JPH01157908A - Cosmetic - Google Patents

Abstract

PURPOSE:To obtain a cosmetic, having a high pigment filling rate and readily regulating color tone without any sense of incompatibility with the skin, by using a composite pigment having a colored layer on the surface of a core consisting of an inorganic compound, specific average particle diameter and particle dispersibility. CONSTITUTION:A cosmetic obtained by mixing an oily base with a composite pigment consisting of a two-layer structure of a core part consisting of particles having 1.0-50.0mum, preferably 2.0-15.0mum average particle diameter (X) and >=80%, preferably >=90% particle dispersibility [ratio (%) of the particles having a particle volume included within the range of pi/6(X+ or -0.5X)<8> based on the total particles] and a colored layer present on the surface of a core part consisting of a dye or a mixture thereof with an inorganic compound or further a three- layer structure of a fixed coating layer consisting of a mixture of a dye and an inorganic compound with a lower dye content than that in the colored layer or the inorganic compound without containing the dye provided on the colored layer.

Description

[Detailed description of the invention] [Industrial application field] The present invention provides a novel cosmetic.

In the present invention, the average particle diameter (X) refers to the value obtained by observing the composite pigment with a transmission electron microscope, measuring the diameter of the particles in the longitudinal direction, and calculating the average diameter. Furthermore, in the present invention, particle dispersibility refers to a particle volume of π/6(X
It refers to the content (%) of particles included in the range of ±O, S

[Prior art and problems to be solved by the invention] Conventionally, cosmetics such as foundations have been used.

Eye shadow makeup cosmetics contain inorganic pigments, organic pigments, and dyes as coloring agents. Typical inorganic pigments include titanium dioxide, iron hydroxide, and Bengara.

Yellow iron oxide 1 ultramarine, iron black, organic pigments Herrington pink CN, phosphorus rubin B.

Examples include Zuriri 7 Ntopuru~, Phthalocyanine Blue, etc. However, these colorants are amorphous fine particles that tend to aggregate, which is a major factor in deteriorating the feel of makeup cosmetics when they are incorporated into them.

Furthermore, by combining and mixing these pigments, desired colors (mainly skin colors) are realized. However, since these pigments have different properties, it is difficult to say that desired colors can be obtained. For example, when looking at the refractive index, titanium dioxide is 2.5-2.9 degrees, iron oxides 2.8-3. In contrast to OK, iron hydroxide is around 2.0,
This is very low compared to the first two. Furthermore, iron hydroxide is a hydrated substance, has high hydrophilicity, and has different dispersion behavior. These are the reasons why when these pigments are actually mixed and applied to the skin, they do not provide a sufficient skin color.

In other words, when mixing pigments to adjust the color, if they are mixed sufficiently, it is usually recognized as a single color, but when pigments with significantly different hues and lightness are mixed, it becomes impossible to tell that it is a mixture at all. That's difficult.

Therefore, to date, pigments that have a uniform shape, feel good when applied to the skin, have uniform properties such as refractive index and hydrophilicity, and can adjust color tone have not yet been provided. Not yet.

The present inventors have conducted extensive research on a method for producing fine particles that are uniformly colored and have good particle dispersibility. As a result, at least a portion of the dye and the raw material hydrolyzed compound (hereinafter simply referred to as the hydrolyzed compound) that is subjected to hydrolysis and becomes an inorganic compound is dissolved, but the reaction product is not dissolved. or K in an alkaline water-containing solvent.
, the average particle diameter is 1.0 to 50.0 by adding a compound to be hydrolyzed and a dye dropwise to the solvent in the presence of an inorganic compound in the form of fine particles that do not dissolve in the solvent, and dropping the dye into the solvent.
Particles with a particle dispersibility of 80% or more and a two-layer structure consisting of a core and a colored layer on the surface of the core, the core being made of an inorganic compound and the colored layer containing a dye and an inorganic compound. It has now been found that pigments formed in mixtures with compounds can be obtained.

Based on this knowledge, we continued our research and found that a cosmetic containing the above-mentioned pigment, which has a uniform particle size, no agglomeration, uniform properties, and can freely change the color tone, solved the above-mentioned problems. This discovery led to the completion of the present invention.

That is, in the present invention, the average particle diameter is 1.0 to 50.0 μm.
and has a particle dispersibility of 80% or more, and has a two-layer structure with a core made of an inorganic compound and a colored layer existing on the surface of the core made of a dye or a mixture of a dye and an inorganic compound, or the color of the core and the core layer. and a fixed coating layer that covers the colored layer and is formed of a mixture of a dye and an inorganic compound that has a lower dye content than the colored layer or an inorganic compound that does not contain a dye.
This cosmetic is made by mixing a composite pigment with a layered structure with an oil base.

The present invention will be explained in detail below.

The composite pigment used in the present invention has an average particle size (X) of 1.0 to 50.0 μm, preferably 2.0 to 15.0 μm.
It is necessary to be within the range of m.

The above average particle diameter (X) is as defined above (the composite pigment is observed with a transmission electron microscope, the longitudinal diameter of the particles is measured, and the average diameter is calculated. In the examples described later) took out 200 composite pigments at random, observed them with a transmission electron microscope, measured the diameter of the particles in the longitudinal direction, calculated the average, and expressed it as the average particle diameter (X).

If the average particle diameter α) of the composite pigment used in the present invention is smaller than the above range, that is, smaller than 1.0 μm, a large amount of particles will be required during compounding, which is not economical, and the dye layer will become smaller, resulting in poor color tone. This is not preferable because adjustment becomes difficult, and if the average particle diameter (X) is larger than 50 μm, a strange feeling occurs during blending, and the composite pigment itself tends to aggregate, which is not preferable.

Furthermore, the composite pigment used in the present invention has a particle dispersibility of 80
% or more, preferably 90% or more.

As defined above, the particle dispersibility is defined as particle volume yr/
6 ()l: 0.5X)817) 1i [Content ratio (%) of K-containing male particles to all particles. The particle dispersibility factor is the most important requirement for the feel of cosmetics containing the composite pigment. The particle dispersibility is 80%
If it becomes smaller, the agglomeration of the composite pigment progresses and the dispersibility becomes poor, causing a sense of discomfort when applied to human skin. The better the particle dispersibility is as a composite pigment to be incorporated into cosmetics, the more preferable it is, and the more preferably 90% or more.

In addition, the particle dispersibility leads to improved light loading and dispersibility when blended into cosmetics.

In addition, the particle volume formula (% formula %) that indicates particle dispersibility is the content ratio (%) of particles in the range of all particles.
It is even better if the composite pigment is 80% or more, preferably 90% or more.

The particle dispersibility of the present invention may be measured by any method, but generally it can be easily measured by using a device that measures the same volume, such as model ZD-1 manufactured by Coal Tar Counter.

