JPH0995418A - Hydrated composition and cosmetic formulated therewith and their production - Google Patents

Abstract

PROBLEM TO BE SOLVED: To obtain a liquid crystal hydrated composition excellent in stability and safety, also excellent in hydrating power to sustain skin dampishness, and having emulsification effect, by using a specific cholesterol ester-included product in combination with water. SOLUTION: This hydrated composition comprises water and a cholesterol clathrate prepared by including a cholesterol ester into a hydroxyalkylated cyclodextrin. The respective amounts of the hydroxyalkylated cyclodextrin, the cholesterol ester, and the water should fall within a range given by the slanting lines in the phase diagram shown in the figure. The hydrated composition is useful as an oil-in-water type emulsified cosmetic. It is recommended that 0.01-20wt. of this composition is contained in the objective oil-in-water type emulsified cosmetic which is produced by mixing and agitating the hydroxyalkylated cyclodextrin, cholesterol ester and water to form a liquid crystal and then is then further agitated and mixed with other ingredients to effect emulsification.

Description

Detailed Description of the Invention

[0001]

TECHNICAL FIELD The present invention relates to a hydrate composition, and more particularly to a hydrate composition using hydroxyalkylated cyclodextrin and cholesterol ester, a cosmetic composition containing the same, and a method for producing the same.

[0002]

2. Description of the Related Art Retention of water in the skin is an essential factor for keeping the skin healthy, and many cosmetics and pharmaceuticals for the purpose of moisturizing are commercially available. A number of moisturizers are provided, and among them, cholesterol ester is widely used in cosmetics because of its excellent water retention and moisturizing properties. Further, conventionally, in an emulsified cosmetic containing oil and water, various surfactants alone are used as emulsifiers.
Or, they have been used in combination.

However, for example, ionic surfactants such as alkyl sulfates and higher fatty acid salts may cause skin irritation when used at high concentrations, and polyoxyethylene type nonionic surfactants may be used. When used, there was a problem with compatibility such as inactivating preservatives such as parabens.

In order to solve such a problem, a technique using cyclodextrin or its derivative as an emulsifier has been developed. JP-A-58-58139 discloses that cyclodextrin is used in combination with an oil-soluble surfactant,
A technique of emulsifying by a specific method is disclosed. Also,
Japanese Patent Application Laid-Open No. 63-194726 discloses a technique of using methylated β-cyclodextrin as an emulsification aid. However, since these techniques use a considerable amount of conventional surfactants in combination, problems such as skin irritation have not been completely solved.

[0005]

In order to solve these problems, an example of obtaining an emulsified cosmetic without using a surfactant is described in JP-A-3-284611. . That is, JP-A-3-284611
The publication describes an emulsified cosmetic containing hydroxyalkylated cyclodextrin, oil and water.
The emulsified cosmetic composition has excellent solubility, stability and safety.

However, the ability to retain water for maintaining moisturization is still insufficient, and further improvement is desired. The present invention was conceived as a subject of the prior art, and an object thereof is to provide a hydrate composition which is excellent in stability and safety, and which has an excellent water-holding power for maintaining moisturization and further has an emulsifying action. And

[0007]

[Means for Solving the Problems] As a result of intensive studies conducted by the present inventors to achieve the above object, a cholesterol ester clathrate in which a cholesterol ester is clathrated with a hydroxyalkylated cyclodextrin has a hydrophilic property of cyclodextrin. It functions as an excellent emulsifier due to the lipophilicity of cholesterol ester and cholesterol, and when a hydrate composition comprising the above-mentioned cholesterol clathrate and water is added to cosmetics and the like, stability and safety are excellent, and moisturizing for continued moisturization. It was found that a cosmetic having an excellent property of being rich in power can be obtained, and completed the present invention.

That is, the liquid crystal hydrate composition according to claim 1 is characterized in that it contains a cholesterol ester clathrate in which a cholesterol ester is clathrated in a hydroxyalkylated cyclodextrin, and water. The water hydrate composition according to claim 2 is the water hydrate composition according to claim 1, wherein the compounding ratio of hydroxyalkylated cyclodextrin, cholesterol ester and water contained in the cholesterol ester clathrate is shown in FIG. It is characterized in that it exists within the range indicated by the diagonal lines in the phase diagram shown.

