JPH10279424A - Preparation for external use for skin - Google Patents

Abstract

PROBLEM TO BE SOLVED: To obtain the subject preparation having moisturizing effect of excellent stability with time and esp. excellent in usability, by including a specific acetylated hyaluronic acid and a silicone oil in specified proportions. SOLUTION: This preparation is obtained by formulating (A) 0.0001-10 wt.% of an acetylated hyaluronic acid 2-4 in the number of substitution of acetyl groups per hyaluronic acid constitutive unit, (B) 0.1-60 wt.% of a silicone oil so as to be (1:1) to (1:40,000) in the weight ratio A/B with a viscosity of pref. 6-100 cSt (e.g. methyl phenylpolysiloxane), and (C) as necessary, surfactant, oil moisturizer, ultraviolet light absorber, alcohol, chelating agent, antiseptic, thickening agent, color, perfume, etc. The ingredient A is formed, for example, by dispersing powdery hyaluronic acid in acetic acid followed by reaction in the presence of trifluoroacetic acid as catalyst.

Description

[Detailed description of the invention]

[0001]

BACKGROUND OF THE INVENTION 1. Field of the Invention The present invention relates to external preparations for skin, and in particular to improvements in usability thereof.

[0002]

2. Description of the Related Art In general, a state in which the stratum corneum of the skin contains 10 to 15% of water is said to be healthy skin. If it contains too much water, it will become fuzzy, and if it contains too little, it will become dry. To solve this, lotion,
Hyaluronic acid, which has excellent moisturizing ability relatively regardless of the humidity of the outside air, is used as a moisturizing agent for external skin preparations such as creams and milky lotions. In addition to hyaluronic acid, moisturizing agents such as sodium lactate,
Glycerin, 1,3-butylene glycol, propylene glycol and the like are used in relatively large amounts from the viewpoint of their affinity for the skin and their feel during use.

[0003]

However, even in a topical preparation for skin containing hyaluronic acid, which has a relatively excellent moisturizing ability, the water in the topical preparation volatilizes to the outside air when used for a long period of time under low humidity conditions. However, not only does the moisturizing effect disappear, but in some cases, moisture is taken in from the skin into the external skin preparation, causing the skin to dry out. I didn't.

[0004] Among the moisturizing agents, hyaluronic acid in particular has a problem that even a small amount of hyaluronic acid causes a strong sticky feeling on the skin. In addition, moisturizing agents other than hyaluronic acid are often blended in an extremely large amount, particularly in external preparations for skin that appeal to a rich feeling, which further increases the stickiness. The present invention has been made in view of the above-mentioned problems of the prior art, and its purpose is to:
To provide an external preparation for skin which has a moisturizing effect with excellent stability over time and is particularly excellent in usability.

[0005]

Means for Solving the Problems As a result of extensive research in order to solve the above-mentioned problems, the present inventors have found that acetylated hyaluronic acid and silicone oil are more effective than skin preparations obtained by simply blending hyaluronic acid. The inventors have found that the external preparation for skin containing the composition is superior in the stability of the moisturizing effect over time, particularly in usability, and have completed the present invention.

The external preparation for skin according to the present invention maintains the excellent moisturizing effect of hyaluronic acid, has a high affinity with the skin, and is less sticky. That is, by forming a film of silicone oil on the skin, it is possible to make the skin smooth, to provide appropriate “moisture”, and to suppress stickiness. As a result, the moisturizing effect has excellent stability over time,
In particular, we were able to complete an external preparation for skin that is excellent in usability.

That is, the present invention comprises 0.0001 to 10% by weight of acetylated hyaluronic acid having 2 to 4 acetyl group substitutions per hyaluronic acid structural unit, and 0.1 to 60% by weight of silicone oil. and the blending weight ratio of acetylated hyaluronic acid and silicone oil is 1/1 to 1
/40000.

[0008]

DETAILED DESCRIPTION OF THE INVENTION Embodiments of the present invention will be described in detail below. The amount of acetylated hyaluronic acid in the present invention is 0.0001 to 1 in the total amount of the external skin preparation.
0% by weight, preferably 0.001 to 5% by weight.
If it is less than 0.0001% by weight, the effect of the present invention may not be exhibited, and if it exceeds 10% by weight, stickiness may occur in terms of usability, which is not preferable.

The acetylated hyaluronic acid used in the present invention preferably has 2 to 4 acetyl group substitutions per hyaluronic acid structural unit. If the number of acetyl group substitutions is less than 2, the feeling of use may be poor, and if the number of acetyl group substitutions is more than 4, it is difficult to produce. The method for producing the acetylated hyaluronic acid according to the present invention is as follows.