The composite pigment used in the present invention is not particularly limited in other shapes as long as it has the above-mentioned shape characteristics, and may be a granular body existing in the form of a polyhedron, 1 column, 1 cone, 2 spheres, etc. . In particular, spherical particles, especially pearl-shaped particles, are suitable because they have excellent particle dispersibility.

The composite pigment used in the present invention preferably has the following five structural characteristics in addition to the above-mentioned shape characteristics.

In other words, it is a particle that has a multilayer structure of two or more layers consisting of a core, a colored layer on the surface of the core, and a fixed coating layer that further covers the colored layer as necessary, and the core has a The colored layer is formed of an inorganic compound, the colored layer is formed of a dye or a mixture of a dye and an inorganic compound, and the fixed coating layer is a mixture of a dye and an inorganic compound containing less dye than the colored layer, or an inorganic compound containing no dye. It is formed of.

The core part has an average particle diameter of 1 of the composite pigment used in the present invention.
．． Since there is a restriction of 0 to 50.0 μm, it is obvious that the particles are smaller than the particle size, and the general K O, 4 to 50.0 μm.
The particle size is 45.0 μm, preferably 1.0 to 10.0 μm. In addition, it is preferable that the core itself has good dispersibility. Further, the material for the core of the composite pigment used in the present invention is not particularly limited, and any known inorganic compound can be used. Specific examples of inorganic compounds that are particularly preferably used include aluminum, silicon, titanium, zirconium, hafnium, tin, lead, iron, and fuvardium.

Oxides of metals in Group 1, Group II, or Group 1 of the periodic table such as nickel, or boron or silicon.

These include oxides of metalloids belonging to Group 1 or Group II of the periodic table, such as germanium. Moreover, as the above-mentioned inorganic compound, the following complex oxides are also suitably used. That is, Group 1 of the periodic table mentioned above.

These are composite oxides between mutual metals of Group 1 or Group 1, or composite oxides of the above metals and metals of Group 1, Group 2, or Group V of the periodic table.

Metals K of Groups 1, 2 and V of the Periodic Table are generally lithium, although not particularly limited.

Sodium, potassium, magnesium, calcium, stone beef, basum, phosphorus.

antimony, bismuth, vanadium, niobium.

Tantalum and the like are preferred. In general, the main component of the above composite oxide is preferably a metal component of Group 1, Group Ⅰ, or Group 1 of the periodic table, and contains 80 mol% or more of these metals. is particularly preferred.

Further, as the inorganic compound constituting the core, carbonates such as calcium carbonate and magnesium carbonate, and sulfates such as barium sulfate and strontium sulfate can also be used. In the composite pigment, the most preferably used inorganic compound forming the core is silica, alumina, titania, zirconia, or a composite oxide containing these as main constituents. These modified metals, semimetal oxides, or composite oxides are known compounds, and the method for producing them is not particularly limited. Typical methods for producing these compounds are described in, for example, the Journal of Colloids and Interfaces Science.
oid and 1nta-rface 5ci
ence) 26.62-69 (1968), % Kaisho 52
-138094, British Patent No. 2.115.799
It may be carried out by the means described in the publication, etc. or in accordance with this method. Further, a representative example of the above-mentioned composite oxide is a group consisting of silica and Groups 1, 1, 1 and It is at least one kind of composite metal oxide selected from the above, and generally contains 80 mol% or more of the silica.

The colored layer on the surface of the core part constituting the composite pigment used in the present invention is formed of a dye or a mixture of a dye and an inorganic compound.

This structure is the most novel and important feature of the composite pigment.

That is, the color tone and coloring depend on the dye, and the chemical or physical properties of the composite pigment depend on the core or the fixed layer described below. This results in a composite pigment whose color tone can be freely changed and whose properties are uniform.

In addition to dyes, there are also metal oxides that have coloring properties, such as cobalt oxide, but uniform coloring cannot be expected due to the effects of humidity, ion concentration, oxidation conditions, etc. First, it cannot be used as a substitute for the above-mentioned dyes.

The second reason is that dyes are various functional materials and can impart functionality as required, such as electrical conductivity, photovoltaic properties, and photochromic properties, to composite pigments. The use of other dyes has the advantage of allowing a wide variety of color tones and degrees of coloring to be selected, and also has the advantage of imparting these properties with a low content. Therefore, it is an extremely important factor that a dye is mixed as a component of the colored layer.

The above dyes can be used alone, but it is also possible to use a mixture of two or more. The use of a mixture of these dyes allows a wider range of color tones to be produced and is therefore often a preferred embodiment.

The dye as a component of the colored layer is not particularly limited,
The dye may be selected from known dyes as necessary. −
For boat fishing, cationic dyes are most effective, followed by metallized dyes, and then reactive dyes and fluorescent whitening dyes. Further, disperse dyes, direct dyes, acid dyes, acid mordant dyes, and other dyes can also be used satisfactorily, although they may be somewhat inferior to the above-mentioned dyes depending on the purpose. More specific examples of typical dyes that are particularly preferably used are as follows.

Cationic dyes include malachite green, rhodamine B, methylene blue, auramine, magenta, bismarck brown, methyl violet, and crystal violet.

Diacrylic (registered trademark of Mitsubishi Kasei ■), Sumiacryl (registered trademark of Sumitomo Chemical ■), and Eisencation (registered trademark of Hodogaya Chemical ■) are examples of disperse dyes.
Diakoton (registered trademark of Mitsubishi Kasei Corporation), Deismizol (registered trademark of ICI Corporation), Miketone Polyester (registered trademark of Mitsui Toatsu Chemical Corporation), Resoline (registered trademark of Mitsui Toatsu Chemical Corporation)
(registered trademark of Bayer AG), Sumikalon (registered trademark of Sumitomo Chemical ■).

Examples include Terrasil (registered trademark of Ciba Geigy). In addition, direct dyes include Fungo Red, Direct Deep Black EV, Chrysofenine G, Penzamine (registered trademark of Bayer AG), Cupurphenyl (
(registered trademark of Ciba Geigy), Japanol, Sumilite (registered trademark of Sumitomo Chemical ■).

Diakoton (registered trademark of Mitsubishi Kasei).

Examples include Risofix (registered trademark of Sandoz),
Examples of acidic dyes include Alizarin Safi μm Le B, Alizarin Direct Blue A, Alizarin Cyanine Green G, Carborane Green G, and Diazid (Mitsubishi Kasei ■
(registered trademark), Calporan (registered trademark of ICI Corporation), Amide, Anthra, Andolan (registered trademark of Hoechst Corporation), and Suminol (registered trademark of Suminen Kasei Corporation).

In addition, acidic mordant dyes include Diamond Grac F, Chrome F7 Stone Bee Blue B, Palatin 7 Asto Blue BN, Anthracene (registered trademark of Sandoz Co., Ltd.), Mitsui (registered trademark of Mitsui Toatsu Chemicals), Solochrome (I.C. Examples of metal-containing dyes include Acitol (registered trademark of BASF) and Eisenoval (registered trademark of BASF).
Hodogaya Chemical (registered trademark), Oleosole (registered trademark of Nichi Kagaku), Lanafast (registered trademark of Mitsui Toatsu Chemical), Lanil, Sumilan (registered trademark of Jumin Chemical), Inlan (registered trademark of Bayer) Examples of reactive dyes include Selmazole (registered trademark of Mitsui Toatsu Chemical Co., Ltd.)
.

