JP2002146261A - Hydrophobized powder dispersion and manufacturing method of emulsified composition - Google Patents

Abstract

PROBLEM TO BE SOLVED: To prepare a dispersion of a hydrophobized powder capable of enhancing stability of the dispersion itself and of a composition into which it is incorporated. SOLUTION: The manufacturing method of the hydrophobized powder dispersion comprises mixing an organomodified clay mineral, a surfactant, a hydrophobic dispersing medium capable of dispersing and swelling the organomodified clay mineral in the presence of the surfactant, an un-hydrophobized powder and a powder-covering agent and applying a high shearing force to the powder to disperse it into a primary particle state or an almost primary particle state thereby to hydrophobize the surface of the powder. The manufacturing method of a cosmetic with a hydrophobized powder incorporated thereinto comprises mixing an ingredient for a cosmetic with the hydrophobized powder dispersion.

Description

DETAILED DESCRIPTION OF THE INVENTION

[0001]

BACKGROUND OF THE INVENTION 1. Field of the Invention The present invention relates to a method for producing a hydrophobized powder dispersion and a cosmetic, and more particularly to an improvement in a mechanism for hydrophobizing powder.

[0002]

2. Description of the Related Art Various powders such as fine particle titanium dioxide and fine particle zinc oxide are blended with various compositions such as cosmetics.
Since these powders, particularly inorganic powders, usually have a hydrophilic surface, it is difficult to mix them directly into an oily base material, and often causes agglomeration. As a result, there is a problem in the stability of the composition, and there is also a problem in exerting the functions inherent to the powder, such as the ultraviolet scattering effect expected of the fine particle titanium dioxide.

[0003] Therefore, conventionally, various techniques have been developed to increase the lipophilicity by subjecting the powder surface to a hydrophobic treatment, or to disperse the powder in advance in an oily dispersion medium together with a specific dispersant. For example, as the latter example, there is a dispersion of fine particle titanium dioxide silicone described in JP-A-9-208438, which disperses fine particle titanium dioxide in silicone together with a dispersant.

[0004]

However, when the surface of the powder is previously subjected to a hydrophobic treatment as described above, it is added when the powder is blended into a composition such as a cosmetic and mixed. In some cases, the surface-treated portion is scraped off by the shearing force, and the dispersibility in the oil-based substrate is reduced. In addition, the conventional dispersion may cause sedimentation of the powder with time in silicone as a dispersion medium, which is not preferable for stable production of the product.

The present invention has been made in view of the above-mentioned problems of the prior art, and has as its object to provide a dispersion itself and a hydrophobized powder dispersion capable of improving the stability of a composition containing the same.
An object of the present invention is to provide a method for producing a cosmetic.

[0006]

Means for Solving the Problems As a result of intensive studies conducted by the present inventors to achieve the above object, the present inventors have found that a system containing an organically modified clay mineral, an unhydrophobized powder, and a coating agent for the same is used. By applying a high shearing force, it has been found that a hydrophobized powder dispersion having extremely high stability can be obtained, and the present invention has been completed.

That is, the method for producing a hydrophobized powder dispersion according to the present invention comprises the steps of:
A hydrophobic dispersion medium capable of dispersing and swelling the organically modified clay mineral in the presence of a surfactant, an unhydrophobized powder, and a powder coating agent are mixed, and the powder is converted into primary particles or primary particles. The powder surface is subjected to a hydrophobic treatment by applying a high shearing force for dispersing the powder to a close state.

In the present invention, an organically modified clay mineral, a surfactant and a hydrophobic dispersing medium are mixed to form an organically modified clay mineral dispersion, and the unhydrophobized powder is added to the organically modified clay mineral dispersion. It is preferable to add a body and a powder coating agent, apply high shearing force, and subject the powder surface to a hydrophobic treatment. In the present invention, it is preferable that the application of high shearing force is performed by a medium stirring mill or a high-pressure disperser.

In the present invention, the concentration of the organically modified clay mineral when applying a high shearing force is preferably 0.1 to 5% by weight. In the present invention, the concentration of the non-hydrophobicized powder when a high shearing force is applied is preferably 5 to 50% by weight. Further, in the present invention, it is preferable that the non-hydrophobized powder is a UV protection powder.

[0010] In the present invention, the powder coating agent is preferably trimethylsiloxysilicic acid. Also,
The method for producing a cosmetic powder-blended cosmetic according to the present invention is characterized in that a cosmetic component is added to the hydrophobic powder dispersion and mixed.

[0011]

DETAILED DESCRIPTION OF THE PREFERRED EMBODIMENTS Preferred embodiments of the present invention will be described below.
explain about.Organic modified clay mineral  The organically modified clay mineral used in the present invention is hydrophobic
Widely includes those that disperse and swell in the medium, especially water swelling
Quaternary ammonium salt type cationic surfactant
Obtained by treating with a surfactant and a nonionic surfactant
It is suitable.

The water-swellable clay mineral used here is a kind of colloidal hydrated aluminum silicate having a three-layer structure and generally has the following general formula (X, Y) A (Si, Al) 4O10 (OH) 2ZB・
nH2O (where X = Al, FeIII, MnIII, CrII
IY = Mg, FeII, Ni, Zn, LiZ = K, Na, Ca A represents 2-3, and B represents 1/3. ), Specifically natural or synthetic, such as montmorillonite, saponite and hectorite, where (OH) in the formula
Montmorillonites whose radicals have been substituted with fluorine (commercially available products include veegum, kunipia, laponite, etc.) and synthetic mica known by the name of sodium silicic mica sodium or lithium teniolite (commercially available dimonite; Topy Industries, Ltd.) And the like).

The quaternary ammonium salt type cationic surfactant is represented by the following general formula:

Embedded image (Wherein, R1 is an alkyl group or benzyl group having 10 to 22 carbon atoms, R2 is a methyl group or an alkyl group having 10 to 22 carbon atoms, R3 and R4 are alkyl groups or hydroxyalkyl groups having 1 to 3 carbon atoms, X Represents a halogen atom or a methyl sulfate residue.).

