JP2002080748A - Powder oily dispersion having ultra dispersion stability and cosmetic formulated with the same - Google Patents

Abstract

PROBLEM TO BE SOLVED: To provide a high powder dispersion that the dispersibility, storage stability and use suitability of the powder particles are high excellent, and to provide a cosmetic or the like formulated with the high dispersion. SOLUTION: This powder oily dispersion capable of containing at least powder, especially coated powder which can be used for cosmetics and which has the following surface-treating agent coating layers A and B formed on at least partially the surfaces of the particles of the powder, and a lipophilic solvent as a dispersant. The layer A: the surface-treating agent coating layer containing a compound selected from reactive organopolysiloxanes, alkylsilanes, polyolefins, hydrogenated lecithin, N-acylamino acids, fatty acids, and dextrin fatty acid esters; and the layer B: the surface-treating agent coating layer containing a compound selected from one terminal functional group-modified organopolysiloxanes, alkylsilanes, perfluoroalkylsilanes and branched fatty acids.

Description

DETAILED DESCRIPTION OF THE INVENTION

[0001]

The present invention relates to the dispersibility of powder particles,
The present invention relates to a novel oily dispersion of a powder having extremely excellent storage stability and suitability for use. More specifically, a coated powder containing two types of layers A and B formed on at least a part of the particle surface of the powder, each containing a solid layer and a liquid surface treatment agent coating layer at room temperature, Preferably, on at least a part of the surface of the powder particles, the first layer is a reactive organopolysiloxane, an alkylsilane, a polyolefin, a hydrogenated lecithin (including a salt thereof), N-layer, which is the A layer.
A surface treatment agent coating layer containing at least one compound selected from acylamino acids (including salts thereof), fatty acids (including salts thereof) and dextrin fatty acid esters and being solid at room temperature; As the second layer, at least one compound selected from the group consisting of organopolysiloxane modified with a functional group at one end, alkylsilane, perfluoroalkylsilane, and branched fatty acid (including a salt thereof), which is a layer B, is provided. The present invention relates to an oily dispersion of a powder containing at least a coated powder forming a surface treatment agent coating layer which is liquid at normal temperature and a lipophilic solvent, and a cosmetic or the like containing these.

[0002] The oily dispersion of the powder of the present invention is very excellent in the dispersibility, storage stability and suitability for use of the powder particles, so that the function of the powder varies greatly depending on the dispersion state of the powder particles, for example, skin Dramatically improved adhesion (adhesion), touch (feel of use), gloss, hiding power, coloring power, transparency, ultraviolet and infrared shielding ability, conductivity, fluorescence, luminescence, catalytic activity, etc. Can be done.

[0003] Accordingly, the cosmetic of the present invention containing the oily dispersion of the powder according to the present invention can greatly improve the function as a cosmetic.

[0004] Further, the oily dispersion of the powder thus obtained can be used not only for cosmetics but also for plastic additives, inks, paints, toners (magnetic powders), chemical fibers, packaging materials,
The present invention is also applicable to oily dispersions of powder widely used in various fields such as electronic materials.

[0005]

2. Description of the Related Art In recent years, there has been a growing need in the industry of handling powders for dispersions in which powders are dispersed and stabilized in some kind of dispersion medium as an intermediate material. The reason is that there is a possibility of respiratory trouble due to the scattering of powder in the workplace and the inhalation of workers, and the volume of powder becomes larger as it becomes finer for environmental protection around the workplace. To take up storage space, there are many technical problems such as the selection of a disperser and dispersion conditions for dispersion of powder, and it takes time and effort.
Work efficiency can be improved by using a stable powder dispersion, and the like.

[0006] The properties of the oily dispersions are divided into two types: a flowing liquid type and a non-flowing clay type. The flowing oily dispersion sediments with the lapse of time due to the difference in specific gravity between the powder and the dispersion liquid, and easily becomes a hard cake. There are many things. The content of the powder was 50% by weight.
The following are mostly: On the other hand, non-flowable dispersions
The content of the powder can be increased, and the sedimentation of the powder and hard cake formation are unlikely to occur, but redispersion is poor at the time of compounding into the formulation, and there has been a problem in the efficiency of work. The oily dispersion of the powder in the present invention can be included in the final product, but can also be used as one of components (raw materials) or an intermediate when formulating (blending) the desired final product. The purpose of using the powder as an oily dispersion is to use various disadvantages when handling the powder as it is as raw material (inhalation of dust by workers, capital investment by installing a dust collection device, labor for dispersion, increase of storage space by powder, etc.) This is to maximize the function of the powder in order to improve the performance. For that purpose, selection of a suitable powder composition or a dispersion medium is required. It is preferable that the content of the powder in the oil-based dispersion is as high as possible and the composition of the oil-based dispersion is as simple as possible (one type of powder and one type of medium). The reason for this is that if the amount of the dispersion medium in the dispersion is large, the degree of freedom in formulation design is reduced, and the versatility to other formulations is also deteriorated.

[0007] Inorganic powders such as fine particle titanium oxide and fine particle zinc oxide for shielding ultraviolet rays and infrared rays have a primary particle diameter of several tens of nanometers.
Since the particle size is as small as m, the agglomeration and scattering properties of the powder particles are particularly high, so that the workability is extremely poor, and it is very difficult to disperse and stabilize the particles. If the dispersion of the fine particles is insufficient, whitening will occur or the desired SPF value will not be obtained in many cases when the composition formulated in the formulation is applied to the skin. Recently, the amount of inorganic powder in cosmetics has been reduced as much as
There is a tendency that the emphasis is on obtaining a high value and high transparency, and high dispersion of inorganic fine particle powder and its stabilization are desired. For this reason, various oil-based dispersions in which fine particle powders are dispersed in a solvent and methods for producing the same are disclosed. For example, an oil dispersion containing oil, titanium dioxide, and an organic dispersant and a method for producing the same (see Japanese Patent Publication No. 6-61457), and a sunscreen containing oil, zinc oxide, titanium dioxide, and an organic dispersant. There is a production method (JP-A-5-201844), a zinc oxide particle dispersion containing an oil, zinc oxide, and an organic dispersant (see JP-A-5-213618). These oil-based dispersions contain an organic dispersant as an essential component, and the final manufacturer has no choice of a lipophilic dispersion solvent, so that the versatility in formulation is very poor. In addition, the dispersing of the organic dispersant in the silicone-based dispersion solvent is poor, and a silicone-based dispersion cannot be obtained. As the silicone dispersion, JP-A-9-2084
No. 38, JP-A-10-167946 and the like also disclose a dispersant as an essential component, and their versatility in formulation is very poor. An oil dispersion in which an inorganic ultraviolet filter is dispersed in a liquid ultraviolet filter (see Japanese Patent Application Laid-Open No. 12-26262) is one which has improved general versatility in the formulation. Whitening phenomena when blended in or target SP
Further improvements are desired for reasons such as the inability to obtain an F value and the inability to use in a so-called chemical-free dosage form that does not contain an organic ultraviolet absorber.

[0008] Titanium oxide, iron oxide, and the like are powders having a large specific gravity and difficult to stabilize dispersion as powders to be blended in the nail lacquer. Dispersions of these powders are prepared using an organic solvent such as ethyl acetate or butyl acetate as a dispersing medium.However, storage stability is poor, causing color separation, color floating, sedimentation and other phenomena. When incorporated into a dosage form, the stability and gloss of the dosage form may decrease.

[0009] On the other hand, powders used in powdery or solid powdery dosage forms such as loose powder, powder foundation, powder eyeshadow, blush, etc., have good feeling of use and high transparency. An extender is added to the powder, and titanium oxide and iron oxide are added to the powder to provide a hiding power and a coloring power. Since these powders greatly differ in their function depending on the state of dispersion, a dispersion in which the powder is highly dispersed in advance at a high concentration is desired.

Examples of the inorganic powder to be incorporated in the oil paint or oil ink include titanium oxide, graphite, cadmium yellow, cadmium red, red iron oxide, iron black, zinc white, navy blue, ultramarine and the like. Since these powders have a higher specific gravity than organic pigments, dispersion stabilization in low-viscosity organic solvents is extremely difficult, and dispersion stabilization is achieved with a multi-component system containing a dispersant and stabilizer. That is the current situation.

Under the circumstances described above, there is a need for a method of dispersing the powder at a high concentration and a stable dispersion for a long period of time in order to maximize the function of the powder, or such a dispersion. ing.

[0012]

SUMMARY OF THE INVENTION An object of the present invention is to improve the above-mentioned various problems and to improve the dispersibility, storage stability and suitability for use (redispersibility and versatility) of powder particles as compared with conventional products. ) Is provided. Another object of the present invention is to provide a cosmetic or the like having a powder function superior to conventional products by blending such an excellent dispersion.

[0013]

Means for Solving the Problems The present inventors have solved the above-mentioned various problems, and have obtained an excellent dispersion in which a powder usable for cosmetics and the like can be stably maintained in a high concentration and stably for a long period of time. As a result of diligent studies for the development of, a coating powder obtained by coating the powder with two layers of a specific surface treating agent was found to have remarkably excellent dispersibility in a lipophilic solvent. In particular, the first layer of powder (substrate) is coated with a surface treatment agent having a solid state, and then the second layer is coated with a surface treatment agent having a liquid state. It has been found that high performance coated powder can be obtained.

Further, as a result of researching to solve the above-mentioned problem, at least two (at least all of the surface or at least a part of) the surface of the powder usable for cosmetics and the like are provided. Layer, preferably layer A on the particle surface of the powder, and layer B on the layer A. The layer A comprises a reactive organopolysiloxane, alkylsilane, polyolefin, hydrogenated lecithin (in the form of a salt such as a metal salt). ), N-acylamino acids (including those in the form of salts such as metal salts),
A surface treatment agent coating layer containing a fatty acid (including a salt in the form of a salt such as a metal salt) and a compound (one or more) selected from dextrin fatty acid esters and preferably in a solid state at normal temperature. The B layer has a compound (1) selected from the group consisting of organopolysiloxane modified with a single-terminal functional group, alkylsilane, perfluoroalkylsilane and branched fatty acid (including those in the form of salts such as metal salts).
Or a plurality of types), preferably by forming a surface treatment agent coating layer which is in a liquid state at room temperature, so that the obtained novel coated powder has a desired stable property when dispersed in the lipophilic solvent. Extremely effective as a high dispersion,
In particular, they have found that they have a very good affinity for a lipophilic solvent, and as a result, they have remarkably excellent dispersibility and dispersion stability, and have completed the present invention based on many of the above findings.

That is, the present invention relates to a powder dispersion which can be used for cosmetics and the like, and comprises a surface treatment agent coating layer of the following A layer and B layer formed on at least a part of the surface of the powder particles. Oily dispersion of a powder characterized in that it contains at least a coated powder having at least a lipophilic solvent as a dispersion medium, A layer: reactive organopolysiloxane, alkylsilane, polyolefin, hydrogenated lecithin (of salt N-acylamino acids (including those in the form of salts), fatty acids (including those in the form of salts)
And a layer of a surface treatment agent which is solid at room temperature and contains a compound (one or more) selected from dextrin fatty acid esters; and B layer: one-terminal functional group-modified organopolysiloxane, alkyl silane, perfluoroalkyl silane and It is present in the surface treatment agent coating layer which is liquid at normal temperature and contains a compound (one or more) selected from branched fatty acids (including those in the form of salts).

Here, it is particularly preferred that the particles are in the form of a composite powder whose surface is coated with layer A and then the surface of layer A is coated with layer B. In addition, A
The layer is solid at room temperature and the layer B is liquid at room temperature.
The present invention also provides a cosmetic or the like characterized by containing, blending or using such a dispersion.

In another embodiment, the present invention includes the following coated powder. A coated powder characterized by containing a powder usable for cosmetics, and a surface treatment agent coating layer of the following A layer and B layer formed on at least a part of the surface of the powder particles; Layer: A layer of a surface treatment agent which is solid at room temperature containing alkylsilane; and Layer B: organopolysiloxane modified with a functional group at one end, alkylsilane, perfluoroalkylsilane, and branched fatty acid (including those in the form of a salt. ) Containing a compound selected from the group consisting of a surface treatment agent and a liquid at room temperature, or a layer A: reactive organopolysiloxane, alkylsilane, polyolefin, hydrogenated lecithin (including those in the form of salt). ), N-acylamino acids (including those in the form of salts), fatty acids (including those in the form of salts)
And a layer of a surface treatment agent which is solid at room temperature and contains a compound selected from dextrin fatty acid esters; and a layer B: a layer of surface treatment agent which is liquid at room temperature and contains perfluoroalkylsilane.