A method of dispersing powdered hyaluronic acid in acetic acid and adding trifluoroacetic anhydride as a catalyst for reaction, a method of dispersing hyaluronic acid in acetic acid and adding p-toluenesulfonic acid and further adding acetic anhydride to react, There is known a method of suspending it in an acetic acid solvent and adding concentrated sulfuric acid for reaction (JP-A-6-9707, JP-A-8-53501).

The silicone oil used in the present invention may be any organosilicon compound having a siloxane bond, such as methylpolysiloxane, dimethylpolysiloxane, methylphenylpolysiloxane, methylhydrogenpolysiloxane, decamethylcyclo Examples include pentasiloxane, octamethylcyclotetrasiloxane, and polyoxyethylene/methylpolysiloxane copolymer.

[0012] The silicone oil used in the present invention preferably has a viscosity of about 6 to 100 cSt. If the viscosity is too low, the stability of the moisturizing effect over time may decrease, and the stickiness of acetylated hyaluronic acid may not be suppressed.
If the viscosity is too high, the silicone oil itself may become sticky, which is not preferable.

[0013] The amount of silicone oil used in the present invention is preferably 0.1 to 60% by weight. If the amount of silicone oil blended is too small, it may be difficult to sufficiently suppress the stickiness of the topical preparation, and the stability of the moisturizing effect over time may not be improved. This is not desirable.

The external preparation for skin of the present invention includes general skin conditioning and nutritional lotions, as well as cosmetic lotions such as astringent lotions, shave lotions, body lotions, and water-based cosmetics such as liquid packs, as well as nutritional creams and eye creams. Creams such as creams, body creams, hand creams, massage creams, cold creams, emulsions such as nutritional emulsions, body emulsions, neck emulsions, hand emulsions, etc.
Packs are the main items.

The external preparation for skin of the present invention contains surfactants, oils, humectants, UV absorbers, alcohols, chelating agents, preservatives, thickeners, which are generally used in cosmetics and quasi-drugs. Ingredients such as pigments and fragrances can be blended.

[0016]

EXAMPLES The present invention will be described in more detail below with reference to examples, comparative examples and test examples, but the present invention is not limited thereto. In addition, all compounding amounts shown below are % by weight. In addition, the degree of acetylation indicates the number of substitutions of acetyl groups per hyaluronic acid structural unit of acetylated hyaluronic acid. First, the present inventors conducted the following tests in the course of examining skin external preparations containing hyaluronic acid and having a moisturizing effect.

Comparison between the present invention and the prior art [Example 1 and Comparative Example] Milky lotions having the following compositions were prepared as Example 1 and Comparative Example.

[0018]

[Table 1] ──────────────────────────────────── Composition (emulsion) Example 1 Comparative example ─ ──────────────────────────────────── A. Stearic acid 2.0 2.0 Cetanol 1.0 1.0 Vaseline 2.0 2.0 Liquid paraffin 6.0 6.0 Cetyl 2-ethylhexanoate 1.0 1.0 Jojoba oil 1.0 1.0 Squalane 2.0 2.0 Tetra-2-ethylhexanoic acid 3.0 3.0 Pentaerythritol methylphenylpolysiloxane ^*1 3.0 3.0 Decamethylpentasiloxane ^*2 2.0 2.0 Evening primrose oil 0.0. 5 0.5 mono-2-di-paramethoxycinnamate 1.5 1.5 glyceryl ethylhexanoate 4-tert-butyl-4'- 3.0 3.0 methoxydi-benzoylmethane POE(10) monooleate 3. 0 3.0 Dibutyl hydroxytoluene 0.1 0.1 Vitamin B6 tripalmitate 0.01 0.01 _Butylparaben 0.2 0.2 Perfume Appropriate amount Appropriate amount Propylene Glycol 5.0 5.0 1,3-Butylene Glycol 2.0 2.0 Acetylated Hyaluronic Acid ^*3 0.1 Hyaluronic Acid ^*4 0.1 Arbutin 5.0 5.0 Carboxyvinyl Polymer 0.2 0 .2 Triethanolamine 0.2 0.2 Purified water Remainder Remainder ────────────────────────────────── ─── *1: Viscosity 50 cSt (manufactured by Shin-Etsu Chemical Co., Ltd.) *2: Viscosity 5 cSt (manufactured by Shin-Etsu Chemical Co., Ltd.) *3: Degree of acetylation 3.5 *4: Molecular weight approximately 1 million (manufactured by Shiseido Co., Ltd.) conductance (manufactured by IBS:
SKICON 200) was examined, and the moisturizing effect of the emulsions shown in Table 1 was evaluated. The method for evaluating the moisturizing effect of emulsion is as follows.

