JPH1112124A - Emulsifying composition - Google Patents

Abstract

PROBLEM TO BE SOLVED: To obtain the subject composition improved in long-term stability and feeling to user without substantially using surfactant and useful for cosmetics and medicines, etc., by including a hydroxyalkylated cyclodextrin, an acetylated hyaluronic acid, oily component and water. SOLUTION: This composition is obtained by including 0.01-10 wt.% hydroxyalkylated cyclodextrin (e.g. hydroxymethylcyclodextrin), 0.0001-5 wt.% acetylated hyaluronic acid [especially in which substituent number of the acetyl group is average 2-4 in recurring structural unit represented by the formula (R<1> to R<4> are each H or acetyl subjected to ester bonding; R<5> is H or an alkali metal atom)] and 0.5-50 wt.% oily component (e.g. macadamia nut oil).

Description

DETAILED DESCRIPTION OF THE INVENTION

[0001]

The present invention relates to an emulsion composition. More specifically, the present invention relates to an emulsified composition which is excellent in long-term emulsion stability without using a surfactant and is mainly used as cosmetics, pharmaceuticals, and quasi-drugs.

[0002]

2. Description of the Related Art As emulsifying compositions for cosmetics, creams and emulsions emulsifying various oily and aqueous raw materials are widely used. In order to produce such an emulsified composition, it has been essential to use a surfactant in order to guarantee the stability over time of the emulsified composition.

However, in recent years, further safety is expected for cosmetics. From this viewpoint, it may be better not to add a surfactant to particularly sensitive skin. Therefore, a method of obtaining an emulsified composition without using a surfactant has also been proposed (Japanese Patent Publication No. 2-38253, Japanese Patent Publication No. 62-31681, Japanese Patent Publication No. 61-38166).

[0004]

However, these emulsified compositions are not always satisfactory in terms of long-term stability of emulsification.

Accordingly, the present inventors have conducted intensive studies from the above-mentioned viewpoints. As a result, by blending hydroxyalkylated cyclodextrin, acetylated hyaluronic acid and an oily component, the long-term stability of emulsification and feeling of use have been improved. It has been found that an improved emulsion composition can be obtained, and the present invention has been completed.

[0006] An object of the present invention is to provide an emulsified composition having a good emulsification stability over time without substantially using a surfactant.

[0007]

That is, the present invention provides an emulsified composition comprising a hydroxyalkylated cyclodextrin, an oily component, and acetylated hyaluronic acid.

Further, the present invention provides the above emulsified composition, wherein the content of the hydroxyalkylated cyclodextrin is 0.01 to 10% by weight based on the total amount of the emulsified composition. is there.

Further, the present invention relates to the present invention, wherein the content of the acetylated hyaluronic acid is 0.0001 to the total amount of the emulsified composition.
To 5% by weight of the emulsified composition.

[0010] The present invention also provides the above emulsion composition, wherein the content of the oily component is 0.5 to 50% by weight based on the total weight of the emulsion composition.

Further, the present invention is characterized in that the acetylated hyaluronic acid has an average of 2 to 4 acetyl groups in the repeating structural unit represented by the following chemical formula (2). To provide an emulsified composition.

Embedded image (Wherein, R ¹ , R ² , R ³ , and R ^{4 each} represent hydrogen or an acetyl group bonded through an ester bond, and on average, at least two or more of R ^{1 to} R ⁴ in each repeating structure are acetyl groups. R ⁵ represents hydrogen or an alkali metal atom.)

Further, the present invention provides the above-mentioned emulsified composition, which is substantially free of a surfactant.

[0013]

DETAILED DESCRIPTION OF THE PREFERRED EMBODIMENTS The configuration of the present invention will be described below in detail.

The hydroxyalkylated cyclodextrin (hereinafter sometimes abbreviated as HACD) used in the present invention is obtained by adding a hydroxyalkyl to the hydroxyl group of cyclodextrin (hereinafter sometimes abbreviated as CD) known as a cyclic oligosaccharide. It is a compound into which a group has been introduced, and is a known compound as a raw material for cosmetics.

Cyclodextrin is known to have a structure of α, β or γ (hereinafter sometimes abbreviated as α-CD, β-CD, γ-CD) depending on the difference in the number of glucose. Although these cyclodextrins are commercially available, the hydroxyalkylated cyclodextrin used in the present invention is produced by hydroxyalkylating the hydroxyl groups of these cyclodextrins.

