JP2001354515A - Composite emulsion and cosmetic formulated with the same - Google Patents

Abstract

PROBLEM TO BE SOLVED: To obtain an O/W/O type composite emulsion at least not requiring a formulation of a surfactant as an O/W/O type emulsion-based stabilizing means and to provide a method for producing the same. SOLUTION: This O/W/O type composite emulsion comprises an O/W type emulsion being an inner phase in which an oil component is included with a cyclodextrin, the diameter of a molecular diameter of a component constituting the oil component to be included is smaller than the diameter of a molecular ring in the cyclodextrin and an oil phase containing a hydrophobic powder/ hydroxyalkylated cyclodextrin is an outer oil phase of the O/W type emulsion and is obtained, for example, by separately preparing the O/W type emulsion in which the oil component is included with a cyclodextrin and an oily mixture containing the hydrophobic powder/hydroxyalkylated cyclodextrin, bringing the O/W type emulsion into contact with the oily mixture and carrying out an emulsifying dispersion operation so as to solve the above-mentioned subject.

Description

DETAILED DESCRIPTION OF THE INVENTION

[0001]

TECHNICAL FIELD The present invention relates to an emulsification technique useful in cosmetics and the like. More specifically, the present invention relates to an oil-in-water (O / W) emulsion in which an oil-in-water (O / W) emulsion is further emulsified and dispersed in an oil phase.
/ W / O) complex emulsion.

[0002]

2. Description of the Related Art The technology relating to O / W / O type composite emulsions is an important technology in cosmetics, foods, pharmaceuticals and many industrial applications.

For example, in the cosmetics field, O / W / O
Type complex emulsions can be used to separate the oil phase into the innermost oil phase and the outermost oil phase in skin care products such as emulsions and creams. Can be contained separately from the other oil phase components of the outermost oil phase to improve the stabilization of these fragrances and drugs. In addition, under high temperature conditions (about 90 ° C.) in the lipstick manufacturing process, iron oxide-based coloring agents and titanium oxide-based ultraviolet scattering agents act as catalysts, tending to destroy drugs and fragrances that are mixed together. There is no denying that there is. However, as noted above, O /
In the W / O-type composite emulsion, it is possible to stabilize these agents and fragrances by enclosing them in the innermost phase separately from the coloring agent and the ultraviolet scattering agent.

Further, when an emulsion or cream is applied to the skin, the emulsified particles are broken on the skin, and the internal phase (in the case of the O / W type composite emulsion, oil seeps out), which affects the usability. There are many. In the case of an emulsion or cream containing an O / W / O type complex emulsion, W
Since the emulsified particles are broken twice, ie, / O / O / W, the usability can be diversified.

Further, the O / W having the above-mentioned features
In the / O type composite emulsion, the active ingredient is encapsulated in the innermost phase to stabilize the active ingredient, and this can be applied to so-called functional foods and pharmaceuticals. In addition, it can be expected to create a new type of food having various textures.

In order to utilize the O / W / O type composite emulsion having such advantages in cosmetics and the like,
To date, various technologies have been provided. For example, a so-called two-stage emulsification method is known in which an O / W emulsion prepared using a hydrophilic surfactant is re-emulsified in an oil phase in which a lipophilic surfactant is dissolved. However, it is known that the composite emulsion thus prepared is inferior in emulsion stability.

O / O prepared by this two-stage emulsification method
In order to overcome the drawbacks of the W / O type complex emulsion, for example, a method of using a milk protein and a sucrose fatty acid ester in combination (Japanese Patent Publication No. 55-33294), and a method of blending a polyglycerin fatty acid ester in an outer oil phase (Tokuhei 3
JP-A-54709), and a method of blending specific bentonite into an aqueous phase and blending dextrin sulfate into an external phase oil (JP-A-63-30405).

[0008]

In recent years, further safety has been demanded in all fields including cosmetics. As a part of such efforts, attempts have been made to reduce the amount of surfactants that may cause irritation to the skin as much as possible. And this trend is
The same applies to the technical field related to the above-mentioned O / W / O type complex emulsion.

However, conventionally, in order to maintain the emulsification stability of the O / W / O type emulsification system, the emulsification system contains
The surfactant had to be incorporated in some form. Therefore, an object of the present invention is to at least eliminate the need to add a surfactant as a stabilizing means of an O / W / O type emulsification system.
An object of the present invention is to provide an O / W / O type composite emulsion and a means for producing it.

[0010]

Means for Solving the Problems The present inventor has made intensive studies to solve the above-mentioned problems. As a result, the O / W emulsion in which the oil component is included in cyclodextrin is the internal phase, and the oil phase containing the hydrophobic powder and / or the hydroxyalkylated cyclodextrin is the O / W emulsion.
O / W / O type composite emulsion which is the outer oil phase of the emulsion is provided, and O / W having excellent stability useful in various fields such as cosmetics without blending a surfactant. The present inventors have found that it is possible to form an / O type emulsification system, and have completed the present invention.

That is, the present invention relates to an O / W type in which the oil component is included by cyclodextrin and the molecular diameter of the component constituting the oil component to be included is smaller than the diameter of the molecular ring in the cyclodextrin. An O / W / O-type composite emulsion (hereinafter, referred to as the “oil phase”), wherein the emulsion is an internal phase, and an oil phase containing a hydrophobic powder and / or a hydroxyalkylated cyclodextrin is an outer oil phase of the O / W emulsion. The present invention provides an O / W / O type composite emulsion).