Diamira, Mikacilon (registered trademark of Mitsubishi Kasei ■), Sumifix (registered trademark of Sumitomo Chemical ■), Revafix (registered trademark of Bayer AG), Remazol (registered trademark of Hoechst AG), etc. are fluorescent whitening dyes. , Mika White (registered trademark of Mitsubishi Kasei ■), White Tex (registered trademark of Sumitomo Chemical IV), etc.

The colored layer of the composite pigment used in the present invention may be formed of only a dye, or may be formed of a mixture of a dye and an inorganic compound. The inorganic compound may be the same as the component of the core without particular limitation, and can be used. Embodiments in which the inorganic compounds are used in mixtures with dyes are often preferred. The reasons for this are, for example, to prevent the color development of the dye from deteriorating due to ultraviolet rays and to improve storage performance, and to maintain a high concentration of the dye to make it easier to handle. Therefore, when forming the colored layer as a mixture of the dye and the inorganic compound, it is preferable that the two components are not easily separated by chemical or physical means, and if possible, they are preferably chemically bonded.

The mixture having such properties is preferably determined in advance, since it varies depending on the method for producing the composite pigment, the type of raw materials used for the production, and the like. The composition ratio of the dye and the inorganic compound in the colored layer of the present invention varies depending on the purpose of use and cannot be unconditionally limited, but generally the dye is present in the composite pigment in an amount of 0.01 to 30'i%, preferably It is preferable to select the content in the range of 0.1 to 5% by weight.

The composite pigment of the present invention is a particle consisting of at least a two-layer structure of a core and a colored layer, as described above, but the thickness of the core and the colored layer is not particularly limited, and the properties can be adjusted depending on the purpose of use. You can decide based on this. Generally, it is suitable to select the core so that it has a diameter of 115 to 415, preferably 115 to 215, of the diameter of the composite extract.

The composite pigment used in the present invention may have a two-layer structure of a core and a colored layer on the surface of the core as described above, and if necessary, a fixed coating layer may be further provided on the colored layer. It is also suitable to have a layered structure or a multilayered structure.

In the case of a multilayer structure of three or more layers, the outermost layer is preferably composed of an inorganic compound containing no dye as much as possible for the purpose of stable storage of color development of the dye, ease of handling, etc.

However, this does not mean that the layer containing dye is excluded from the outermost layer; in general, the outermost layer contains up to about 20% by weight of dye, compared to the dye contained in the colored layer on the surface of the core. If the content is high, there are few disadvantageous factors.

In addition, in the case of a multilayer structure of three or more layers, the thickness of the third layer or more is not particularly limited (it may be determined as appropriate depending on the purpose of use, but it is generally 21 mm thick of the diameter of the composite pigment).
A range of 5 to 1/10, preferably 215 to 115 is suitable.

The composite pigment used in the present invention is a novel particle as explained above. In particular, a dye that is an organic compound or a mixture of a dye and an inorganic compound grows thickly in the core of the inorganic compound.
It is a surprising phenomenon that the particles exist in the form of particles with a particle dispersibility of 80% or more.

The method for producing the above-mentioned composite pigment is not particularly limited, but representative examples are as follows.

In the method for producing the above-mentioned composite pigment, a solvent is used that dissolves the raw material dye and the compound to be hydrolyzed, but does not dissolve it during hydrolysis. The solvent may have the above properties determined in advance depending on the type of dye or compound to be hydrolyzed. However, these raw materials do not need to be completely dissolved, and can be used as long as they partially dissolve. Specifically speaking, solvents that are usually preferably employed include methanol, ethanol, isobutanol, butanol, inamyl alcohol, ethylene glycol, Alcohol solvents such as propylene glycol are preferably used. Further, organic solvents such as ether solvents such as dioxane and diethyl ether, and ester solvents such as ethyl acetate may be used by partially mixing them with the above alcohol solvent.

The solvent must contain water because the compound to be hydrolyzed needs to be hydrolyzed as described below. The content of water varies depending on the type of compound to be hydrolyzed, the alkalinity of the solvent, etc., and cannot be limited to a certain amount. Generally, it is preferable to select from the range of 0.05 to 5%. Some of the above-mentioned specific solvents, such as alcohol, generally contain water within the above range, and there is no need to particularly control the water content of such solvents.

Further, the above-mentioned solvent is generally used in a neutral or alkaline state. If the solvent is acidic, the particle dispersibility of the composite pigment obtained by hydrolysis is extremely low, and in most cases it becomes a gel-like powder, making it impossible to obtain the desired particles, which is not preferable. Any method may be used to make the solvent alkaline, but generally it is a method of adding aqueous ammonia or an alkali hydroxide such as sodium hydroxide, potassium hydroxide, lithium hydroxide, or a combination of these compounds. suitable. The amount of these compounds to be added is not particularly limited and may be determined as appropriate, but generally when using 7-ammonium 7-water, the 7-ammonia concentration is in the range of 5 to 30% by weight, preferably io to 25% by weight. It is preferable to select such a value. Further, when aqueous ammonia and alkali hydroxide are used in combination, the size of the particles obtained can be controlled by the amount of alkali hydroxide added, so it is often used as a preferred embodiment. For example, the ammonia water used has an alkali hydroxide concentration in the range of 0.05 to 0.15% by weight, and as the alkali hydroxide concentration increases, the resulting particle size tends to increase.

In the method for producing specific composite particles, in the water-containing solvent,
It is preferable that an inorganic compound serving as a core that does not dissolve in the solvent is present, and the compound to be hydrolyzed and the dye are added dropwise to the solvent to perform a hydrolysis reaction.

The inorganic compounds described above can be used as the core, but generally the compound to be hydrolyzed, which will be described later, is previously hydrolyzed in a solvent to precipitate compounds that do not dissolve in the solvent, and the precipitate is added to the core. A method is also suitably adopted. The concentration of cores present in the solvent is not particularly limited and may be determined in advance as necessary, but it is generally preferred to select it from the range of 0.1 to 10% by weight.

The dye and the compound to be hydrolyzed are dropped into the solvent in which the core is present. Therefore, it is preferable to use the dye by dissolving it in a solvent in advance or by dissolving it in a solution of a metal to be hydrolyzed. Similarly, it is preferable to use the compound to be hydrolyzed in the form of a solution. Of course, it is also possible to dissolve the dye and the compound to be hydrolyzed in the same solvent and drop them simultaneously into the water-containing solvent, or to drop them separately into the water-containing solvent from separate dropping devices, as necessary.