<Test Method for Moisturizing Effect> Twenty women were divided into two groups to form a panel.
The second group was applied with the emulsion of the comparative example. Moisturizing effect was evaluated by measuring conductance over time. Table 2 shows the results.

[0020]

[Table 2] ──────────────────────────────────── Moisturizing effect Immediately After 1 hour After 3 hours 6 hours later ──────────────────────────────────── Example 1 255 μS 220 μS 200 μS 190 μS Comparative example 270 200 150 120 ──────────────────────────────────── From the results of Table 2, the acetyl The milky lotion (Example 1) containing modified hyaluronic acid and silicone oil was
It can be seen that it has a moisturizing effect with excellent stability over time similar to that of a normal milky lotion containing hyaluronic acid and silicone oil (comparative example).

<Method of Feeling Test> When measuring the moisturizing effect of the above panel, the feeling of use was evaluated in terms of familiarity with the skin and stickiness. The evaluation criteria for feeling in use are as follows. [Evaluation Criteria for Feeling in Use] ○: Good compatibility with skin △: Neither can be said ×: Poor compatibility with skin ○: Not sticky △: Neither can be said ×: Stickiness The results are shown in Table 3.

[0022]

[Table 3] ──────────────────────────────────── Usability test Skin familiarity Stickiness ──────────────────────────────────── Example 1 ○ 9 people ○ 8 people △ 1 △ 2 × 0 × 0 Comparative example ○ 5 ○ 1 △ 4 △ 3 × 1 × 6 ────────────────────────────────────

From the results in Table 3, the emulsion (Example 1) containing acetylated hyaluronic acid and silicone oil has excellent skin affinity (compatibility with the skin), and the stickiness of hyaluronic acid is remarkably improved by silicone oil. It can be seen that On the other hand, in the case of the milky lotion (comparative example) containing normal hyaluronic acid and silicone oil, it is found that the compatibility with the skin is inferior to that of Example 1, and the stickiness is not improved. Furthermore, the effects of the emulsions of Example 1 and Comparative Examples were confirmed by use tests.

<Test method for use test> The use test is
A panel of 20 women was divided into two groups each. The emulsion of Example 1 was applied to the first group, and the emulsion of the comparative example was applied to the second group, twice daily in the morning and at night. The effectiveness was evaluated for three items: firmness and skin moisture in the next morning. Table 4 shows the results.

[0025]

[Table 4] ──────────────────────────────────── Emulsion use test Effective Somewhat ineffective Effective rate Effectiveness (%) ──────────────────────────────────── Example 1 Skin moisture 9 people 1 person 0 people 100 Skin firmness 9 1 0 100 Skin moisture the next morning 7 2 1 90 Comparative example Skin moisture 9 people 1 person 0 people 100 Skin firmness 8 2 0 100 Skin moisture the next morning 6 3 1 90 ────────────────────────────────────

As is clear from the results in Table 4, the emulsion containing acetylated hyaluronic acid and silicone oil (Example 1), like the usual emulsion containing hyaluronic acid and silicone oil (Comparative Example), It had excellent effects on skin moisture, skin firmness, and skin moisture in the next morning.

Acetylated Hyaluronic Acid and Silicone Oil
Formulation [Test Examples 1 to 4] Milky lotions having various compositions shown in Table 5 were prepared as Test Examples 1 to 4. The manufacturing method conforms to Example 1 and Comparative Example.

[0028]

[Table 5] ──────────────────────────────────── Composition (Emulsion) Test Example No. 1 2 3 4 ──────────────────────────────────── A. Stearic acid 2.0 2.0 2.0 2.0 Cetanol 1.0 1.0 1.0 1.0 Vaseline 2.0 2.0 2.0 2.0 Liquid paraffin 6.0 6.0 6.0 6.0 Cetyl 2-ethylhexanoate 1.0 1.0 1.0 1.0 ^Jojoba oil 1.0 1.0 1.0 1.0 Squalane 2.0 2.0 2.0 2.0 ¹ 3.0 - 3.0 -Dekamethylpentasiloxane ^*2 2.0 - 2.0 - Evening primrose oil 0.5 0.5 0.5 0.5 Di-paramethoxycinnamic acid Glyceryl mono-2-ethylhexanoate 1.5 1.5 1.5 1.5 4-tert-butyl-4'-methoxy-シ゛ヘ゛ンソ゛イルメタン 3.0 3.0 3.0 3.0 POE(10)モノオレート 3.0 3.0 3.0 3.0 シ゛フ゛チルヒト゛ロキシトルエン 0.1 0.1 0.1 0.1 ヒ゛タミンB ₆トリハ゜ルミテート 0.01 0.01 0.01 0.01 ブチルパラベン 0.2 0.2 0.2 0.2 香料 適量 適量 適量 適量B.プロピレングリコール 5.0 5.0 5.0 5.0 1,3-Butylene Glycol 2.0 2.0 2.0 2.0 Acetylated Hyaluronic Acid ^*3 0.1 - - 0.1 Arbutin 5.0 5.0 5.0 5.0 Carboxyvinyl Polymer 0.2 0.2 0.2 0.2 Triethanolamine 0.2 0.2 0.2 0.2 Purified Water Remainder Remainder Remainder ─── ──────────────────────────────────