The oil-in-water emulsified cosmetic composition according to claim 3 comprises:
It is characterized by containing a hydroxyalkylated cyclodextrin, a cholesterol ester, and water. The oil-in-water emulsified cosmetic composition according to claim 4 is the cosmetic composition according to claim 3, which contains the hydrate composition according to claim 1 or 2 in an amount of 0.01 to 20% by weight based on the total amount of the cosmetic composition. It is characterized by

The method for producing a hydrate composition according to claim 5 is characterized in that a liquid crystal is formed by stirring and mixing a hydroxyalkylated cyclodextrin, a cholesterol ester and water. The method for producing an oil-in-water emulsion cosmetic according to claim 6, wherein a hydroxyalkylated cyclodextrin, cholesterol ester and water are stirred and mixed to produce a liquid crystal hydrate composition, which is stirred and mixed with other components. And further emulsify.

[0011]

BEST MODE FOR CARRYING OUT THE INVENTION Embodiments of the present invention will be described in more detail below. Hydroxyalkylated cyclodextrin used in the present invention (hereinafter referred to as HACD)
Is a product in which a hydroxyalkyl group is introduced into the hydroxyl group of cyclodextrin (hereinafter referred to as CD), which has been conventionally well known as a cyclic oligosaccharide. That is, CD
Hydrophobic hydroxyalkyl groups are introduced into the hydroxyl groups of to improve the hydrophobicity.

[0012] CD is an oligosaccharide in which glucose residues are cyclically linked by α-1,4 bonds, α-CD consisting of 6 glucose residues, β-CD consisting of 7 residues, Γ-CD consisting of 8 is generally known. In the present invention, one or more of these CDs can be selected and used. Further, it can be used in the form of a starch hydrolyzate containing α, β, and γ CDs at the same time.

As the hydroxyalkyl group substituting the hydroxyl group of CD, a hydroxyethyl group, a hydroxypropyl group, etc. are mainly used. HACD can be obtained by performing a substitution reaction of these with a hydroxyl group. HAC
Examples of D include hydroxyethylated CD, hydroxypropylated CD, hydroxybutylated CD, dihydroxypropylated CD and the like. In the present invention, the preferred degree of substitution of hydroxyl group and hydroxyalkyl group is 1 CD.
It is 1 to 14.

Of these HACDs, hydroxyethylated β-CD or hydroxypropylated β-CD is preferable in consideration of price, ease of manufacture, usability, and water solubility, but is not limited thereto. Absent. Several methods have been conventionally known as a method for producing HACD, but one example is shown below.

That is, 100 g of β-CD (Nippon Shokuhin Kako Co., Ltd., trade name: Celldex N) was dissolved in 150 ml of a 20% NaOH aqueous solution, and 50 ml of propylene oxide was gradually dropped while maintaining the temperature at 30 ° C., and stirred for 20 hours. And 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. After that, it is dried with a freeze dryer to obtain hydroxypropylated β
-About 90 g of CD were obtained. The substitution degree per CD of the hydroxypropylated β-CD was 5.1.

In the present invention, cholesterol ester is an ester of cholesterol and higher fatty acid. As the higher fatty acid constituting the ester bond with cholesterol of the present invention, a linear or branched fatty acid having 12 to 24 carbon atoms can be used, and examples thereof include myristic acid, palmitic acid, palmitoleic acid, stearic acid, oleic acid, and linole. Acids, linolenic acid, arachidonic acid, macadamia nut oil fatty acids. In the present invention, one or more of these higher fatty acids are selected and used. As the higher fatty acid constituting the ester bond with cholesterol used in the present invention, especially stearic acid,
Oleic acid, palmitoleic acid and macadamia nut oil fatty acid are preferred.

The cholesterol ester used in the present invention is preferably cholesterol stearate, cholesterol oleate, cholesterol palmitrate, or macadamia nut oil fatty acid cholesteryl. The cholesterol ester clathrate used in the present invention is
It can be obtained by thoroughly stirring and mixing HACD, cholesteryl ester and water and then evaporating the water content.