[0018]

BEST MODE FOR CARRYING OUT THE INVENTION As a particularly preferred embodiment of the present invention, a surface-treated powder obtained by coating the surface of powder particles for cosmetics with an A layer and further coating the surface with a B layer is described below. The embodiment of the present invention will be described in detail focusing on an oily dispersion dispersed in a plurality (or more). However, a particularly preferred embodiment is included in the present invention, but is not limited thereto.

The powder (substrate before being coated with the A layer and the B layer) used in the present invention is not particularly limited as long as it is a powder (substrate) which can be usually used for cosmetics. The average particle diameter is preferably about 500 to 0.01 μm, more preferably about 100 to 0.01 μm.

Incidentally, regarding the method of measuring the particle diameter, 0.1 μm
In the case of particles having a particle size of not less than m, a laser diffraction method or a sedimentation method is used, and in the case of particles having a particle size of not more than 0.1 μm, a photon correlation method, an electron microscope, or the like is used.

For example, as inorganic powder, extender pigments such as mica, sericite, talc, clay, kaolin,
Synthetic mica, calcium carbonate, magnesium carbonate, magnesium silicate, aluminum silicate, calcium phosphate, silicic anhydride, alumina, magnesium oxide, zirconium oxide, aluminum hydroxide, barium sulfate, magnesium silicate magnesium, magnesium metasilicate, Examples thereof include boron nitride, zeolite, hydroxyapatite, and ceramic powder.

White pigments include basic lead carbonate, basic sulfate, titanium oxide, zinc oxide, cerium oxide, zinc phosphate, aluminum phosphate, and the like. Color pigments include red iron oxide, yellow iron oxide, and black oxide. Iron, cobalt oxide, chromium oxide, chromium hydroxide, navy blue, ultramarine, carbon black, low titanium oxide, mango violet, cuprous oxide, graphite,
As a fluorescent pigment, zinc sulfide, zinc silicate, cadmium zinc sulfate, calcium sulfide, strontium sulfide, calcium tungstate, etc .; and as a pearl pigment, for example, graphite, cadmium yellow, cadmium red, cobalt blue, molybdate orange, etc. Bismuth oxychloride,
Titanium mica, fish scale foil, etc., as fine particle powder, fine particle titanium oxide, fine particle zinc oxide, fine particle iron oxide, fine particle cerium oxide, etc., and as metallic luster pigment, aluminum powder, zinc powder, gold powder, silver powder, tin powder , Stainless powder, diamond powder, copper powder, nickel powder, bronze powder, etc .; fluorescent pigments such as zinc sulfide and calcium tungstate; and other powders such as tin oxide, ATO (antimony-doped tin oxide), I
TO (tin-doped indium oxide), Al-doped zinc oxide, and the like can be given.

If necessary, a composite of these powders can be used. For example, a powder in which an inorganic coloring pigment such as red iron oxide is coated with silicic anhydride, a powder in which an extender is coated with a fine white pigment, and the like are included.

As the organic powder, polyamide, polyester, polyethylene, polypropylene, polystyrene,
Polyurethane, vinyl resin, urea resin, phenol resin, fluororesin, acrylic resin, melamine resin, epoxy resin, polycarbonate resin, silicone resin, silicone rubber powder, divinylbenzene-styrene copolymer, and monomers of these And celluloid, acetylcellulose, cellulose, polysaccharides, proteins, organic tar dyes, and the like.

Further, the powder to be surface-treated in the present invention is used in order to improve the affinity with the surface-treating agent and the adhesion.
For example, it may be coated with at least one oxide or hydrated oxide of aluminum, calcium, magnesium, cerium, silicon, zirconium, titanium, zinc, iron, cobalt, manganese, nickel and tin. In such a case, the powder coated in this way corresponds to the powder (substrate) before coating the A layer in the present invention, such as the powder to be coated or the powder to be processed in the present invention. I do.

In the present invention, the surface of the powder to be surface-treated is coated on at least a part thereof with at least the A layer and the B layer. Typically, the layer A first contacts the surface of the powder particles, and the layer B
Each layer is coated with a layer. In this case, it is desirable to form a double coating layer of the A layer and the B layer on the entire surface of the powder particles in that the effect of the present invention can be sufficiently obtained. In some cases, only the coating layer of the layer may be provided, or in rare cases, the coating layer of either the A layer or the B layer may not be present on a small part of the surface of the powder particles.

As far as the object of the present invention and the effects obtained by the present invention are not impaired, if necessary, another layer may be formed between the A layer and the B layer or between the A layer and the powder (substrate) surface. It may be provided between layers.

The following description focuses on the powder which is in contact with the surface of the powder (for cosmetics) and which is coated with the layer A and further in contact with the surface of the layer A with the layer B. As described above, the present invention is not limited to this.

The layer A is a surface treatment agent coating layer which is coated in contact with the surface of the powder particles, and has a solid state at normal temperature.
The layer is a surface treatment agent coating layer coated in contact with the surface of the powder particles coated with the layer A, and is in a liquid state at normal temperature. Solid at room temperature means that the surface treatment agent coating layer coated on the surface of the powder particles exhibits a solid state at room temperature, and liquid at room temperature means the surface treatment coated on the surface of the powder particles. The agent coating layer is liquid at room temperature. Therefore, it may be solid (layer A) or liquid (layer B) at room temperature in the state of being coated on the surface of the powder particles. In this case, in the state of the surface treatment agent before being coated on the particle surface, it may be in a liquid state or a solid state, and it is desirable to take such a target state in a state of being coated.

The term "solid at ordinary temperature" or "liquid at ordinary temperature" means a solid or a liquid at ordinary temperature, respectively. In particular, as a method for judging a liquid, it is judged to be liquid with "oily feel". be able to.

Some of the solids at room temperature show an oily feel. For example, medium-chain fatty acids such as myristic acid and stearic acid and salts thereof, N-lauroyl-
L-Lysine, lecithin, boron nitride, silicone resin powder, silicone rubber powder, polytetrafluoroethylene powder, etc. are in the form of flakes or spherical particles and have a very smooth feel due to the properties of those compounds. Therefore, the powder coated with these compounds (layer B) may have an oily feel, but the effect of the present invention cannot be obtained.

The layer A comprises a reactive organopolysiloxane,
Alkylsilanes, polyolefins (polyethylene, polypropylene, etc.), hydrogenated lecithin (including those in the form of salts), N-acylamino acids (including those in the form of salts), fatty acids (in the form of salts) And a dextrin fatty acid ester. B
The layer is a surface treatment that is liquid at normal temperature and contains a compound selected from one end functional group-modified organopolysiloxane, alkylsilane, perfluoroalkylsilane, and branched fatty acid (including those in the form of salt). It is an agent coating layer.

In the present invention, A formed on the powder surface
The coating layer of the layer and the B layer is included in the surface treatment agent coating layer of the A layer or the B layer in the present invention if the above-mentioned components used for the A layer or the B layer in the present invention adhere to the powder. It is.

(Reactive Organopolysiloxane) The reactive organopolysiloxane preferably includes organohydrogenpolysiloxane, polyalkoxyorganopolysiloxane, triorganosiloxysilicic acid, and organopolysiloxane modified with a trialkoxy group at both terminals. It is.

As the reactive organopolysiloxane used in the present invention, a linear or cyclic reactive organopolysiloxane represented by any of the following general formulas (1) to (6) is particularly preferred. In the general formulas (1) to (6), preferably, a plurality of R ^{1 (} over all general formulas as well as ^one general formula) are all mutually independent,
A plurality of lower alkyl groups each having 1 to 4 carbon atoms, and a plurality of R ^{2 s} are all independently of each other similarly, and each represents a hydrogen atom, a hydroxyl group, or a lower alkoxy group having 1 to 4 carbon atoms, and n is M represents 0 or an integer, and n + m is an integer of 2 to 10,000.

[0036]

## STR1 ## _{^{(R 1 3 SiO) (R}} 1 R 2 SiO) n (R 1 2 SiO) m (SiR 1 3) (1)

[0037]

Embedded image

[0038]

Embedded image

[0039]

Embedded image

With respect to the compound represented by the general formula (1), when n is 0 or 1, the reactivity on the surface of the powder particles is poor, and the compound does not have a three-dimensional network structure and exhibits an oily smooth feel. However, it is not preferable because it does not contribute to the hydrophobicity or lipophilicity of the powder.

In the organohydrogenpolysiloxane represented by the general formula (2), n is more preferably an integer of 3 to 7.

For the organohydrogenpolysiloxane represented by the general formula (3), n is 2 or more and n + m
Is more preferably an integer of 3 to 7. The above-mentioned cyclic hydrogen polysiloxane has a three-dimensional network structure by ring opening on the surface of the powder particles.

In the polyalkoxyorganopolysiloxane represented by the general formula (4), m is preferably an integer of 1 to 100, and the value of n / m is more preferably 0.5 or more.

The general formulas (1) to (4) used in the present invention.
The reactive organopolysiloxane contained in the above may be a resin which is three-dimensionally cross-linked and resinified (solidified) irrespective of the cyclic or linear form as described above. For viscosity, 2
When measured at 5 ° C., preferably 0.5 to 500 cs
It has a viscosity of about 0.5 to 100 cs, more preferably about 1 to 50 cs. The viscosity is 0.
If it is less than 5 cs, the reaction is extremely fast, so that the powder particles are easily agglomerated, and the coating layer formed on the particle surface is very weak to physical impact and easily peeled off. On the other hand, if it exceeds 500 cs, the oil (oil) does not easily spread, and it is difficult to uniformly coat the surface of the powder particles. Examples of such surface treatment agents include “KF-99” and “KF-990” manufactured by Shin-Etsu Chemical Co., Ltd.
1 ”, Dow Corning Toray“ SH-110 ”
7 ”,“ TSF484 ”manufactured by GE Toshiba Silicone Co., Ltd.
And "TSF483" and "FZ" manufactured by Nippon Unicar Co., Ltd.
3704 "and" AZ6200 "can be used.

The compound represented by the following general formula (5) is triorganosiloxysilicic acid.

[0046]

Embedded image ^{_{(R 1 3 SiO 1/2) n}} (SiO 2) m (5)

M and n are integers, and m + n is an integer of 2 to 100, and the n / m ratio is more preferably 1.0 or less.

When the ratio of n / m exceeds 1.0, the coating layer on the surface of the powder particles is not a solid hard coating layer but an oily smooth coating layer. It is not preferable because strong water repellency and lipophilicity cannot be obtained.

When trimethylsiloxysilicic acid is used in the present invention, an M / Q ratio (n / n in the general formula (5)) obtained by dissolving water glass obtained by substituting sodium with a trimethylsilyl group in a solvent is used. In many cases, the hardness of the cured coating layer is controlled by the value of a ratio corresponding to m), and these are suitably used. For example, “KF-7312” manufactured by Shin-Etsu Chemical Co., Ltd.
F "," KF-7312J "," KF-7312K ",
“KF-9001”, “KF-9002”, “X-21”
-5249 "and" X-21-5250 "," DC593 "manufactured by Dow Corning Toray Co., Ltd.," BY-11 "
015 "," BY-11-018 "and" BY-11-
022 "and" TSF "manufactured by GE Toshiba Silicone Co., Ltd.
4600 "can be used.

The compound represented by the following general formula (6) is an organopolysiloxane modified at both ends with a functional group, and includes an organopolysiloxane modified at both ends with a trialkoxy group.

[0051]

Embedded image _{^{(R 2 3 SiO) (R}} 1 2 SiO) n (SiR 2 3) (6)

In the above formula, a compound in which n represents an integer of 1 to 100 is more preferable.

As the organopolysiloxane modified with a trialkoxy group at both ends used in the present invention, those having a linear or T-shaped chain and having a repeating unit of siloxane of 1 to 100 can be preferably used. As described above, when the n value exceeds 100, the reactivity with the surface of the powder particles deteriorates, and the coating layer after the reaction changes from a semi-solid state (gel state) to a liquid state, resulting in a feeling according to the result. The favorable effects of the present invention are hardly obtained. Examples of easily available surface treatment agents include, for example, “X-24-9817” and “X-98” manufactured by Shin-Etsu Chemical Co., Ltd.
24-9221 "can be purchased and used.

(Alkylsilane) As the alkylsilane, it is particularly preferable to use a compound represented by the following general formula (7).

