0040]

[Table 13] レ プ リ カ Replica test example number Evaluation 21 22 23 24 25 26 ──────────────────────────────────── 1 point 1 person 0 people 0 people 0 people 0 people 0 people 2 3 0 0 0 0 0 3 6 3 2 1 0 0 0 4 0 4 4 2 2 2 5 0 3 4 7 8 8} ────────────────── Panel total 10 people 10 people 10 people 10 people 10 people 10 people ────────────────── ──────────────────

As is clear from the results shown in Table 13, the cream (Test Example 21) in which the amount of the α-hydroxy acid is less than 0.001% by weight does not have a remarkable skin roughness improving effect. A cream containing 0.001 to 10% by weight of the α-hydroxy acid (Test Examples 22 to
In 25), the effect of improving skin roughness is improved by increasing the amount of the α-hydroxy acid. On the other hand, a cream containing more than 10% by weight (Test Example 2)
6) shows that no improvement is seen in the effect of improving skin roughness as compared with a cream containing 10% by weight of α-hydroxy acid (Test Example 25). Therefore, it is understood that the compounding amount of the α-hydroxy acid is suitably 0.001 to 10% by weight.

Acetylated hyaluronic acid and α-hydroxy
Combination weight ratio of acid and salt thereof [Test Examples 27 to 32] Aceylated hyaluronic acid (AcHA) and α-hydroxy acid and salt thereof (A
A test for improving skin roughness of creams of various formulas having different blending weight ratios of HA) was conducted by 30 panelists with rough skin, and the results are shown in Table 15. In addition, the production method of cream,
The method of the skin roughness improvement effect test is performed according to Example 1 and Comparative Example, and the evaluation criteria are as shown in Table 2.

[0043]

[Table 14] ──────────────────────────────────── Composition (cream) Test example No. 27 28 29 30 31 32 A. Cetanol 0.5 0.5 0.5 0.5 0.5 0.5 Vaseline 2.0 2.0 2.0 2.0 2.0 2.0 Squalane 7.0 7.0 7.0 7.0 7.0 7.0 Self-emulsifying glycerin monostearate 2.5 2.5 2.5 2.5 2.5 2.5 POE (20) sorbitan monostearate 1.5 1.5 1.5 1.5 1.5 1.5 Pantothenyl ethyl ether 0.5 0.5 0.5 0.5 0.5 0.5 Jojoba oil 5.0 5.0 5.0 5.0 5.0 5.0 B. propylene glycol 5.0 5.0 5.0 5.0 5.0 5.0 glycerin 5.0 5.0 5.0 5.0 5.0 5.0 pericamu (montmorillonite) 5.0 5.0 5.0 5.0 5.0 5.0 acetylated hyaluronic acid ^{* 1} 10 1 0.01 0.0001 0.0001 0.0001 Glycolic acid 0.01 0.01 0.01 0.1 1 10 KOH 0. 3 0.3 0.3 0.3 0.3 0.3 Water Residue Residue Residue Residue Residue ──────────────────────────────────── Formula Ratio (AcHA / AHA) 1000/100/1/1/1/1/1/1 1 1 1000 10000 100000 ────────────────────────── ──────────

[0044]

[Table 15] レ プ リ カ Replica test example number Evaluation 27 28 29 30 31 32 ──────────────────────────────────── 1 point 0 people 0 people 0 people 0 people 0 people 0 people 2 0 0 0 0 0 0 3 2 1 3 2 1 1 1 2 4 3 3 3 3 2 2 5 6 6 4 5 7 7 ────────────────── Panel total 10 people 10 people 10 people 10 people 10 people 10 people ────────────────── ──────────────────

As is clear from the results in Table 15, the compounding weight ratio of acetylated hyaluronic acid to α-hydroxy acid is 1
/ 100 compared to the cream (Test Example 29)
/ 1 cream (Test Example 28) shows an improvement in skin roughness improvement effect. On the other hand, the cream (Test Example 27) in which the ratio of acetylated hyaluronic acid was increased beyond 100/1 showed an improvement in the effect of improving skin roughness as compared with the cream of 100/1 (Test Example 28). You can see that it cannot be done.

The cream (Test Example 31) in which the weight ratio of acetylated hyaluronic acid to α-hydroxy acid was 1/10000 (Test Example 31) was replaced by the cream (Test Example 3) of 1/1000.
Compared with 0), the effect of improving skin roughness is recognized. On the other hand, it can be seen that the cream containing more than 1 / 10,000 (Test Example 32) cannot improve the skin roughness improvement effect compared to the cream of 1 / 10,000 (Test Example 31). . Therefore, the blending weight ratio of acetylated hyaluronic acid and α-hydroxy acid is 100/1 to 1/10.
000 is found to be appropriate.

Examples will be shown below to make the external preparation for skin according to the present invention more specific. The same evaluation as in Example 1 was performed. As a result, the external preparation for skin of each example exhibited an excellent skin roughness improving effect as in Example 1.