<Test of moisturizing effect> Next, 40 women were divided into four groups to form panels, and the milky lotions of Test Examples 1 to 4 were applied to the first to fourth groups, respectively. Moisturizing effect was evaluated by measuring conductance over time. Table 6 shows the results.

[0030]

[Table 6] ──────────────────────────────────── Test example number Immediately after 1 hour after 3 hours after 6 hours ──────────────────────────────────── 1 255μS 220μS 200μS 190μS 2 230 70 30 10 3 260 150 50 35 4 245 135 50 30 ────────────────────────────────────

From the results in Table 6, the milky lotion containing only silicone oil (Test Example 3) or the milky lotion containing only acetylated hyaluronic acid (Test Example 4) did not contain both (Test Example 2). Although it has a slightly moisturizing effect compared to , it is inevitable that the moisturizing effect will decrease over time.
On the other hand, it can be seen that the milky lotion containing acetylated hyaluronic acid and silicone oil (Test Example 1) dramatically increases the stability of the moisturizing effect over time.

<Test of feeling in use> When measuring the moisturizing effect of the above panel, the feeling in use was evaluated in terms of compatibility with the skin and stickiness according to the following evaluation criteria. [Evaluation Criteria for Feeling in Use] ○: Good compatibility with skin △: Neither can be said ×: Poor compatibility with skin ○: Not sticky △: Neither can be said ×: Stickiness The results are shown in Table 7.

[0033]

[Table 7] ──────────────────────────────────── Test example No. Skin familiarity Stickiness ──────────────────────────────────── 1 ○ 9 people ○ 8 people △ 1 △ 2 × 0 × 0 2 ○ 3 ○ 4 △ 4 △ 3 × 3 × 3 3 ○ 5 ○ 9 △ 2 △ 1 × 3 × 0 4 ○ 8 ○ 2 △ 1 △ 2 × 1 × 6 ────────────────────────────────────

As can be seen from the results in Table 7, the emulsion containing only acetylated hyaluronic acid (Test Example 4) was considerably sticky compared to the emulsion containing neither acetylated hyaluronic acid nor silicone oil (Test Example 2). I know there is. On the other hand, it can be seen that the milky lotion containing only silicone oil (Test Example 3) is comparable to Test Example 2 in skin compatibility, but is not so good. On the other hand, it can be seen that the milky lotion containing both acetylated hyaluronic acid and silicone oil (Test Example 1) blends well with the skin and is almost non-sticky.

[0035] Therefore, it can be seen that by combining acetylated hyaluronic acid and silicone oil, it is possible to obtain an external preparation for skin that is well compatible with the skin and does not make the hyaluronic acid sticky.

Degree of acetylation of acetylated hyaluronic acid [Test Examples 5 to 8] Various milky lotions containing acetylated hyaluronic acid having different degrees of acetylation shown in Table 8 were prepared.
The manufacturing method conforms to Example 1 and Comparative Example.

<Test Method for Moisturizing Effect> Next, 40 women were divided into 4 groups to form panels. After a period of time, the conductance was measured to evaluate the moisturizing effect. The evaluation criteria for the moisturizing effect are as follows. [Evaluation Criteria for Moisturizing Effect] ○: Conductance after 3 hours is 100 μS or more △: Conductance after 3 hours is 50 to 100 μS ×: Conductance after 3 hours is 50 μS or less

<Method for Testing Feeling on Use> When measuring the moisturizing effect of the above panel, the feeling on use was evaluated with respect to skin compatibility and lack of stickiness according to the following evaluation criteria. [Evaluation criteria for familiarity with skin] ○: 8 or more people answered that it was good △: 3 to 7 people answered that it was good ×: Less than 3 people answered that it was good [Evaluation criteria for lack of stickiness] ○ : 8 or more persons answered that it was not sticky △: 3 to 7 persons answered that it was not sticky ×: Less than 3 persons answered that it was not sticky Table 8 shows the results together with the composition of the emulsion.