[0055]

Embedded image R ⁵ _n SiR ⁶ _(4-n) (7)

In the above general formula, preferably, R ⁵ is an alkyl group having a linear or side chain having less than 6 carbon atoms, and a plurality of R ⁶ are all independent of each other, and are each a hydrogen atom, a hydroxyl group, Any one of a halogen atom (Cl, Br, I, etc.) and a lower alkoxy group having 1 to 4 carbon atoms, n is 1
To 3 respectively. For example, monomethyltrimethoxysilane, ethyltrimethoxysilane, butyltrimethoxysilane, propyltrimethoxysilane, phenyltrimethoxysilane, diphenyltrimethoxysilane and the like can be mentioned. When the number of carbon atoms is 6 or more, it becomes liquid at normal temperature, so that it is not suitable as a treatment agent for phase A.

(Polyolefin) Polyolefin such as polyethylene and polypropylene is preferably a polyolefin resin having at least one carboxyl group (for example, see JP-A-63-17972 proposed by the present inventors). ). For example, commercially available products such as low molecular weight polyethylene having a molecular weight of 500 to 20,000 and a melting point of 40 ° C. or higher, polyethylene oxide obtained by oxidizing polypropylene, maleated polyethylene, and polypropylene oxide can be used.

(Hydrogenated lecithin) Hydrogenated lecithin (including those in salt form) is obtained by hydrogenating natural lecithin extracted from egg yolk, soybean, corn, rapeseed and the like, and synthetic lecithin. Hydrogenated lecithin having an iodine value of preferably 30 or less, more preferably 15 or less, and glyceride having a phosphate group. As a salt, a water-insoluble hydrogenated lecithin metal salt such as Al, Mg, Ca, Zn, Zr, and Ti is preferable. Hydrogenated lecithin having a melting point of 50 ° C. or more (including those in the form of a salt) is particularly preferable (for example, JP-A-60-184571, JP-A-60-190705, proposed by the present inventors).
See Japanese Patent Publication No. 4-58443. ). For example, a commercially available product such as "Hydrogenated Egg Yolk Oil No. 5" manufactured by Asahi Kasei Corporation or hydrogenated soybean phospholipid ("Basis LS-60HR") manufactured by Nisshin Oil Co., Ltd. is purchased and used. can do.

(N-acylamino acid) The N-acylamino acid is obtained by acylating the amino group and / or imino group of the amino acid. The amino acid constituting the N-acyl amino acid may be one kind or a mixture of plural kinds. For amino acids constituting N-acyl amino acids, L-form, D-form
When the isomer and the DL-isomer exist, they may be any isomers or a mixture thereof. Naturally occurring isomer L
-Body is more preferred.

Examples of the types of amino acids include glycine, alanine, β-alanine, valine, leucine, isoleucine, phenylalanine, proline, threonine, serine, arginine, histidine, lysine, aspartic acid, glutamic acid, tyrosine, methionine, cystine,
Cysteine and the like can be mentioned.

The fatty acid constituting the N-acyl derivative is preferably a saturated or unsaturated fatty acid having 1 to 23 carbon atoms or a fatty acid having a saturated or unsaturated alicyclic structure having 1 to 23 carbon atoms. Can be mentioned. Examples thereof include N-acylated glycine, N-acylated-N-methyl-β-alanine, N-acylated glutamic acid and salts thereof (Japanese Patent Application Laid-Open No. Sho 61-61 proposed by the present inventors). 7
3775, Japanese Patent Publication No. 1-50202 and the like. ).

The fatty acids to be constituted are preferably long-chain fatty acids, for example, caprylic acid, capric acid, lauric acid, myristic acid, isomyristic acid, palmitic acid, isopalmitic acid, stearic acid, isostearic acid, arachinic acid, undecylenic acid, Oleic acid, myristoleic acid, elaidic acid, linoleic acid, linolenic acid, arachidonic acid, coconut oil fatty acid, tallow fatty acid, resin acid (abietic acid) and the like can be mentioned.

The N-acyl amino acid can be used in the free form or in the form of a salt.
K, Ba, Zn, Ca, Mg, Fe, Zr, Co, A
l, Zr, metal salts such as Ti, ammonium salts, monoethanolamine, diethanolamine, triethanolamine, 2-amino-2-methyl-propanol, 2-
Examples thereof include various alkanolamine salts such as amino-2-methyl-1,3-propanediol and triisopropanolamine.

It can be easily purchased and used. For example, acylation with N-coconut oil fatty acid or N-lauroyl-β-alanine (Kawaken Fine Chemical Co., Ltd.)
And its Ca and Al salts, myristoyl silk amino acid (PHYTOCOS, France) and its Al salts and N-lauroyl-L-lysine and N-stearoyl-L
-Glutamic acid (manufactured by Ajinomoto Co., Inc.) is preferred.

As for the N-acylation method, known methods (for example, JP-A-6-256274 and JP-A-6-256274) are used.
See, for example, Japanese Patent Publication No. -502010. ). For example, for amino acids obtained by totally hydrolyzing proteins derived from animals such as silk and pearl and plants such as wheat and soybeans, N-
An N-acyl amino acid obtained by acylation and, if necessary, further forming a salt can also be used. This N-
Amino acids used for preparing the acyl form include:
Glycine, L-alanine, L-valine, L-leucine,
L-isoleucine, L-phenylalanine, L-proline, L-threonine, L-serine, L-arginine, L
-Histidine, L-lysine, L-aspartic acid and L
-Glutamic acid containing at least 14 types of L-tyrosine, L-methionine, L-cystine,
-It may contain an N-acyl compound such as cysteine.

(Fatty Acid) As the fatty acid used in the present invention, the fatty acids described for the fatty acids constituting the N-acylamino acids can be used. Also includes those in the form of salts. As for the salt, the content of the salt described in the case where the N-acylamino acid is in the form of a salt is employed as it is. In particular, straight-chain saturated fatty acids having 12 to 26 carbon atoms, for example, fatty acids such as lauric acid, myristic acid, palmitic acid, stearic acid, behenic acid, lignoceric acid, and cerotic acid, or Ca, M thereof
g, Zn, Zr, Al, Ti and the like metal salts are preferable (for example, JP-A-60-69011 proposed by the present inventors).
No. reference. ). Particularly, fatty acids having a melting point of 40 ° C. or more are suitable.

If the number of carbon atoms is less than 12, the problem of skin irritation is likely to occur. On the other hand, if the number of carbon atoms is more than 26, the reactivity is deteriorated and the effects obtained by the present invention are hardly obtained.

(Dextrin fatty acid ester) The dextrin fatty acid ester used in the present invention is not particularly limited, and can be selected from an ester composed of dextrin and a fatty acid or a derivative thereof. Preferably, for one molecule of dextrin, an ester or a derivative thereof having at least a partial structure in which one molecule of a fatty acid having 8 to 24 carbon atoms is esterified in one of its hydroxyl groups,
For example, one or more fatty acids having 8 to 24 carbon atoms per one molecule of dextrin, an ester having a structure in which one or more of the hydroxyl groups are ester-bonded, or an ester in which the hydroxyl group is further esterified with another fatty acid And the like.

The esterification degree of the ester is preferably about 30 to 95%, more preferably 50 to 90%.
% Degree of esterification can be employed. If the degree of esterification is less than 30%, the lipophilicity is insufficient, while if it is more than 95%, the adhesion to the surface of the powder particles deteriorates. Specific examples include dextrin myristic acid ester, dextrin palmitic acid ester, dextrin stearic acid ester, dextrin coconut oil fatty acid ester, dextrin behenic acid ester, and dextrin palmitic acid 2-ethylhexanoate. If necessary, it can be prepared by a conventional method. To easily obtain such a treating agent, for example, “Leopearl KL”, “Leopearl MKL”, “Leopearl TT”, “Leopearl K”
E "and" Leopearl TL "(both are Chiba Flour Milling)
(Manufactured by K.K.) or the like, and can be used as it is.

When the various surface treating agents described above are used for forming the surface treating agent coating layer (A layer) in the present invention, only one of the above-mentioned surface treating agents or a mixture of two or more thereof may be used. To form a coating layer (layer A) by subjecting to a desired surface treatment.

(One-Terminal Functional Group-Modified Organopolysiloxane) The one-terminal functional group-modified organopolysiloxane such as one-terminal trialkoxy group-modified organopolysiloxane used as the surface treatment agent coating layer of the layer B in the present invention includes the following general compounds. Compounds represented by any of formulas (8) and (9) are preferred.

[0072]

Embedded image _{^{[(R 3 3 SiO) (}} R 3 2 SiO) m] n SiR 4 (4-n) (8)

Embedded image

In the above general formula, preferably, a plurality of the above formulas are present.
R^ThreeAre all mutually independent, each having 1 to 1 carbon atoms
0, a plurality of saturated or unsaturated hydrocarbon groups
R ^FourAre all independent of each other,
Hydroxyl group, halogen atom (Cl, Br, I, etc.), silazane
Group, isopropenoxy group and lower alcohol having 1 to 4 carbon atoms
Any one of the xyl groups, m is an integer of 10 to 100, and n is
1, 2 or 3 is respectively represented.

When the value of n is less than 10, the reaction is too fast and hydrolysis is promoted by a small amount of water adhering to the surface of the powder particles or the acid point or basic point of the powder, resulting in cross-linking polymerization. The coating layer is in the form of a gel (semi-solid), and the desired oily coating layer cannot be obtained. On the other hand, if the n value exceeds 100, the reactivity becomes extremely poor and the coating layer on the surface of the powder particles becomes uneven, so that dispersibility in a lipophilic liquid cannot be expected. Does not contribute.

As a surface treating agent for such a layer B, for example, dimethylpolysiloxysilazane, α
-Monohydroxysiloxane, α-monoalkoxypolydimethylsiloxane, α-dialkoxypolydimethylsiloxane, α-trialkoxypolydimethylsiloxane and the like. Examples of commercially available products include “X-24-9826” and “X-24-9” manufactured by Shin-Etsu Chemical Co., Ltd.
171 "and" X-24-9174 ", etc., which can be purchased and used.

(Alkylsilane) Alkylsilanes include:
It is particularly preferable to use a compound represented by the following general formula (10).

[0077]

Embedded image R ⁵ _n SiR ⁶ _(4-n) (10)

In the above general formula, preferably, R ⁵ is an alkyl group having 6 to 30 carbon atoms having a straight chain or a side chain, and a plurality of R ^{6 s} are all independent of each other, and are each a hydrogen atom or a hydroxyl group. , Halogen atoms (Cl, Br, I, etc.),
And n represents 1, 2 or 3 each of lower alkoxy groups having 1 to 4 carbon atoms.

When the carbon number of R ⁵ is less than 6, no oily feeling can be obtained, while when it exceeds 30, the reactivity becomes extremely poor and the coating layer on the surface of the powder particles tends to be uneven. As a result, it is difficult to obtain dispersibility in a lipophilic liquid, not only does not contribute to the hydrophobicity and lipophilicity of the powder to be treated, but also becomes a solid coating layer, resulting in the effects obtained in the present invention and an oily feel. It is hard to obtain.

Conveniently, such surface treatment agents include, for example, hexyltrimethoxysilane, octyltrimethoxysilane, isooctyltrimethoxysilanedecyltrimethoxysilane, dodecyltrimethoxysilane, hexadecyltrimethoxysilane, octadecyl Trimethoxylane, triacontyltrimethoxysilane and the like can be mentioned. Examples of commercially available products include “TSL8185” and “TSL8185” manufactured by GE Toshiba Silicone Co., Ltd.
8186 "and" SID4632.5 "manufactured by Chisso Corporation.
B "," SIH5925.0 "and" SIO6645.B ".
0 "," KBM-3103 "manufactured by Shin-Etsu Chemical Co., Ltd. and" A-137 "manufactured by Nippon Unicar Co., Ltd. can be used.

(Perfluoroalkylsilane) As the perfluoroalkylsilane, a compound represented by the following formula (11) is preferably used.

[0082]

Embedded image ^{_{Rf (CH 2) n SiR 7}} 3 (11)

In the above general formula, Rf represents a perfluoroalkyl group, the number of fluorocarbons of which is 1 to 30, n represents an integer of 1 to 5, and a plurality of R ⁷ are all independently of each other; It represents any of a hydrogen atom, a hydroxyl group, a halogen atom (Cl, Br, I, etc.) and a lower alkoxy group having 1 to 4 carbon atoms, respectively. For example, trifluoromethyltrimethoxysilane, pentafluoroethyltrimethoxysilane, heptafluoropropyltrimethoxysilane, nonafluoropropyltrimethoxysilane, heptadecafluorodecanyltrimethoxysilane, henicosafluorododecyltrimethoxysilane, and the like. Can be Examples of commercially available products include “KBM-7803” manufactured by Shin-Etsu Chemical Co., Ltd., and “TSL-8233” and “TSL-825” manufactured by GE Toshiba Silicone Co., Ltd.
7 "can be purchased and used.