In addition, the concentration of the solution in which the raw materials are dissolved is generally preferably low, but if it is too low, the amount of solvent used will increase significantly, and if the concentration is too high, it will be difficult to control the reaction and it will be inconvenient to handle. Therefore, it is advisable to take these into account and decide accordingly. Generally, it is most preferable to use the raw material concentration at 60% by weight or less, preferably in the range of 5 to 50% by weight.

Furthermore, since the dropping rate of the dye and the compound to be hydrolyzed affects the particle size and particle dispersibility of the resulting composite particles, it is preferable to determine the dropping rate in advance depending on other conditions.

Generally, it is advisable to drip 0.5 to 10% by weight of the water-containing solvent, preferably 0.5 to 2% by weight, with the lid on for one hour. For example, if the water-containing solvent 2 is used, the raw material may be heated at a rate of 10 to 200 ν/hour.

The compound to be hydrolysed used as the raw material is not particularly limited and may be used as long as a portion thereof, for example 103 or more, can be dissolved in a solvent and hydrolyzed. The compound to be hydrolyzed that is generally preferably used is the metal alkoxide described as the component constituting the core.

That is, a fulfside compound represented by the general formula M (OR) x (where 1M represents a metal or metalloid, and X represents the valence of M) is preferred. In the general formula, R is an alkyl group, generally a methyl group, an ethyl group, or an inpropyl group.

Lower furkyl groups such as butyl groups are preferably used. In addition, some of the metal alphoxides mentioned above can form a colored layer of metal oxide by themselves through hydrolysis, but they cannot form the colored layer unless they form a composite oxide with other metal components. There is also. Since these distinctions can be easily determined by hydrolysis in advance, it is preferable to determine them in advance during implementation. Generally, there is a tendency similar to that described for the inorganic compound constituting the core. That is, in general, oxides of metals from Groups 1, 2, or 1 of the periodic table can form the above-mentioned colored layer alone, but oxides of metals from groups 1, 2, or V of the periodic table can form the colored layer alone. It is preferable that the metal is used as a composite oxide with a metal of Group Ⅰ, Group Ⅰ or Group 1 of the periodic table.Furthermore, in the above general formula, M represents the above-mentioned properties. Although it can be used without any particular limitation, the following are examples of those that are generally preferably used.

That is, generally the general formula M (OR).

M"(OR1), ,Mg(OR1), ,M'(OR")
,.

M5(OR1),, Mg(OR”),, (However,
R1 is preferably a metal alkoxide represented by a furkyl group) or a compound in which one or two furkoxyl groups (OR) in the above general formula are substituted with a carboxyl group. Here, Ml is a metal of Group 1. 9M is a metal of Group 1.

M3 is a metal of Group 1; y4 is a metal of Group II.

M5 is a Group V metal. Mg is a Group 1 metal, specifically, for example, lithium or sodium.

Potassium, magnesium, calcium, strontium, barium, aluminum, titanium, silicon, zirconium. germanium, hafnium, tin, lead, phosphorus,
vanadium.

Niobium, tantalum, iron, cobalt, nickel, etc. are preferably used. Specific examples of the above-mentioned compounds that are generally preferably used include Na0CH,, Na0C,H,, Na
Sodium alkoxide such as 0C8H, and the above Na
Group II metal alkoxide substituted with Li, K, etc.; Mg(OCHa)*9Mg(
OCtHs)z.

Mg(OC,H,), ,Mg(OC,H,),.

Magnesium alkoxides such as Mg (QC, H, ), and Group 1 alkoxides in which Cm, Sr, Ba, etc. are substituted for the above Mg K; AtCOC, H, >
81 At(QC,H,)8tAt(QC,H,)a, etc.+7) Aluminum alfoxide and Group 1 metal flufoxide in which B or the like is substituted for the above At.

Ti (O1aocsH7)4.

Ti(O-nC4H9)4.

Ti (0-CI(,CI((C,H,)C,)I,)
,.

T I (0-01,H,,') 4゜Tt (o-i
110c8H? )z *[0CH(CH)CHCO
CH, ),.

Ti(0-nC,H,), (QC,H,N(C,H,O
H), ), ITi (OI(), (OCH(CH8)C
OOH),.

Ti(OCRCH(CH)CH(OH)C,H,).

Titanium alkoxides such as Ti(0-nC,H,), (OCOC,,H3,), and Si, Z in place of the above Ti.
Alkoxides of group II metals substituted with r, Ge, Hf, Sn, Pb, etc.; v(ocH), V(Oi s oC8H?
) 4 *S! 14 V (0-n C4H9) 4- V (Ot@r
Vanadium alkoxides such as t C4H1+ ) 4 and group V metal alkoxides in which Nb, Ta, P, Sb, Bi, etc. are substituted for the above V; Fe (oc,) (, ) B , F (1 (onc@H
1) B +F @ (On C4Hg) @ * F
e (0-aeec4Hg) 6 *Fe(0-ter
These include iron flukoxides such as tC4H, ), and alkoxides of group Ⅰ metals in which Co, Ni, etc. are substituted for the above-mentioned Fe. Also, CaCZs.

Compounds such as Ca(HOC6H,C00), -2H, and O can also be used by mixing with the above-mentioned metal alkoxides.

As explained above, it is not necessary to use only one type of compound to be hydrolyzed, and it is often a preferable embodiment to use two or more types at the same time. For example, as described in the example of British Patent No. 2,115.977, a low condensate of alkoxysilane and an alkoxide of another metal are mixed in advance to prepare a mixed solution, and this mixed solution is used as a raw material. It can also be used as

Some of the dyes used as other raw materials for the composite pigment are, for example, solvent 100
Any material can be used without particular limitation as long as it dissolves 1 part by weight or more, preferably 5 parts by weight or more, more preferably 10 parts by weight or more. Generally, the various dyes described as constituent components of the colored layer can be suitably used. The dye is preferably used in a concentration of KO, 001 to 1% by weight. Furthermore, trap always KO in solvent, 05~0.5
It may be chosen such that % by weight of dye is present, preferably from 0.05 to 0.2 % by weight.

The raw material immediately undergoes a hydrolysis reaction in the solvent and becomes a particulate insoluble precipitate. The conditions for the hydrolysis are not particularly limited and any conditions may be selected, but it is generally suitable to carry out the hydrolysis at a temperature in the range of 5 to 50°C, preferably 10 to 30°C, with or without stirring.

The composite particles of the precipitate and the inorganic compound obtained by hydrolysis in the above method have an average particle diameter (X) of 1.0 to 50.0 μm.
It is non-agglomerative and its particle dispersibility is 80% or more, but in most cases 90% or more. It is completely surprising that if such a busy core exists in the solvent, the hydrolysis reaction proceeds to form a colored layer in the core even in the presence of a dye that is thought to inhibit the growth reaction. (This is a phenomenon that should occur. Moreover, the dye is firmly fixed in the colored layer, and becomes a composite pigment with coloring properties corresponding to the dye. Furthermore, the composite pigment obtained by K. It is a composite pigment in which a colored layer composed of a mixture of a dye and an inorganic compound exists in the core.