For example, dodecyltrimethylammonium chloride, myristyltrimethylammonium chloride, cetyltrimethylammonium chloride, stearyltrimethylammonium chloride, aralkyltrimethylammonium chloride, behenyltrimethylammonium chloride, myristyldimethylethylammonium chloride, cetyldimethylethylammonium chloride, stearyldimethyl Ethyl ammonium chloride,
Aralkyl dimethyl ethyl ammonium chloride, behenyl dimethyl ethyl ammonium chloride, myristyl diethyl methyl ammonium chloride, cetyl diethyl methyl ammonium chloride, stearyl diethyl methyl ammonium chloride, aralkyl diethyl methyl ammonium chloride, behenyl diethyl methyl ammonium chloride, benzyl dimethyl myristyl ammonium chloride, Benzyldimethylcetylammonium chloride, benzyldimethylstearylammonium chloride, benzyldimethylbehenylammonium chloride,
Benzyl methyl ethyl cetyl ammonium chloride, benzyl methyl ethyl stearyl ammonium chloride,
Dibehenyl dihydroxyethyl ammonium chloride,
And the corresponding bromides, and dipalmitylpropylethylammonium methyl sulfate. In the present invention, one or more of these are arbitrarily selected.

The nonionic surfactant used in the organically modified clay mineral of the present invention has an HLB value in the range of 2 to 16, more preferably 3 to 12. H here
The LB value is calculated by the following Kawakami equation. HLB = 7 + 11.7 · log (Mw / Mo) (where Mw represents the molecular weight of the hydrophilic base and Mo represents the molecular weight of the lipophilic base, respectively)

For example, polyoxyethylene 2-30
Molar addition (hereinafter abbreviated as POE (2 to 30)) Oleyl ether, POE (2 to 35) stearyl ether, PO
E (2-20) lauryl ether, POE (1-20)
Alkyl phenyl ether, POE (6-18) behenyl ether, POE (5-25) 2-decyl pentadecyl ether, POE (3-20) 2-decyl tetradecyl ether, POE (3-20) 2-decyl tetradecyl Ethers, ether-type activators such as POE (8-16) 2-octyldecyl ether, and POEs (4-6
0) hydrogenated castor oil, POE (3-14) fatty acid monoester, POE (6-30) fatty acid diester, POE
(5-20) ester-type activators such as sorbitan fatty acid ether, POE (2-30) glyceryl monoisostearate, POE (10-60) glyceryl triisostearate, POE (7-50) cured castor Surfactants such as oil monoisostearate, ether ester type surfactants such as POE (12-60) hydrogenated castor oil triisostearate, and decaglyceryl tetraolate, hexaglyceryl triisostearate, and tetraglyceryl Polyhydric alcohol fatty acid ester surfactants such as polyglycerin fatty acid esters such as diisostearate and diglyceryl diisostearate, and glycerin fatty acid esters such as glyceryl monoisostearate and glyceryl monooleate; nonionic modified silicone activators , And modified silicone dimethyl polysiloxane polyoxyalkylene copolymer represented by the following formula are mentioned if e.

[0017]

Embedded image

Among them, particularly, polyglycerol fatty acid esters of triglycerin or more such as decaglyceryl tetraolate, hexaglyceryl triisostearate, tetraglyceryl diisostearate, POE (2 to 1)
2) Oleyl ether, POE (3-12) stearyl ether, POE (2-10) lauryl ether, P
OE (2-10) nonylphenyl ether, POE
(6-15) behenyl ether, POE (5-20) 2
-Decyl pentadecyl ether, POE (5-17)
2-decyltetradecyl ether, POE (8-1
6) POE addition ether type activator such as 2-octyldecyl ether; POE (10-20) hydrogenated castor oil; POE (5-14) oleic acid monoester;
OE (6-20) oleic diester, POE (5-
10) POE addition ester type activators such as sorbitan oleate, POE (3-15) glyceryl monoisostearate, POE (10-40) POE addition ether ester type activators such as glyceryl triisostearate, etc. An addition type nonionic surfactant is preferably used.

In the present invention, one or more of these nonionic surfactants can be arbitrarily selected and used. The method for treating the organically modified clay mineral used in the present invention includes, for example, water, acetone, or a water-swellable clay mineral and a quaternary ammonium salt-type cationic surfactant in a low-boiling solvent such as a lower alcohol. Dispersion and agitation treatment of a surfactant or a water-swellable clay mineral and a quaternary ammonium salt type cationic surfactant in a low boiling solvent to obtain a cation-modified clay mineral It is obtained by treating with a surfactant and then removing the low boiling solvent.

The organically modified clay mineral adjusted as described above will be described. Among the clay minerals, for example, Na-type montmorillonite that belongs to the smectite family and exhibits water swelling properties is converted into a hydrophobic organically modified montmorillonite by a cation exchange reaction with a quaternary ammonium salt-type organic cation. Furthermore, a nonionic surfactant is included to form an inclusion compound (complex), which swells in oil to produce a viscous oily gel. The nonionic surfactant is considered to be included in the polar sites between the montmorillonite layers (silicate layers) that do not participate in the cation exchange reaction. (Yuyu Kagaku Vol. 40, No. 6, 491-4)
96 1991).

The structure of the resulting organically modified clay mineral is such that the interlaminar space between the water-swellable clay mineral is widened by the interposition of the quaternary ammonium salt type cationic surfactant and the nonionic surfactant. Has become. Therefore, the presence or absence of the adsorption of the quaternary ammonium salt type cationic surfactant and the nonionic surfactant can be confirmed by measuring the long plane distance by X-ray diffraction.

When the obtained organically modified clay mineral is subjected to Soxhlet extraction using chloroform, ether, or the like, the surfactant between layers is washed away, and the extract is subjected to gas chromatography analysis, thermal decomposition temperature measurement, or the like. The presence of the surfactant can be confirmed by measuring the amount of thermal decomposition (DTA-TG measurement) or the like. Although the content of the quaternary ammonium salt type cationic surfactant in the organically modified clay mineral used in the present invention is not particularly limited, it is 60 to 140 milliequivalents (hereinafter meq) with respect to 100 g of the water-swellable clay mineral.
Is abbreviated). The content of the nonionic surfactant in the organically modified clay mineral is determined by the water-swelling clay mineral 1
The amount is preferably 5 to 100 g, more preferably 15 to 50 g, based on 00 g.