(Branched Fatty Acid) The branched fatty acid used in the present invention is not particularly limited as long as it has a branched alkyl group. It is preferable to use a branched fatty acid having 8 to 22 carbon atoms so as to obtain an oily feel and to be excellent in dispersibility when processed into powder. Specifically, isononanoic acid, 2-ethylhexanoic acid, isotridecanoic acid, isomyristic acid, isopalmitic acid,
Commercial products such as isostearic acid and isobehenic acid can be purchased and used. If the number of carbon atoms is smaller than 8 or larger than 22, the effects of the present invention cannot be obtained, which is not preferable.

When the above-described various surface treatment agents are used, any one of them may be used alone, or a plurality of them may be mixed to perform the surface coating treatment.

The treating agent used in the layer B is a compound that covers the outermost layer of the powder outside the layer A, and greatly affects the dispersibility, feel, and the like of the treated powder. Since these treating agents have a functional group only at one end, the organopolysiloxane chain, linear alkyl chain, branched alkyl chain, and perfluoroalkyl chain, which are the main chain molecules, are in a state where they can move freely and are converted to lipophilic solvents. The dispersibility and oily feel of the product depend largely on the length of the main chain. In the case of a one-terminal functional group-modified organopolysiloxane, the degree of polymerization is 10 to 10
About 0, in the case of alkylsilane, the number of carbon atoms of the alkyl group is about 6 to 30, and in the case of perfluoroalkylsilane, the number of fluorocarbons (the number of carbon atoms to which fluorine atoms are bonded) is about 1 to 30. In the case of branched fatty acids, those having about 8 to 22 carbon atoms can be obtained by dispersing the coated powder in a lipophilic solvent to obtain a novel oily dispersion.

In the case of one-terminal functional group-modified organopolysiloxane, the one having a degree of polymerization of less than 10 is coated, the degree of polymerization is too high (in the case of more than 100), or the number of carbon atoms of alkylsilane or branched fatty acid is less than 10. In the case of a powder coated with a large amount or a perfluoroalkylsilane having a large number of fluorocarbons (when the number of carbons exceeds 30 or in the case of a branched fatty acid the number of carbons exceeds 22), dispersibility in a lipophilic solvent And the dispersion stability is inferior.

In the present invention, the layer A needs to be solid at room temperature. This is because it is easier to coat the outermost surface of the powder particles as a uniform lipophilic film with a necessary minimum amount than a compound that is liquid at room temperature. Also, B
The layer must be liquid at room temperature. This is because the liquid particles cover the outermost layer of the powder particles, so that the surface properties of the particles can be made liquid-like. In addition, although the appearance is powdery, it is preferable that, when viewed microscopically, a state in which powder particles are dispersed in a liquid is obtained. It is considered that since these liquid molecules are coated on the particle surface, even if the powder particles approach, excellent dispersibility can be obtained without aggregation. In addition, since the surface of the powder particles is already wet, the powder particles have excellent affinity for the lipophilic solvent and have extremely good dispersibility. In particular, it is considered that in the lipophilic solvent, the liquid molecules of the coated B layer extend and disperse, and hinder the contact between the particles, thereby achieving dispersion stabilization. The compounds of the A layer and the B layer are appropriately selected depending on the system in which the powder to be coated is blended and the type of the lipophilic solvent as the dispersion medium. For example, when it is desired to prepare a pressed powder to which no binder is added, the layer A is coated with a dextrin fatty acid ester and the layer B is coated with a branched fatty acid.
When dispersibility in silicone oil is required, layer A is coated with an organopolysiloxane, and layer B is coated with an organopolysiloxane modified with a functional group at one end. When dispersibility in volatile hydrocarbons is required, layer A is coated with a fatty acid and layer B is coated with an alkylsilane. When dispersibility in ester oil is required, it is possible to select, for example, coating layer A with an N-acylated amino acid and coating layer B with a branched fatty acid.

The amount of the surface treatment agent forming the solid coating layer is preferably equal to or less than the amount of the liquid surface treatment agent in terms of weight (A ≦ B). Accordingly, the surface of the powder is coated with the surface treatment agent that forms a solid coating layer at room temperature and the surface treatment agent that forms a liquid coating layer at room temperature, respectively. It is preferable that the amount of the surface treatment agent for the liquid coating layer (layer B) is not less than the amount (weight) of the surface treatment agent for the solid coating layer (layer A).

If the amount of the surface treatment agent for the solid coating layer is larger than the amount of the surface treatment agent for the liquid coating layer (by weight), the dispersibility of the obtained coated powder in the lipophilic solvent is rather poor. There is a tendency.

As described above, the amount of the surface treatment agent for the solid coating layer is preferably the minimum amount required to uniformly coat the powder particles, and if it is larger than the minimum amount, the powder particles are aggregated. However, even when coated with a surface treatment agent for a coating layer having a liquid state at normal temperature, the obtained coated powder cannot have excellent dispersibility in a lipophilic liquid. Since the required minimum amount varies depending on the type of powder and the method of treatment, it is necessary to conduct an experiment in advance to check an appropriate coating amount.

The coating amount of the surface treating agent of the layer A having a solid state at normal temperature varies depending on the type of the powder to be treated in the present invention and its specific surface area. Preferably about 0.1 to 15 parts by weight,
More preferably, it is about 0.1 to 10 parts by weight, further preferably about 1 to 8 parts by weight. If the coating amount is less than 0.1 part by weight, a uniform coating layer on the surface of the powder particles cannot be obtained, while if it is more than 15 parts by weight, only the powder particles are agglomerated, and the coating layer has a liquid state at room temperature. , It is difficult to obtain excellent dispersibility of the resulting coated powder in a lipophilic liquid.

Similarly, the coating amount of the surface treatment agent of the layer B is preferably 0.1 to 0.1% with respect to the powder before the surface treatment.
About 30 parts by weight, more preferably about 0.5 to 25 parts by weight, and still more preferably about 1 to 20 parts by weight. If it is less than the above range, feel, adhesion to skin, dispersibility is poor, while if it exceeds the above range, only a large number of free treating agents that do not react with the surface of the powder particles increase, and the lipophilicity of the obtained coated powder is increased. Since the dispersibility in a liquid is not improved, each is not preferable.

(Coating Method) In the present invention, the first layer of the powder to be treated is the A layer, preferably a surface treatment agent for forming a solid coating layer at room temperature, and the second layer is the B layer. Preferably, as a method of coating the surface treatment agent for forming the liquid coating layer at room temperature, a method known as a method of coating the surface treatment agent can be appropriately employed. For example: 1. A dry method in which, for example, a solid surface treating agent is mixed with a Hensyl mixer or a super mixer, and then the liquid surface treating agent is mixed and dried; After the powder to be treated is dispersed in water or an organic solvent with a mechanochemical type mill such as a ball mill or a sand grinder, for example, a solid surface treatment agent is mixed and fixed, and for example, a liquid surface treatment agent is mixed. After drying, removing the solvent and drying; and The powder to be treated in a high-speed air current such as a JET mill described in Japanese Patent Publication No. 6-59379 proposed by the inventors, for example, is contacted with a solid surface treatment agent, and further coated,
For example, there is a method in which a liquid surface treatment agent is brought into contact with and coated. In particular, it is preferable to adopt a processing method by a jet (JET) method for fine particle powder having a primary particle diameter of submicron or less.

The term "treatment method" used herein means a treatment method for hydrophobization which can be generally applied to the surface treatment of powder (base material), and the dispersibility in a lipophilic solvent is slightly inferior.
It is also possible to mix and coat simultaneously a layer, preferably a surface treatment agent which is solid at room temperature, and a layer B, preferably a surface treatment agent which is liquid at room temperature.

In the present invention, the dispersion medium of the oily dispersion may be any lipophilic dispersion medium, and may be liquid or solid at normal temperature. It is preferable to use solvents that can be used for various cosmetics. Specifically, monohydric alcohol solvents such as ethanol, propyl alcohol, isopropyl alcohol, butanol, amyl alcohol, hexyl alcohol, heptyl alcohol, octyl alcohol, caprylic alcohol, nonyl alcohol, decyl alcohol, phenol and benzyl alcohol, and normal Pentane,
Petroleum hydrocarbons such as normal hexane, normal heptane, normal octane, isohexane, isooctane, gasoline, mineral spirits, aromatic hydrocarbon solvents such as benzene, toluene, xylene, cyclohexane, ethylbenzene, amylbenzene, dipentene,
Vegetable hydrocarbon solvents such as turpentine oil, nitroparaffins, nitrohydrocarbon solvents such as nitrobenzene, ketone solvents such as acetone, methyl ethyl ketone, methyl isobutyl ketone, ethyl butyl ketone, diisobutyl ketone, methylene chloride, chloroform, Halogenated hydrocarbon solvents such as carbon tetrachloride, perchlorethylene, monochlorobenzene, etc., ethyl ether, isopropyl ether, butyl ether, hexyl ether, propylene oxide, ethylene glycol monomethyl ether, ethylene glycol monoethyl ether, propylene glycol monomethyl ether, etc. Ether solvents, methyl formate, ethyl formate, butyl formate, methyl acetate, ethyl acetate, butyl acetate, amyl acetate, ethyl propionate, butyl propionate Ester solvents such as isobutyl propionate, isobutyl propionate, ethyl butyrate, butyl butyrate, methyl lactate, ethyl lactate, butyl lactate, amyl lactate, safflower oil, soybean oil, evening primrose oil, grape seed oil, rosehip oil, kukui nut oil , Almond oil, sesame oil, wheat germ oil, corn oil, cottonseed oil, avocado oil, olive oil, camellia oil, persic oil, castor oil, peanut oil, hazelnut oil, macadamia nut oil, medofoam oil, cocoa butter, shea butter, wax , Palm oil, palm oil, palm kernel oil, beef tallow, horse fat, mink oil, fats such as milk fat, egg yolk oil, turtle oil, liquid paraffin, liquid isoparaffin, squalane, squalene, petrolatum, paraffin, ceresin, microcrystalline wax Such as hydrocarbon oils, lauric acid, myristic acid, Michin acid, stearic acid, behenic acid, oleic acid, linoleic acid, undecylenic acid, hydroxy stearic acid, fatty acids such as lanolin fatty acids, myristyl alcohol, cetyl alcohol, cetostearyl alcohol, stearyl alcohol, aralkyl alcohol, behenyl alcohol,
Higher alcohols such as oleyl alcohol, jojoba alcohol, batyl alcohol, cholesterol, phytosterol, lanolin alcohol, isostearyl alcohol, isopropyl isostearate, ethyl oleate, isopropyl myristate, isoisopropyl palmitate, cetyl octanoate, diisomalate Stearyl, glyceryl tricaprylate, isooctyl isononanoate, isononyl isononanoate, isotridecyl isononanoate, octyldodecyl neopentanoate, isotridecyl neopentanoate, myristyl neopentanate, propylene glycol diisononanoate, glyceryl tri-2-ethylhexanoate, tri2-ethylhexanoate Ester oils such as trimethylolpropane, beeswax, candelilla wax, whale wax, Wax, carnauba wax, bayberry wax, rice bran wax, insect wax, orange roughy oil,
Waxes such as montan wax, sugar cane wax, shellac wax, lanolin, jojoba oil, etc., methyl polysiloxane, methyl phenyl polysiloxane, decamethylcyclotetrasiloxane, alkyl-modified silicone, alcohol-modified silicone, amino-modified silicone, epoxy-modified silicone, olefin-modified Silicones such as silicone, carboxyl-modified silicone, carbinol-modified silicone, phenol-modified silicone, methacryl-modified silicone, mercapto-modified silicone, phosphoric acid-modified silicone, fluorine-modified silicone, higher fatty acid-modified silicone, polyether-modified silicone, and other perfluoropolyethers , Hydrofluoroether, perfluoromethylcyclopentane, perfluorodimethylcyclohexane, perflu B dimethylcyclobutane, methoxy nonafluorobutane, ethoxy-nonafluorobutane,
Dodecafluoropentane, tetradecafluorohexane, perfluorodecane, perfluorooctane, 4-
Trifluoromethyl perfluoromorpholine, 4-
Fluorinated oils such as pentafluoroethyl perfluoromorpholine, para-aminobenzoic acid, para-aminobenzoic acid monoglycerin ester, N, N-dimethylpara-aminobenzoic acid ethyl ester, N, N-diethoxypara-aminobenzoic acid ethyl ester as UV absorbers Benzoic acids such as N, N-dipropoxyparaaminobenzoic acid ethyl ester; anthranilic acids such as homomenthyl-N-acetylanthranilate; , Octylcinnamate, ethyl-4-isopropylcinnamate, methyl-2,5-diisopropylcinnamate, ethyl-2,4-diisopropylcinnamate Propyl-p-methoxycinnamate, isopropyl-p-methoxycinnamate, isoamyl-p-methoxycinnamate, octyl-p-methoxycinnamate, 2-ethoxyethyl-p-methoxycinnamate, cyclohexyl-p-methoxycinnamate Cinnamic acids such as 2,4-dihydroxybenzophenone, 2,2'-dihydroxy-4-methoxybenzophenone, 2-hydroxy-4-methoxybenzophenone, 2-hydroxy-4-methoxybenzophenone-5
Benzophenones such as sulfonate, 4-phenylbenzophenone, 4-hydroxy-3-carboxybenzophenone, 3-benzylidene-d, l-camphor, urocanic acid, urocanic acid ethyl ester, 2-phenyl-5-methylbenzoxa Examples thereof include sol, dibenzarazine, dianisoylmethane, 4-tert-butyl-4′-methoxydibenzoylmethane, a silicone-modified ultraviolet absorber, and a fluorine-modified ultraviolet absorber. One or more of these can be used as the lipophilic solvent in the present invention. When the lipophilic solvent used in the present invention is composed of a mixture of a plurality of components, if the solvent itself obtained by mixing the plurality of components is a lipophilic and uniform solution, one or more of the components are lipophilic. It does not have to be oily.