As another example of a manufacturing method, the following method is also suitable. Select porous particles with good particle dispersibility, for example, 80% or more, as the metal oxide particles that will become the core of the composite pigment,
Contacting the porous particles with a solution in which a dye is dissolved K
As a result, a composite pigment in which the porous particles are impregnated with a dye is obtained. In the method for producing the above-mentioned composite pigment, selection of porous particles is an important requirement.

Of course, the method for producing the porous particles is not limited.

However, in general, porous particles obtained by the following method are particularly suitable. For example, a composite oxide comprising a metal of Group Ⅰ, Group Ⅰ or Group Ⅰ of the periodic table and an alkali metal such as potassium, sodium or lithium is produced by the hydrolysis method of the metal alkoxide. Next, the alkali metal components contained are eluted by contacting the obtained composite oxide with a mineral acid solution such as sulfuric acid, nitric acid, or salt vinegar.
The resulting particles are porous and have excellent particle dispersibility of 80% or more. By using such particles, a composite pigment can be obtained which is impregnated with the dye, that is, the dye is present on the surface of the core portion. The composite pigment may be used after drying or may be subjected to post-treatment, if necessary.

In some cases, the dye may be eluted from the colored layer composed of the dye or a mixture of the dye and an inorganic compound. In such a case, the colored layer may be further coated with a fixed coating layer of an inorganic compound having a low dye content or an inorganic compound containing no dye at all, or the above three-layer structure may be further laminated to form a four-layer structure. A composite pigment having the above structure can be obtained. The means for forming the multilayer structure of three or more layers is not particularly limited, and any means may be used.

To give an example of a method that is generally preferably employed, a dye and a compound to be hydrolyzed are dropped into a water-containing solvent in which the inorganic compound serving as the core is present, and the raw material is hydrolyzed to generate particles with a two-layer structure. or after producing porous particles impregnated with dye, the compound to be hydrolyzed is further dropped into a reaction vessel for hydrolysis, or the porosity of the two-layer structure particles or dye impregnation is In this method, unreacted or unimpregnated dye is separated from the particle production system, and then a compound to be hydrolyzed is further added dropwise and hydrolyzed to obtain a composite pigment. In the former case, when the reactions are carried out in the same system, a composite pigment with a three-layer structure is obtained, but in the third fixed coating layer, when the colored layer is formed on the core, the remaining dye that has been digested is dissolved in the solvent. However, when no dye is contained in the solution of the compound to be hydrolyzed which is added dropwise, the composition has a significantly low dye content. In this case, the dye amount is about 175 or less, preferably 1/10 or less, of the dye contained in the colored layer that is normally formed directly on the core. Although this phenomenon is also a surprising phenomenon when compared with general reactions, its effect is not clear at present. Therefore, the method for producing the composite pigment does not require a special reaction format, and can also be obtained by laminating three or more layers in a single reactor. In the composite pigment obtained by K in this way, even if a small amount of dye is contained in the third layer, the dye hardly elutes and becomes excellent spherical particles.

From the above, when manufacturing the inorganic compound core and the colored layer in a series of operations, the timing of adding the dye is important in order to keep the particle size of the resulting composite pigment within a specific range and to In order to prevent dye elution, the total synthesis time required to form the nucleus and colored layer is 0.1 to 0.9,
Particularly preferably, the desired composite pigment can be obtained by starting and completing the addition of the dye within a time range of 0.2 to 0.8.

When obtaining the composite pigment with a multilayer structure of three or more layers, unreacted or unimpregnated dye is separated from the two-layer structure particles coated with a colored layer on the surface of the core part, and then used, for example, in the production of the particles. After washing with the same solvent several times, a dye-free hydrolyzable compound is dropped into the solvent containing the particles and the hydrolyzable compound is hydrolyzed, and the third fixed coating layer is free of dye. This is a layer that contains almost no liquid.

By further subjecting the composite pigment having a two-layer structure or three-layer structure to the above-described treatment, a composite pigment having a multi-layer structure of three or more layers can be obtained. In the case of the composite pigment having a multilayer structure, the fixed coating layer is preferably selected from a translucent material in order to more clearly display the degree of coloring of the colored layer. In this sense, the solid coating layer is a metal of group 1 or group Ⅰ of the periodic table, or a combination of the metal and group 1 of the periodic table.
Preferably, it is a composite oxide with a metal of group Ⅰ or group V.

The surface of the composite pigment used in the present invention is often hydrophilic due to its characteristics. Although it is of course possible to use it as it is when blending it as a component of cosmetics, surface treatment of the i-composite pigment is often a suitable means to improve its affinity with oil. This surface treatment method is not particularly limited, and known methods are preferably employed. For example, the surface can be treated with a silane coupling agent or a titanium coupling agent. As a silane coupling agent, vinyl trichlorosilane, vinyl tris (β-
methoxyethoxy)silane, γ-methacrypoxypropyltrimethoxysilane, γ-methacryoxypropylmethyldimethoxysilane, r-glycidoxypropyltrimethoxysilane, r-chloropropyltrimethoxysilane, β-(3,4- Examples include epoxycyclohexyl)ethyltrimethoxysilane, trimethylchlorosilane, dimethyldichlorosilane, hexamethyldisilazane, methyltriethoxysilane, and phenyltriethoxysilane. Examples of titanium coupling agents include isopropyl triisoste 7-yl titanate, inpropyl tridecylbenzenesulfonyl titanate, and isopropyl trisdioctyl pyrophosphate titanate.

Tetrainpropyl bisdioctyl phosphite titanate, tetraoctyl bisditridecyl phosphite titanate, bisdioctyl byle phosphate ethylene titanate.

Isopropyltrioctanoyl titanate.

Examples include diisostearate ethylenenathanate.

In addition to the above, known surface treatment agents such as organic zirco sluminate compounds can be used. Further, as the surface treatment method, both known methods, ie, dry methods and wet methods, can be used, but a wet method in which the surface treatment is performed in a dispersed state is preferably employed. In surface treatment, the hydrophobicity of the composite pigment varies greatly depending on treatment conditions such as surface treatment agent concentration, treatment temperature, treatment time, etc., so treatment conditions may be selected depending on the purpose.

The composite pigment obtained as described above can be colored in any color depending on the type of dye, has a specific particle size, has uniform properties, can freely change the color tone, and can be used in cosmetics. It can be suitably used as a pigment.

The blending ratio of the pigment in the present invention varies depending on the type of cosmetic and cannot be limited to a certain amount, but generally it is suitable if it is selected from a range of 50 to 95% by weight in the cosmetic. The oil base used in the present invention is not particularly limited, and any known oil base can be used. Typical oil bases that are particularly preferably used include, for example, beeswax,
Carnauba, Candelilla, Moresin. Paraffin, spermaceti, lanolin, lanolin absorbent.