The amount of the organically modified clay mineral used is preferably 0.1 to 5% in the dispersion, more preferably 0.5 to 5%.
~ 3%. If the amount is less than 0.1%, the effect of adding the organically modified clay mineral cannot be obtained, and a stable dispersion may not be obtained. On the other hand, if it exceeds 5%, the viscosity of the prepared dispersion is high, and an excessive load is applied to the application of a high shearing force. In addition, when it is blended with a composition such as a cosmetic, it has poor elongation and lacks transparency. This causes problems in practical use.

[0024]Hydrophobic dispersion medium  In the present invention, the organic compound obtained as described above is used.
Dispersion is achieved by blending a hydrophobic clay mineral with a hydrophobic dispersion medium.
・ It is necessary to swell. Such hydrophobic dispersion
Liquid paraffin, squalane, isopa
Hydrocarbon oils such as raffin and branched-chain light paraffin, iso
Propyl myristate, cetyl isooctanoate,
Ester oils such as lyseryl trioctanoate, decamethi
Lepentasiloxane, dimethylpolysiloxane, methyl
Silicone oils such as phenylpolysiloxane;
You.

In the present invention, silicone oils are preferably used, but those having a boiling point of 200 ° C. or less at normal pressure are particularly preferable from the viewpoint of usability and formulation. For example, chain polysiloxanes such as dimethylpolysiloxane, methylphenylpolysiloxane, methylhydrogenpolysiloxane, octamethylcyclotetrasiloxane, decamethylcyclopentasiloxane, dodecamethylcyclohexasiloxane, tetramethyltetrahydrogencyclotetrasiloxane, etc. And the like. Among these, volatile linear polysiloxanes such as low-polymerization degree dimethylpolysiloxane (polymerization degree 3 to 7) and volatile silicones such as cyclic volatile polysiloxanes such as decamethylcyclopentasiloxane and octamethylcyclotetrasiloxane The use of oil is particularly suitable when an oily feeling is less likely to remain when applied to the skin as compared with ordinary silicone oil, and a refreshing feeling is required.

In the dispersion of the present invention, the amount of the hydrophobic dispersion medium can be appropriately selected, but is preferably 40 to 95% by weight, particularly preferably 50% by weight, based on the total amount of the dispersion.
~ 80% by weight. When the amount of the dispersion medium is small, an excessive load may be applied when a high shearing force is applied, and when the amount of the dispersion medium is large, the ratio of the powder becomes relatively low, and the hydrophobic powder is added. The meaning as a body dispersion becomes low.

[0027]Surfactant  Surfactants suitably used in the present invention are organic surfactants.
Dispersible clay minerals well in the dispersion medium
There is no particular limitation as long as it is acceptable. example
Sorbitan sesquiisostearate, sorbitan dii
Sostearate, sorbitan sesquiolate, sorbitan
Dioliolate, glyceryldiolate, glyceryldiyl
Sostearate, polyoxyalkylene-modified organopo
And siloxane. Silicon as dispersion medium
Polyoxyethylene methyl
Silicone-based surfactants such as polysiloxane copolymers
It is preferable to use an agent.

The amount of the surfactant according to the present invention is preferably about 0.1 to 5% by weight in the dispersion. If the amount is less than this, the dispersion and swelling of the organically modified clay mineral may be insufficient. Even if the amount is larger, improvement of the addition effect is often not recognized.

[0029]Unhydrophobicized powder  The non-hydrophobicized powder in the present invention is used for cosmetics production.
In other words, the powder surface has a hydrophilic meaning. In the present invention
As the powder component in the above, titanium oxide, zinc oxide,
Aluminum oxide, zirconium oxide, red iron, yellow acid
Iron fossil, black iron oxide, ultramarine, cerium oxide, talc, my
Mosquito, sericite, kaolin, silica, stearic acid
Lead, fluorophlogopite, synthetic talc, barium sulfate, carbonic acid
Inorganic powders such as magnesium, boron nitride and titanate
Powder, inorganic white pigments such as titanium oxide and zinc oxide,
La, yellow iron oxide, black iron oxide, carbon black, titanium
Rack, manganese violet, cobalt violet
Inorganic pigments such as blue, ultramarine and navy blue, titanium oxide coating
Mica, titanium oxide coated talc, colored oxide
Tank coated mica, bismuth oxychloride, fish phosphor foil
Which include pearl pigments, metal powder pigments such as alumina
It is.

In the present invention, an organic or inorganic powder coated with an oxide or a hydrated oxide such as aluminum, silicon, titanium, zirconium, magnesium or zinc can also be used. Further, a material doped with another element, a composite oxide of two or more metals, or the like may be used. Further, as a powder, tetraethoxysilane is coated on zinc oxide in an amount of 10 to 30% by weight, and
It is also preferable to use a zinc oxide powder having a silica layer formed thereon.

Considering that the dispersion of the present invention is particularly effective for fine powder having excellent ultraviolet protection effect, fine titanium oxide, fine zinc oxide, fine iron oxide red, fine particles having an average particle diameter of 0.001 to 0.5 μm. Iron oxide yellow, fine-particle iron oxide black, fine-particle cobalt blue, and the like. It is known that fine particle powder is superior to ordinary powder in ultraviolet protection effect, transparency and the like.

It is preferable that one or more of these are contained in the dispersion in an amount of 5 to 50% by weight, particularly preferably 10 to 35% by weight. If the amount is less than 5% by weight, the effect of the fine particle powder may not be exhibited.

[0033]Powder coating  The powder coating preferably used in the present invention is particularly limited.
Although not specified, it can be dispersed in the non-aqueous solvent.
Especially, dimethylpoly which is a silicone compound
Siloxane methyl (polyoxyalkylene) siloxa
Polymer, trimethylsiloxysilicic acid, carboxy-modified
Silicone oil, amino-modified silicone oil, etc.
Can be raised. These silicone-based powder coatings are
1 to 40% by weight, preferably 5 to 30% by weight
Is preferred.

[0034]High shear force treatment  In the present invention, the powder is a primary particle in the essential components.
High shear force treatment to disperse it to a state close to it
Need to perform this high shear force treatment
High pressure disperser or batch type, continuous horizontal type, vertical type
It is preferable to use a medium mill such as a shape and an annular type.
is there. Particularly preferably used in the production method of the present invention
A batch-type media mill, which is a dispersing device, shows one aspect thereof.
Then, FIG. 1A is obtained.

