JP3113160B2 - Cyclodextrin composite particles - Google Patents

Description

DETAILED DESCRIPTION OF THE INVENTION

[0001]

BACKGROUND OF THE INVENTION 1. Field of the Invention The present invention relates to a cosmetic composition capable of gradually supplying a moisturizing component to dry skin and the like, removing excess fatty acids and peroxides on the skin, and maintaining a healthy skin. The present invention relates to cyclodextrin composite particles suitable as a material.

[0002]

2. Description of the Related Art Conventionally, squalane is a colorless, odorless, low freezing point oil that has good stability and has been used in cosmetics as a moisturizing ingredient for covering the skin and preventing dryness of the skin. ing. Such squalanes are usually
It is obtained by hydrogenating squalene.

[0003] However, when squalane is added as a moisturizing component of a cosmetic to a cosmetic such as a foundation, for example, in such an amount that the moisturizing property can be sufficiently exhibited, the squalane is oily. Problems such as oil floating are more likely to occur.

Therefore, Japanese Patent Publication No. Sho 62-21500 proposes a powdery composition obtained by mixing and emulsifying squalene with a protein such as casein and a carbohydrate such as dextrin at a fixed ratio and spray-drying the mixture. And proteins,
It is described that by coating squalene on a carbohydrate, stability against oxidation and solubility in water are imparted, and the above problem can be avoided.

[0005]

However, when the above-mentioned conventional composition is blended into a cosmetic as a moisturizing component, the moisturizing effect is exhibited without stickiness immediately after use, but comes out of human skin with the passage of time. Sebum wastes, such as free fatty acids and their peroxides, cause problems such as stickiness and oil floating.

[0006]

The cyclodextrin composite particles of the present invention, particularly when used in cosmetics, can exhibit a sufficient moisturizing effect without stickiness immediately after use of the cosmetics, and with the passage of time. It is suitable for use as a cosmetic material that can selectively adsorb and remove sebum waste products from human skin only, and uses squalane or purified liquid polybutene as an oily moisturizing component.
It is characterized in that it contains an inclusion compound in which the oily moisturizing component is included in cyclodextrin and amorphous calcium phosphate.

The above-mentioned cyclodextrin composite particles include, for example, amorphous calcium phosphate (Amorphous Calcium Phosphate).
Osphate (hereinafter referred to as ACP) A mixed slurry in which cyclodextrin is mixed with a slurry containing fine particles is prepared, and an oily moisturizing component such as squalane is gradually added to the mixed slurry while stirring the mixed slurry. A clathrate slurry containing a clathrate compound in which a moisturizing component is clad with the cyclodextrin is prepared, and the clathrate slurry is granulated.

The slurry is prepared by adjusting the pH of the suspension of calcium hydroxide under stirring to 10 to 5 by dropping a phosphoric acid aqueous solution to form ACP fine particles in the suspension. An organic dispersant, which is an alkaline water-soluble polymer, such as a weakly alkaline ammonium triacrylate, is suspended in the above ACP fine particles in an amount of 0.1 to 10% by weight, preferably 0.1 to 3% by weight. ACP fine particles having a particle size of about 0.1 .mu.m or less are prepared by adding to a liquid and stably dispersed therein.

ACP fine particles are obtained by powder X-ray diffraction.
The pattern of the X-ray diffraction pattern of the CP fine particles is calcium phosphate [Ca ₃ (PO ₄ ) ₂ .nH ₂ O], and since the pattern is broad, it is confirmed that the calcium phosphate is amorphous calcium phosphate. . In addition, the ACP fine particles
Since it contains water of crystallization, it is considered to be an electrostatically active substance, and it is presumed that various proteins and ionic substances such as amino acids and fatty acids are easily adsorbed.

As an oily moisturizing component, any oil that is oily at normal temperature, has high safety to the skin, can cover the skin surface thinly and can suppress evaporation of moisture on the skin to the outside. Although not particularly limited, examples thereof include squalane obtained by hydrogenating natural squalene, squalane synthesized from isoprene, and purified liquid polybutene.

[0011] These oily moisturizing components are used as inclusion compounds that are included in cyclodextrin. By including the moisturizing component in cyclodextrin in this way, when the obtained cyclodextrin composite particles are used in cosmetics, there is no stickiness, and the oily moisturizing component is gradually released from the cyclodextrin to the outside. Therefore, the skin can be protected from drying for a long period of time.