The O / W / O type composite emulsion of the present invention comprises:
For example, an oily mixture containing an O / W emulsion in which the oil is included in cyclodextrin and an oily mixture containing a hydrophobic powder and / or a hydroxyalkylated cyclodextrin is separately prepared, and the O / W is added to the oily mixture. It can be produced by adding a W-type emulsion and performing an emulsion dispersion operation. In the present invention, this O
Also provided is a method for producing a / W / O type composite emulsion (hereinafter referred to as the emulsion production method of the present invention).

Further, the present invention provides the above-mentioned O / W / O of the present invention.
The present invention also provides a cosmetic containing the type complex emulsion (hereinafter, referred to as the present cosmetic).

[0014]

Embodiments of the present invention will be described below. As described above, the O / W / O type composite emulsion of the present invention is a composite emulsion having the following constitution: O / W oil is included in cyclodextrin
The type emulsion is the internal phase. B. The inner aqueous phase may contain hydroxyalkylated cyclodextrin. C. The oil phase that may contain hydrophobic powder is the outer oil phase of the O / W emulsion.

First, the components A, B, and C of the O / W / O type composite emulsion of the present invention will be described. A. O / W oil is included in cyclodextrin
Type emulsion: cyclodextrin is D-
D-glucose 6 is defined as “natural cyclodextrin” which is a naturally occurring cyclodextrin in which 6 or more units of glucose are α-1,4 linked cyclically.
The cyclodextrin consisting of units is known as α-cyclodextrin, the cyclodextrin consisting of 7 units is known as β-cyclodextrin, and the cyclodextrin consisting of 8 units is known as γ-cyclodextrin. It is a substance that is hydrophobic and hydrophilic on the outside.

In the present invention, not only can these three types of natural cyclodextrins be used, but also cyclodextrins having 9 units or more of D-glucose can be used. In consideration of the availability in the above, these three types of natural cyclodextrins are usually used in the O / W / O complex emulsion of the present invention.

Among these three types of natural cyclodextrins, γ-cyclodextrin is excellent in water solubility and has a larger molecular ring diameter than other cyclodextrins. Even when the amount of the oil component becomes larger than the amount of cyclodextrin, inclusion emulsification is possible, and the most preferred cyclodextrin can be mentioned.

In order to improve the water solubility of cyclodextrin, a modified cyclodextrin having a hydrophilic functional group such as a hydroxypropyl group bonded thereto (a hydroxyalkylated cyclodextrin will be described later) is also used in the present invention. Although it is possible, the inclusion complex formed in this case (refers to a complex in which the oil component is included in cyclodextrin; the same applies hereinafter) becomes amorphous. Therefore, the formation of an inclusion complex with a long-chain alkyl oil that protrudes from the molecular ring of cyclodextrin is in an equilibrium state, and therefore,
The oil inclusion (O / W) emulsification efficiency tends to be inferior to the above-mentioned natural type cyclodextrin, which is not preferred.

As the various cyclodextrins used in the emulsion composition of the present invention, those produced by a generally known method can be used, and commercially available products can also be used.

Α-cyclodextrin and β-cyclodextrin can be obtained by degrading starch with cyclodextrin glucosyltransferase, respectively, by a generally known method.

Commercial products of α-cyclodextrin include, for example, Lindex A (manufactured by Mercian), Celdex A-100 (manufactured by Nippon Shokuhin Kako), Toyoderin (manufactured by Asahi Kasei), Dexipearl (manufactured by Saltwater Port Sugar), Cyclodextrin (manufactured by Hayashibara) and the like can be mentioned.

Commercial products of β-cyclodextrin include, for example, Lindex B (manufactured by Mercian), Celdex B-100 (manufactured by Nippon Shokuhin Kako), and dexpearl β-cyclodextrin.
100 (manufactured by Shimizu Port Sugar), Oligo Seven H (manufactured by Dainippon Pharmaceutical), β-cyclodextrin (manufactured by Hayashibara), and the like.

Since β-cyclodextrin has extremely low water solubility as compared with other cyclodextrins, it cannot be denied that there is an unsuitable aspect when a high inclusion emulsification efficiency is desired. γ-cyclodextrin can be produced, for example, according to the following production method.

Usually, it is necessary to first remove the acyclic high molecular fraction from the cyclodextrin mixture obtained by liquefaction and saccharification of the raw starch. As the removing method, for example, treatment with a separation membrane such as a UF membrane can be mentioned.

Then, this treated fraction was further subjected to Ryzopus
By treating with a glucoamylase derived from sp. and a small amount of α-amylase, it is possible to hydrolyze a low molecular weight acyclic dextrin that is not removed by the treatment with the separation membrane or the like.

After the enzyme treatment, the enzyme-treated product is desalted and decolored according to a generally known method, and concentrated and allowed to cool to precipitate β-cyclodextrin crystals. , Can be removed. The commonly known desalting and decoloring methods include, for example, ion exchange,
Activated carbon treatment and the like can be mentioned.

Next, glucose generated by the glucoamylase treatment is removed by column fractionation, for example, with a dianion, etc., and the resulting cyclodextrin fraction is subjected to
High-purity γ-cyclodextrin can be produced by subjecting it to molecular weight fractionation, for example, treatment with Toyopearl or the like.

Commercial products of γ-cyclodextrin include, for example, Lindex C (manufactured by Mercian), Dexipearl γ-100 (manufactured by Saltwater Port Sugar), Celdex G-1
00 (manufactured by Nippon Shokuhin Kako) and the like.

Recently, a new and highly efficient production method of γ-cyclodextrin using a recombinant enzyme has been disclosed in WACK.
Offered by ER (Germany). Γ-cyclodextrin produced by this method is also used in WACK.
Released by ER as GAMMA W8. And
This γ-cyclodextrin can of course be used in the present invention. The kind of the oil component to be included in the cyclodextrin is not particularly limited.