As shown in FIG. 1 (A), a batch type media mill used in the production method of the present invention has a tank 18.
The apparatus includes a basket unit 10 and one or more in-tank agitating devices 20 provided for the pre-mixing and the dispersion flow provided in the basket unit 10. The basket section 10 has an upper cover jacket 28 and is fixed in position by the rod 16. A large number of small holes formed of slits are provided on the side wall of the basket portion 10. Also,
The basket unit 10 has an in-basket stirring device 14 for stirring the inside of the basket unit 10.

First, the organically modified clay mineral, the surfactant, and the hydrophobic dispersion medium, which are the raw materials for the dispersion of the present invention, are preliminarily mixed by a stirring device 20 in a tank provided to form a mixed solution.
It flows into the basket portion 10 through an opening around the rotation axis of the in-basket stirring device 14 above the basket portion 10 attached to the device.

Here, the inside of the basket section 10 is shown in FIG.
It is shown in (B). The inside of the basket portion 10 is filled with a solid dispersion medium (beads) 22, and the stirring device 14 in the basket has a stirring pin disk 26 (or a stirring disk) mounted perpendicular to the rotation axis. . The stirring pin disk 26 has a pin 24 for stirring.

The mixed liquid that has flowed into the basket section 10 is crushed and dispersed by the solid dispersion medium (beads) 22 by the high-speed rotating stirring pin disk 26 to crush various powder agglomerated particles in the powder component. It flows out from a small hole 12 composed of a number of slits provided on the side wall of the ten. The arrows in FIG. 1 (A) indicate the overall fluid path.

The outflowing dispersion liquid is supplied to the tank stirring device 2
0, a part of the fluid flows into the basket portion 10 again through the opening above the basket portion 10 and the tank 1
Circulate in 8. It is important that the agitating portion of the in-tank agitator 20 is located at a position that does not obstruct the fluid path that enters and exits the basket section 10. A batch-type media mill is an apparatus having a process in which the dispersion of powder in the tank 18 is kept uniform. As a suitable dispersing apparatus for the method for producing a hydrophobized powder dispersion of the present invention, a dispersing apparatus described in JP-B-8-17930 can be mentioned.

The basket section filled with the solid dispersion medium (beads) installed in the batch type medium mill is as follows:
The side wall has a large number of small holes made of slits, and the size is set so that the solid dispersion medium (beads) to be used does not flow out of the basket portion. Is not included.

As described above, the batch type media mill preferably used in the present invention has small holes in the side wall of the basket portion filled with the solid dispersion medium.
Since the solid dispersion medium is concentrated on the side wall by centrifugal force due to the rotation of the shaft, the powder including the fine particle powder passes through a place where the density of the solid dispersion medium is high, so that the dispersion efficiency can be increased.

As the solid dispersion medium in the present invention, beads made of glass, alumina, titania, zircon, zirconia, steel, flint stone or the like can be used, but those made of zirconia are particularly preferable. Also,
As for the size of the beads, those having a diameter of about 0.3 to 2 mm are usually used, and in the present invention, those having a diameter of about 1 mm are preferable.

As the stirring device having both the pre-mixing and the dispersion and flowing in the present invention, a stirring device suitable for ordinary cosmetics production can be used. It is particularly preferable to use a disper or a homogenizer to which the above-mentioned rotor is attached.

FIG. 2 shows an example of a continuous medium stirring mill attached to a pre-stirring tank suitably used in the production method of the present invention. The continuous medium agitating mill device shown in FIG.
This is a device in which a medium including a medium mill 30 containing therein and a preliminary stirring tank 32 capable of being stirred by a disper 42 by rotation of a motor 38 are connected by a pipe via a pump 34 so that a liquid containing powder can be circulated. First, the raw material containing the powder is premixed by the disperser 42 by the preparatory stirring device 32 to form a mixed liquid, and then flows into the medium stirring mill 30 connected by a pipe by the pump 34.

The mixed liquid that has flowed into the medium mill 30 is crushed and dispersed by a solid dispersion medium (beads) 40 by a high-speed rotating stirring rotor to break up various powder aggregate particles in the powder component. It is sent to the preliminary stirring tank 32 again by the pump 34. The continuous medium stirring mill is an apparatus having a process of making the dispersion of powder uniform in this way. The stirring time in the preliminary stirring tank, the stirring time in the medium stirring mill, and the number of Passes of the present apparatus can be appropriately determined as needed.

As a stirrer for the pre-stirring tank suitably used in the present invention, a stirrer suitable for ordinary production of cosmetics and the like can be used. It is particularly preferable to use a disperser or a homogenizer equipped with. A biaxial type disper with a disper blade and a scraping blade can also be suitably used.

Next, the method for producing the hydrophobized powder dispersion and the emulsified cosmetic of the present invention will be described more specifically by way of examples. When using a batch-type medium stirring mill having a stirring device in the tank, using a batch-type medium mill having a stirring device in the tank, the dispersion medium such as silicone oil, the organic modified clay mineral, and the surfactant are used. After mixing with a stirrer in the tank, the mixture is dispersed and mixed for a short period of time, for example, about 3 to 10 minutes, in a basket section, which is a medium mill section. The coating agent is added, and the mixture is further dispersed and mixed for a long time, for example, about 10 minutes to 10 hours with a high shearing force. During this time, the titanium dioxide is coated with trimethylsiloxysilicic acid to become hydrophobic titanium dioxide. As a result, it is possible to produce the hydrophobized powder dispersion in one tank at a short time and at low cost. In addition, cleaning after manufacturing is greatly simplified as compared with conventional manufacturing. In addition, an oily powder cosmetic can be obtained by adding another oil component, powder or the like as it is to the hydrophobized powder dispersion in the medium mill and filling and molding the mixture into a predetermined mold. Since it contains a hydrophobic powder, an oily powder cosmetic such as an oily foundation can have a smooth, smooth texture, a transparent finish, and a high ultraviolet protection effect.