As cyclodextrins, α-type, β-type
Type and γ-type can be used, and a mixture thereof can be used. However, in order to include a relatively large molecule such as an oily moisturizing component, particularly squalane, a β-type is required. And γ-type cyclodextrin.

[0013] In order to gradually release the oily moisturizing component included in the cyclodextrin from the cyclodextrin to the outside while preventing the sticky feeling from being generated, the moisturizing component is added to the cyclodextrin with respect to the cyclodextrin. 80 mol% or less, more specifically, for example, squalane (mol wt 443) is used as an oily moisturizing component, and β-cyclodextrin (mol wt 443) is used as a cyclodextrin.
1134), the amount of squalane to be included is β
-It is desirable that the content be 50% by weight or less based on cyclodextrin. If an attempt is made to include a larger amount of squalane in cyclodextrin, the possibility of stickiness due to insufficient squalane increases, which is not preferable.

In the granulation, ACP in the slurry is used.
By changing the total content of the fine particles and the clathrate compound within the range of 1 to 90% by weight, it is possible to obtain cyclodextrin composite particles having a desired average particle size composed of the ACP fine particles and the clathrate compound. The AC in the slurry
If the total amount of the P fine particles and the clathrate exceeds 90% by weight, the viscosity of the slurry becomes high, which makes the slurry unsuitable for granulation. If it is less than 1% by weight, the time required for granulation becomes uneconomical.

The granulation method is not particularly limited as long as the obtained cyclodextrin composite particles are substantially spherical with a size of 200 μm or less and can have a large specific surface area (80 m ² / g or more). However, for example, a spray-drying granulation method can be used. Alternatively, a granulation method obtained by freeze-drying followed by pulverization, or a high-speed stirring type granulation method may be used. Further, the shape of the cyclodextrin composite particles is not limited to any shape such as a substantially spherical shape, a plate shape, and a needle shape.

The above-mentioned cyclodextrin composite particles can be suitably used particularly as a cosmetic material, and include powder foundation, face powder, stick-like foundation, under makeup, body powder, eye liner, eyeshadow, sun cream, Sweat, lipstick, liquid foundation, latex,
It can be used as a cosmetic material such as lotion.

In particular, when the cyclodextrin composite particles are used in powder foundations, face powders, stick-like foundations, etc., they can maintain an excellent moisturizing effect, and can free fatty acids from the skin and their peroxides. Since only sebum wastes such as substances can be efficiently adsorbed and removed by the amorphous calcium phosphate, stickiness and oil floating can be prevented for a long period of time.

[0018]

DETAILED DESCRIPTION OF THE PREFERRED EMBODIMENTS Embodiments of the present invention will be described below with reference to FIGS. The cyclodextrin composite particles of the present invention include a mixture of an inclusion compound in which squalane or a purified liquid polybutene as an oily moisturizing component is included in cyclodextrin, and ACP.

Next, the method for producing the cyclodextrin composite particles will be described. First, a mixed slurry in which β-cyclodextrin is dispersed in an adjusted slurry containing ACP fine particles is prepared, and the mixed slurry is stirred. Squalane as a moisturizing component is gradually added to the mixed slurry, and the mixed slurry contains, as shown in FIG. 1, an inclusion compound 2 in which squalane is included in cyclodextrin, and ACP fine particles 1. The clathrate slurry 3 is prepared, and the clathrate slurry 3 is obtained by granulation by a spray drying granulation method (spray dryer method).

Next, the method of preparing the adjusted slurry will be described. First, a phosphoric acid aqueous solution obtained by diluting phosphoric acid 2 to 4 times with water is added dropwise to a stirred suspension of calcium hydroxide. After adjusting the suspension to about pH 11,
An aqueous solution of phosphoric acid obtained by diluting phosphoric acid 5 to 8 times with water is added dropwise to the suspension to adjust the suspension to pH 10 to pH 9, whereby ACP having a particle size of about 0.1 μm or less is obtained. A slurry containing the fine particles was obtained.

By changing the amount of the phosphoric acid aqueous solution dropped, the pH of the suspension can be changed, and the molar ratio of calcium to phosphorus in the obtained ACP fine particles can be changed.