That is, natural animal and vegetable fats and oils such as saturated fatty acids, unsaturated fatty acids, silicone oils, macadamia nut oils, etc.
Hydrocarbons such as squalane, fatty acid ester oils such as fatty acid glycerides, silicone oils such as dimethylpolysiloxane, and the like can be widely covered by cyclodextrin.

Of these, linear (or partially methylated) hydrocarbon oils, linear (or partially methylated) fatty acid ester oils or silicone oils have no branched chains which hinder inclusion, Since it is easy to include a plurality of beads in a bead shape, it can be selected as a preferable oil component in that the inclusion efficiency with natural cyclodextrin is good.

In addition, oil-soluble drugs such as vitamin C derivatives such as vitamin C palmitate and vitamin E or vitamin E derivatives may be selected as the oil component. However,
It is preferable that the molecular diameter is smaller than the diameter of the molecular ring formed in the cyclodextrin (hereinafter, the diameter of the molecular ring may be referred to as “pore diameter” or “molecular ring diameter”). If the molecular diameter of the component to be included is larger than the diameter of the pore, it is not preferable because the component is fitted into the molecular ring formed in the cyclodextrin and is not included.

The specific mode of the cyclodextrin and the oil to be included is determined by the relative relationship between the pore diameter of the cyclodextrin and the molecular diameter of the component constituting the oil. That is, the larger the pore diameter of the cyclodextrin, the wider the range of components constituting the oil to be included. The molecular ring diameter of α-cyclodextrin is about 4.5 °, the molecular ring diameter of β-cyclodextrin is about 6.0 °, and the molecular ring diameter of γ-cyclodextrin is about 8.5 °. Thus, γ-cyclodextrin can be used in the present invention as a suitable cyclodextrin even in consideration of the size of the molecular ring diameter.

The mixing ratio of the two components when the oil component is included in the cyclodextrin should also be appropriately selected according to the type of the cyclodextrin used. When a specific combination of cyclodextrin and an oil component is a suitable combination in terms of their molecular ring diameter and molecular diameter, when α-cyclodextrin is selected, α-cyclodextrin is selected.
The mixing ratio of cyclodextrin to oil is 1: 0.01
１ ： 1: 2 [α-cyclodextrin: oil (weight ratio)]
When β-cyclodextrin is selected, the ratio is also 1: 0.01 to 1: 1.5 (weight ratio), and
When cyclodextrin is selected, 1: 0.
01 to 1: 4 (weight ratio).

The above-mentioned O / W emulsion using cyclodextrin can be produced, for example, by the following method. That is, it can be prepared by preparing an aqueous phase in which cyclodextrin is dissolved in water, mixing the oil to be included with the aqueous phase, and stirring with a homomixer or a stirrer. In this O / W type emulsion, as the ratio of the internal oil phase increases, low-speed stirring by a stirrer is more preferable.

For example, a system obtained by mixing the above oil components is
The mixture can be stirred at about 40 ° C. for 1 to 2 minutes using a homomixer, or for 6 hours or more using a magnetic stirrer. As described above, the present invention O
When encapsulating oil-soluble drugs or the like that are easily decomposed in the / W / O-type composite emulsion, it is necessary to mix these drugs and the like in the above-mentioned oil component and include them with cyclodextrin.

In addition, O by the above-mentioned cyclodextrin
/ W type emulsions can greatly improve the stability against various factors that alter the emulsified oil content, so they are expected to be moisturizing and antioxidant, but may be used because of their instability. Unsaturated fatty acids, which have been difficult, can be incorporated into this O / W emulsion to become the innermost phase of the O / W / O complex emulsion of the present invention.

Further, natural cyclodextrin, which can be preferably used as a cyclodextrin constituting the above-mentioned O / W emulsion, is biodegradable.
Compared with synthetic surfactants conventionally used as emulsifying means, they are superior from the viewpoint of skin safety and environmental protection.

B. Regarding the internal aqueous phase which may contain a hydroxyalkylated cyclodextrin: The aqueous phase in the above O / W type emulsion (corresponding to the internal aqueous phase of the O / W / O type composite emulsion of the present invention) includes / W /
In order to improve the emulsion stability of the O-type composite emulsion, a hydroxyalkylated cyclodextrin can be blended.

Hydroxyalkylated cyclodextrin (hereinafter referred to as HACD) is a modified cyclodextrin in which a hydroxyalkyl group has been introduced into the hydroxyl group of cyclodextrin, and which has an increased hydrophobicity.

The hydroxyalkyl group to be introduced into the hydroxyl group of cyclodextrin is not particularly limited, but mainly includes a hydroxyethyl group, a hydroxypropyl group, a dihydroxypropyl group and the like.

As the HACD used in the present invention, the substitution degree of the hydroxyl group and the hydroxyalkyl group of the HACD is preferably 4 to 5 per molecule of cyclodextrin. If the degree of substitution is less than 3, the solubility of cyclodextrin in water decreases, and if it is higher, steric hindrance occurs and the efficiency of inclusion of guest molecules decreases, which is not preferable.

HACD can be produced by hydroxyalkylating the hydroxyl group of cyclodextrin by a generally known method. The cyclodextrin serving as the HACD group may be any of α-, β- and γ-cyclodextrin.

The compounding amount of HACD in the O / W / O type composite emulsion of the present invention is preferably 0.1 to 30.0% by weight based on the whole composite emulsion. If the amount is less than 0.1% by weight based on the entire composite emulsion, a sufficient emulsification stabilizing effect cannot be obtained, which is not preferable. If the amount exceeds 30.0% by weight, HACD is sufficiently dissolved in the aqueous phase. It is difficult to perform this, which is not preferable.