When a continuous medium stirring mill provided with a pre-stirring device is used, a dispersion medium such as silicone oil is stirred and mixed in the pre-stirring device, and then an unhydrophobized powder such as titanium oxide and trimethyl are mixed. A powder coating agent such as siloxysilicic acid is added to the preliminary stirring tank, and the mixture is stirred and mixed for a short period of time, for example, about 3 to 10 minutes, and then mixed with a medium mill for a long time, for example, 10 minutes.
The dispersion and mixing process is performed by high shearing force and high impact force for about 10 minutes to about 10 hours, about 3 to 10 times of pass, or about 3 to 10 minutes of pass. During this time, the non-hydrophobicized powder such as the titanium oxide is coated with trimethylsiloxysilicic acid to become hydrophobic titanium oxide. The hydrophobized powder dispersion can also be obtained by adding an unhydrophobicized powder and a powder coating agent to a dispersion medium together with an organically modified clay mineral or the like from the beginning.

An example of a method for producing an emulsified cosmetic is as follows. In the case of a water-in-oil type emulsified cosmetic, a batch-type medium mill having a stirring device in a tank is used. Similarly prepared, then, an aqueous component is added and emulsification is performed using a medium mill while mixing the dispersion in the tank with a mixing and stirring section, whereby a water-in-oil emulsified cosmetic can be obtained. Further, after preparing the above dispersion, an aqueous component was added, mixed and phase-inverted with a stirring device in a tank, dispersed and mixed in a basket portion which was a medium mill portion, and then an oil component was added and mixed by a mixing and stirring portion. By emulsifying using a medium mill while mixing the dispersion in the tank, an oil-in-water emulsified cosmetic can be obtained. According to the present manufacturing method, in one tank, short operability, easy operability,
It is possible to manufacture an emulsified cosmetic containing a hydrophobic powder at low cost. In addition, the emulsified cosmetic containing the hydrophobized powder obtained according to the present invention has a high dispersibility and thus exhibits a high UV protection effect, and has a smooth and creamy texture due to being emulsified by a medium mill. can do.

[0050]Other ingredients  In the present invention, when preparing cosmetics,
Add an oily component to the hydrophobized powder dispersion.
Can be. Such oily components include cosmetics
It is not particularly limited as long as it is an oily component used for
No, for example, cetyl isooctanoate, glyceryl
S such as lihexanoate and isopropyl myristate
Charcoal such as tellurium oil, petrolatum, liquid paraffin, squalane
Hydrogenated oil, castor oil, olive oil, camellia oil, jojoba
Oil, natural animal and vegetable oils such as lanolin in combination
You.

In the present invention, when producing a solid oily powder cosmetic, it is preferable to incorporate a wax component as a solid agent. As the wax component of the solid agent,
Microcrystalline wax, carnauba wax, candelilla wax, polyethylene wax, ceresin wax and the like can be used in combination. It is preferred that the wax component be contained in a total amount of 3 to 25% by weight.

Examples of the aqueous component in the present invention include polyhydric alcohols such as glycerin, water-soluble substances such as ethyl alcohol, and water. In the cosmetic of the present invention, further, a surfactant, a dispersant, a stabilizer, a coloring agent, a preservative, an antioxidant, an ultraviolet absorber, a humectant, a fragrance, and the like are also included in the range in which the object of the present invention is achieved. They can be appropriately blended.

The production method of the present invention is applicable to, for example, the production of oily powder cosmetics such as eyeliner pencils, eyebrow pencils, oily foundations, oily stick foundations, oily eye colors, and emulsified cosmetics such as emulsified sunscreens and emulsified foundations. Is done. Further, the composition containing the dispersion according to the present invention, in addition to the excellent ultraviolet shielding effect of the highly dispersed ultraviolet protective powder, feeling of use, water resistance, oil resistance is good, emulsion stability and It has the advantage of being excellent in drug stability.

Next, test examples of the present invention will be described.
First, the present inventors prepared hydrophobized powder dispersions by various production methods and evaluated them. Table 1 shows the results.

[Table 1]Dispersion Test Example 1 2 3 4 5  Volatile Silicone 61 61 60 60 60 Methylpolysiloxane 5.555.5 Polyoxyethylene-methylpolysiloxane Copolymer 1 1 1 1 1 1Organically modified bentonite 0 0 1 1 1  Fine particle zinc oxide 25 25 25 25 25 25Trimethylsiloxysilicic acid 8 8 8 8 8 Manufacturing method A B A B C  Separation Immediately after production (room temperature) ○ ○ ○ ○ ○ After 4 weeks (room temperature) △ △ ○ ○ × Viscosity Immediately after production (room temperature) 480 520 650 710 155After 4 weeks (room temperature) 300 280 410 380 60   The following standards were used for separation. ○: Almost no sedimentation of the powder was observed △: Sedimentation of the powder was observed, but redispersion was easy ×: Powder sedimented and redispersion was difficult due to caking

Production method A : All components are mixed and dispersed by a medium mill for 55 minutes. Production method B : volatile silicone, methylpolysiloxane, polyoxyethylene / methylpolysiloxane copolymer, and organically modified bentonite are premixed (medium mill 5).
Min), and zinc oxide particles and trimethylsiloxysilicic acid are added thereto and dispersed by a media mill for 50 minutes. Production method C : Volatile silicone, methylpolysiloxane, polyoxyethylene / methylpolysiloxane copolymer, and organically modified bentonite are premixed (dispers for 5 minutes), and fine zinc oxide and trimethylsiloxysilicic acid are added thereto. And dispersed for 50 minutes by a disperser usually used in the manufacture of cosmetics.

As is clear from Table 1, when the organically modified clay mineral was not used (Test Examples 1 and 2), the fine zinc oxide was hardly hydrophobized by any of the methods, and separated over time. , Resulting in a decrease in viscosity. Also,
Even when an ordinary disper having low shearing force was used for the dispersion treatment (Test Example 5), the stability was low despite the addition of the organically modified clay mineral. On the other hand, when a high shearing force is applied by a medium mill using fine particles of zinc oxide and trimethylsiloxysilicic acid in a system using an organically modified clay mineral (Test Examples 3 and 4), excellent stability is exhibited. In particular, when a gel was formed in advance from an organically modified clay mineral and fine particles of zinc oxide and trimethylsiloxysilicic acid were added thereto (Test Example 4), extremely high stability was exhibited.

Next, the present inventors prepared and evaluated a water-in-oil emulsion composition using the dispersions of Test Examples 1 to 5. The results are shown in Table 2 below.