The oily dispersion of the powder in the present invention has a composition as simple as possible and the content of the coated powder is preferably as large as possible. However, in order to further disperse the coated powder and to stabilize the dispersion. Alternatively, other components than the third component may be added for various purposes, such as to further improve the function of the oily dispersion by a synergistic effect with the third component. Components incorporated for such purposes include various surfactants, for example, alkyl ether sulfates such as POE lauryl sulfate triethanolamine, alkylbenzene sulfonates such as sodium dodecylbenzene sulfonate, and lauryl sulfate. Higher alkyl sulfates such as sodium and potassium lauryl sulfate; higher fatty acid amide sulfonates such as N-acyl sarcosine acid and sodium N-myristoyl-N-methyltaurine; higher fatty acid ester sulfates such as hardened coconut oil fatty acid sodium glycerin sulfate Ester salts, higher fatty acid ester sulfonates,
Higher fatty acid alkylolamide sulfate, fatty acid soap, sulfosuccinate, secondary alcohol sulfate, POE alkyl ether carboxylic acid, POE alkyl allyl ether carboxylate, α-olefin sulfonate, lauroyl monoethanolamide succinate Sodium, N-palmitoylaspartic acid diethanolamine, anionic surfactants such as sodium caseinate, alkyltrimethylammonium salts such as stearyltrimethylammonium chloride, alkylpyridinium salts such as distearyldimethylammoniumdialkyldimethylammonium chloride, and alkyl quaternary ammonium salts , An alkylamine salt, an alkyldimethylbenzylammonium salt, an alkylisoquinolinium salt, a dialkylmorphonium salt, OE alkylamines, polyamine fatty acid derivatives, amyl alcohol fatty acid derivatives, cationic surfactants such as benzalkonium chloride, benzethonium chloride, 2-cocoyl-2-imitazolinium hydroxide-1-carboxyethyloxy disodium salt, etc. Imidazoline amphoteric surfactants, alkyl betaines, amido betaines, betaine amphoteric surfactants such as betaine lauryldimethylaminoacetate, glycerin sesquioleate, glycerin fatty acid esters such as glyceryl monostearate, hexaglyceryl polyricinoleate, mono Polyglycerin fatty acid esters such as diglyceryl stearate and decaglyceryl decaoleate; sorbitan fatty acid esters such as sorbitan monooleate and sorbitan sesquioleate; monostearic acid Propylene glycol fatty acid esters such as propylene glycol, POE
POE sorbitan fatty acid esters such as sorbitan monooleate, POE glycerin fatty acid esters such as POE glycerin triisostearate, POE monooleates, POE fatty acid esters such as POE distearate,
POE lauryl ether, POE alkyl ether such as POE stearyl ether, POE / POP alkyl ether such as POE / POP hydrogenated lanolin, hydrogenated castor oil derivative, glycerin alkyl ether, alkanolamide, sucrose fatty acid ester, dextrin fatty acid ester, starch fatty acid ester , Nonionic surfactants such as hydroxystearic acid, other phospholipids such as lecithin, glycolipids such as trehalose lipid, perfluoroalkyl phosphate, perfluoroalkyl sulfonate, perfluoroalkyl carboxylate, etc. Natural or synthetic clay minerals such as fluorinated surfactants, alkyl methacrylate copolymers, bentonite, smectite, kaolin, etc., and organically modified clays such as organic amine cation modified bentonite Thing, aerosols, etc., can be cited.

The method of kneading or mixing and dispersing the coated powder in the dispersion medium in the present invention is not particularly limited as long as a known method is employed. For example, kneading mixers such as kneader kneading, hensyl kneading, roll kneading, extruder kneading, propeller mixer, high speed mixer, dissolver, homogenizer, artemizer, wet jet mill, colloid mill, mass colloider, bead mill,
An oily dispersion can be produced using a wet mixing and dispersing machine such as a sand mill.

There is no particular difficulty in dispersing the coated powder in a lipophilic solvent which is solid at room temperature (including a single solvent or a mixture of a plurality of solvents). For example, the powder may be dispersed in a state where the lipophilic solvent is liquefied by heating to a temperature equal to or higher than the melting point. This method is a method commonly used for a dosage form containing a lot of solid wax at room temperature such as lipstick.

The effect of the present invention is that the oil-based dispersion of the present invention can be made into a dispersion only with the coated powder used in the present invention without blending a conventionally used powder or coated powder. However, it is also possible to form an oily dispersion by partially blending a conventionally used powder within a range that does not impair the effects of the present invention.

(Cosmetic) The present invention includes a cosmetic containing an oily dispersion and a cosmetic produced using the dispersion.

The amount of the oily dispersion obtained in this manner in a cosmetic is arbitrarily selected according to the properties of the cosmetic, but is preferably about 0.1 to 100% by weight in the total composition.
More preferably, it is about 1 to 99% by weight.

These coated powders may be used, if necessary,
One or more of the coated powders obtained in the present invention can be blended.

Further, the oily dispersion of the present invention is characterized in that at least one of the oily dispersions of the present invention is blended in a cosmetic or the like without using other conventionally used oily dispersions. Is preferred in that the effect of the present invention is more exhibited, but it is also possible to mix and use a part of a conventionally used oily dispersion as long as the effect of the present invention is not impaired.

The cosmetics containing the oily dispersion containing the coated powder used in the present invention include powder foundation, liquid foundation, oily foundation, stick foundation, pressed powder, face powder, lipstick, lip gloss, blusher ,
Eyeshadow, eyebrow, eyeliner, mascara,
Aqueous nail enamel, oily nail enamel, emulsified nail enamel, enamel top coat, enamel base coat, etc., cosmetics for finishing, emollient cream, cold cream, whitening cream, milky lotion, lotion, serum, carmine lotion, liquid face wash, Cosmetic for skin such as facial cleansing foam, facial cleansing cream, facial cleansing powder, makeup cleansing, body gloss, hair gloss, hair cream, hair shampoo, hair rinse, hair coloring, hair brushing agent, etc. Examples include sun creams, emulsions, soaps, bath agents, perfumes, and the like.

In the present invention, a cosmetic containing an oily dispersion containing a powder coated with two layers (surface layer A and layer B) of a surface treating agent may be used as far as the effects of the present invention are not impaired. Pigment dispersants, oils, surfactants, UV absorbers, preservatives, antioxidants, film-forming agents, humectants, etc.
Thickeners, dyes, pigments, fragrances and the like can be appropriately compounded.

(Uses Other than Cosmetic) The oily dispersion of the powder obtained in the present invention can be used not only for cosmetics but also for plastic additives, inks, paints, toners (magnetic powders), chemical fibers, packaging materials, electronic materials, etc. The present invention is also applicable to powdery oily dispersions widely used in various fields such as materials. In particular, when a powder that can be used in cosmetics is used in another field and a dispersion is similarly required, the oil-based dispersion described for the above-mentioned cosmetics is similarly employed in the other fields. It is possible.

Hereinafter, the present invention will be described in detail with reference to Examples and Comparative Examples. The two-layer-coated powder (coated powder) blended in the oil-based dispersion of the present invention is hereinafter referred to as a “mybrid-treated powder”, and the oil-based dispersion blended with the mibrid-treated powder is referred to as “Mybrid-treated powder”. It is referred to as "brid dispersion". Of course, these examples do not limit the invention in any way.

(Example 1) An example of the production of an oily dispersion (mibrid dispersion) containing the hybridized powder of the present invention is shown below.

[Example 1] A methylhydrogenpolysiloxane (Shin-Etsu Chemical Co., Ltd.) as a solid surface treatment agent was added to 5000 g of sericite (“FSE” manufactured by Sanshin Mining Co., Ltd.).
(KF-9901) and 500 g of a 50% aqueous solution of isopropanol were added and mixed at 80 ° C. for 30 minutes under reduced pressure using a jacketed high-speed Hensyl (“FM20BX” manufactured by Mitsui Mining Co., Ltd.). Further, as a liquid surface treating agent, 250 g of a linear dimethylpolysiloxane having a degree of polymerization of 20 and having a monosilanol group at one end (“X-24-9825” manufactured by Shin-Etsu Chemical Co., Ltd.) and 50% aqueous solution of isopropanol 250 g was added, and the mixture was mixed at 100 ° C. for 60 minutes under reduced pressure with the high-speed hensyl to obtain a hybridized sericite. Dimethyl polysiloxane (Shin-Etsu Chemical Co., Ltd.)
100 g of “KF-96 (6cs)” and 900 g of the above-mentioned hybridized sericite were placed in a 1-liter SUS container, and homogenized with a homomixer (“TK Robomix” manufactured by Tokushu Kika Kogyo Co., Ltd.) at 3000 rpm / 5 min. To obtain a hybrid dispersion.

[Example 2] In Example 1, the sericite was replaced with silica beads ("P-150" manufactured by Catalyst Chemical Industry Co., Ltd.).
0 "), the degree of polymerization, which is a liquid surface treatment agent, is 2
The same treatment was carried out except that the amount of the linear dimethylpolysiloxane having a monosilanol group at one end was changed to 350 g at 0, thereby obtaining hybridized silica beads. Light liquid isoparaffin ("Pearl Dream 4" manufactured by NOF Corporation) 2
00 g and the above-mentioned hybridized silica beads (800 g) were placed in a 1-liter SUS container, and a homomixer 3000 was added.
The mixture was mixed and dispersed under the condition of rpm / 5 min to obtain a hybrid dispersion.

[Example 3] Titanium dioxide (Ishihara Sangyo Co., Ltd.)
50 g of dextrin alumitate ("Leopearl KL" manufactured by Chiba Flour Milling Co., Ltd.) as a solid surface treatment agent 250 g of volatile isoparaffin "IP Solvent 1620" (manufactured by Idemitsu Petrochemical Co., Ltd.) To 6
The solution heated and dissolved at 0 ° C. was added and mixed at 60 ° C. for 30 minutes under reduced pressure using a jacketed high-speed Hensyl (“FM20BX” manufactured by Mitsui Mining Co., Ltd.). Further, 300 g of octyltriethoxysilane ("A-174" manufactured by Nippon Unicar Co., Ltd.) was added as a liquid surface treatment agent, and the mixture was mixed at 100 ° C. for 30 minutes. After mixing 200 g of isopropyl myristate (“Kodamol IPM” manufactured by Croda Japan K.K.) and 800 g of the above-mentioned Mybrid-treated titanium dioxide, 3
The mixture was passed twice through this roll mill (“HR500” manufactured by Ashizawa Co., Ltd.) to obtain a hybrid dispersion.

Example 4 In Example 3, titanium dioxide was replaced with yellow iron oxide (“Mapico Yellow Lemon” manufactured by Titanium Industry Co., Ltd.), and a solid surface treating agent was methyltrimethoxysilane (Shin-Etsu). "KBM" manufactured by Chemical Industry Co., Ltd.
13)) and decyltrimethoxysilane ("KBM310" manufactured by Shin-Etsu Chemical Co., Ltd.) instead of the liquid surface treatment agent.
3 "), and the same treatment as in Example 3 was carried out to obtain a hybrid-treated yellow iron oxide. Squalane (Iwase Cosfa
After mixing 250 g of "phytosqualane" and 750 g of the hybridized titanium dioxide, the mixture was passed twice using a three-roll mill ("HR500" manufactured by Ashizawa Corporation) to obtain a hybrid dispersion.