Vaseline, liquid halafine, castor oil, cacao oil, butyl stearate, squalane, tetrafreel alcohol ester, cetanol, isopvir myristate,
Fats and oils such as ste7lyl alcohol and hydrogenated vegetable oil, -C.

Examples include hydrocarbons and higher alcohols.

Although the mixing ratio of the oily base varies depending on the type of cosmetic and cannot be limited to a certain amount, it is generally 5 to 50% by weight, more preferably 10 to 20% by weight in the cosmetic. If the mixing ratio is less than 5% by weight, it loses its adhesion to the skin,
It is preferable to determine this in advance, since the moldability may deteriorate, and if it exceeds 5otl1%, the stickiness may become large and cause discomfort.

The cosmetic composition of the present invention can be obtained by mixing the above-mentioned composite pigment with an oil base, but in order to precisely adjust the color tone, it can also be used in combination with a known inorganic pigment or organic pigment. It is. Particularly suitable inorganic pigments include titanium oxide and Bengara.

Yellow iron oxide 1 ultramarine, navy blue, iron black, carbon black, kaolin, talc, calcium oxide.

Order magnesium, barium sulfate, mica.

Examples include mica titanium and sericite.

Specific examples of organic pigments that are generally suitable for use include phosphorus rubine, lake red,
Lysol Red series, Brilliant Lake Red R, Deve Maroon, Toluidine Red, Permanent Orange, Indigo, Calpens Rangel, Penzidine T
y-G and other tar pigments.

Although the mixing ratio of these known inorganic pigments or organic pigments depends on the adjustment of color tone, it is generally 1 to 50% by weight, more preferably 5 to 10% by weight in cosmetics. This is the extent that is included.

The cosmetics of the present invention are produced by uniformly mixing the composite pigment, an oily base, an inorganic pigment or an organic pigment as necessary, a fragrance commonly used in cosmetics, a surfactant, a solvent, etc. in a mixer, and then It can be made into cosmetic products by molding it into a specific shape depending on the temperature.

〔effect〕

Cosmetics containing composite pigments, such as makeup cosmetics, have a good feel when applied to the skin and have a high pigment filling chamber. In addition, the color tone can be easily adjusted, making it suitable for all skin tones (
It is possible to get close. This is because the particle size of the composite pigment is uniform, so there is no discomfort on the skin due to aggregation, and the filling rate can be increased. Furthermore, since it is possible to color the product in any color by selecting the type of dye, it becomes easy to adjust one color tone. Moreover, since the physical and chemical properties depend on the inorganic compound, they have uniformity such as the same refractive index, specific gravity, hydrophilicity, and hydrophobicity.

Furthermore, in general, when using known pigments, adjusting a specific color tone is carried out by mixing several types of specific pigments.

This requires many years of skill, whereas the composite pigment of the present application can be made into a pigment of a predetermined color tone by selecting the dye. For this purpose, not only can composite pigments with a wide variety of colors be prepared, but also the colors can be fixed with a fixing coating layer made of an inorganic compound as required, resulting in a very stable product. Therefore, it has the advantage that it is extremely easy to adjust the color tone of cosmetics.

EXAMPLES In order to explain the present invention more specifically, the present invention will be described below with reference to Examples, but the present invention is not limited to these Examples.

In addition, the properties of the composite pigments in the following examples were measured by the following method.

(11 Average particles! (X) The average particle diameter (X) is calculated by measuring the longitudinal diameter of 200 particles randomly taken out in 7 strands by observation using a transmission disk electron microscope, and calculating the average diameter. be.

(2) Particle size dispersion value (SD) Particle size dispersion value (SD) is the value obtained by dividing the standard deviation of the particle size of each particle by the average particle size and multiplying by 100.

(3) Particle dispersion value (PD) Particle dispersion value (PD) is the value (%) obtained by dividing the number of particles having a volume in the range of π/6 (X±o, sX) by the total number of particles and multiplying by 100. It was displayed in

Note that measurement of the volume of one particle and counting of the number of particles were performed using Model ZD-1 manufactured by Fulter Counter.

Total number of particles (%) (4) Elution amount of dye (SC) The absorbance at the concentration of the dye dissolved in methanol and the concentration of nuclei is spectroscopically analyzed to determine the extinction coefficient (ε) of the dye. Separately, the composite pigment is dispersed in 5 m/m of methanol to a concentration of 5% by weight, and after being left for one week, the supernatant 41 is taken and subjected to spectroscopic analysis to determine the absorbance (A) of the supernatant.

The amount of dye eluted (C) was calculated from the following formula.

C=A/ε (5) Dye content (DC) in composite pigment First, the extinction coefficient (ε) of the dye is determined by the same method as in (4) above. Separately, the composite pigment is dispersed in methanol at a concentration of 0.5% by weight, and this dispersion is taken, and its weight and absorbance (A) are spectroscopically analyzed. Inorganic compound particles having the same average particle diameter as the composite pigment are dispersed in methanol at a concentration of 0.5% by weight, and the absorbance (A1) of this dispersion is spectroscopically analyzed.

From the above measurement results, the weight (DW) of the dye contained in the composite pigment is calculated using the following formula.

DW=(A'-A")/g Next, the weight of the furfur liquid is subtracted from the weight of 4 ml of the methanol dispersion of the composite pigment to calculate the weight of the composite pigment (PW) in 4-.

Finally, the dye content (DC) in the composite pigment is calculated using the following formula.

PW (6) Measurement of color tone The composite pigment obtained in each example was mixed with the components shown in the example, and after molding, the color was visually observed. Next, the molded product was exposed to a colorimeter (model: TC-i s 00MC, manufactured by Tokyo Denshoku ■) to measure the color difference from the skin color.

The color difference was expressed in NBS units.

(7) Sensory evaluation of cosmetics 10 subjects C (average age 23 years old, 1 female) were selected, and the cosmetics obtained in the examples were evaluated as 1), 2) adhesion to the skin, and 2) spreadability on the skin. 3. We asked them to rate us on a 5-point scale based on 3 points, and the average score was displayed. The 5 stages are from bad to good,
Good items were given high points.

Example 1 Synthesis of composite pigment Glass flask with stirrer Methanol 2800
rd, ammonia water (25 wt%) 720 mj, hydroxide) IJium aqueous solution (5 mol/1) 25 at was added and kept at 10°C, and then 510 ml of methanol solution of tetraethyl silicate (22 wt) was added to 25.5 rm
It was added at a rate of 1/hr to form silica shells (average particle size 1.64 μm). Into this reaction solution containing silica particles, a methanol solution of tetraethyl silicate (33% by weight) 624- and a methanol solution of the six dyes shown in Table 1 (1.25% by weight) 625117 were simultaneously added at a rate of 15.0 id/hr. The methanol solution of the tetraethyl silicate and the methanol solution of the dye were completed at the same time to synthesize silica particles colored with the dye. The obtained silica particles were repeatedly purified by decantation and washed with methanol.