As described above, by mixing HACD with the aqueous phase of the O / W emulsion, the emulsion stability of the O / W / O composite emulsion of the present invention, which is used as an internal emulsion, is improved. be able to.

The HACD is added together with the hydrophobic powder in the outermost oil phase of the O / W / O type composite emulsion of the present invention to improve the emulsion stability of the O / W / O type composite emulsion of the present invention. Or separately, it is possible to perform both together, according to the present invention O / W / O
It is preferable in order to further improve the emulsion stability of the type composite emulsion.

C. Regarding the outermost oil phase that may contain a hydrophobic powder: This oil phase is the oil phase that constitutes the outermost phase of the O / W / O type composite emulsion of the present invention.

By adding a hydrophobic powder to the outermost oil phase, the emulsion stability of the O / W / O type composite emulsion of the present invention can be improved. The oil component serving as a main component of this oil phase is not particularly limited as long as it is a hydrocarbon-based liquid oil component.For example, linseed oil, camellia oil, macadamia nut oil, corn oil, mink oil, olive oil, avocado oil, sasanqua oil , Castor oil, safflower oil, ginger oil, cinnamon oil, jojoba oil, grape oil, sunflower oil, almond oil, rapeseed oil, sesame oil, wheat germ oil, rice germ oil, rice bran oil, cottonseed oil, soybean oil, peanut oil Liquid oils such as teaseed oil, evening primrose oil, egg yolk oil, cow leg oil, liver oil, triglycerin, glyceryl trioctanoate, glycerin triisopalmitate, octanoic acid esters such as cetyl octanoate, tri-2-ethylhexa Isooctanoic acid esters such as glycerin enoate, pentaerythrit tetra-2-ethylhexanoate, and hexyl laurate; Gaulin esters, isopropyl myristate, myristyl esters such as octyldodecyl myristate, palmitate esters of octyl palmitate,
Stearic acid esters such as isocetyl stearate; isostearic acid esters such as isopropyl isostearate; isopalmitic acid esters such as octyl isopalmitate; oleic acid esters such as isodecyl oleate; adipic acid diesters such as diisopropyl adipate; diethyl sebacate Hydrocarbon oils such as ester oils such as sebacic acid diester, diisostearyl malate, cholesterol stearate, cholesterol oleate, cholesterol palmitate, cholesteryl ester such as macadamia nut oil fatty acid cholesteryl can be used as the above oil component. .

The hydrophobic powder contained in the oil phase is blended for improving emulsifying power (W / O type) and dispersibility of emulsified particles by powder emulsifying property. Examples of the hydrophobic powder include hydrophobic powders having a particle size of about 0.01 to 3 (μm), for example, metals such as silicon, titanium, calcium, aluminum, and magnesium, or oxidation of these metals. Hydrophobized powder obtained by subjecting a product powder to a hydrophobizing treatment. Specific examples include hydrophobized silicon dioxide powder, hydrophobized titanium dioxide powder, and hydrophobized alumina.

The hydrophobizing agent which can be used in the hydrophobizing step of these hydrophobizing powders can be selected according to the specific mode of the hydrophobizing treatment. For example, dextrin fatty acid ester, metal Organic compounds such as soap, silicone compounds, dibenzylidene sorbitol and the like can be selected. Moreover, the method of the hydrophobizing treatment using these hydrophobizing agents can be performed according to a generally known method.

The blending amount of the above-mentioned hydrophobic powder in the O / W / O type composite emulsion of the present invention is preferably 0.01 to 20.0% by weight based on the whole composite emulsion. If the amount is less than 0.01% by weight based on the entire composite emulsion, a sufficient emulsification stabilizing effect cannot be obtained, which is not preferable. If the amount exceeds 20.0% by weight, the viscosity of the outermost oil phase is reduced. And the dispersibility of the hydrophobized powder itself and the internal aqueous phase becomes poor, which is not preferable.

As described above, by blending a hydrophobic powder with the outermost oil phase of the O / W / O type composite emulsion of the present invention, the emulsion stability of this composite emulsion may be improved. As described above, the blending of the hydrophobic powder in the outermost oil phase can be carried out together with or separately from the blending of the HACD in the inner aqueous phase described above. This is preferred for further improving the emulsion stability of the / W / O type composite emulsion.

In the O / W / O type composite emulsion of the present invention, in order to secure the emulsification stability that can be put to practical use, it is necessary to mix HACD in the above-mentioned inner aqueous phase and the hydrophobicity in the outermost oil phase. It is necessary to perform at least one of the compounding of the powder.

The O / W / O type composite emulsion of the present invention comprises:
Thus, separately prepared, an O / W emulsion in which the oil component is included with cyclodextrin and the aqueous phase may contain hydroxyalkylcyclodextrin, and an oil phase which may contain hydrophobic powder The O / W emulsion in which the former oil is included in cyclodextrin and the aqueous phase may contain hydroxyalkylcyclodextrin becomes an internal phase (internal phase emulsion) and may contain the latter hydrophobic powder Oil phase is the outermost phase (outermost oil phase)
It is manufactured so that it becomes.

In this production method, for example, the above-mentioned internal phase emulsion is added to the above-mentioned outermost oil phase component, and the mixture is emulsified and dispersed, for example, by a stirring treatment with a disper or a homogenizer. The desired O / W / O type composite emulsion of the present invention can be produced.

When the hydrophobic powder is blended with the outermost oil phase, the hydrophobicized powder is added and dispersed in the outermost oil phase component, and this is brought into contact with the internal emulsion. Thereby, it is preferable to produce the O / W / O type composite emulsion of the present invention.