[0039]

[Table 8] ──────────────────────────────────── Composition (emulsion) Test example No. 5 6 7 8 ──────────────────────────────────── A. Stearic acid 2.0 2.0 2.0 2.0 Cetanol 1.0 1.0 1.0 1.0 Vaseline 2.0 2.0 2.0 2.0 Liquid paraffin 6.0 6.0 6.0 6.0 Cetyl 2-ethylhexanoate 1.0 1.0 1.0 1.0 Jojoba oil 1.0 1.0 1.0 1.0 Squalane 2.0 2.0 2.0 2.0 Pentaerythritol tetra-2-ethylhexanoate 3.0 3.0 3.0 3.0 Methylphenylpolysiloxane *1 3.0 3.0 3.0 3.0 Decamethylpentasiloxane *2 2.0 2.0 2.0 2.0 Evening primrose oil 0.5 0.5 0.5 0.5 Diparamethoxycinnamic acid Glyceryl mono-2-ethylhexanoate 1.5 1.5 1.5 1.5 4-tert-butyl-4′-methoxy- Jin soil methane 3.0 3.0 3.0 3.0 POE(10) monooleate 3.0 3.0 3.0 3.0 Dibutyl hydroxytoluene 0.1 0.1 0.1 0.1 Vitamin B₆Tripalmitate 0.01 0.01 0.01 0.01 Butylparaben 0.2 0.2 0.2 0.2 Perfume Appropriate amount Appropriate amount Appropriate amount B. Propylene glycol 5.0 5.0 5.0 5.0 1,3 butylene glycol 2.0 2.0 2.0 2.0 Acetylated hyaluronic acid Degree of acetylation 1 0.1 Degree of acetylation 1.5 0.1 Degree of acetylation 2 0.1 Degree of acetylation 4 0.1 Arbutin 5.0 5.0 5.0 5.0 Carboxyvinyl polymer 0.2 0.2 0.2 0.2 Triethanolamine 0.2 0.2 0.2 0.2 purified water residue residue residue residue ──────────────────────────────────── Skin compatibility × △ ○ ○ No stickiness × × ○ ○ ────────────────────────────────────

As is clear from the results in Table 8, the milky lotions containing acetylated hyaluronic acid having a degree of acetylation of 2 or more (Test Examples 7 and 8) are extremely compatible with the skin and are not sticky. On the other hand, the degree of acetylation is 2
When it is lower, it can be seen that the compatibility with the skin is slightly poor and stickiness occurs (Test Examples 5 and 6).

Amount of acetylated hyaluronic acid blended [Test Examples 9 to 14] Milky lotions having various compositions were prepared by changing the blended amount of acetylated hyaluronic acid shown in Table 9.
~14. The manufacturing method conforms to Example 1 and Comparative Example. In addition, the moisturizing effect and feeling of use of the milky lotions of Test Examples 9 to 14 were tested, and the results are shown in Table 9 together with the composition. The test method and evaluation criteria conform to Test Examples 5-8.

[0042]

[Table 9] ──────────────────────────────────── Composition (emulsion) Test example No. 9 10 11 12 13 14 ──────────────────────────────────── A. Stearic acid 2.0 2.0 2.0 2.0 2.0 2.0 Cetanol 1.0 1.0 1.0 1.0 1.0 1.0 Vaseline 2.0 2.0 2.0 2.0 2.0 2.0 Liquid Paraffin 6.0 6.0 6.0 6.0 6.0 6.0 Cetyl 2-ethylhexanoate 1.0 1.0 1.0 1.0 1.0 1.0 Jojoba oil 1.0 1.0 1.0 1.0 1.0 1.0 Squalane 2.0 2.0 2.0 2.0 2.0 2.0 Pentaerythritol Tetra-2-ethylhexanoate 3.0 3.0 3.0 3.0 3.0 3.0 Methylphenylpolysiloxane *1 1.0 1.0 1.0 10.0 10.0 10.0 Decamethylpentasiloxane *2 1.0 1.0 1.0 5.0 5.0 5.0 Evening primrose oil 0.5 0.5 0.5 0.5 0.5 0.5 Diparamethoxycinnamic acid Glyceryl mono-2-ethylhexanoate 1.5 1.5 1.5 1.5 1.5 1.5 4-tert-butyl-4′- Methoxydi-benzene methane 3.0 3.0 3.0 3.0 3.0 3.0 POE(10) monooleate 3.0 3.0 3.0 3.0 3.0 3.0 Dibutyl hydroxytoluene 0.1 0.1 0.1 0.1 0.1 0.1 Vitamin B₆Tripalmitate 0.01 0.01 0.01 0.01 0.01 0.01 Butylparaben 0.2 0.2 0.2 0.2 0.2 0.2 Fragrance Appropriate Appropriate Appropriate Appropriate Appropriate B. Propylene glycol 5.0 5.0 5.0 5.0 5.0 5.0 1,3-butylene glycol 2.0 2.0 2.0 2.0 2.0 2.0 Acetylated hyaluronic acid ^*30.00005 0.0001 0.01 5 10 15 Arbutin 5.0 5.0 5.0 5.0 5.0 5.0 Carboxy vinyl polymer 0.2 0.2 0.2 0.2 0.2 0.2 Triethanolamine 0.2 0.2 0.2 0.2 0.2 0.2 Purified water Residual Residual Residual Residual Residual Residual ──────────────────────────────────── Moisturizing effect × ○ ○ ○ ○ ○ Skin familiarity △ ○ ○ ○ ○ ○ No stickiness ○ ○ ○ ○ ○ × ────────────────────────────────────