[Example 5] In Example 3, titanium dioxide was replaced by Bengala ("Bengara Cloisonne" manufactured by Morishita Benga Kogyo Co., Ltd.), and the liquid surface treatment agent was isostearic acid (Higher Alcohol Industry Co., Ltd.). ) Produced in the same manner as in Example 3 except that "isostearic acid EX") was used. Liquid paraffin (Kaneda
After mixing 200 g of "Hi-Coal K-230" and 800 g of the hybridized titanium dioxide, the mixture was passed twice using a three-roll mill ("HR500" manufactured by Ashizawa Corporation) to obtain a hybrid dispersion.

[Example 6] In Example 3, titanium dioxide was replaced with black iron oxide ("BL-10" manufactured by Titanium Industry Co., Ltd.).
0 "), and the same treatment as in Example 3 was carried out to obtain a hybridized black iron oxide. Macadamia nut oil ("CROPURE MACADAM" manufactured by Croda Japan KK)
IA ") and 800 g of the above-mentioned Mybrid-treated titanium dioxide, and then a three-roll mill (Ashizawa Co., Ltd.)
("HR500" manufactured by KK) and a hybrid dispersion was obtained twice.

[Example 7] 200 g of the hybridized Bengala obtained in Example 5 and 800 g of butyl acetate
, And a three-roll mill (“HR” manufactured by Ashizawa Co., Ltd.)
500 ") to obtain a hybrid dispersion twice. .

Example 8 3000 g of fine particle titanium oxide ("TTO-55A" manufactured by Ishihara Sangyo Co., Ltd.) and lecithin ("PL-1" manufactured by Kewpie Co., Ltd.) as a solid surface treatment agent were used.
00P ") and mixed with a Hensyl mixer for 30 minutes. Further, octadecyltrimethoxysilane ("TSL8" manufactured by GE Toshiba Silicon Co., Ltd.) is used as a liquid surface treatment agent.
186 ") and mixed with a Hensyl mixer for 15 minutes. These mixtures were simultaneously pulverized using a JET mill (100AFG, manufactured by Alpine GmbH, Germany), and then dried at 130 ° C. for 7 hours to obtain hybridized fine particle titanium oxide. C12-15 alkyl benzoate (“FINSOLV TN” manufactured by Ina Trading Co., Ltd.) 40
0 g and 600 g of hybridized fine-particle titanium oxide were mixed and filled with 0.5 mmφ zirconia beads by a sand mill (“Ultraviscomil: UV” manufactured by Imex Co., Ltd.)
M ") twice to obtain a hybrid dispersion.

Example 9 4000 g of fine zinc oxide (“FINEX-50” manufactured by Sakai Chemical Industry Co., Ltd.) and maleated polyethylene as a solid surface treating agent (“POWAX S-30” manufactured by Nippon Petrochemical Co., Ltd.) ) 120 g was mixed with a heater Hensyl mixer for 30 minutes, and then a perfluoroalkyltrimethoxysilane ("TSL8233" manufactured by GE Toshiba Silicone Co., Ltd.) was used as a liquid surface treatment agent.
400 g and 500 g of IPA were added and mixed under reduced pressure at 50 ° C. for 30 minutes using a heater Hensyl mixer. Furthermore,
After simultaneous pulverization using JET mill,
Drying was carried out for a time to obtain fine particles of zinc oxide treated with hybrid.
Perfluoromethylcyclopentane (Fluorochemicals
Ltd. "Flutec PCI") 400 g and hybridized fine particle zinc oxide 600 g were mixed, and the mixture was passed twice through a sand mill ("Ultra Visco Mill: UVM2" manufactured by Imex Co., Ltd.) filled with zirconia beads having a diameter of 0.5 mm. I got

Example 10 1000 g of fine zinc oxide (“UFZO-350” manufactured by Sumitomo Osaka Cement Co., Ltd.)
Trimethylsiloxysilicic acid (“BY-11-022” manufactured by Dow Corning Toray Co., Ltd.) as a solid surface treatment agent 3
0 g, octadecyltrimethoxysilane (TSL818 manufactured by GE Toshiba Silicone Co., Ltd.) as a liquid surface treatment agent
6)) 50 g, 50 g of linear dimethylpolysiloxane having a degree of polymerization of 50 and having a trimethoxy group at one end (“X-24-9826” manufactured by Shin-Etsu Chemical Co., Ltd.), perfluoroalkyltrimethoxysilane (GE Toshiba silicone
"TSL8233" manufactured by Co., Ltd.) 50 g and toluene 2000
g was put into an agitator mill (“LMK4” manufactured by Ashizawa Co., Ltd.) filled with 1 mmφ zirconia beads, and dispersed three times. This dispersion was dried with a slurry drier (“Slurry Drier SFD-Mini” manufactured by Okawara Seisakusho Co., Ltd.) to obtain fine particles of treated zinc oxide. Cyclomethicone (“VS-7158” manufactured by Nippon Unicar Co., Ltd.)
200 g, UV absorber (“Pars” manufactured by Nippon Roche Co., Ltd.)
ol MCX ”) and a mixture of 200 g of finely divided zinc oxide and 600 g of ultrafine high-pressure homogenizer (“ Microfluidizer M-140 ”manufactured by Mizuho Industry Co., Ltd.).
K)), and passed once at a pressure of 2000 kg / cm ² to obtain a hybrid dispersion.

[Example 11] (Production of dispersion in which mixed hybridized powder was dispersed) [0120] The hybridized powder sericite and silica obtained in Examples 1, 2, 3, 4, 5, and 6, respectively. 25 each of beads, titanium dioxide, yellow iron oxide, red iron oxide, black iron oxide
0 g, 130 g, 180 g, 100 g, 65 g, 25 g
And the isotridecyl isononanoate (Nippon Emulsion Co., Ltd. “INTD-13
9 ") Mix with 250 g. These were passed twice through a three-roll mill (“HR500” manufactured by Ashizawa Co., Ltd.) to obtain a hybrid dispersion.

[Example 12] (Production of dispersion in which powder having a large particle diameter is dispersed) Bronze powder ("TT-" manufactured by Nakajima Metal Foil Industry Co., Ltd.)
777 ") and 1,000 g of ethyltrimethoxysilane as a solid surface treatment agent (" SIE4901. Manufactured by Chisso Corporation ").
4)) 30 g of IPA and 50 g of IPA were mixed by a mixer ("Granulator NMG-3" manufactured by Nara Machinery Co., Ltd.) for 30 minutes. Further, as a liquid surface treatment agent, isooctyltrimethoxysilane (“SII645” manufactured by Chisso Corporation)
8.0 ") and 100 g of IPA were added and mixed again with a mixer for 30 minutes. After drying at 70 ° C. for 3 hours with a hot air drier, further drying at 130 ° C. for 10 hours and pulverization were performed to obtain a mybridized bronze powder. 100 g of butyl acetate and 900 g of hybridized bronze powder were kneaded with a universal mixing stirrer (“5DM-r” manufactured by Dalton Co., Ltd.) for 20 minutes to obtain a hybrid dispersion.

[Example 13] (Production of a dispersion having a processed powder concentration of 50 wt% or more and a viscosity of 1000 mPa · s or less) 550 g of the hybridized fine particle titanium oxide obtained in Example 8 was added to cyclomethicone (Nihon Unicar Co., Ltd.). ) "VS-7158") 450g
And a sand mill filled with 0.5 mmφ zirconia beads (“Ultraviscomil: U” manufactured by Imex Co., Ltd.)
VM2 ") twice to obtain a hybrid dispersion.

[Example 14] (Production of clay-like dispersion) 750 g of the hybridized fine particle titanium oxide obtained in Example 8 was added to cyclomethicone (“VS-7158” manufactured by Nippon Unicar Co., Ltd.) 2
50 g and a three-roll mill (“HR” manufactured by Ashizawa Co., Ltd.)
500 ") three times to obtain a hybrid dispersion.

[Example 15] (Use in combination with a conventional surface-treated powder) 300 g of the hybridized fine particle titanium oxide obtained in Example 8 and the octadecylsilane-treated fine particle zinc oxide 250 obtained in Comparative Example 8
g of cyclomethicone (“VS-71” manufactured by Nippon Unicar Co., Ltd.)
58 "), and passed twice through a sand mill (" Ultra Visco Mill: UVM2 "manufactured by Imex Co., Ltd.) filled with 0.5 mmφ zirconia beads to obtain a hybrid dispersion.

[Example 16] (The inorganic filter of Example 1 in JP-A-12-26262 was subjected to a hybrid treatment and dispersed.) Oisolex T-2
000 (Germany: MERCK) fine particle titanium oxide 4
000 g and N-lauroyl-L as a solid surface treatment agent
-Glutamic acid (“Amisoft LA” manufactured by Ajinomoto Co., Inc.)
After mixing 120 g of the mixture with a heater Hensyl mixer for 30 minutes, 40 g of isooctyltrimethoxysilane (“SII6458.0” manufactured by Chisso Corporation) was used as a liquid surface treatment agent.
0 g was added and mixed with a heater Hensyl mixer for 30 minutes. Furthermore, after the simultaneous pulverization using a JET mill,
Drying was performed at 30 ° C. for 7 hours to obtain finely divided microparticles of titanium oxide. After mixing 300 g of the obtained fine particle titanium oxide and 50 g of Aerosol R812 (Degussa, Germany), Oisolex OCR (MERCK, Germany)
650 g and a three-roll mill (“H” manufactured by Ashizawa Co., Ltd.)
R500 ”) twice to obtain a hybrid dispersion.

(Comparative Example) Next, as a comparison of the hybrid dispersion, a production example of a conventional dispersion prepared by mixing and dispersing a surface-treated powder will be described.

Comparative Example 1 The solid surface treatment agent and the liquid surface treatment agent of Example 1 were replaced with methyl hydrogen polysiloxane (“KF-9901” manufactured by Shin-Etsu Chemical Co., Ltd.) 250
500 g of a 50% aqueous solution of isopropanol was added instead of g, and a high speed Hensyl (“FM20B” manufactured by Mitsui Mining Co., Ltd.
X ") for 30 minutes. Further, the mixture was mixed at 100 ° C. for 60 minutes under reduced pressure with a high-speed hensyl to obtain sericite treated with methyl hydrogen polysiloxane. Dimethyl polysiloxane (KF-96 (6c, manufactured by Shin-Etsu Chemical Co., Ltd.)
s ") 100 g and the above-mentioned methylhydrogenpolysiloxane-treated sericite 900 g were charged into a 1-liter SUS container and mixed, but the viscosity was too high to be dispersed by a homomixer. In order to obtain a viscosity that can be dispersed with a homomixer, the mixture is further added with 50 parts of dimethylpolysiloxane.
0 g was added, mixed and dispersed under the condition of 3000 rpm / 5 min to obtain a dispersion.

COMPARATIVE EXAMPLE 2 The solid surface treating agent and the liquid surface treating agent of Example 2 were prepared by using linear dimethylpolysiloxane 40 having a degree of polymerization of 20 and having a monosilanol group at one end.
The same treatment as in Comparative Example 1 was performed instead of 0 g to obtain dimethylpolysiloxane-treated silica beads. Light liquid isoparaffin ("Pearl Dream 4" manufactured by NOF Corporation) 200
g and the silica beads 80 treated with dimethylpolysiloxane.
0 g is placed in a 1-liter SUS container, and a homomixer 3
The mixture was mixed and dispersed under the conditions of 000 rpm / 5 min to obtain a dispersion.

Comparative Example 3 The solid surface treating agent and the liquid surface treating agent of Example 3 were dextrin alumitate 350
In addition, 500 g of volatile isoparaffin was added in place of g, and the mixture was mixed at 100 ° C. for 60 minutes under reduced pressure using a high-speed Hensyl, and then dextrin alumitated titanium dioxide was obtained through an atomizer. Thereafter, a dispersion was obtained in the same manner as in Example 3.

Comparative Example 4 The solid surface treating agent and the liquid surface treating agent of Example 4 were replaced with decyltrimethoxysilane 350
In place of g, 500 g of 50% isopropanol was added, and the mixture was mixed under reduced pressure at 100 ° C. for 60 minutes using a high-speed Hensyl, and then decyltrimethoxysilane-treated yellow iron oxide was obtained through an atomizer. Thereafter, a dispersion was obtained in the same manner as in Example 4.

Comparative Example 5 The solid surface treating agent and the liquid surface treating agent of Example 5 were replaced with 350 g of isostearic acid, 500 g of volatile isoparaffin was added, and the mixture was mixed under reduced pressure at 100 ° C. for 60 minutes using a high-speed hensyl. After that, isgaric acid-treated Bengala was obtained through an atomizer. Thereafter, a dispersion was obtained in the same manner as in Example 5.