When HACD is blended in the internal aqueous phase, when the internal phase emulsion is prepared, H is added to the aqueous phase.
After mixing the ACD, it is preferable to prepare an internal phase emulsion and bring this into contact with the outermost oil phase component.
It is also possible to add HACD separately to the system when contacting the internal phase emulsion without ACD, which may contain hydrophobic powder. When adding, it is also possible to add hydrophobic powder together with the internal emulsion.

The O / W of the present invention thus produced
Unlike the conventional O / W / O type composite emulsion, the / O type composite emulsion does not require the use of a surfactant as an emulsifying means (the use of a surfactant for any purpose other than emulsification). This is not a hindrance to the complex emulsion), and in this respect, it is a highly safe composite emulsion. Further, the O / W / O type composite emulsion of the present invention comprises:
It is epoch-making in terms of stability over time and temperature stability, and excellent moisture retention due to the properties of cyclodextrin used as an emulsifying means of the internal phase emulsion.

Further, as described above, unsaturated fatty acids and unstable oil-soluble drugs which have conventionally been very difficult to use as ingredients for cosmetics or the like due to their instability have been used.
In the O / W / O type composite emulsion of the present invention, stabilization can be achieved by incorporating these into the innermost phase.

The O / W / O type composite emulsion of the present invention comprises:
Since it has the above-mentioned excellent properties, it can be applied to cosmetics and foods, as well as pharmaceuticals and quasi-drugs.

The O / W / O type composite emulsion of the present invention is
When used in the cosmetics field, this O / W / O type composite emulsion is used according to the specific purpose of cosmetics.
Can be blended.

This cosmetic (hereinafter referred to as the cosmetic of the present invention)
The blending amount of the O / W / O type composite emulsion of the present invention should be appropriately selected according to the specific dosage form and purpose of the cosmetic of the present invention, and is not particularly limited. Therefore, it is possible to select the compounding amount from a very wide range of approximately 0.1 to 99.9% by weight based on the cosmetic.

The cosmetic of the present invention containing the above-mentioned O / W / O type complex emulsion of the present invention may contain other components which are usually added to the cosmetic as required, without impairing the intended effects of the present invention. As long as it can be blended.

For example, an ultraviolet shielding agent, a humectant, various chemicals, various components derived from animals and plants, and other base components can be blended. The cosmetic of the present invention does not need to be blended in principle, but various surfactants can be blended mainly for purposes other than emulsification. In particular, it is necessary to carefully mix the surfactant and oil.

Further, the blending form of the other components can be appropriately selected depending on the chemical and physical properties of the other components themselves and the purpose of blending the other components.

For example, when an unstable oil-soluble drug or pigment is compounded as another compounding component, these other compounding components are encapsulated in the innermost phase of the O / W / O type composite emulsion. It is preferable to mix them in an embodiment (described above), and it is also possible to mix a water-soluble drug or the like as a water phase component in the gap between the innermost oil phase and the outermost oil phase.

It is also possible to incorporate the oily component which is not preferably contacted with the above-mentioned unstable oil-soluble drug or dye in the outermost oil phase component. Furthermore, in cosmetics, it has been recognized that normally stable oils and chemicals may cause a chemical change when inorganic powders or the like blended in the cosmetics serve as a catalyst. . Therefore, when inorganic powders and the like are blended in the cosmetic, especially in a foundation and the like in which the inorganic powder and the like are blended in a relatively large amount, there is a great possibility that the stability of the cosmetic over time is reduced. In such a case, by applying the present invention, oils and chemicals that are not preferable to come into contact with the powder are removed from the O / W /
By enclosing in the innermost phase of the O-type composite emulsion, it is possible to dramatically improve the temporal stability of the cosmetic in which the inorganic powder and the like are positively incorporated.

The cosmetics of the present invention include basic cosmetics such as facial cleansers, milky lotions, creams, gels, essences (cosmetics), packs and masks, makeup cosmetics such as foundations, lipsticks, oral cosmetics, aromatic cosmetics, hair cosmetics, and bodies. It is widely applicable to cosmetics and other forms. And the form which the cosmetics of this invention can take is not limited to these forms.

The dosage forms are aqueous, solubilizing, emulsifying, powder, oil-liquid, gel, ointment, aerosol,
A wide range of dosage forms such as a water-oil two-layer system and a water-oil-powder three-layer system can be adopted.

The specific formulation of the cosmetic composition of the present invention will be described in Examples described later. In the food field,
The O / W / O type composite emulsion of the present invention, particularly the O / W / O type composite emulsion of the embodiment containing HACD in the outermost oil phase instead of hydrophobic powder.
W / O type multiple emulsions are very useful. That is, in the food containing the O / W / O type composite emulsion of the present invention, there is no need to use a surfactant to improve the emulsion stability of the O / W / O type composite emulsion of the present invention, and
The cyclodextrin that is blended is decomposed into D-glycol by an enzyme in the body, and thus has a characteristic of being particularly excellent in safety.

[0071]

EXAMPLES Hereinafter, the present invention will be described more specifically with reference to examples, but the technical scope of the present invention is not limited to these examples. [Examples] Preparation of O / W / O complex emulsion of the present invention (1) 20 parts by weight of γ-cyclodextrin (manufactured by WACKER) and triolein 10 in 70 parts by weight of purified water
A part by weight was added, and a homogenizer treatment (4500 rpm) was performed at 60 ° C. for 10 minutes, and O / W in which triolein as an oil component was included in γ-cyclodextrin was included.
A type emulsion was obtained. Next, 30 parts by weight of commercially available hydroxypropyl-β-cyclodextrin was added to this emulsified system, and a homogenizer treatment (4500 rpm) was performed at 60 ° C. for 1 minute to prepare an O / W emulsion (1). Obtained. FIG. 1 shows an optical microscope image (300 times) of the O / W emulsion (1).