As the cyclodextrin used as the mother nucleus of the hydroxyalkylated cyclodextrin used in the present invention, β-CD is usually used, but α-CD or γ-CD may be used as the mother nucleus. In addition, a starch degradation product containing all of α-CD, β-CD and γ-CD can be used as the mother nucleus.

The substitution of the hydroxyl group of the cyclodextrin with the hydroxyalkyl group can be carried out by a generally known method (for example, see JP-A-2-196709). Further, the molar substitution degree of the hydroxyalkyl group is preferably from 1 to 14.

Examples of the hydroxyalkyl group for substituting a hydroxyl group include substituents such as a hydroxymethyl group, a hydroxyethyl group and a hydroxypropyl group.

As a result of this substitution reaction, it is possible to produce, for example, hydroxyalkylated cyclodextrins such as hydroxymethylcyclodextrin, hydroxyethylcyclodextrin, hydroxypropylcyclodextrin, hydroxybutylcyclodextrin, dihydroxypropylcyclodextrin and the like. And can be used in the present invention.

Among these HACDs, the price and ease of production are as follows: considering the usability and water solubility, 2-hydroxyethyl β-CD or 2-hydroxypropyl β-CD.
CD, 3-hydroxypropyl β-CD and 2,3-dihydroxypropyl β-CD are preferred, but not limited thereto.

Next, a specific method for producing a hydroxyalkylated cyclodextrin using β-CD as a mother nucleus will be exemplified. That is, β-CD (manufactured by Nippon Shokuhin Kako, brand name:
100 g of Celdex N) in 20% NaOH aqueous solution 15
0 ml of propylene oxide 5 while maintaining at 30 ° C.
0 ml is gradually added dropwise, and the mixture is stirred for 20 hours to continue the reaction.
After the completion of the reaction, the mixture was neutralized to pH 6.0 with hydrochloric acid, placed in a dialysis membrane tube, and desalted under flowing water for 24 hours. Thereafter, drying with a freeze dryer is performed to obtain hydroxypropylated β-CD.
About 90 g were obtained. This hydroxypropylated β-C
The degree of substitution of D per β-CD was 5.1.

In the present invention, one kind of hydroxyalkylated cyclodextrin can be used alone in the present invention, but a mixture of two or more kinds (hydroxyalkylated α-, β-substituted with various hydroxyalkyl groups). −,
and a mixture appropriately selected from γ-CD).

The amount of the hydroxyalkylated cyclodextrin is preferably from 0.01 to 10% by weight, more preferably from 0.2 to 5% by weight, based on the total weight of the emulsified composition. If the amount is less than 0.01% by weight, it is difficult to emulsify, and if the amount exceeds 10% by weight, no increase in the emulsifying action and the effect of improving the emulsion stability can be expected, and the product cost will increase. From the viewpoint of usability, the range of 0.2 to 5% by weight is most preferable.

The acetylated hyaluronic acid used in the present invention is a high molecular compound in which the hydroxyl group of hyaluronic acid is partially acetylated, and the acetylation rate of the hydroxyl group is not particularly limited. The number of substitution of the acetyl group in the repeating structural unit is 2 to 2 on average
Four are preferred.

Embedded image (Wherein, R ¹ , R ² , R ³ , and R ^{4 each} represent hydrogen or an acetyl group bonded through an ester bond, and on average, at least two or more of R ^{1 to} R ⁴ in each repeating structure are acetyl groups. R ⁵ represents hydrogen or an alkali metal atom.)

The method for producing acetylated hyaluronic acid is, for example, a method in which powdery hyaluronic acid is dispersed in acetic acid and reacted by adding trifluoroacetic anhydride as a catalyst, or a method in which p-toluenesulfonic acid is added after dispersing in acetic acid and adding A method of reacting by adding acetic anhydride or a method of suspending in acetic anhydride solvent and adding concentrated sulfuric acid to react is known (see JP-A-6-9707 and JP-A-8-53501).