Comparative Example 6 500 g of volatile isoparaffin was used in place of dextrin palmitate instead of the solid surface treating agent and the liquid surface treating agent of Example 6, and the mixture was mixed at 100 ° C. for 60 minutes under reduced pressure using a high-speed hensyl. Thereafter, dextrin alumite-treated black iron oxide was obtained through an atomizer. Thereafter, a dispersion was obtained in the same manner as in Example 6.

[Comparative Example 7] A dispersion was obtained in the same manner as in Example 7 using the isgaric acid-treated red iron oxide obtained in Comparative Example 5.

Comparative Example 8 The solid surface treating agent and the liquid surface treating agent of Example 8 were mixed for 30 minutes with a Hensyl mixer instead of 360 g of octadecyltrimethoxysilane, and then pulverized simultaneously using a JET mill. Did. 13 more
After drying at 0 ° C. for 7 hours, octadecylsilane-treated fine particle titanium oxide was obtained. Thereafter, a dispersion was obtained in the same manner as in Example 8.

Comparative Example 9 The solid surface treatment agent and the liquid surface treatment agent of Example 9 were replaced with perfluoroalkylsilane 52.
Instead of 0 g, it was added with 500 g of IPA, mixed with a heater Hensyl under reduced pressure at 50 ° C. for 30 minutes, and then subjected to simultaneous pulverization using a JET mill. Further drying at 130 ° C. for 7 hours gave perfluoroalkylsilane-treated fine particle zinc oxide. Thereafter, a dispersion was obtained in the same manner as in Example 9.

Comparative Example 10 The solid surface treatment agent and the liquid surface treatment agent of Example 10 were 60 g of octadecyltrimethoxysilane, and 60 g of linear dimethylpolysiloxane having a degree of polymerization of 50 and having a trimethoxy group at one end. In the same manner as in Example 10 except that 60 g of perfluoroalkyltrimethoxysilane and perfluoroalkyltrimethoxysilane were used, zinc oxide fine particles treated by mixing octadecylsilane, dimethylpolysiloxane and perfluoroalkylsilane were obtained. Thereafter, a dispersion was obtained in the same manner as in Example 10.

Comparative Example 11 Comparative Examples 1, 2, 3, 4, 5
A dispersion was obtained from the treated powder obtained in each of Examples 6 and 6 in the same manner as in Example 11.

[Comparative Example 12] The solid surface treating agent and the liquid surface treating agent of Example 12 were replaced with ethyltrimethoxysilane 1
Example 12
A dispersion was obtained in the same manner.

[Comparative Example 13] (Production of a dispersion having a treated powder concentration of 50 wt% or more and a viscosity of 1000 mPa · s or less) 550 g of the octadecylsilane-treated fine particle titanium oxide obtained in Comparative Example 8 was added to cyclomethicone (Nihon Unicar Co., Ltd.). ) "VS-7158") 4
The mixture was passed through a sand mill (“Ultraviscomil: UVM2” manufactured by Imex Co., Ltd.) twice, which had been mixed with 50 g and filled with 0.5 mmφ zirconia beads. The resulting dispersion had a viscosity of 58,000 mPa · s. Polyether-modified silicone ("KF-6017" manufactured by Shin-Etsu Chemical Co., Ltd.) was added to reduce the viscosity. Formulation is octadecylsilane-treated fine particle titanium oxide / cyclomethicone / polyether-modified silicone = 550 g / 300 g / 150 g
The dispersion was performed under the same conditions as above to obtain a dispersion.

[Comparative Example 14] (Production of clay-like dispersion) 750 g of the octadecylsilane-treated fine particle titanium oxide obtained in Comparative Example 8 was mixed with cyclomethicone (“VS-715” manufactured by Nippon Unicar Co., Ltd.).
8 ") mixed with 250 g and roll mill (Ashizawa Co., Ltd.)
("HR500" manufactured by EIZO Corporation) three times to obtain a dispersion.

Comparative Example 15 (Trial Production of Ultraviolet Filter Suspension of Example 1 of JP-A-12-26262) 300 g of fine particle titanium oxide of Oisolex T-2000 (MERCK, Germany) and Aerosol R812 (Germany: Degussa) 50 g of Oisolex OCR after mixing (Germany: MERCK)
650 g and a three-roll mill (“H” manufactured by Ashizawa Co., Ltd.)
R500 ") twice to obtain a dispersion.

Next, the hybrid dispersion of the present invention obtained as described above and the dispersion obtained in Comparative Example were evaluated by the following test methods. The results are shown in Table 1.

(1) Viscosity The sample temperature was set to 25 ° C. and a B-type viscometer (Shibaura System Co., Ltd.)
(VDA type) and the viscosity (mPa · s) after 60 seconds was measured.

(2) Particle Size The average particle diameter (D50: μm) of each dispersion was measured using a high-concentration particle size measuring device of a laser diffraction type particle size measuring device (“SALD-2000J” manufactured by Shimadzu Corporation). .

(3) Dispersion stability over time Each dispersion was placed in a 50 cc transparent glass container for 30 minutes.
The sample was taken in a 50 ° C. oven for 1 month, and the solid-liquid separation state (stable: Δ, separation: ×) was observed.

(4) In-vitro SPF value measurement The dispersions of the fine particle titanium oxide and the fine particle zinc oxide of the examples and the comparative examples were applied to quartz glass plates (100 mm × 100 mm ×
Make a coating surface of 40cm ² on 3mm / length × width × thickness).
03 g was applied. This coated surface is treated with an SPF analyzer (O
Nine spots were measured with POMETORICS (USA), and the average value was taken as the SPF value.

(5) Transparency The coated quartz plate sample prepared in the above (4) was measured for 9 spots of transmittance at 560 nm using a spectral colorimeter (“SZ- # 90” manufactured by Nippon Denshoku Industries Co., Ltd.) and averaged. The value was defined as transmittance (%).

(6) Feeling (feel of use; slipperiness) 10 g of the dispersion obtained in each of Examples and Comparative Examples 1, 2 and 11 and titanium oxide (“CR-” manufactured by Ishihara Sangyo Co., Ltd.)
50 ") and mixed with an atomizer. This crushed material was placed on a piece of 8 cm × 5 cm piece of collagen paper (“Sapare” manufactured by Idemitsu Petrochemical Co., Ltd.) at 1.5 mg / cm.
² handy compression tester (Kato Tech
The average value of the resistance (gf) when reciprocating 10 times with “KES-G5” manufactured by K.K.) was determined. The lower the resistance, the better the slipperiness.

(7) Hiding Power The dispersions obtained in Examples and Comparative Examples 3, 8, and 13 were applied on a hiding rate test paper (manufactured by Nippon Test Panel Industry Co., Ltd.) on a multi-applicator (manufactured by Taiyo Kiki Co., Ltd.). ). At this time, the thickness (μm) of the coating film on which the black-and-white border of the test paper became invisible was determined. In the case of titanium oxide (Examples and Comparative Example 3), the smaller the thickness of the coating film, the higher the hiding power and the more the particles are dispersed.
And Comparative Examples 8 and 13) show that the smaller the thickness of the coating film, the stronger the hiding power, and the more the particles are aggregated.

(8) Coloring Power The dispersions obtained in each of the Examples and Comparative Examples 4, 5, 6, and 11 were tested for concealment rate test paper (Nihon Test Panel Kogyo Co., Ltd.).
The product was coated on a black plate (manufactured by Co., Ltd.) at 10 mil using a baker type applicator (manufactured by Taisuke Kiki Co., Ltd.). The coating film was measured with a spectral colorimeter (“SZ- $ 90” manufactured by Nippon Denshoku Industries Co., Ltd.) and the chroma was measured. I asked. The higher the saturation, the higher the coloring power.

(9) Redispersibility The dispersibility of the dispersion of the clay-like material obtained in Example 14 and Comparative Example 14 was evaluated by the following test method. 20 g of a clay-like dispersion was added to 100 g of the same cyclomethicone as the dispersion medium of the dispersion, and dispersed at 70 ° C. with a disper mixer (“TK Robomix” manufactured by Tokushu Kika Kogyo Co., Ltd.) at 1400 rpm / 5 min. .
325 mesh sieve (mesh size 45 μm)
And the residue on the sieve was observed. (No residue: Δ, residue: X) As is clear from Table 1, the oil-based dispersion of the present invention has the functions of powder, such as touch (feel of use; slipperiness), hiding power, coloring power, and ultraviolet light. The shielding ability and the optical characteristics can be dramatically improved. In addition, from the evaluation of redispersibility of Example 14 and Comparative Example 14, the hybrid dispersion of the clay-like material has good redispersibility and excellent useability. Further, from the results of Example 16 and Comparative Example 15, in comparison of the dispersion of the liquid ultraviolet absorber and the inorganic ultraviolet shielding powder, the hybrid dispersion has an average particle diameter and the transparency of the visible portion which are higher than those of the conventional one. It is overwhelmingly excellent in ultraviolet shielding ability.

[0152]

[Table 1]

[Example 17, Comparative Examples 16 and 17] (Production of 2-way powder foundation) A 2-way powder foundation having the composition shown in Table 2 was produced by the following method. The numerical values represent parts by weight.

[0154]

[Table 2] * 1: Formulated in Example 17 * 2: Formulated in Comparative Example 17 * 3: Dextrin palmitate-treated titanium dioxide obtained in Comparative Example 3 * 4: Methylhydrogenpolysiloxane-treated sericite obtained in Comparative Example 1 .

(Production method) The above components (1) to (7) were mixed and pulverized through a pulverizer. Transfer this to a high speed blender
The mixture obtained by mixing (8) to (12) and making the mixture uniform was added, and further mixed and made uniform. This was passed through a pulverizer, sieved and uniformed in particle size, and then compression-molded to produce a 2-way foundation.

Example 18 and Comparative Example 18 (Production of Emulsion Type Foundation) An emulsion type foundation having the composition shown in Table 3 was produced by the following method.

[Table 3] * 1: Formulated in Example 18 * 2: Formulated in Comparative Example 18. The numerical values represent parts by weight.

(Production method) At 70 ° C., components (1) to (7) were uniformly dissolved and mixed. The aqueous phase obtained by uniformly mixing and dissolving the components (8) to (12) at 70 ° C. was gradually added to the oil phase, uniformly dispersed with a homomixer, cooled, and the component (13) was added thereto to prepare emulsified particles. Was manufactured.

Example 19, Comparative Examples 19 and 20 (Production of Powder Eye Shadow) A powder eye shadow having the composition shown in Table 4 was produced by the following method.

[0159]

[Table 4] * 1: Compounded in Example 19 * 2: Compounded in Comparative Example 20 * 3: Sericite treated with methyl hydrogen polysiloxane obtained in Comparative Example 1. The numerical values represent parts by weight.

(Production method) Of the above components, components (1) to (4) other than titanium mica were mixed with a Hensyl mixer, and then pulverized with an atomizer. The mica titanium of the component (3) was mixed with the mixture, and the components (5) to (10) obtained by uniformly heating and dissolving were added and mixed. This was pulverized with an atomizer, passed through a sieve, and compression-molded into a middle plate to produce a powder eye shadow.

In Comparative Example 20, when the content of sericite was adjusted, the amount of dimethylpolysiloxane became excessive, and the preparation could not be made. The dispersion produced in Comparative Example 1 has a low powder content and low versatility in formulation (poor useability).

With respect to the above examples of the present invention, the sensory evaluation of cosmetics was carried out by 20 specialized panelists. As evaluation items, four items of smoothness at the time of use, adhesion to the skin, elongation on the skin, and finished feeling were selected and evaluated on a five-point scale. Table 5 shows the results.

(Evaluation criteria) 5: good; 4: somewhat good; 3: normal; 2: somewhat bad; and 1: bad.

[0164]

[Table 5]

As is clear from Table 5, the cosmetics containing the oily dispersion of the present invention have greatly improved organoleptic values such as smoothness during use, adhesion to the skin, elongation on the skin and finished feeling. did. In addition, in order to compound a dispersion into a dosage form having a high powder loading ratio such as a powder foundation or a powder eye shadow, the oily agent becomes excessive due to an excessive amount of the oily agent if the powder content is not high, or the dosage form cannot be formed. However, the amount of the other oil agent components is limited. Since the hybrid dispersion can increase the content of the powder compared to the conventional dispersion, it has high versatility for prescription and excellent usability.

Example 20 and Comparative Example 21 (Production of UV emulsion) A UV emulsion having the composition shown in Table 6 was produced by the following method. The numerical values represent parts by weight.