Separately from the preparation of this O / W emulsion (1), 68 parts by weight of a commercially available macadamia nut oil fatty acid cholesteryl, 20 parts by weight of squalane and 3 parts by weight of a commercially available hydrophobic silicon dioxide (alkylsilylated silicic anhydride) The parts were mixed and subjected to a dispersion treatment at 60 ° C. for 30 seconds by a disper (4500 rpm) to obtain a dispersion (1).

Next, 91 parts by weight of this dispersion (1) was added to
26 parts by weight of the above O / W type emulsion (1) was added, and a dispersion treatment was performed at room temperature for 10 minutes by a disper (4500 rpm) to obtain an O / W / O type composite emulsion (1). (Example 1).

This O / W / O type complex emulsion (1)
2 is shown in FIG. According to FIG. 2, an O / W emulsion is formed in the outermost oil phase,
It can be seen that an O / W / O type composite emulsion was formed. The temperature stability (60 ° C., 90 ° C.) of each sample in the following formulation (see Table 1) prepared by the above method was used.
° C) is described below.

The evaluation criteria of the emulsion stability in Table 1 are as follows. ：: O / W / O emulsion is formed stably. Δ: O / W / O emulsion was formed, but dispersibility was somewhat poor. X: O / W / O emulsion was not formed. Or
Formed temporarily, but is quickly destroyed.

[0076]

[Table 1]

According to Table 1, in the emulsified system of the composite emulsion, Comparative Example 1 in which both hydrophobized silicon dioxide (alkylsilylated silicic anhydride) and HACD (hydroxypropyl β-cyclodextrin) were removed, shows that at 60 ° C. No stability was observed even at 90 ° C.

On the other hand, an example in which either the hydrophobized silicon dioxide or HACD was added to the emulsified system (Example 2)
-Example 4) had a problem in stability at 90 ° C, but was stable at 60 ° C.

Then, hydrophobized silicon dioxide and HAC
It was found that the example in which both of D and D were added (Example 5) was stable both at 60 ° C. and at 90 ° C. From these facts, in order for the O / W / O composite emulsion of the present invention to have emulsion stability, it is necessary to add at least one of a hydrophobic powder and HACD to the system, It became clear that it is preferable to add both of these.

Next, with the same prescription (see Table 2),
Emulsion formation when the production method was changed as described below was examined. Step 1 (Comparative Example 2: One-Step Preparation) 68 parts by weight of cholesteryl macadamia nut fatty acid, 20 parts by weight of squalane, 2 parts by weight of triolein and 3 parts by weight of alkylsilylated silicic anhydride were mixed at 60 ° C.
Perform a dispersion process for 0 second with a disper (4500 rpm),
Waited for Dispersion (1). There, 14 parts by weight of purified water, γ
An aqueous phase part to which 4 parts by weight of cyclodextrin and 6 parts by weight of hydroxypropyl-β-cyclodextrin was added was added to the dispersion (1), and a dispersion treatment for 10 minutes was performed by a disper (4500 rpm).

Step 2 (Example 6: Two-Step Preparation Method) To 70 parts by weight of purified water, 20 parts by weight of γ-cyclodextrin and 10 parts by weight of triolein were added, and treated with a homogenizer at 60 ° C. for 10 minutes. (4500rpm)
An O / W emulsion was obtained in which triolein as an oil component was included in γ-cyclodextrin. Then
To this emulsified system, 30 parts by weight of hydroxypropyl-β-cyclodextrin was added, and a homogenizer treatment (4500 rpm) was performed at 60 ° C. for 1 minute to obtain an O / W emulsion (1). Separately from the preparation of this O / W emulsion, macadamia nut oil fatty acid cholesteryl 68
Parts by weight, 20 parts by weight of squalane and 3 parts by weight of alkylsilylated silicic anhydride were mixed and subjected to a dispersion treatment at 60 ° C. for 30 seconds by a disper (4500 rpm) to obtain a dispersion (1). .

Next, 91 parts by weight of the dispersion (1) was added to
26 parts by weight of the O / W type emulsion (1) from the episode were added, and a dispersion treatment was performed at room temperature for 10 minutes by a disper (4600 rpm) to obtain an O / W / O type composite emulsion.

[0083]

[Table 2]

According to the results in Table 2, it is difficult to prepare the O / W / O type composite emulsion of the present invention unless the preparation method for forming the emulsion in a stepwise manner is selected even with the same formulation. Was revealed. The second
The evaluation of the emulsion formation in the table was made by visually judging the formed emulsified system with an optical microscope (○: complex emulsion was formed, x: complex emulsion was not formed).

Hereinafter, a formulation example of the cosmetic of the present invention containing the O / W / O type composite emulsion of the present invention will be described. All of the cosmetics of the present invention were stable over time both at 60 ° C and at 90 ° C.