The above slurry is diluted with ion-exchanged water to adjust the concentration of ACP fine particles to 10% by weight, and furthermore, ammonium triacrylate as an organic dispersant which is a weakly alkaline water-soluble polymer is used. A salt (manufactured by Daiichi Kogyo Seiyaku Co., Ltd., trade name: Ceramo D-134) was added to the above ACP fine particles in an amount of 0.5% by weight to obtain the above-mentioned adjusted slurry.

However, in the above-mentioned adjusted slurry, ACP particles having a particle size of about 0.1 μm or less are prevented from aggregating, and
In order to maintain the dispersion stability of the fine particles, it is necessary to add the above-mentioned organic dispersant.

Further, regarding the above ACP fine particles, powder X
When the generated phase of the ACP fine particles was examined by the X-ray diffraction method, as shown in FIG. 2, the obtained ACP fine particles showed that calcium phosphate [Ca ₃ (PO ₄ ) _2.
nH ₂ O], and the X-ray diffraction pattern is broad and, although not shown, is different from the X-ray diffraction patterns of hydroxyapatite crystals and tricalcium phosphate crystals. It was confirmed to be calcium phosphate.

Example 1 A cyclodextrin was mixed with the above-mentioned adjusted slurry, and one example of squalane as a moisturizing component is described below as Example 1. First, 1500 g of the above-mentioned adjusted slurry (solid content) (10% by weight), 100 g of β-cyclodextrin was mixed and dispersed to prepare a mixed slurry, and the mixed slurry was charged into a homomixer.

Thereafter, 10 g of squalane was gradually added dropwise while convectively stirring the mixed slurry in the homomixer at a rotation speed of a rotary turbine of the homomixer of 5000 rpm, and stirring was continued for another 90 minutes. Thereafter, the particles were granulated by a spray drying granulation method to obtain composite particles 7.

That is, while the adjusted slurry 3 containing the ACP fine particles 1 and the clathrate compound 2 is supplied to the atomizer 6 of the spray dryer (L-8 manufactured by Okawara Kakoki Kikai Co., Ltd.) 5 by the metering pump 4, the atomizer 6 is operated at high speed. By rotating, the prepared slurry 3 was granulated and dried by spraying into a hot air stream dried at a high temperature in a spray dryer 5 to obtain 230 g of composite particles 7.

The composite particles 7 obtained by the granulation and drying are substantially spherical, and have a predetermined average particle size,
For example, those of 40 μm were classified and collected. The ultrafine powder that could not be collected by the cyclone 8 was separately collected by a bag filter (not shown).

The operating conditions in the spray granulation are as follows. The supply amount of the adjusted slurry 3 to the spray drier 5 by the metering pump 4 is set to 1 to 3 kg / h, and the temperature of the hot air for drying heated by the electric heater 10 through the air filter 9 is determined by the spray drier. The inlet temperature of the hot gas chamber 11 at 5 is 180 ° C
In addition, the outlet temperature of the discharge hole 12 of the spray dryer 5 connected to the cyclone 8 is controlled to be 70 ° C.,
The rotation speed of the atomizer 6 was set to 25000 rpm.

Further, using two types of spray dryers (FOC-20, OD-25G, FOC-25, OC-25 manufactured by Okawara Kako Kikai Co., Ltd.) obtained by scaling up the spray dryer 5,
When the supply amount of the adjusted slurry 3 was set to 100 kg / hr and the other conditions were used to prepare composite particles in the same manner as above, composite particles similar to the composite particles 7 obtained by the spray dryer 5 were obtained.

Next, the homomixer will be described. The homomixer includes a cylindrical stirring tank having a bottom, a substantially cylindrical stator detachable from the stirring tank, and a suspension in the stirring tank. A turbine rotatably provided in the stator for stirring the liquid, a motor for driving the turbine, a rotating shaft connecting a rotating shaft of the motor and the turbine, and a support portion for the motor. A stator lot connected to the stator and fixed to each other; and a radial baffle-shaped commutation plate slidable with respect to the rotary shaft and the stator lot and set at a predetermined position.

In such a homomixer, a turbine is coaxially mounted on the stirring tank from above in the vicinity of the bottom of the stirring tank, and the direction of the fluid from the turbine is adjusted in the stirring tank. A commutation plate is set in the upper layer of the stirring liquid so as to change to the inner wall of the stirring tank.