The properties of the silica/dye composite pigment having a two-layer structure thus obtained were as shown in Table 1.

Next, each of the obtained composite pigments was dispersed in methanol to a concentration of 10% by weight, and the dispersion was diluted with 100% by weight.
The surface treatment agents shown in Table IK in Table IK were added at a concentration of 0.5% by weight, and the mixture was reacted at 10° C. for 16 hours to perform surface treatment, thereby obtaining a surface-treated composite pigment.

Next, after naturally drying the composite pigments of Examples 1.41 to 4, 87.5 parts by weight of the composite pigments and a heated mixture of the following component 1 were added, thoroughly mixed in a Henshil mixer, and filled into a medium tray to a temperature of about zKp/ A disc-shaped cosmetic with a diameter of 5α and a thickness of 5mm was obtained by pressure molding using cnl.

Ingredients 1 Squalane 5.0 parts by weight Methylpolysiloxane 3.0 Impropyl myristate 2.0 Paraffin 1.0
Surfactant 1.0 Fragrance
0.5 The performance of the obtained cosmetic is shown in Table 1.

Example 2 2800 m of methanol in a glass flask with a stirrer
/, ammonia water (25 wt.) 616111j, hydroxide) IJum aqueous solution (5 mol/l) 3 om was added to 1
After keeping the temperature at 0°C, a mixture of 792ν of a methanol solution of tetraethylsilicate (22% by weight) and 88WLt of a methanol solution of sodium methylate (22% by weight) was added in succession at a rate of 25.5a//hr. , silica/su) lram composite particles were obtained.

The composite particles were manufactured by Kff in the same manner as in Example 1, and dispersed in methanol to a concentration of 10% by weight. Next, in a glass flask equipped with a stirrer, a 5% by weight sulfuric acid aqueous solution was added.
117 was prepared, and the composite particle dispersion liquid was added to the composite particle dispersion liquid under stirring at room temperature.
Acid treatment was performed by adding dropwise at a rate of d/ytjt.

After the acid treatment, cleaning and ff production were performed in the same manner as in Example 1.

The properties of the obtained porous particles are shown in Table 2i1. Separately, in a glass flask with a stirrer, inpropyl alcohol (
After adding IPA) 2800c1: and keeping it at 10 ° C., 855 iu of IPA solution (20% by weight) of the raw materials shown in Table 2 (42, 3 and 4) K and 95 iu of IPA solution (20% by weight) of sodium methylate were added. A mixed solution containing the above was added in the same manner as above, and nm was performed after acid treatment. The properties of the porous particles obtained are shown in Tables 2 to 4.

After precipitating the obtained porous particles and removing the supernatant methanol, 1000 d of a methanol solution of the dye shown in Table 2 dissolved at 10% by weight was added, and impregnation dyeing was carried out at room temperature for 16 hours under stirring. did. After impregnating and dyeing, washing in the same manner as in Example 1,
Purified. The properties of each composite pigment obtained are shown in Table 2.

These composite pigments were surface-treated using trimethylchlorsilane in the same manner as in Example 1.

The obtained composite pigment was mixed and molded in the same manner as in Example 1 to obtain a cosmetic. Table 2 shows the performance of the obtained cosmetic.

Example 3 2800 methanol in a glass flask with a stirrer
yrl, ammonia water (25tJi%) 720111
7. Sodium hydroxide aqueous solution (5 mol/l) 25m
After adding and holding 10-CK, add 510 d of methanol solution of tetraethyl silicate (22 weight) at 25. !
It was added in succession at a rate of M+j/hr to produce silica particles (average particle size 164 μm). Into this reaction solution containing silica particles, 624 m of a methanol solution of tetraethyl silicate (44% by weight) and 40 ON of methanol solutions of various dyes shown in Table 3 (1.25'% by weight) were added at the same time for 15.0 a//hr. The silica particles colored with the dye were synthesized by adding the dye dropwise at a rate of 1 to 100 ml, so that the dropping of the methanol solution of the dye was completed first. The obtained silica particles were repeatedly purified by decantation and washed with methanol. All of the silica particles containing this dye were spherical, and even when dispersed in methanol, no elution of the dye was observed.

In addition, ultrathin sections were cut using the method of embedding silica particles in epoxy resin as shown in Table 3, and the ultrathin sections were observed using a transmission electron microscope. Electron micrograph showing the particle structure (40,000
0x) is shown in Figure 1. From FIG. 1, it can be seen that it has a triple structure consisting of one core, a colored layer, and a fixed coating layer.

Also Table 3. For silica particles containing %1 dye,
The particle dispersion value is shown in FIG. 2(a).

Next, the silica particles colored with the obtained dye were subjected to surface treatment in the same manner as in Example 1. Table 3/Figure 2 (b) shows the particle dispersibility after surface treatment of silica particles colored with I61 dye.
It was shown to.

The obtained colored silica particles (composite pigment) were mixed and molded in the same manner as in Example 1 to obtain a cosmetic. Table 3 shows the performance of the obtained cosmetic.

Example 4 Add isopropyl alfur (IPA) 2800 g and distilled water 281 to a glass flask equipped with a stirrer and heat at 10°C.
After maintaining the IPA solution of the raw materials shown in Table 5 (20% by weight)
)350d was added dropwise at a rate of 22.5icj/hr,
Hydrolyzed. After that, the raw material IPA#! liquid (40
wt%) 830m and a methanol solution of the dye shown in Table 5 (
1.25 wt. This composite pigment had a three-layer structure. These composite pigments were purified and washed in the same manner as in Example 1 (1). Each of the composite pigments was spherical, and no elution of the dye was observed even when dispersed in methanol.

The obtained composite pigment was surface treated in the same manner as in Example 1 using the surface treatment agent shown in Table 4. Table 4 shows the characteristics of each particle.

The obtained composite pigment was mixed and molded in the same manner as in Example 1 to obtain a cosmetic. Table 4 shows the performance of the obtained cosmetic.