As is clear from the results in Table 9, emulsions containing 0.0001 to 10% by weight of acetylated hyaluronic acid (Test Examples 10 to 13) are excellent in moisturizing effect and have good skin compatibility. It can be seen that there is no stickiness. On the other hand, the blending amount of acetylated hyaluronic acid is 0.0001
It can be seen that the milky lotion (Test Example 9) with less than 10 wt. In addition, the blending amount of acetylated hyaluronic acid is 1
It can be seen that the milky lotion exceeding 0% by weight (Test Example 14) has strong stickiness.

Compounding amount of silicone oil [Test Examples 15 to 19] Various milky lotions were prepared by changing the compounding amount of silicone oil shown in Table 10 and designated as Test Examples 15 to 19. The manufacturing method conforms to Example 1 and Comparative Example.
In addition, the moisturizing effect and usability of the emulsions of Test Examples 15 to 19 were tested, and the results are shown in Table 10 together with the composition.
The test method and evaluation criteria conform to Test Examples 5-8.

[0045]

[Table 10] ──────────────────────────────────── Composition (Emulsion) Test Example No. 15 16 17 18 19 ────────────────────────────────────── A. Stearic acid 2.0 2.0 2.0 2.0 2.0 Cetanol 1.0 1.0 1.0 1.0 1.0 ワセリン 2.0 2.0 2.0 2.0 2.0 流動パラフィン 6.0 6.0 6.0 6.0 6.0 ２-エチルヘキサン酸セチル 1.0 1.0 1.0 1.0 1.0 ホホバオイル 1.0 1.0 1.0 1.0 1.0 スクワラン 2.0 2.0 2.0 2.0 2.0 テトラ-2-エチルヘキサン酸ヘ゜ンタErythritol 3.0 3.0 3.0 3.0 3.0 Methylphenylpolysiloxane ^*1 0.05 0.1 1.0 5.0 20.0 Decamethylpentasiloxane ^*2 - - 1.0 10.0 40.0 Evening primrose oil 0.5 0.5 0.5 0.5 0.5 Glyceryl di-paramethoxycinnamate mono-2-ethylhexanoate 1.5 1.5 1.5 1.5 1.5 4-tert-フ゛チル-4′- メトキシシ゛-ヘ゛ンソ゛イルメタン 3.0 3.0 3.0 3.0 3.0 ＰＯＥ(10)モノオレート 3.0 3.0 3.0 3.0 3.0 ジブチルヒドロキシトルエン 0.1 0.1 0.1 0.1 0.1 ヒ゛タミンB ₆トリハ゜ルミテート 0.01 0.01 0.01 0.01 0.01 Butylparaben 0.2 0.2 0.2 0.2 0.2 Perfume qs qs qs qs qs qs qs B. Propylene glycol 5.0 5.0 5.0 5.0 5.0 1,3-butylene glycol 2.0 2.0 2.0 2.0 2.0 Acetylated hyaluronic acid ^*3 0.1 0.1 0.1 5.0 5.0 5.1 0.1 5.0 Carboxyvinyl polymer 0.2 0.2 0.2 0.2 0.2 Triethanolamine 0.2 0.2 0.2 0.2 0.2 Purified water Remainder Remainder Remainder Remainder Remainder ────────────────────────── ────────── Moisturizing effect × ○ ○ ○ ○ Blends well with skin ○ ○ ○ ○ ○ Sticky Lack of luck × ○ ○ ○ ○ ──────────────────────────────────────

As is clear from the results in Table 10, emulsion containing 0.1% by weight or more of silicone oil (Test Example 16
19) are excellent in moisturizing effect and have no stickiness. On the other hand, it can be seen that the milky lotion containing less than 0.1% by weight of silicone oil (Test Example 15) has an extremely low moisturizing effect and is sticky.

[0047] Therefore, the blending amount of the silicone oil is 0.5.
It can be seen that there is no effect unless it is blended in an amount of 1% by weight or more. Also, it can be seen that the upper limit of the amount of silicone oil to be blended is at least 60% by weight.