When the cholesterol ester clathrate is mixed with a cosmetic or the like, it is well dispersed in the aqueous phase in the product form,
When applied to the skin, it is considered that the cholesterol ester clathrate forms a thin film on the skin surface and suppresses the evaporation of water from the skin. The cholesterol ester clathrate of the present invention can obtain the effect aimed at by the present invention even if the clathrate itself is blended, but as a hydrate composition comprising the cholesterol ester clathrate and water, It is possible to obtain a higher emollient effect by obtaining the product by mixing with the ingredients of.

The hydrate composition of the present invention comprises stirring and mixing a cholesterol ester clathrate and water, or HAC.
It can be obtained by stirring and mixing D, cholesterol ester, and water. The hydrate composition is such that the cholesterol ester clathrate forms a micellar structure and retains unencapsulated cholesterol ester.
FIG. 1 shows a phase diagram of the results of the water retention experiment conducted by the present inventors using hydroxypropyl β-CD (hereinafter referred to as HP-β-CD) as HACD and macadamia nut oil fatty acid cholesteryl as cholesterol ester. In 1 and 2 in the phase diagram, two layers are separated and a good hydrate composition cannot be obtained. On the other hand, in 3 to 6, the composition becomes an emulsion and becomes a stable hydrate composition.

Therefore, in the cholesterol ester clathrate of the present invention, it is preferable that the amount ratio of HACD to cholesterol ester is within the range shown by the shaded area in FIG. In particular, by incorporating the hydrate composition of the present invention into a cosmetic, it is possible to obtain a cosmetic having excellent stability and safety and excellent water retention. Further, the emulsified type by the inclusion product of cholesterol ester is preferably an oil-in-water type, and particularly preferably used as an oil-in-water type cosmetic.

The hydrate composition of the present invention needs to be blended to such an extent that the effects of the clathrate can be sufficiently exerted. It is 0.1 to 10% by weight. The cosmetic containing the hydrate composition of the present invention can be produced, for example, by the following method. That is, the liquid crystal hydrate composition is produced by stirring and mixing HACD, cholesterol ester, and water. On the other hand, it can be obtained by stirring and mixing the water phase part and the oil phase part in another container to obtain an emulsified composition, blending the hydrate composition therein, and further stirring and mixing.

The hydrate composition of the present invention can obtain the intended effect of the present invention by blending the cholesterol ester clathrate itself, but the cholesterol ester clathrate and water, or HACD It is possible to enhance the effect of the present invention by stirring and mixing cholesterol ester and water to form a liquid crystal in advance and then adding the liquid crystal to other cosmetic ingredients and the like.

In the present invention, various oil components can be blended in addition to the above essential components. Examples of the oil used in the cosmetic of the present invention include macadamia nut oil, evening primrose oil, castor oil, olive oil, mink oil, jojoba oil, lanolin, natural animal and vegetable oils such as squalene, liquid paraffin, paraffin wax, polyethylene wax, squalane. Hydrocarbons such as whale wax, beeswax, candelilla wax, carnauba wax, etc., higher alcohols such as cetanol, isocetanol, stearyl alcohol, isostearyl alcohol, myristic acid, palmitic acid, stearic acid, behenic acid , Higher fatty acids such as isostearic acid, isopropyl myristic acid, isopropyl palmitic acid, isopropyl isostearic acid, diisostearyl malate, trimethylolpropane triisostearyl, and isostearic acid Roll, dicaprate neopentyl glycol, esters such as 2-ethylhexanoic acid glycerol, other diethylene Gree mono propylene pentaerythritol ether, ethyl linoleate, polar oils and silicone oils such as polyoxypropylene butyl ether. These oil components can be blended within a range that does not impair the effects of the present invention.

In the cosmetic of the present invention, cholesterol ester is contained in an amount of 0.01 to 10% by weight in the total amount of the cosmetic.
It is more preferable to add 0.1 to 7% by weight. If it is 0.01% by weight or less, the inclusion compound with cyclodextrin is insufficient to bring out the effect, whereas if it is 10% by weight or more, it is difficult to suitably perform the oil-in-water emulsification.