The amount of the acetylated hyaluronic acid is 0.1%.
It is preferably from 0001 to 5% by weight, more preferably from 0.
001 to 5% by weight. If the amount is less than 0.0001% by weight, the effect is not exhibited. If the amount exceeds 5% by weight, stickiness is caused in terms of usability, which is not preferable.

As the oil component used in the present invention, any of polar oils and non-polar oils usually used in cosmetics can be used.
For example, macadamia nut oil, evening primrose oil, olive oil,
Natural animal and vegetable fats and oils such as mink oil, jojoba oil, lanolin, squalene, hydrocarbons such as liquid paraffin, squalane, petrolatum, paraffin wax, spermaceti, beeswax,
Waxes such as candelilla wax, carnauba wax,
Cetanol, stearyl alcohol, higher alcohols such as cetyl alcohol, myristic acid, palmitic acid,
Higher fatty acids such as stearic acid, behenic acid, isostearic acid, oleic acid, linolenic acid, linoleic acid, linoleic acid, oxystearic acid, pentaerythritol tetra-2-ethylhexanoate, isopropyl myristate, isopropyl palmitic acid, and isopropyl isostearin Acids, esters such as glyceryl 2-ethylhexanoate, polar oils such as diethylene glycol monopropyl ether, polyoxyethylene polyoxypropylene pentaerythritol ether, polyoxypropylene butyl ether, ethyl linoleate, and other silicone oils can also be added. When a large amount of solid or semi-solid oily components are blended, the aggregating action becomes stronger,
It is desirable to use a large amount of liquid oil because the appearance and the state of the particles deteriorate. The ratio of the liquid oil to the entire oil component is preferably 50% by weight or more.

The amount of the oily component is preferably 0.5 to 50% by weight, more preferably 1.0 to 30% by weight, based on the total weight of the emulsion composition. If the amount is less than 0.5% by weight, an emulsified composition is hardly produced, and if the amount exceeds 50% by weight, stickiness may occur in use.

The water constituting the emulsified composition of the present invention is obtained by dissolving the essential components HADC, acetylated hyaluronic acid and other water-soluble components to form an aqueous component, and mixing with the above oil component by stirring. The desired emulsion composition is produced. An alcohol solvent such as ethanol can be mixed with water. The amount of water is not particularly limited, and is appropriately determined according to the intended product.

The emulsified composition of the present invention can produce an emulsified composition having excellent emulsification stability substantially without using a surfactant, and is safe for a person having skin particularly sensitive to a surfactant. Surfactant-free emulsified cosmetics can be provided,
When lipophilic activators such as monoglyceride, sorbitan fatty acid ester and diglycerin isostearate are used together, the emulsion stability is further improved.

The emulsion composition of the present invention contains, in addition to the above-mentioned essential components, components which are usually blended in cosmetics, pharmaceuticals, and the like as long as the effects of the present invention such as emulsion stability and feeling of use are not impaired. For example, vitamins and vitamin-like active substances such as vitamin A, vitamin B, vitamin D, vitamin E, tocopherol acetate, ascorbic acid ester, vitamin A acid, lecithin, γ-oryzanol, folic acid, estradiol, estradiol valerate, ethinyl Hormones such as estradiol, prostaglandin and testosterone propionate, benzophenone, 4-tert-butyl-4-methoxy-dibenzoylmethane, dimethoxycinnamate ethylhexanoate glyceryl, p-aminobenzoate, paramethoxycinnamate UV of octyl acid, phenyl salicylate, etc. Absorbing agents, L- menthol, anti-inflammatory agents such as camphor, methyl paraben, ethyl paraben,
Preservatives such as butylparaben and bactericides such as triclosan and dibutylhydroxytoluene can be added.

Although the use of the emulsified composition of the present invention is not limited, it is preferably used as cosmetics, quasi-drugs, pharmaceuticals and the like, and can be used as products such as creams, emulsions and ointments.

[0033]

The present invention will be described below in more detail with reference to Examples and Comparative Examples. The present invention is not limited only to these examples. The amounts shown below are all by weight.

Example 1, Comparative Examples 1-2: Emulsions The emulsion compositions for cosmetics of various compositions shown in Table 1 were emulsified by an emulsifier while adding an oil phase component to an aqueous phase component. Manufacturing,
The emulsion composition was allowed to stand for one month in a high-temperature bath at 50 ° C. to evaluate the emulsion stability of the emulsion composition. The evaluation results are also shown in Table 1. The evaluation criteria for the stability of the emulsion composition were as follows.