Example 2 Cream Ingredient Content (%) Stearic acid 10.0 Stearyl alcohol 4.0 Butyl stearate 8.0 Monoglycerin stearate 2.0 Vitamin E acetate 0.5 Vitamin A palmitate 0.1 Macadamia nut oil 1.0 Fragrance 0.4 Preservative Adequate amount B . Glycerin 4.0 1,2, pentanediol 3.0 Acetylated hyaluronic acid (acetylation degree 3.1) 1.0 Potassium hydroxide 0.4 Magnesium phosphate ascorbate 0.1 Tartaric acid 0.01 Trisodium edetate 0 .05 Purified water residue -Preparation method- The oil phase of A and the water phase of B were each heated to 70 ° C. and completely dissolved. Add phase A to phase B and emulsify with an emulsifier. The emulsion was cooled using a heat exchanger to obtain a cream.

Example 3 Cream Ingredient Content (%) Cetanol 4.0 Vaseline 7.0 Isopropyl myristate 8.0 Squalane 15.0 Monoglycerin stearate 2.2 POE (20) Sorbitan monostearate 2.8 Vitamin E nicotinate 2.0 Fragrance 0.3 Antioxidant Appropriate amount Preservative Appropriate amount B. Glycerin 10.0 Acetylated hyaluronic acid (acetylation degree 2.6) 0.02 Dipropylene glycol 4.0 Sodium pyrrolidonecarboxylate 1.0 Sodium lactate 3.0 Disodium edetate 0.01 Purified water Remaining Examples A cream was obtained according to 2.

Example 4 Emulsion Component Compounding Amount (%) Squalane 5.0 Oleyl oleate 3.0 Vaseline 2.0 Sorbitan sesquioleate 0.8 POE (20) oleyl ether 1.2 Evening primrose oil 0.5 Fragrance 0.3 Preservatives Appropriate amount B. 1.3 Butylene glycol 4.5 Melissa extract 1.5 Acetylated hyaluronic acid (acetylation degree 3.9) 0.001 Ethanol 3.0 Carboxyvinylporlimer 0.2 Potassium hydroxide 0.1 Lactic acid 0.01 Sodium hexametaphosphate 0.05 Purified water Residue An emulsion was obtained according to Example 2.

Example 5 Foundation Component Compounding Amount (%) Cetanol 3.5 Deodorized lanolin 4.0 Jojoba oil 5.0 Vaseline 2.0 Squalane 6.0 Monoglycerin stearate 2.5 POE (60) hydrogenated castor oil 1.5 POE (20) cetyl ether 1.0 Pyridoxine Tripalmitate 0.1 Preservative qs perfume 0.3 B. Propylene glycol 10.0 Acetylated hyaluronic acid (acetylation degree 3.4) 0.05 Compounded powder 12.0 Sodium citrate 5.0 Trisodium edetate 0.2 Purified water Residue A foundation according to Example 2 Obtained.

Example 6 Lotion Component Content (%) Ethanol 5.0 POE oleyl alcohol ether 2.0 2-ethylhexyl-P-dimethylaminobenzoate 0.18 preservatives qs perfume 0.05 B. 1,3 butylene glycol 9.5 sodium pyrrolidonecarboxylate 0.5 acetylated hyaluronic acid (degree of acetylation 2.1) 5.0 nicotinamide 0.3 glycerin 5.0 hydroxypropyl β-cyclodextrin 1.0 citric acid 0.1 Sodium citrate 0.3 Purified water Residue The alcohol phase of A was added to the aqueous phase of B and solubilized to obtain a lotion.

Example 7 Packing Component Content (%) (1) Polyvinyl alcohol 10.0 (2) Polyethylene glycol (molecular weight 400) 0.4 (3) Glycerin 3.0 (4) Ethanol (95%) 8.0) (5) Acetylated hyaluronic acid (acetylation degree 3.5) 0.1 (6) Lactic acid 0.1 (7) Preservative 0.1 (8) Fragrance 0.1 (9) Purified water residue Excess -Production- (4) (7) (8) are mixed and dissolved at room temperature, and (1) (2)
(3), (5), (6) and (9) were mixed and dissolved at 80 ° C., and the mixture was stirred and added, and then allowed to cool to room temperature to obtain a pack.

Example 8 Lipstick Ingredient Content (%) Castor oil 20.0 Cetyl alcohol 20.0 Beeswax 5.0 Candelilla wax 30.0 Acetylated hyaluronic acid (acetylation degree 3.1) 0001 Squalane 13.0 Carnauba wax 5.0 Pigment 5.0 Glycolic acid 0.01 Fragrance Appropriate amount -Preparation method- Mix and dissolve at 80 ° C, pour into mold, allow to cool to room temperature, remove from mold, stick lipstick I got

[0055]

The external preparation for skin of the present invention has an advantage that by mixing acetylated hyaluronic acid, α-hydroxy acid and its salt, the effect of preventing and improving skin roughness can be significantly increased without side effects. I have.

──────────────────────────────────────────────────続 き Continued on the front page (51) Int.Cl. ⁶ Identification code FI A61K 7/48 A61K 7/48

Claims (2)

[Claims] 1. An acetylated hyaluronic acid having 0.004 to 10% by weight of an acetyl group having a substitution number of 2 to 4 per hyaluronic acid structural unit, and one or two selected from α-hydroxy acids and salts thereof. 0.001 for seeds or more
Acetylated hyaluronic acid and α
The compounding weight ratio of hydroxy acid and its salt is 100/1
An external preparation for skin, characterized in that the ratio is １ ／ 1 / 10,000. 2. The external preparation for skin according to claim 1, wherein
An external preparation for skin, wherein the α-hydroxy acid is lactic acid, tartaric acid, citric acid, or glycolic acid.