Acetylated Hyaluronic Acid and Silicone Oil
Blending Weight Ratio [Test Examples 20-24] Various milky lotions were prepared by varying the blending weight ratio of acetylated hyaluronic acid (AcHA) and silicone oil shown in Table 11 as Test Examples 20-24. note that,
The manufacturing method conforms to Example 1 and Comparative Example. In addition, the moisturizing effect and usability (skin familiarity, stickiness) of the milky lotions of Test Examples 20 to 24 were tested. Test methods and evaluation criteria are test examples 5 to 8
according to

[0049]

[Table 11] ──────────────────────────────────── Composition (Emulsion) Test Example No. 20 21 22 23 24 ────────────────────────────────────── A. Stearic acid 2.0 2.0 2.0 2.0 2.0 Cetanol 1.0 1.0 1.0 1.0 1.0 ワセリン 2.0 2.0 2.0 2.0 2.0 流動パラフィン 6.0 6.0 6.0 6.0 6.0 ２-エチルヘキサン酸セチル 1.0 1.0 1.0 1.0 1.0 ホホバオイル 1.0 1.0 1.0 1.0 1.0 スクワラン 2.0 2.0 2.0 2.0 2.0 テトラ-2-エチルヘキサン酸ヘ゜ンタErythritol 3.0 3.0 3.0 3.0 3.0 Methylphenylpolysiloxane ^*1 0.1 0.1 5.0 20.0 25.0 Decamethylpentasiloxane ^*2 - - 5.0 20.0 25.0 Evening primrose oil 0.5 0.5 0.5 0.5 0.5 Glyceryl mono-2-ethylhexanoate diparamethoxycinnamate 1.5 1.5 1.5 1.5 4-tert-フ゛チル-4′- メトキシシ゛-ヘ゛ンソ゛イルメタン 3.0 3.0 3.0 3.0 3.0 ＰＯＥ(10)モノオレート 3.0 3.0 3.0 3.0 3.0 ジブチルヒドロキシトルエン 0.1 0.1 0.1 0.1 0.1 ヒ゛タミンB ₆トリハ゜ルミテート 0.01 0.01 0.01 0.01 0.01 ブチルパラベン 0.2 0.2 0.2 0.2 0.2 香料 適量 適量 適量 適量 適量B.プロピレングリコール 5.0 5.0 5.0 5.0 5.0 １,３-ブチレングリコール 2.0 2.0 2.0 2.0 2.0アセチル化ヒアルロン酸 ^*3 0.2 0.1 0.1 0.001 0.0005 アルブチン 5.0 5.0 5.0 5.0 5.0 Carboxyvinyl polymer 0.2 0.2 0.2 0.2 0.2 Triethanolamine 0.2 0.2 0.2 0.2 0.2 Purified water Remainder Remainder Remainder Remainder Remainder ────────────────────────── ────────── Blending weight ratio (AcHA/Silicone) 2/1 1/1 1/100 1/ 40000 1/100000 ──────────────────────────────────── Familiarity with skin ○ ○ ○ ○ × Sticky Noness × ○ ○ ○ ○ ──────────────────────────────────────

From the results in Table 11, the blending weight ratio of acetylated hyaluronic acid and silicone oil was 1/1 to 1/4000.
It can be seen that the milky lotions (Test Examples 21 to 23) with a value of 0 have good compatibility with the skin and are not sticky. On the other hand, emulsions with blending weight ratios outside this ratio (Test Examples 20 and 24)
It can be seen that the excellent usability of the present invention cannot be obtained.

[0051] Next, in order to make the external preparation for skin of the present invention more specific, further examples will be given. In addition, the blending amount is % by weight
indicates When evaluated according to Example 1, the external preparations for skin of each Example showed excellent moisturizing effect and usability as in Example 1.

Example 2 Cream A. Cetanol 0.5% Vaseline 2.0 Squalane 7.0 Decamethylcyclopentasiloxane ^*5 10.0 Self-emulsifying glycerin monostearate 2.5 POE (20) sorbitan monostearate 1.5 Pantothenyl ethyl ether 0 .5 jojoba oil 5.0 B.I. Propylene glycol 5.0 Glycerin 5.0 Veegum (montmorillonite) 5.0 Acetylated hyaluronic acid (degree of acetylation 3.8) 1.0 Water Balance *5: Execol D-5 (5 cSt; manufactured by Shin-Etsu Chemical Co., Ltd.)

-Production method- A (oil phase) and B (aqueous phase) are 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.