[Table 2]Test example 6 7 8 9 10  Dispersion Test Example 1 60 2 60 3 60 4 605 60  Nylon powder 55 55 55 Octyl methoxycinnamate 77 77 77 polyoxyethylene-methylpolysiloxane copolymer 0.5 0.5 0.5 0.5 0.5 isostearic acid 0.5 0.5 0 0.5 0.5 0.5 Moisturizer 5.5 5 5.5 5Ion-exchanged water Remaining Remaining Remaining Remaining Remaining  Viscosity Immediately after production (room temperature) 675 810 1040 1160 310After 4 weeks (room temperature) 540 660 930 1070 205  Smoothness ○ ○ ○ ○ × Powdery ○ ○ ○ ○ × Uniform finish △ △ ○ ○ × Whiteness of coating △ △ ○ ○ ×SPF 41 43 49 51 30

Smoothness, powderiness, uniform by sensory evaluation
The finish and transparency, and measure the SPF.
I got this. The evaluation criteria are as follows.Evaluation criteria  Apply the sample to 20 female panelists,
The length, uniform finish, and transparency were evaluated. (Evaluation) 17 or more respondents are good ◎ 12 to 16 respondents are good ○ 9 to 11 respondents are good △ 5 to 8 respondents are good × 4 or less respondents are good ××

The preparation is performed by adding nylon powder, octyl methoxycinnamate, polyoxyethylene / methyl polysiloxane copolymer and isostearic acid to each dispersion, stirring and mixing with a disper for 2 minutes, further adding a humectant, Ion exchange water was added, and the mixture was further stirred and mixed with a disper for 2 minutes. With respect to these water-in-oil type sunscreen agents, smoothness, powderiness, uniform finish, and whiteness at the time of application were evaluated by sensory evaluation, and SPF was measured.

As is clear from Table 2, Test Examples 6, 7, and 1 in which the fine zinc oxide is not considered to be hydrophobized.
Regarding 0, not only the stability was low, but also the evaluation as a cosmetic was low. In contrast, the cosmetics according to the present invention (Test Examples 8 and 9) all showed excellent effects. In this test, untreated zinc oxide that has not been subjected to hydrophobic treatment is used, so if the hydrophobic treatment is insufficient, the powder will aggregate and the SPF will be low.

From the results shown in Tables 1 and 2, the dispersion according to the present invention not only has improved dispersibility of the fine zinc oxide, but also has the surface of the fine zinc oxide which is hydrophobic or coated with the coating agent. In addition, it can be understood that the presence of an organically modified clay mineral and the application of a high shearing force such as a media mill are required for hydrophobic coating of the particulate zinc oxide with trimethylsiloxysilicic acid.

Next, the present inventors examined the amount of the organically modified clay mineral added when producing the dispersion. Table 3 shows the results.

[Table 3]Dispersion test example 11 12 13 14 15 16 17 18  Volatile silicone 61.0 60.9 60.5 60.0 59.5 58.0 56.0 54.0 Methylpolysiloxane 5.0 5.0 5.0 5.0 5.0 5.0 5.0 5.0 Polyoxyethylene-methylpolysiloxane copolymer 1.0 1.0 1.0 1.0 1.0 1.0 1.0 1.0 1.0Organically modified bentonite 0 0.1 0.5 1.0 1.5 3.0 5.0 7.0  Fine particle zinc oxide 25.0 25.0 25.0 25.0 25.0 25.0 25.0 25.0Trimethylsiloxysilicic acid 8.0 8.0 8.0 8.0 8.0 8.0 8.0 8.0 Production by media mill △ ○ ○ ○ ○ ○ △ ×   The suitability for production was evaluated according to the following criteria. ：: sufficiently dispersed powder in a medium stirring mill △: increased in viscosity or powder agglomeration in a medium stirring mill
Dispersion of powder is slightly poor ×: Dispersion in medium stirring mill is not possible due to increase in viscosity

As is clear from Table 3, the effect of the organically modified clay mineral is observed from the addition of about 0.1%.
If it is 7%, the viscosity is rather too high, which is not preferable. Therefore, the amount of the organically modified clay mineral added is preferably from 0.1% by weight to 5% by weight, particularly preferably from 0.5% by weight to 3.0% by weight when subjected to a medium mill.

Next, the present inventors studied the amount of powder added. The results are shown in Table 4 below.

[Table 4]Dispersion Test Example 19 20 21 22 23 24 25 26 27  Volatile silicone 86.4 79.8 73.2 66.6 60.0 53.4 40.2 27.0 13.4 Methylpolysiloxane 5.0 5.0 5.0 5.0 5.0 5.0 5.0 5.0 5.0 Polyoxyethylene-methylpolysiloxane copolymer 1.0 1.0 1.0 1.0 1.0 1.0 1.0 1.0 1.0Organically modified bentonite 1.0 1.0 1.0 1.0 1.0 1.0 1.0 1.0 1.0 1.0  Fine particle zinc oxide 5.0 10.0 15.0 20.0 25.0 30.0 40.0 50.0 60.0Trimethylsiloxysilicic acid 1.6 3.2 4.8 6.4 8.0 9.6 12.8 16.0 19.6 Production by media mill ○ ○ ○ ○ ○ ○ ○ △ ×  Immediately after production 45 50 210 445 710 990 4350 12600 651004 weeks later 25 25 95 280 380 475 3860 10800 61400 

As is evident from Table 4, when the amount of the powder added is 60%, the viscosity at the time of preparation becomes too high, and the addition to the medium mill becomes extremely high. On the other hand, when the added amount of the powder is small, there is almost no effect on the stability and the like, but when considering the efficient supply of the hydrophobized powder to other compositions, it is about 5 to 50% by weight. It is preferred to do so.

[0066]

Embodiments of the present invention will be described below. What
The present invention is not limited to these examples.
No.Example 1 Preparation of hydrophobized powder dispersion  0.5 parts by weight of organically modified clay mineral, 0.5 parts by weight of surfactant
Parts, 54.8 parts by weight of silicone oil were stirred with a medium stirring mill
Then, 23.7 parts by weight of titanium oxide,
14.2 parts of methylsiloxysilicic acid, 6.3 of silicone oil
Parts, and then dispersed by a medium stirring mill to
A titanium oxide dispersion was obtained.