[Criteria for Evaluation of Stability] A: No oil separation is observed. Δ: Oil separation was slightly observed. X: Oil separation is clearly recognized.

[0036]

[Table 1]

As is clear from Table 1, it is found that a stable emulsion composition can be obtained by using hydroxypropyl β-cyclodextrin and acetylated hyaluronic acid in combination.

Example 2: Cream Component Ingredient Amount Oil phase Dimethylpolysiloxane 10% by weight Macadamia nut oil 5 Vaseline 10 Stearic acid 1 B. Aqueous phase hydroxyethyl β-cyclodextrin 0.1 acetylated hyaluronic acid 1 polyethylene glycol 5 dipropylene glycol 7 triethanolamine 0.6 sodium metaphosphate 0.1 methylparaben 0.1 chondroitin sulfate 0.3 ion-exchanged water balance An emulsion composition having the above composition was produced in the same manner as in Example 1. When the same evaluation as in Example 1 was performed, the emulsion composition of this example showed excellent stability as in Example 1.

"Example 3: Cream" Component Ingredient Amount Oil phase Liquid paraffin 10% by weight Olive oil 1 Lanolin 3 Stearyl alcohol 2 Glyceryl tri-2-ethylhexanoate 2 2-Ethylhexyl paramethoxycinnamate 1 Vitamin E acetate 0.3 Butylparaben 0.2 Perfume 0.1 B. Aqueous phase propylene glycol 6 1,3 butylene glycol 4 acetylated hyaluronic acid 0.001 trisodium edetate 0.1 hydroxypropyl β-cyclodextrin 5.0 hydroxypropyl α-cyclodextrin 1.0 magnesium ascorbate 1 placenta Extract 0.3 KOH 0.2 Deionized water Residue An emulsified composition having the above composition was produced in the same manner as in Example 1. When the same evaluation as in Example 1 was performed, the emulsion composition of this example showed excellent stability as in Example 1.

Example 4: Emulsion Component Ingredient Amount Oil phase dimethyl polysiloxane 0.5% by weight Decamethylcyclopentasiloxane 1 Jojoba oil 0.5 Aqueous phase arbutin 1 carrot extract 0.5 hydroxypropyl β-cyclodextrin 0.05 Hibiswako 105 0.3 acetylated hyaluronic acid 0.05 ethyl alcohol 8 edetate trisodium 0.1 methyl paraben 0.1 phenoxyethanol 0.2 KOH 0.15 ion-exchanged water residue An emulsified composition having the above composition was produced in the same manner as in Example 1. When the same evaluation as in Example 1 was performed, the emulsion composition of this example showed excellent stability as in Example 1.

[0041]

According to the present invention, hydroxypropyl β
-By mixing cyclodextrin and acetylated hyaluronic acid, it is possible to provide an emulsified composition having excellent long-term stability of emulsification.

Claims (6)

[Claims] 1. An emulsion composition comprising a hydroxyalkylated cyclodextrin, acetylated hyaluronic acid, an oily component, and water. 2. The content of the hydroxyalkylated cyclodextrin is 0.01 to 1 with respect to the total amount of the emulsified composition.
The emulsion composition according to claim 1, wherein the amount is 0% by weight. 3. The emulsion composition according to claim 1, wherein the content of the acetylated hyaluronic acid is 0.0001 to 5% by weight based on the total weight of the emulsion composition. 4. The emulsion composition according to claim 1, wherein the content of the oil component is 0.5 to 50% by weight based on the total weight of the emulsion composition. 5. The acetylated hyaluronic acid according to claim 1, wherein the substitution number of the acetyl group is 2 to 4 on average in the repeating structural unit represented by the following chemical formula (1). 5. The emulsion composition according to 3 or 4, above. Embedded image (Wherein, R ¹ , R ² , R ³ , and R ^{4 each} represent hydrogen or an acetyl group bonded through an ester bond, and on average, at least two or more of R ^{1 to} R ⁴ in each repeating structure are acetyl groups. R ⁵ represents hydrogen or an alkali metal atom.) 6. The emulsion composition according to claim 1, wherein the emulsion composition is substantially free of a surfactant.