The cosmetic of the present invention can be in a form suitable for various uses, for example, vanishing cream, emulsion, cold cream, cleansing cream, foundation cream, hand cream, lipstick, beauty essence, ointment for external use and the like. . The cholesterol ester clathrate of the present invention itself functions as an emulsifier. Therefore, when the clathrate is blended with a cosmetic or the like, the cholesterol ester end shows the lipophilic CD end showing hydrophilicity, so that the oil is surrounded in a state where there is a large amount of aqueous phase to form a micelle structure as shown in FIG. It seems to be.

In the hydrate composition of the present invention, since the clathrate itself acts as an emulsifier and the clathrate and water are used to produce a hydrate composition in advance, the clathrate is It is considered that the oil component is stably retained by forming a micelle structure and surrounding the oil phase component by the cholesterol ester end which is the lipophilic side of the inclusion body of the cholesterol ester as shown in FIG. By incorporating the hydrate composition into cosmetics, the cyclodextrin end of the cholesterol ester clathrate is hydrophilic, and thus it is considered that oil components are stably retained in oil-in-water type cosmetics.

When the cosmetic containing the hydrate composition is applied to the skin or the like, since the skin or the like is lipophilic, the micelle structure in FIG. 2 is broken, and as shown in FIG. The clathrates are arranged so that the cholesterol ester ends contact the skin surface. It is considered that the CD functions as a cap, controls the evaporation of water from the coated surface, and appropriately holds the water.

[0028]

The present invention will be described in more detail with reference to the following examples. The present invention is not limited to this. The compounding amount is shown by weight%. First, the present inventors examined the physical properties of the cholesterol ester clathrate according to the present invention. That is, a hydrated composition comprising a cholesterol clathrate in which macadamia nut oil fatty acid cholesteryl was clathrated in hydroxypropylated CD (hereinafter referred to as HP-β-CD) and water was prepared by the following formulation, and the composition was prepared. It was taken on a slide and observed under a microscope. A photograph obtained by microscopic observation is shown in FIG. 4, and the results are shown in Table 1.

[0029]

[Table 1] ──────────────────────────────────── Example 1 ─────── ───────────────────────────── Deionized water 33 HP-β-CD 65 Macadamia nut oil fatty acid cholesteryl 2 ─────── ────────────────────────────── Emulsified particle size (μm) 1-3 μm ───────── ────────────────────────────

The hydrated composition having the above composition is preferably emulsified with a cholesterol ester clathrate. Further, as is clear from the optical micrograph shown in FIG. 4, the shape of the emulsified particles is nearly spherical and uniform, and the particle size is 1 to 3 μm. Further, when observed using a polarization microscope, Maltese cross peculiar to liquid crystals is observed, and the liquid crystal particles are also observed in product systems. It is generally known that cholesterol ester, which is a hydrated oil, is most likely to be hydrated when it exists in a liquid crystal state rather than in a crystalline or low-viscosity liquid state. It is possible to maximize the water retention of.

Further, the present inventors have prepared a beauty essence (Example 2) containing a hydrate composition comprising the cholesterol ester clathrate of the present invention and water, and HP-β having the same composition.
-CD-free serum (Comparative Example 1), HP-β-C
The moisturizing effect was compared using D and a serum containing no cholesterol ester (Comparative Example 2). First, prior to the examination, the evaluation method and the evaluation standard will be described.

Measurement of Moisturizing Effect by Moisture Evaporation Rate As a test for measuring the moisturizing effect of the moisturizer, the moisture evaporation rate was measured. That is, 10 μl of the sample liquid was dropped on a 2.0 × 2.0 cm filter paper, and the weight reduction was measured at 1-minute intervals for 10 minutes to determine the weight reduction per minute. Distilled water was used as a target.