[0067]Example 2 Preparation of hydrophobized powder dispersion  0.3 parts by weight of organically modified clay mineral, 0.3 parts by weight of activator,
34.7 parts by weight of silicone oil was stirred with a medium stirring mill and adjusted.
15.0 parts by weight of zinc oxide,
9.0 parts by weight of roxysilicic acid, 4.0 parts by weight of silicone oil
And then dispersed in a medium stirring mill to
A zinc oxide dispersion was obtained.

[0068]Example 3 Preparation of sunscreen cosmetics  0.3 parts by weight of organically modified clay mineral, 0.3 parts by weight of surfactant
Parts, 34.7 parts by weight of silicone oil with a medium stirring mill
The prepared gel was mixed with 15.0 parts by weight of zinc oxide,
9.0 parts by weight of lusiloxysilicic acid, 4.0 weight of silicone oil
Then, the mixture was dispersed in a medium stirring mill. This minute
1.05 parts by weight of surfactant, octyl methoxy
After adding 7.5 parts by weight of nanamate and redispersing, ion exchange
Add 19.75 parts by weight of water and emulsify to give sunscreen cosmetics
Obtained.

[0069]Example 4 Preparation of Foundation  1 part by weight of organically modified clay mineral, 1 part by weight of surfactant,
Ges prepared by stirring 35 parts by weight of corn oil with a medium stirring mill
5 parts by weight of fine particle titanium oxide, 11.5 parts by weight of coloring material
Parts, extender 10 parts by weight, trimethylsiloxysilicic acid
4.5 parts by weight were added and dispersed by a medium stirring mill. to this
Add 1 part by weight of surfactant and 3 parts by weight of nylon powder,
After redispersion, add 20 parts by weight of ion-exchanged water and emulsify.
With this, a foundation was obtained.

[0070]Example 5 Water-in-oil type sunscreen cosmetics  (Method) Volatile silicone in oil phase, methyl polysilo
Xanth, organic modified clay mineral in batch type medium stirring mill
After dispersion with a disper for 5 minutes, fine particles of zinc oxide and trim
Add tilsiloxysilicic acid and dispers for 5 minutes
After the dispersion, the mixture is dispersed in a medium mill for 30 minutes. Then add
After adding the aqueous phase and dispersing for 5 minutes with a disper, 5 minutes
The mixture is dispersed and emulsified in an intermediary mill. (Method) Volatile silicone in oil phase, methyl polysilo
Xan, organic metamorphic clay mineral continuous with pre-mixing tank
5 minutes with a disperser in a pre-stirring tank of a continuous media stirring mill
After dispersion, fine particles of zinc oxide and trimethylsiloxysilicic acid
After adding and dispersing for 5 minutes with a disper, Pa
ss and disperse. After that, the additional components and the aqueous phase are pre-stirred
And after dispersing for 5 minutes with a disper,
Disperse and emulsify for 1 pass.

(Oil phase) Volatile silicone 30 Methylpolysiloxane 5 Polyoxyethylene-methylpolysiloxane copolymer 0.3 Organically modified bentonite 0.3 Fine zinc oxide (untreated product) 15 Trimethylsiloxysilicic acid 4 5 (Additive component) Silicone resin powder 3 Octyl methoxycinnamate 7.5 Polyoxyethylene-methyl polysiloxane copolymer 1.2 Isostearic acid 0.5 Perfume Appropriate amount (aqueous phase) Moisturizer 5 Preservative Appropriate amount Ion exchange water to 100

[0072]Example 6 Water-in-oil emulsification foundation  (Method) Volatile silicone in oil phase, methyl polysilo
Xanth, organic modified clay mineral in batch type medium stirring mill
After dispersing with a disper for 5 minutes,
Add Limethylsiloxysilicic acid and dispers for 5 minutes
After the dispersion, the mixture is dispersed in a medium mill for 30 minutes. Then add
After adding the components and the aqueous phase and dispersing with a disper for 5 minutes, 1
The mixture is dispersed and emulsified in a medium mill for 0 minutes. (Method) Volatile silicone in oil phase, methyl polysilo
Xan, organic metamorphic clay mineral continuous with pre-mixing tank
5 minutes with a disperser in a pre-stirring tank of a continuous media stirring mill
After dispersion, fine particle titanium oxide, trimethylsiloxysilicic acid
And after dispersing for 5 minutes with a disper, 3 times with a media mill
Pass and disperse. After that, the additional components and the aqueous phase are preliminarily stirred.
After adding to the tank and dispersing with a disper for 5 minutes,
Disperse and emulsify for 2 passes.

(Oil phase) Volatile silicone 20 Methylpolysiloxane 15 Polyoxyethylene-methylpolysiloxane copolymer 1 Organically modified bentonite 1 Fine particle titanium oxide (aluminum-treated product) 5 Trimethylsiloxysilicic acid 1.5 (Addition component Nylon powder 3 Silicone-treated talc 10 Silicone-treated titanium oxide 8 Silicone-treated yellow iron oxide 2 Silicone-treated red iron oxide 1 Silicone-treated black iron oxide 0.5 Polyoxyethylene-methylpolysiloxane copolymer 1.5 Isostearic acid 0. 5 (Aqueous phase) Moisturizer 8 Preservatives Appropriate amount Deionized water to 100

[0074]Example 7 Water-in-oil emulsification foundation  (Method) Volatile silicone in oil phase, methyl polysilo
Xanth, organic modified clay mineral in batch type medium stirring mill
After dispersion with a disper for 5 minutes, fine titanium oxide, color
Materials, extenders and trimethylsiloxysilicic acid.
After dispersing for 5 minutes in Disper, dispersing for 30 minutes in media mill
I do. Then add the added ingredients and the aqueous phase and disperse
After dispersion for 5 minutes, the mixture is dispersed and emulsified in a medium mill for 5 minutes. (Method) Volatile silicone in oil phase, methyl polysilo
Xan, organic metamorphic clay mineral continuous with pre-mixing tank
5 minutes with a disperser in a pre-stirring tank of a continuous media stirring mill
After dispersion, fine particle titanium oxide, coloring material, extender pigment, trimethyl
Add lusiloxysilicic acid and disperse with Disper for 5 minutes
Thereafter, the mixture is dispersed by passing three times using a media mill. Then add
Minutes, add the aqueous phase to the pre-mixing tank and disperse for 5 minutes
After dispersion, the mixture is dispersed and emulsified by 2 passes in a medium mill.