Example 3 Emulsion A. Squalane 5.0% Oleyl oleate 3.0 Vaseline 2.0 Sorbitan sesquioleate 0.8 POE(20) oleyl ether 1.2 Trimethylsiloxysilicate-5.0 Octamethylcyclotetrasiloxane ^*6 solution Dimethylpolysiloxane ^*7 1.0 evening primrose oil 0.5 fragrance 0.3 preservative appropriate amountB. 1,3 Butylene glycol 4.5 Melissa extract 1.5 Acetylated hyaluronic acid (degree of acetylation 3.2) 0.001 Ethanol 3.0 Carboxyvinyl polymer 0.2 Potassium hydroxide 0.1 Sodium hexametaphosphate 0 .05 Purified water Remainder *6: SSD-R-1 (100 cSt; manufactured by Shin-Etsu Chemical Co., Ltd.) *7: KF-96A6CS (6 cSt; manufactured by Shin-Etsu Chemical Co., Ltd.) Heat to 70°C and dissolve completely. Add phase A to phase B and emulsify with an emulsifier. The emulsion was cooled using a heat exchanger to obtain a latex.

Example 4 Cream A. Cetanol 4.0% Vaseline 7.0 Isopropyl myristate 8.0 Squalane 15.0 Stearic acid monoglycerin ester 2.2 POE (20) sorbitan monostearate 2.8 Polyoxyethylene/polyoxypropylene copolymer 0. 5 Dimethyl polysiloxane ^*8 10.0 Vitamin E nicotinate 2.0 Perfume 0.3 Antioxidant Appropriate amount Preservative Appropriate amountB. Glycerin 10.0 Acetylated hyaluronic acid (degree of acetylation 2.7) 0.02 Dipropylene glycol 4.0 Sodium pyrrolidonecarboxylate 1.0 Disodium edetate 0.01 Purified water Balance *8: KF-96A20CS (20cSt ; manufactured by Shin-Etsu Chemical Co., Ltd.) A cream was obtained according to Example 2.

[Example 5] Pack (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 (degree of acetylation 3.5) 0.1 (6) Dimethylpolysiloxane ^*9 2.0 (7) Preservative 0.1 (8) Perfume 0.1 (9) Purified water Remainder *9 : KF-96A100CS (100cSt; manufactured by Shin-Etsu Chemical Co., Ltd.)

-Manufacturing method- (4), (7) and (8) were mixed and dissolved at room temperature, and (1) and (2)
After mixing and dissolving (3), (5), (6), and (9) at 80° C., the mixture was stirred and added, and then allowed to cool to room temperature to obtain a pack.

[0058] [Example 6] Solid powder foundation (1) Talc 5 (2) Sericite 10 (3) Acetylated hyaluronic acid (degree of acetylation 2.4) 4 (4) porous silicic anhydride powder 15 (5) boron nitride 5 (6) Titanium dioxide 3 (7) iron oxide 5 (8) Zinc myristate 5 (9) liquid paraffin remainder (10) Dimethylpolysiloxane 15 (11) Silicone resin 5 (12) Sorbitan sesquiolilate 1.5 (13) Preservative Appropriate amount (14) Perfume Appropriate amount

-Manufacturing method- The components (1) to (8) were mixed and pulverized,
A mixture of components (9) to (14) was added, mixed and stirred, and molded into a container to obtain a solid powder foundation.

[0060] [Example 7] Lipstick (1) Carnauba wax 0.5 (2) Candelilla wax 5.0 (3) Seresin 10.0 (4) Squalane residue (5) Glyceryl triisostearate 7.0 (6) Glyceryl diisostearate 15.0 (7) Dimethylpolysiloxane 5.0 (8) Silicone resin 3.0 (9) Hydroxypropyl-β-cyclodextrin 1.0 (10) Acetylated hyaluronic acid (degree of acetylation 3.3) 1.0 (11) Purified water 2.0 (12) Macadamia nut oil fatty acid cholesteryl 3.5 (13) Synthetic sodium-magnesium silicate 0.5 (14) Hydrophobic silica 0.5 (15) Colorant Appropriate amount (16) Preservative Appropriate amount (17) Perfume Appropriate amount

-Production method- (13) to (14) were dispersed in (12) heated to 60°C,
Uniformly dissolved (9) to (11) are added thereto and thoroughly stirred. This was added to (1) to (8), which had been heated and dissolved separately, and stirred sufficiently.

[0062]

EFFECTS OF THE INVENTION The topical preparation for skin of the present invention is excellent in the stability of its moisturizing effect over time, is not particularly sticky, is well compatible with the skin, and has excellent usability.

Claims (1)

[Claims] 1. 0.0001 to 10% by weight of acetylated hyaluronic acid having 2 to 4 acetyl group substitutions per hyaluronic acid structural unit, and 0.1 to 6 silicone oil
and acetylated hyaluronic acid and silicone oil in a weight ratio of 1/1 to 1/40000.