The criteria for judgment are as follows. ⊚: Moisture evaporation rate of 0.50 μg / min or less ◯: Moisture evaporation rate of greater than 0.50 μg / min and 0.
55 μg / or less Δ: Moisture evaporation rate greater than 0.55 μg / min, 0.
60 μg / or less ×: Moisture evaporation rate greater than 0.60 μg / min

The prepared samples were actually used by 10 panelists specializing in sensory evaluation to carry out a sensory test. Each evaluation is described by the following criteria.

[Moisture] ◎: Answer when 8 or more people are moist ○: Answer when 5 to 8 people are moist △: Answer when 3 to 5 people are moist ×: Answer when 3 or less people are moist

[Stickiness] ◎: Answered if 8 or more people were not sticky ○: Answered if 5 to 8 people were not sticky △: Answered if 3 to 5 people were not sticky ×: Answered if 3 or less people were not sticky

[Improvement of rough skin] ◎: 8 or more people answered that they improved ◯: 5-8 people answered that they improved △: 3-5 people answered that they improved ×: 3 people or less answered that they improved

[0038]

[Table 2] ──────────────────────────────────── Example 2 Example 3 Comparative Example 1 Comparative Example 1 Example 2 ──────────────────────────────────── A. Water phase part Dynamite glycerin 10.0 10.0 10.0 10.0 10. 0 propylene glycol 7.0 7.0 7.0 7.0. 0 ethanol 4.0 4.0 4.0 4.0 0 methylparaben 0.2 0.2 0.2 0.2. 2 Alkyl-modified carboxyl vinyl polymer 0.1 0.1 0.1 0.1. 1 Carboxyl vinyl polymer 0.2 0.2 0.2 0.2. 2 Purified water Residual Residual Residual B. Oil phase part Cetyl isooctanoate 4.0 4.0 4.0 4.0 0 p-Methoxycinnamate 2-ethylhexyl 0.1 0.1 0.1 0.1 1 C. Hydrating composition HP-β-CD 1.9 1.9-1. 9 Cholesterol ester 0.1 0.1 − − Purified water − 1.0 − − ──────────────────────────────── ───── Moisturizing effect (water evaporation rate) ○ ◎ △ ○ Moisture ○ ◎ △ ○ Stickiness ○ ◎ × ○ Improvement of rough skin ○ ◎ △ △ ──────────────── ────────────────────

As is clear from the above results, in Comparative Example 1 in which the cholesterol ester clathrate of the present invention is not blended, the moisturizing effect is insufficient and the sensory evaluation is also poor. Further, in Comparative Example 2 containing CD, although the moisturizing effect and the moisturizing effect are improved, a sufficient effect cannot be obtained in terms of improvement of stickiness and rough skin. On the other hand, with the serum containing the cholesterol ester clathrate of the present invention (Example 2), it is possible to obtain a serum with all aspects improved, and the clathrate before mixing with other ingredients. It is possible to obtain a beauty essence that is excellent in all evaluations with the beauty essence (Example 3) containing a hydrate composition in which emulsified particles are formed with water and water.

Further, more specific formulation examples of the present invention will be shown. The compounding amount is shown by weight%. In addition, in each formulation example, high evaluation was obtained in the moisture evaporation rate and the sensory evaluation. Also,
There is no concern about skin irritation and it has excellent storage stability.

Formulation Example 1 Cosmetic liquid A. Aqueous phase part Glycerin 10.0% by weight Propylene glycol 5.0 Ethanol 5.0 Methylparaben 0.2 Alkyl-modified carboxyl vinyl polymer 0.05 Carboxyl vinyl polymer 0.15 Purified water Residual B. Oil phase portion Cetyl isooctanoate 4.0 P-Methoxycinnamate 2-ethylhexyl 0.1 C.I. Hydrating composition HP-β-CD 1.0 Cholesterol ester 0.05 Purified water 0.5

<Production Method> The oil phase part was added to the water phase part, and the mixture was stirred for 10 minutes with a homomixer to obtain a main part. Next, a cholesterol ester at 60 ° C. is added to a solution of HP-β-CD dissolved in 0.5% of purified water, and the mixture is stirred with a homomixer for 10 minutes to produce a hydrate composition. This hydrate composition is added to the main part and then stirred with a homomixer for 10 minutes to obtain a beauty essence.