(Oil Phase) Volatile Silicone 20 Methylpolysiloxane 15 Polyoxyethylene-methylpolysiloxane Copolymer 1 Organically Modified Bentonite 1 Fine Particle Titanium Oxide (Aluminum Treated Product) 5 Titanium Oxide 8 Yellow Iron Oxide 2 Red Iron Oxide Reference Signs List 1 black iron oxide 0.5 talc 10 trimethylsiloxysilicic acid 4.5 (additive component) nylon powder 3 polyoxyethylene-methylpolysiloxane copolymer 1 (aqueous phase) humectant 8 preservative proper amount ion-exchanged water to 100

[0076]Example 8 Water-in-oil emulsification foundation  (Method) Volatile silicone in oil phase, methyl polysilo
Xane, fine particle titanium oxide, coloring material, extender pigment, trimethyl
Dispersing luciroxysilicic acid in a batch media stirring mill
And then disperse for 30 minutes in the media mill.
You. After that, the additional component and the aqueous phase were added, and 5
After dispersion for 5 minutes, the mixture is dispersed and emulsified in a medium mill for 5 minutes. (Method) Volatile silicone in oil phase, methyl polysilo
Xane, fine particle titanium oxide, coloring material, extender pigment, trimethyl
Continuous media stirring with a pre-stirring tank
After dispersing for 5 minutes with a disperser in a pre-stirring tank of a stirring mill,
Pass 3 times with a media mill to disperse. Then add ingredients, water
Add the phase to the pre-stirring tank and disperse for 5 minutes with a disper
Thereafter, the mixture is dispersed and emulsified by 2 passes in a medium mill.

(Oil phase) Volatile silicone 20 Methyl polysiloxane 15 Fine particle titanium oxide (aluminum-treated product) 5 Organically modified bentonite 1 Titanium oxide 8 Yellow iron oxide 2 Red iron oxide 1 Black iron oxide 0.5 Talc 10 Trimethylsiloxy Silicic acid 4.5 (Additional component) Nylon powder 3 Polyoxyethylene-methylpolysiloxane copolymer 2 Sorhitan sesquiisostearate 1 (Water phase) Moisturizer 8 Preservatives Appropriate amount Sodium glutamate 2 Ion exchange water to 100

[0078]

As described above, according to the method for producing the dispersion and the cosmetic according to the present invention, a high shearing force is applied to the unhydrophobized powder in the swelling medium of the organically modified clay mineral. By coating with a body coating agent, a hydrophobicized powder dispersion and a hydrophobicized powder-containing cosmetic composition having extremely high stability can be obtained. In addition, by using the powder as an ultraviolet protection powder, the dispersibility thereof can be improved, and the ultraviolet protection ability can be improved.

[Brief description of the drawings]

FIG. 1 is an explanatory diagram of an example of a media mill suitably used in the method for producing a hydrophobized powder dispersion of the present invention.

FIG. 2 is an explanatory diagram of an example of a medium stirring mill suitably used in the method for producing an emulsified cosmetic containing a hydrophobic powder according to the present invention.

[Explanation of symbols]

DESCRIPTION OF SYMBOLS 10 Basket part (medium mill part) 12 Small hole which consists of a slit 14 Stirring device in a basket 16 Rod 18 Tank 20 Stirring device (disper) in a tank which has both premixing and dispersion fluid 22 Solid dispersion medium (beads) 24 Pin 26 Stirring Pin Disc 28 Jacket 30 Medium Mill 32 Pre-stirring Tank 34 Pump 36 Motor 38 Motor 40 Bead 42 Disper

──────────────────────────────────────────────────の Continued on the front page (51) Int.Cl. ⁷ Identification symbol FI Theme coat ゛ (Reference) A61K 7/42 A61K 7/42 B01J 13/00 B01J 13/00 B (72) Inventor Kazuhisa Ohno Yokohama, Kanagawa Prefecture 2-2-1 Hayabuchi, Tsuzuki-ku, Shizuido City Shiseido Research Center (Shin-Yokohama) F-term (reference) 4C083 AB171 AB212 AB232 AB242 AB441 AB442 AC242 AC342 AC582 AD072 AD152 BB46 CC05 CC12 DD31 DD32 EE17 FF05 4G065 AA03 AA06 AB28Y BA07 BA15 BB01 BB03 CA11 DA02 EA01 EA03 4J037 AA27 EE03 EE28

Claims (8)

[Claims] 1. An organically modified clay mineral, a surfactant, a hydrophobic dispersion medium capable of dispersing and swelling the organically modified clay mineral in the presence of a surfactant, an unhydrophobized powder, and powder coating. A method for producing a hydrophobized powder dispersion, comprising applying a high shear force to disperse the powder to a state close to the primary particles or the primary particles, and subjecting the powder surface to a hydrophobic treatment. . 2. The method of claim 1, wherein the organically modified clay mineral, a surfactant, and a hydrophobic dispersion medium are mixed to form an organically modified clay mineral dispersion, wherein the organically modified clay mineral dispersion comprises: A method for producing a hydrophobized powder dispersion, comprising adding an unhydrophobicized powder and a powder coating agent, applying a high shearing force, and subjecting the powder surface to a hydrophobizing treatment. 3. The method according to claim 1, wherein
A method for producing a hydrophobized powder dispersion, wherein high shearing force is applied by a medium stirring mill or a high-pressure disperser. 4. The method according to claim 1, wherein the concentration of the organically modified clay mineral when applying a high shearing force is 0.1 to 5% by weight. A method for producing a powder dispersion. 5. The method according to claim 1, wherein the concentration of the non-hydrophobicized powder when applying a high shearing force is:
A method for producing a hydrophobized powder dispersion, which is 5 to 50% by weight. 6. The method according to claim 1, wherein the non-hydrophobicized powder is an ultraviolet protection powder. 7. The method for producing a hydrophobized powder dispersion according to claim 1, wherein the powder coating agent is trimethylsiloxysilicic acid. 8. A hydrophobized powder-containing cosmetic, comprising adding a cosmetic component to the hydrophobized powder dispersion obtained by the method according to any one of claims 1 to 7, followed by mixing. Method of manufacturing the ingredients.