Example 5 0.1% hydrochloric acid4. OI and tetraethyl silicate 316
N (St (QC,H,), manufactured by Nippon Colcourt Chemical Co., Ltd.: product name: ethyl siligate 28) and methanol 1
200111jK was dissolved and the solution was hydrolyzed at room temperature with stirring for about 2 hours. After that, this was converted into tetrabutyl titanate (Ti(0-nCH), manufactured by Nippon Guchitatsu).
81.8.9 was added to a solution dissolved in Improper Tool 500- while stirring to prepare a mixed solution of hydrolyzed tetraethyl silicate and tetrabutyl titanate. Next, 2.5 tons of methanol was introduced into a glass reaction vessel with an internal volume of 10 tons equipped with a stirrer, and 500 g of ammonia aqueous solution (concentration 25 wt%) was added thereto to prepare an ammoniacal alcohol solution, and silica seeds were added to this. 4.0g of tetraethylsilicate to make 10g of methanol
Add the solution dissolved at 0d for about 5 minutes, and when the reaction liquid turns slightly milky 5 minutes after the addition is complete, continue adding the above mixed solution for about 6 hours while keeping the temperature of the reaction vessel at 10℃. The reaction product was precipitated. Thereafter, a methanol solution of tetraethyl silicate (44% by weight) 720- and a methanol solution of methylene blue (cationic dye) (1.25% by weight) 2501
The hydrolysis was carried out under the condition that the addition of each of the dye solutions 17 and 17 was started at the same time at a rate of 2512//hr, and the dropwise addition of the dye solution was completed before the dropwise addition of the tetraethylsilicate solution. Furthermore, silica-titania particles containing dye were purified and washed in the same manner as in Example 1 (the core part is an inorganic compound shown in Table 5, and the inorganic compound of the colored layer and fixed coating layer is 3
layer structure particles) were obtained.

Furthermore, in the above operation, tetrabutyl titanate) 40
．． Composite pigments with various compositions were obtained in the same manner as above except that 911 was changed to the raw materials and dyes shown in Table 5. Each of the obtained composite pigments was surface treated using a surface treatment agent in the same manner as in Example 1.

Note that each particle was spherical, and no elution of the dye into methanol was observed.

The obtained composite pigment was mixed and molded in the same manner as in Example 1 to obtain a cosmetic. Table 5 shows the performance of the obtained cosmetic.

Example 6 In a glass flask equipped with a stirrer, 2800d of a methanol dispersion in which 2% by weight of inorganic compound nuclei prepared in advance as shown in Table 6 were dispersed and aqueous ammonia (25% by weight) were added.
) 616 ml and kept at 10°C, then methanol solution of tetraethyl silicate (44mfTh%) 75O
A methanol solution (1,25i mass %) 4001117 of N and Diacryl Red MS-N (manufactured by Mitsubishi Kasei ■) was added simultaneously at a rate of 25.5 txt/hr, and the dye solution was added dropwise. The hydrolysis was carried out under conditions such that the addition of the tetraethylsilicate solution was completed before the dropwise addition of the tetraethylsilicate solution. The properties of the obtained composite pigment are shown in Table 6.

Furthermore, each composite pigment was subjected to surface treatment using triphenylc I:+rosilane in the same manner as in Example 1.

The obtained composite pigment was mixed and produced in the same manner as in Example 1 to obtain a cosmetic. Table 6 shows the performance of the obtained cosmetic.

Example 7 In a glass flask equipped with a stirrer, 56p of the inorganic compound shown in Table 7, which will become the core and which has been pre-screened, was added at 1000V!
! A methanol solution (10% by weight) of the dye shown in Table 7 K
Disperse and stir at room temperature for 16 hours. After stirring, let stand,
The supernatant was removed by decantation, 1000 d of methanol was added, and the mixture was stirred for 10 minutes.

After stirring, let it stand still, remove the supernatant, add 2,800 methanol and 616 m of ammonia water (25% by weight),
After keeping at 10°C, 1024d of methanol solution (22% by weight) of tetraethylsilicate was heated at 25.5au/hr.
The mixture was added dropwise at a rate of 100 to 100 ml, and hydrolysis was performed to obtain a composite pigment.

The properties of the obtained composite pigment are shown in Table 7. Furthermore, each of the composite pigments described in No. 1 was subjected to surface treatment in the same manner as in Example 1, and the resulting composite pigments were mixed and molded in the same manner as in Example 1 to obtain cosmetics. Table 7 shows the performance of the obtained cosmetic.

Example 8 The dyed porous particles obtained in Examples 241 to A64 were subjected to 2.
Add methanol/ammonia (4% by weight) to a concentration of 5% by weight.
:1) Dispersed in 1000 m/liquid mixture. This dispersion was placed in a glass flask equipped with a stirrer and kept at 10°C, followed by a methanol solution of tetraethylsilicate (20% by weight).
160IL/,! :, methanol/ammonia (4:
1) A composite pigment was obtained by simultaneously adding 160 d of the mixed liquid at a rate of 22.5 mj/hr.

The properties of the obtained composite pigment are shown in Table 8. Furthermore, the surface was treated with trimethylchlorosilane in the same manner as in Example 1.

The obtained composite pigment was mixed and molded in the same manner as in Example 1 to obtain a cosmetic. Table 8 shows the performance of the obtained cosmetic.

Example 9 The composite pigment obtained in each of the above examples shown in Table 9 was
It was dispersed in 1000 m of methanol/ammonia mixed solution to give a concentration of % by weight.

This dispersion was placed in a glass flask equipped with a stirrer and heated to 10°C.
I kept it. Add to this solution 250 d of a methanol solution (1.25% by weight) of the dye shown in Table 9, 7 ml of methanol
(4: 1) 450ml of mixed solution and a methanol solution of tetraethylsilicate (40% by weight) 45011/! were added in succession at a rate of 22.5 m/hr. That is, the hydrolysis reaction was carried out under conditions such that the dropwise addition of the dye solution was first completed, and then the tetraethylsilicate solution and the methanol/ammonia mixture were simultaneously added directly.

As a result, a composite pigment having a five-layer structure was obtained.

The properties of the obtained composite pigment are shown in Table 9.

Next, the surface treatment was performed in the same manner as in Example 1.

The obtained composite pigment was mixed and molded in the same manner as in Example 1 to obtain a cosmetic. Table 9 shows the performance of the obtained cosmetics.

Example 10 Component 2 shown in Table 10 was mixed with a Henshil mixer, pulverized with an atomizer, then the composite pigment shown in Table 10 was added, and mixed again with a Henshil mixer. The resulting mixture was mixed with component 1 in the same manner as in Example 1, and a cosmetic was obtained. Table 11 shows the performance of the obtained cosmetics. Incidentally, in the composite pigment column of Table 10, a plurality of composite pigments are indicated as a mixture of a plurality of composite pigments for color tone adjustment.

Table 11

[Brief explanation of the drawing]

FIG. 1 is an electron micrograph showing the particle structure of the dye-containing silica particles obtained in Example 3. Figure 2 shows
Silica particles (a) containing the dye obtained in Example 3,
After the surface treatment, (b) showed monoparticle properties.

Claims (2)

[Claims] (1) Coloring that has an average particle diameter of 1.0 to 50.0 μm and a particle dispersibility of 80% or more, and exists on the surface of the core made of an inorganic compound and the core made of a dye or a mixture of a dye and an inorganic compound. A two-layer structure with a layer, or a mixture of a dye and an inorganic compound with a lower dye content than the colored layer, or an inorganic compound containing no dye, covering the core part, the colored layer, and the colored layer. A cosmetic product made by mixing a composite pigment with a three-layer structure of a fixed coating layer and an oil base. (2) The cosmetic according to claim (1), which contains 5 to 50% by weight of an oily base.