[0167]

[Table 6] * 1: Formulated in Example 20 * 2: Formulated in Comparative Example 21

(Preparation method) The component (7) was added to an oil phase obtained by mixing and dissolving the components (1) to (8) at 75 ° C., and the mixture was uniformly dispersed with a homodisper. The aqueous phase obtained by uniformly mixing and dissolving the components (9) to (13) at 75 ° C. was gradually added to the oil phase, and after uniform dispersion with a homomixer, and emulsified particles were adjusted, the component (14) was added and the emulsion was added. Manufactured.

[Example 21 and Comparative Example 22] (Production of sunscreen UV cream) A sunscreen cream having the composition shown in Table 7 was produced by the following method. The numerical values represent parts by weight.

[0170]

[Table 7] * 1: Formulated in Example 21 * 2: Formulated in Comparative Example 22

(Preparation method) The oil phase components (1) to (9) were uniformly dispersed and dissolved at 75 ° C. The aqueous phase components (10) to (14) are dissolved at 75 ° C., and the homogenized one is added to the oil phase component, emulsified with a homomixer, and the component (15) is added thereto, followed by cooling and sunscreen cream. Was manufactured.

Example 22 and Comparative Example 23 (Sunscreen U of Example 1 of JP-A-12-26262)
Production of V Cream) A sunscreen having the composition shown in Table 8 was produced by the following method. The numerical values represent parts by weight.

[0173]

[Table 8] * 1: Formulated in Example 22 * 2: Formulated in Comparative Example 23 * 3: Merck KGaA, Darmstadt * 4: Th. Goldshmidt, Essen * 5: Henkel KGaA, Dusseldorf * 6: Unichema, Emmerich * 7: Fuller, Luneburg * 8: Merck KGaA, Darmstadt.

(Production method) The oil phase components (1) to (9) were uniformly dispersed and dissolved at 75 ° C. The aqueous phase components (10) to (13) were dissolved at 75 ° C., and the resulting mixture was added to the oil phase component and emulsified with a homomixer to produce a sunscreen.

Example 23 and Comparative Example 24 (Production of Sunscreen UV Lotion) A lotion having the composition shown in Table 9 was produced by the following method. The numerical values represent parts by weight.

[0176]

[Table 9] * 1: Formulated in Example 23 * 2: Formulated in Comparative Example 24 (Production method) The above components (1) to (8) were mixed and dissolved at 70 ° C.
The aqueous phase obtained by uniformly mixing and dissolving the components (9) to (13) at 70 ° C. was gradually added to the oil phase, and after uniform dispersion with a homomixer, the emulsified particles were prepared. A lotion was manufactured. The viscosity immediately after the production was 150 ± 50 mPa · s in each of the lotions of Examples and Comparative Examples. This lotion formulation contains 25 wt% of dispersion, and the concentration of surface-treated fine particle titanium oxide is 13.75 wt%.
It is. In order to obtain an even higher SPF value and increase the concentration of fine particle titanium oxide, it is possible to increase the amount of the hybrid dispersion, but the conventional dispersion contains polyether-modified silicone as a dispersion stabilizer. As the amount of the dispersion increases, the amount of the polyether-modified silicone also increases, so that the formulation is broken and the amount cannot be increased. This indicates that the hybrid dispersion is excellent in versatility for prescription.

Examples 20 to 23 of the present invention and Comparative Example 21
The in-vitro PA value, the in-vitro SPF value (SPF analyzer), and the transmittance of the visible part were evaluated for Examples 23 and 24. The storage stability over time (−10 ° C. to 50 ° C./2) was obtained for Example 23 and Comparative Example 24. (One month for each day). Table 10 shows the results.

(Measurement of in-vitro PA value and in-vitro SPF value) Transpore surgical tape (3M Health Care
USA) was stuck on a quartz plate (100 × 100 × 3 mm: vertical / horizontal Takasaka), applied to a 4.5 × 4.5 cm area with a sponge under the condition of ² mg / cm ² , and allowed to stand for 15 minutes. Twelve spots were measured on the coated surface with an SPF analyzer, and an average value was obtained. (Measurement of Visible Part Transmittance) The sample coated surface prepared with the above PA and SPF was measured with a spectrophotometer equipped with an integrating sphere (“UV-3100PC: attached to LISR-3100” manufactured by Shimadzu Corporation) to a transmittance of 560 nm. The spot was measured and the average was determined.

[0179]

[Table 10]

As is clear from Table 10, the cosmetics containing the oily dispersion of the present invention are excellent in affinity and dispersibility for the oily agent, so that the visible portion of the fine titanium oxide and the fine zinc oxide is transparent. Properties and ultraviolet shielding ability can be greatly improved. Further, the cosmetic obtained in this manner is excellent in stability over time. Example 22 and Comparative Example 23
From the results of the above, it was found that the dispersion of the liquid ultraviolet absorber and the inorganic ultraviolet shielding powder showed that even when the dispersion was blended into the formulation, the blend containing the hybrid dispersion was more transparent than the conventional one and the transparency of the visible part was higher than that of the conventional one. It turns out that it is overwhelmingly superior in Noh.

Example 24 and Comparative Example 25 (Production of Hair Cream) A hair cream having the composition shown in Table 11 was produced by the following method. The numerical values represent parts by weight.

[0182]

[Table 11] * 1: Formulated in Example 24 * 2: Formulated in Comparative Example 25 (Production method) The above components (1) to (9) were mixed and dissolved at 80 ° C.
The components (10) to (13) were uniformly mixed and dissolved at 80 ° C., and the oil phase was gradually added. After uniform dispersion with a homomixer, the emulsified particles were adjusted and cooled to produce a hair cream.

The hair creams obtained in Example 24 and Comparative Example 25 were subjected to a sensory test by 20 panelists regarding absence of stiffness, flexibility and luster. The sensory test was performed in a five-point scale. Table 12 shows the results.

(Evaluation criteria for sensory evaluation) 5: Very good; 4: Good; 3: Normal; 2: Slightly bad 1: Bad.

[0185]

[Table 12] As is clear from Table 12, the hair cream containing the hybrid dispersion of the present invention has a super-dispersed powder so that the powder has functions such as touch and luster and has no stiffness. In addition, the sensory evaluation of flexibility and glossiness is superior to that in which a conventional dispersion is blended.

Example 25 and Comparative Example 26 (Production of Nail Enamel) Nail enamel having the composition shown in Table 13 was produced by the following method. The numerical values represent parts by weight.

[0187]

[Table 13] * 1: Formulated in Example 25 * 2: Formulated in Comparative Example 26 (Preparation method) The above components (5) to (9) were mixed, and components (1) to (4) were added and uniformly dissolved. Further, components (10) to (12) were added and dispersed to prepare a nail enamel.

The nail enamels obtained in Example 25 and Comparative Example 26 of the present invention were evaluated for gloss, chroma, and dispersion stability over time. Table 14 shows the results.

(Glossy) The sample was hung in the form of a glass plate, and a coating film having a thickness of 300 μm was prepared with a doctor blade. For this coating film, a gloss meter (“VGS-3” manufactured by Nippon Denshoku Industries Co., Ltd.)
00A ") and measured the gloss value at 60 ° -60 °. (Saturation) The gloss was measured by measuring the gloss with a spectral color difference meter (“SZ- # 90” manufactured by Nippon Denshoku Industries Co., Ltd.). (Dispersion Stability) The sample was stored for one month at a cycle of −10 ° C. to 50 ° C. for 48 hours and observed for sedimentation and color separation.

[0190]

[Table 14]

As is clear from Table 14, the nail enamel blended with the oil-based dispersion of the present invention is excellent in the dispersibility of the powder, so that the functions of the powder, such as chroma and gloss, can be maximized. it can. Further, the dispersion stability over time is excellent.

[0192]

As described above in detail, according to the present invention, an oily dispersion which can disperse a powder at a high concentration and a high concentration and has a high dispersion stability can be obtained. In particular, the coated powder used in the present invention is excellent in dispersibility in a lipophilic solvent due to the coating layer including at least the A and B2 layers, so that a high dispersion can be obtained. For this reason, this oil-based dispersion is a function of the powder base material that greatly changes depending on the dispersion state of the powder particles,
For example, the adhesion to the skin, the feel (feel of use; slipperiness), the hiding power, the coloring power, the ability to block ultraviolet and infrared rays, the optical properties, and the like can be dramatically improved as compared with conventional coated powders. . In addition, the cosmetics of the present invention in which an oily dispersion having the superdispersion stability of these powders is blended contain such excellent powders as cosmetics, and thus have extremely excellent usability and stability over time. ing.

In the coated powder used in the oil-based dispersion of the present invention, if the powder (substrate) or the like usable for cosmetics is used, the powder (substrate) used for other than cosmetics is used. Similarly, the excellent effect (high dispersion of powder) obtained by the present invention can be obtained, so that the coated powder used in the present invention can also be suitably applied to fields other than cosmetics, and It can be a dispersion.

──────────────────────────────────────────────────続 き Continued on the front page (51) Int.Cl. ⁷ Identification symbol FI Theme coat ゛ (Reference) A61K 7/00 A61K 7/00 EB 7/02 7/02 PC09C 3/08 C09C 3/08 3 / 10 3/10 3/12 3/12 F term (reference) 4C083 AA122 AB052 AB172 AB212 AB232 AB242 AB332 AB432 AB442 AC022 AC032 AC102 AC122 AC132 AC172 AC241 AC262 AC342 AC352 AC392 AC441 AC442 AC482 AC581 AC582 AC661 AC662 AC851 AC852 AC911 AC912 AD021 AD022 AD072 AD092 AD151 AD152 AD161 AD162 AD172 AD222 AD262 AD412 AD572 BB13 BB25 BB46 CC05 CC12 CC14 CC19 CC28 CC33 DD17 DD23 DD31 EE01 EE05 4J037 AA02 AA04 AA08 AA10 AA11 AA12 AA15 AA16 AA17 AA19 AA22 EECB CB CB CB CB EE43 FF15

Claims (10)

[Claims] 1. A coating powder having a surface treatment agent coating layer of the following A layer and B layer formed on at least a part of the surface of powder particles, and at least a lipophilic solvent as a dispersion medium thereof. An oily dispersion of a powder characterized by the following: Layer A: reactive organopolysiloxane, alkylsilane, polyolefin, hydrogenated lecithin (including those in the form of a salt), N-acylamino acid (in the form of a salt) ), Fatty acids (including those in the form of salts)
And a layer of a surface treatment agent which is solid at room temperature and contains a compound selected from dextrin fatty acid esters; and B layer: one-terminal functional group-modified organopolysiloxane, alkylsilane, perfluoroalkylsilane and branched fatty acid (salt And a liquid at room temperature containing a compound selected from the group consisting of: 2. The dispersion according to claim 1, wherein the powder is a powder usable for cosmetics. 3. The dispersion according to claim 1, wherein the coated powder is a powder coated on at least a part of the surface of the powder particles with a layer A, and further coated with a layer B thereon. 4. The organopolysiloxane modified with a functional group at one end used in the layer B is linear and has a degree of polymerization of 10 to 100. The alkylsilane has an alkyl group having 6 to 30 carbon atoms. The dispersion according to claim 1, which comprises a coated powder in which the alkylsilane has 1 to 30 fluorocarbons and the branched fatty acid has 8 to 22 carbon atoms. 5. The dispersion according to claim 1, wherein the A layer and the B layer in the coated powder have a relation of A ≦ B in weight comparison. 6. The coated powder, wherein the weight ratio of the A layer to the powder to be coated is 100: 0.1 to 10;
The weight ratio of the layers is from 100 to 0.1 to 30.
The dispersion according to any one of the above. 7. The dispersion according to claim 1, wherein the coated powder is a coated powder treated by a jet method. 8. A cosmetic comprising the dispersion according to any one of claims 1 to 7. 9. The cosmetic according to claim 8, wherein the dispersion is incorporated in an amount of 1 to 99% by weight. 10. A powder which can be used in cosmetics, and a surface treatment agent coating layer of the following A layer and B layer formed on at least a part of the surface of the powder particles. Coated powder, A layer: room temperature solid surface treatment agent coating layer containing alkylsilane; and B layer: one-terminal functional group-modified organopolysiloxane, alkylsilane, perfluoroalkylsilane and branched fatty acid (in the form of salt) Layer containing a compound selected from the group consisting of: a) a reactive surface-active agent coating layer containing a compound selected from the group consisting of: a reactive organopolysiloxane, an alkylsilane, a polyolefin, and hydrogenated lecithin (in the form of a salt); Certain), N-acylamino acids (including those in the form of salts), fatty acids (including those in the form of salts)
And a layer of a surface treatment agent which is solid at room temperature and contains a compound selected from dextrin fatty acid esters; and a layer B: a layer of surface treatment agent which is liquid at room temperature and contains perfluoroalkylsilane.