Formulation Example 1-1 Cream A. Outer oil phase Microcrystalline wax 8.0 (parts by weight) Solid paraffin 2.0 Beeswax 3.0 Vaseline 6.0 Reduced lanolin 5.0 Squalane 30.0 Hexadecyl adipate 4.0 Glycerin monooleate 3. 5 POE (20) Sorbitan monooleate 1.0 B. Other bases Preservatives qs Antioxidants qs perfume qs Water phase Purified water 15.0 Propylene glycol 5.0 D. O / W / O emulsion base macadamia nut oil fatty acid cholesteryl 7.0 squalane 2.0 alkylsilylated silicic anhydride 0.3 purified water 0.15 γ-cyclodextrin 0.04 vitamin E 0.02 hydroxyproh Ru-β-cyclodextrin 0.03 <Production method> To 0.15 parts by weight of purified water, 0.04 parts by weight of γ-cyclodextrin and 0.02 parts by weight of vitamin E are added, and homogenized at 60 ° C for 10 minutes ( 45
Then, 0.03 parts by weight of hydroxypropyl-β-cyclodextrin was added to the emulsified system, and the mixture was homogenized at 60 ° C. for 1 minute (4500 rpm).
) To obtain an O / W emulsion (D-1). Separately from the preparation of this O / W emulsion, 7.0 parts by weight of cholesteryl macadamia nut oil fatty acid, 2.0 parts by weight of squalane and 0.3 parts by weight of alkylsilylated silicic anhydride are mixed, and then mixed at 60 ° C. A dispersion treatment for 30 seconds was performed with a day spar (4500 rpm) to obtain a dispersion (D-2).
I got Next, 0.24 parts by weight of the above O / W emulsion (D-1) was added to 9.3 parts by weight of this dispersion (D-2), and dispersion treatment was performed at room temperature for 10 minutes. (4500 rpm) to obtain an O / W / O emulsion haze (D). After adding the O / W / O emulsion base (D) and the other base (B) to the main oil phase part (A), put the water phase part (C) and stir for 10 minutes with a homomixer. I got a cream.

Formulation 1-2 Cream A. Outermost oil phase Microcrystalline wax 8.0 (parts by weight) Solid paraffin 2.0 Beeswax 3.0 Vaseline 6.0 Reduced lanolin 5.0 Squalane 40.0 Hexadecyl adipate 4.0 Glycerine monooleate 3. 5 POE (20) Sorbitan monooleate 1.0 Alkyl silylated silicic anhydride 3.0 Other bases Preservatives qs Antioxidants qs perfume qs Aqueous phase Purified water 15.0 Propylene glycol 5.0 γ-cyclodextrin 4.0 β-cyclodextrin 0.1 Innermost oil phase triolein 2.0 <Production method> To 15 parts by weight of purified water, 4.0 parts by weight of γ-cyclodextrin and 2.0 parts by weight of triolein were added,
A homogenizer treatment (4500 rpm) was performed at 60 ° C. for 10 minutes to obtain an O / W emulsion (D-1). This O
Separately from the preparation of / W emulsion, 3.0 parts by weight of alkylsilylated silicic anhydride was mixed with the oil phase part (A) and subjected to a dispersion treatment at 60 ° C. for 30 seconds by a disper (4500 rpm). The O / W emulsion (D-1) was added thereto, and the mixture was stirred with a homomixer for 10 minutes to obtain an O / W / O cream.

Formulation 1-3 Cream A. Outermost oil phase Microcrystalline wax 8.0 (parts by weight) Solid paraffin 2.0 Beeswax 3.0 Vaseline 6.0 Reduced lanolin 5.0 Dimethyl polysiloxane 20.0 Chrysine isostearate 20.0 Hexadecyl adipic acid Ester 4.0 Glycerin monooleate 3.5 POE (20) Sorbitan monooleate 1.0 Alkyl silylated silicic anhydride 3.0 B. Other bases Preservatives appropriate amount antioxidant appropriate amount perfume appropriate amount C, aqueous phase purified water 15.0 propylene glycol 5.0 γ-cyclodextrin 4.0 β-cyclodextrin 0.1 D. Innermost oil phase Hitamin E 0.5 Triolein 2.0 <Production method> A cream was obtained in the same manner as in Formulation Example 1-2.

Formulation Example 2-1 Lipstick Lipstick base Carnauba wax 0.5 (parts by weight) Candelilla wax 5.0 Selecin 10.0 Squalane 30.0 Glycerin triisostearate 10.0 Glycerin diisostearate 20.0 Hexadecyl adipate 4.0 B . Other bases Coloring agent Appropriate amount Fragrance appropriate amount Preservative appropriate amount O / W / O emulsion base macadamia nut oil fatty acid cholesteryl 7.0 squalane 2.0 alkylated silicic anhydride 0.3 purified water 0.15 γ-cyclodextrin 0.04 histamine E 0.02 hydroxypropyl-β -Cyclodextrin 0.03 <Production method> 0.04 parts by weight of γ-cyclodextrin and 0.02 parts by weight of vitamin E are added to 0.15 parts by weight of purified water, and homogenizer treatment (4500 rpm) is performed at 60 ° C for 10 minutes. ) And then add 0.03 parts by weight of hydroxypropyl-β-cyclodextrin to the emulsified system, and homogenize at 4 ° C. for 1 minute (4500 rp).
m) to obtain an O / W emulsion (C-1). Separately from the preparation of this O / W emulsion, 7.0 parts by weight of cholesteryl fatty acid of macadamia nut oil, 2.0 parts by weight of squalane and 0.3 parts by weight of alkylsilylated silicic anhydride are mixed and heated at 60 ° C. A dispersion treatment for 30 seconds was performed with a disper (4500 rpm), and the dispersion (C-
2) was obtained. Next, 0.23 parts of the above O / W emulsion (C-1) was added to 9.3 parts by weight of this dispersion (C-2).
A part by weight was added, and a dispersion treatment was performed at room temperature for 10 minutes by a disperser (4500 rpm) to obtain an O / W / O emulsion base (C). The lipstick base (A) is melted at 80 ° C., and the O / W / O emulsion base (C) and other bases (B) are lacquered and stirred with a homomixer for 10 minutes. I got