The operation of such a homomixer will be described. The pressure difference between the bottom side and the top side of the blade of the turbine caused by the high-speed rotation of the turbine acts like a pump, and the inside of the stirring tank is used. Is sucked from the lower part of the stator, and the liquid is agitated by a strong shear force, impact, and turbulence generated between the turbine rotating at high speed and the stator, and is discharged upward from a discharge port of the stator.

The rising flow is changed by the commutation plate on the upper surface, descends along the inner surface of the stirring tank, and reaches the bottom of the stirring tank again. In this way, the stirring liquid in the stirring tank is convected while being sheared by the blades of the turbine in a direction substantially orthogonal to the convection direction, and is constantly stirred.

Example 2 The amount of squalane added in Example 1 was changed to 30 g instead of 10 g, and the other manufacturing conditions were the same as in Example 1 except that 250 g of composite particles 7 were used.
Obtained.

[Comparative Example 1] Composite particles were prepared in the same manner as in Example 1 except that the amount of squalane added in Example 1 was changed to 10 g, and 60 g was used. Squalene oozed out into the obtained composite particles visually and stickiness was observed, indicating that the composite particles were unsuitable as a cosmetic material.

Next, oleic acid (mol wt 282) and oleyl oleate (mol wt 53) are used as model substances of sebum components as sebum waste products such as free fatty acids and their peroxides.
3), and the composite particles 7 of Examples 1 and 2 described above were selected.
Was used as a sample to measure the adsorption amount of each sebum component and squalane (mol wt 443) in each of the composite particles 7. The results are shown in Table 1.

As another comparative example considered to adsorb sebum components, commercially available spherical hydroxyapatite, sericite, titanium oxide and zirconium oxide were used as samples, and as another comparative example, the above-mentioned ACP particles were used. Crystallization by heating (heating temperature 1000 ℃, heating time 1hr)
The measured results were used in Comparative Example 2 and the measured results are shown in Table 1.

The amount of sebum component and squalane adsorbed was determined by mixing a mixture of 0.5 g of sample powder and 5 ml of oleic acid, oleyl oleate or squalane at 37 ° C.
After incubation for 24 hours, the mixture was suction-filtered three times with 15 ml of ethyl ether, air-dried, and the mixture was subjected to DTA-TG, that is, a method of quantifying the amount of adsorbed sebum component or squalane by thermography by differential thermal analysis.

[0040]

[Table 1]

In Table 1, (-) indicates a blank, OA indicates oleic acid, OO indicates oleyl oleate,
Sq represents squalane, and HAp represents hydroxyapatite.

As is clear from Table 1, each composite particle 7
Although the adsorption amount of each sebum component is extremely high with respect to each comparative example, the adsorption amount of squalane as a moisturizing component is extremely lower than the adsorption amount of each sebum component, and each sebum component is It was found that squalane was hardly adsorbed while maintaining the adsorption ability of squalane.

The reason that each composite particle 7 shows a large sebum adsorbing ability with respect to each comparative example is that the obtained composite particles 7 are uniformly dispersed by an organic dispersing agent into ACP fine particles having a particle size of about 0.1 μm or less. , And is prepared by granulating from the stably dispersed adjustment slurry 3, so that it becomes porous with a large specific surface area. In addition, since the ACP fine particles are amorphous, they are ionic substances. It was presumed that this was due to the fact that free fatty acids and their peroxides were more easily adsorbed.

When the composite particles 7 are used in cosmetics, when the squalane compounded as an inclusion compound 2 in the composite particles 7 is gradually released to the outside, for example, on the skin by cyclodextrin, the composite particles 7 7 is hardly adsorbed by the ACP fine particles. From this, the squalane can cover the skin and protect the skin from drying.In addition, since the squalane is gradually released from the cyclodextrin, the skin can be dried for a long time. It can be protected.

As a result, the composite particles 7 can quickly remove sebum wastes such as free fatty acids and their peroxides from the skin, which have a bad effect on the skin generated from sebum contained in sweat and the like, by adsorbing, and the makeup collapses. It can prevent skin and acne, and can avoid inflammation of the skin due to acne, etc., can maintain good skin hygiene, and can protect the skin from dryness for a long time, so that the skin is in a normal healthy state Can be maintained for a long time.