Formulation 2 Cosmetic liquid A. Aqueous phase part Glycerin 7.0% by weight Propylene glycol 6.0 Ethanol 3.0 Methylparaben 0.2 Polyoxyethylene (60 mol) Hydrogenated castor oil 0.2 Carboxyvinyl polymer 0.15 Purified water Residual B. Oil phase part Squalane 2.0 Liquid paraffin 1.5 C.I. Hydrating composition HP-β-CD 2.0 Cholesterol ester 0.2 Purified water 1.0 <Production method> A beauty essence is obtained in the same manner as in Formulation Example 1.

Formulation Example 3 Cosmetic liquid A. Aqueous phase part Glycerin 10.0% by weight Propylene glycol 7.0 Ethanol 4.0 Methylparaben 0.2 Polyoxyethylene (60 mol) hydrogenated castor oil 0.2 Carboxyvinyl polymer 0.15 Purified water Residual B. Oil phase part Vaseline 2.0 Squalane 2.0 C.I. Hydrating composition HP-β-CD 1.0 Cholesterol ester 0.03 Purified water 0.5 <Production method> In the same manner as in Formulation Example 1, a beauty essence is obtained.

[045]

Industrial Applicability The hydrate composition of the present invention contains a cholesterol clathrate in which CD is clathrate ester clathrate, wherein the cholesterol ester clathrate has a CD end that is hydrophilic and a cholesterol ester end that is lipophilic. Therefore, the cholesterol ester clathrate has an emulsifying action, and when the hydrate composition is incorporated into a cosmetic composition, it exhibits high moisturizing properties, excellent moisturizing and sustaining properties, and high moisturizing effect, while the conventional method is used. It is possible to obtain a cosmetic having good emulsification stability without the use of a surfactant and having the property that there is no concern about skin irritation.

[Brief description of drawings]

FIG. 1 is a phase diagram showing the mixing ratio of HACD, cholesterol ester and water.

FIG. 2 is a conceptual diagram of the emulsifying action of the cholesterol ester clathrate of the present invention.

FIG. 3 is an explanatory view of the action of the hydrate composition on the skin surface when the cosmetic containing the hydrate composition of the present invention is applied to the skin.

FIG. 4 is a micrograph showing emulsified particles of the hydrate composition of Example 1.

─────────────────────────────────────────────────── ─── Continuation of the front page (51) Int.Cl. ⁶ Identification number Reference number within the agency FI Technical indication location B01F 17/56 B01F 17/56 C08B 37/16 C08B 37/16 (72) Inventor Kenzo Ito Kanagawa Shiseido Daiichi Research Center, Inc. 1050 Shinba-cho, Kohoku-ku, Yokohama-shi, Japan

Claims (6)

[Claims] 1. A liquid crystal hydrate composition comprising a cholesterol ester clathrate in which a hydroxyester is included in a hydroxyalkylated cyclodextrin, and water. 2. The hydrate composition according to claim 1, wherein
A hydrate composition, wherein the compounding ratio of the hydroxyalkylated cyclodextrin, cholesterol ester and water contained in the cholesterol ester inclusion complex is within the range shown by the diagonal lines in the phase diagram shown in FIG. 3. An oil-in-water type emulsified cosmetic containing hydroxyalkylated cyclodextrin, cholesterol ester, and water. 4. The cosmetic composition according to claim 3, wherein the hydrate composition according to claim 1 or 2 is contained in 0.01% of the total amount of the cosmetic composition.
The oil-in-water emulsion cosmetic is characterized by containing 20 to 20% by weight. 5. A method for producing a liquid crystal hydrate composition, which comprises mixing a hydroxyalkylated cyclodextrin, a cholesterol ester and water with stirring to form a liquid crystal. 6. An oil-in-water type characterized in that a hydroxyalkylated cyclodextrin, cholesterol ester and water are stirred and mixed to produce a liquid crystal hydrate composition, which is stirred and mixed with other components to further emulsify. Method for producing emulsified cosmetic.