Formulation Example 3-1 Foundation A. Oil Dimethylpolysiloxane 25.0 (parts by weight) Methylpolyphenylsiloxane 22.0 Squalane 15.0 Behenyl alcohol 1.0 B. Powder and other bases Silicone-treated titanium dioxide 5.8 Silicone-treated sericite 4.2 Silicone-treated iron oxide 2.1 Octylmethoxycinnamate 2.5 Perfume Appropriate amount Preservative Appropriate amount O / W / O emulsion heart Macadamia nut oil Fatty acid cholesteryl 7.0 Squalane 2.0 Alkyl silylated silicic anhydride 0.3 Purified water 0.15 γ-cyclodextrin 0.04 Hitamin E 0.02 Hydroxypropyl-β -Cyclodextrin 0.03 <Preparation method> To 0.15 parts by weight of purified water, 0.04 parts by weight of γ-cyclodextrin and 0.02 parts by weight of vitamin E are added, and a homogenizer treatment (45 minutes) is performed at 60 ° C for 10 minutes.
00 rpm), and then 0.03 parts by weight of hydroxypropyl-β-cyclodextrin was added to the emulsified system,
An O / W emulsion (C-1) is obtained by performing a homogenizer treatment (4500 rpm) at 60 ° C. for 1 minute. Separately from the preparation of this O / W emulsion, 7.0 parts by weight of macadamia nut oil fatty acid cholestyryl, 2.0 parts by weight of squalane and 0.3 parts by weight of alkylsilylated silicic anhydride are mixed, and then mixed at 60 ° C. A dispersion treatment for 30 seconds was performed by a disper (4500 rpm) to obtain a dispersion (C-2). Next, 0.24 parts by weight of the above O / W emulsion (C-1) was added to 9.3 parts by weight of this dispersion (C-2), and dispersion treatment was performed at room temperature for 10 minutes. (4500 rpm) to obtain an O / W / O emulsion base (C). A. Oil and B. The powder and other base villages were heated and stirred to make them uniform, to which an O / W / O emulsion haze (C) was added, heated and stirred, and then cooled to produce a fender.

[0091]

According to the present invention, since a surfactant is not used as an emulsification stabilizing means, O / W / which is excellent in safety and stability is applicable in various fields such as cosmetics. An O-type multiple emulsion is provided.

[Brief description of the drawings]

FIG. 1 is an optical micrograph (× 300) of an O / W emulsion formed as an internal emulsion of the O / W / O complex emulsion of the present invention.

FIG. 2 is an optical micrograph of the O / W / O type composite emulsion of the present invention (× 300).

──────────────────────────────────────────────────の Continued on the front page (51) Int.Cl. ⁷ Identification symbol FI Theme coat ゛ (Reference) A61K 7/027 A61K 7/027 B01J 13/00 B01J 13/00 A F-term (Reference) 4C083 AA082 AB172 AB211 AC011 AC012 AC022 AC072 AC122 AC342 AC351 AC422 AC442 AD151 AD152 AD162 AD251 AD252 AD492 AD512 AD662 BB13 CC01 CC05 CC12 CC13 DD27 DD31 DD34 EE01 EE10 4G065 AA01 AA06 AB01Y AB02Y AB06Y AB12Y AB14Y AB28Y AB33Y AB35Y BA14 CA05 DA03 FA

Claims (9)

[Claims] 1. An O / W emulsion in which an oil component is included by cyclodextrin and the molecular diameter of a component constituting the oil component to be included is smaller than the molecular ring diameter of the cyclodextrin. O / W / O type composite emulsion, and the aqueous phase of the O / W / O type composite emulsion may contain hydroxyalkylated cyclodextrin, and the outermost oil phase contains hydrophobic powder. O / W / O complex emulsions that may be included (but not both the hydroxyalkylated cyclodextrin in the aqueous phase and the hydrophobic powder in the outermost oil phase). 2. The oil contained in cyclodextrin,
The O / W / O type composite according to claim 1, which is one or more oil components selected from the group consisting of a linear hydrocarbon-based oil, a linear fatty acid ester oil, a silicone oil and an oil-soluble drug. Emulsion. (3) The cyclodextrin which includes an oil component is α
-Cyclodextrin, β-cyclodextrin and γ
1 or 2 or more cyclodextrins selected from the group consisting of -cyclodextrins.
The described O / W / O type complex emulsion. 4. A cyclodextrin that includes an oil component,
3. O as claimed in claim 1 or 2, which is -cyclodextrin.
/ W / O complex emulsion. 5. The O / W / O composite emulsion according to claim 1, wherein the hydrophobic powder is a metal oxide powder subjected to a hydrophobic treatment. 6. The O / W according to claim 1, wherein the outermost oil phase contains a hydrocarbon oil as an oil component.
/ O complex emulsion. 7. The method according to claim 1, wherein a surfactant is not contained as a means for stabilizing the emulsified system.
/ W / O complex emulsion. 8. A cosmetic comprising the O / W / O type complex emulsion according to claim 1. 9. The method according to claim 1, wherein the oil is encapsulated with cyclodextrin, and the molecular diameter of the component constituting the oil to be included is smaller than the molecular ring of the cyclodextrin. O / W emulsions, which may contain cyclodextrin, and oily mixtures, which may contain hydrophobic powders (including both the hydroxyalkylated cyclodextrin in the aqueous phase of the O / W emulsion and the hydrophobic powder of the oily mixture. Is prepared separately), and the O / W emulsion is added as an internal phase by adding the O / W emulsion to the oily mixture and performing an emulsification dispersion operation. O / W / O wherein the oily mixture is present as an outer oil phase
The method for producing an O / W / O composite emulsion according to any one of claims 1 to 8, wherein the composite emulsion is produced.