Further, in the above configuration, since the shape of the composite particles 7 is spherical, “glue” or “slip” on the skin is caused.
Is also good. From these facts, when the above-mentioned composition is blended in cosmetics such as foundations, the skin can be maintained in a normal and healthy state for a long period of time, and the sticky feeling is prevented because the moisturizing component is gradually released. Therefore, it has an excellent property that it can be used on the skin, has a good feeling in use, and prevents a decrease in cosmetic paste due to excessive sebum.

Conventionally, in the case of an inclusion compound of an oily substance using cyclodextrin, the release rate of the above-mentioned oily substance changes depending on the humidity around the inclusion compound. Although the substance can be released from the clathrate, it is known that the release of the oily substance from the clathrate is suppressed in an environment with a moderate humidity of about 60%.

However, the structure of the above embodiment is
Since P has water of crystallization, even in an environment of moderate humidity, the vicinity of the inclusion compound can be brought into an environment similar to high humidity by the water of crystallization. Humidity 60 that can be released, especially when moisturizing is required
% Even under a dry environment of not more than 5%, the effect of effectively exhibiting the moisturizing properties of the moisturizing component is exhibited.

Furthermore, conventionally, when ACP is blended alone in the above-mentioned cosmetics, it is necessary to blend the above-mentioned ACP in an amount of 5% by weight or more in order to sufficiently exhibit the function of removing sebum waste in the above-mentioned ACP. However, when the ACP is added in an amount exceeding 20% by weight, sebum on the skin is unnecessarily adsorbed and removed, so that the skin may feel rough.

However, in the above configuration, when used in cosmetics such as foundations, A
Even if CP is added in an amount exceeding 20% by weight, the ACP hardly adsorbs squalane, and therefore does not inhibit the moisturizing function of squalane which is gradually released onto the skin from clathrate 2. For this reason, the above configuration can prevent the rough feeling of the skin while sufficiently exhibiting the function of removing the sebum waste from the skin in the ACP.

[0051]

As described above, the cyclodextrin composite particles of the present invention can be used as squalane as an oily moisturizing component .
Alternatively, use purified liquid polybutene to keep this oily moisturizer
The composition includes an inclusion compound in which the components are included in cyclodextrin, and amorphous calcium phosphate.

Therefore, in the above configuration, since amorphous calcium phosphate having a high sebum adsorbing ability is mixed, free fatty acids and their peroxides which adversely affect the skin formed from sebum contained in sweat or the like are adversely affected. Sebum waste can be quickly removed from the skin to prevent makeup collapse, acne, and the like, and skin irritation due to acne and the like can be avoided.

On the other hand, in the above configuration, since the amorphous calcium phosphate which adsorbs free fatty acids and its peroxides hardly adsorbs oily moisturizing components, the moisturizing components are converted from the inclusion compound included in cyclodextrin. Even if it is released, the skin can be covered with the moisturizing component, so that the skin can be prevented from drying.In addition, the moisturizing component can be gradually released from the inclusion compound by cyclodextrin, and the skin is dried. Can be maintained for a long period of time.

As a result, the above-described structure is characterized in that the amorphous calcium phosphate and the inclusion compound supply an oily moisturizing component onto the skin to prevent the skin from drying out for a long period of time and to release the moisturizing component from the skin. Fatty acids and sebum wastes that are peroxides can be removed, and the hygiene condition of the skin can be maintained well, so that the effect of maintaining the skin in a healthy state for a long time is achieved.

[Brief description of the drawings]

FIG. 1 is a schematic configuration diagram of a spray drier used when producing cyclodextrin composite particles of the present invention.

FIG. 2 shows A used in the cyclodextrin composite particles.
4 is a graph showing an X-ray diffraction pattern of CP fine particles.

[Explanation of symbols]

 7 Composite particles (cyclodextrin composite particles)

──────────────────────────────────────────────────続 き Continued on front page (58) Field surveyed (Int.Cl. ⁷ , DB name) A61K ^7/ 00-7/50 C01B 25/32 C08B 37/16

Claims (1)

(57) [Claims] 1. Squalane or squalane as an oily moisturizing component
Is a cyclodextrin composite particle comprising purified liquid polybutene, an inclusion compound in which the oily moisturizing component is included in cyclodextrin, and amorphous calcium phosphate.