JP2003165921A - Colored spherical fine particle, and cosmetic containing the same - Google Patents

Abstract

<P>PROBLEM TO BE SOLVED: To develop colored fine particles undergoing no change in color hue even when in contact with an oil or water, and cosmetics containing the particles. <P>SOLUTION: Almost perfectly spherical colored fine particles comprising an inorganic porous substance including an organic or inorganic pigment having a Munsell hue of 2.5Y to 9R, optionally treated with an oil or a fluororesin, are incorporated into a cosmetic composition. <P>COPYRIGHT: (C)2003,JPO

Description

Detailed Description of the Invention

[0001]

TECHNICAL FIELD The present invention relates to a make-up cosmetic composition which is excellent in coloring power and hiding power, and which is excellent in spreadability upon application, and which has an excellent makeup lasting property in which hue does not change over time. The present invention relates to a cosmetic containing colored spherical fine particles having properties.

[0002]

2. Description of the Related Art In general, makeup cosmetics such as white powder, foundation, etc., express all colors using extender pigments and coloring pigments. These include white pigments such as titanium oxide and zinc oxide, inorganic pigments such as red iron oxide, yellow iron oxide, black iron oxide, ultramarine blue and dark blue, and organic coloring pigments such as tar dyes. However, these pigments are generally granular or acicular, have different surface properties, and have a particle size of 0.001.
Approximately 1 μm, and therefore, the coloring power and the hiding power are sufficient, but the cohesive force and adhesive force of the particles are large, and therefore, when incorporated in makeup cosmetics, color unevenness or the like occurs, or when applied. There were times when it was not easy to stretch and the finish was unnatural. In addition, coloring pigments are a factor that causes makeup discoloration with the progress of wetting due to the secretion of sebum and perspiration over time after makeup operation, resulting in a decrease in brightness and dullness of the color, or a marked loss of the hue of the makeup film. It was Therefore, a cosmetic pigment characterized in that inorganic non-porous fine particles are encapsulated with a layer of an inorganic porous material containing a dye (Japanese Patent Application Laid-Open No. H7-71952).
-258025) or a cosmetic pigment which does not lose its lightness even when a cosmetic is applied to the skin and has no color blemishes, and the coloring is brilliant and has no color unevenness, and the makeup has an appropriate coloring power and hiding power. A makeup cosmetic (JP-A-7-145021) has been proposed which has both effects and good spreadability upon application, and which has excellent durability of makeup such that color does not fade over time.
However, all of these compounds contain white spherical silica fine particles in which about 50% of rutile type titanium oxide is clathrated, and red 226 silica-treated spherical cosmetic pigment is mixed to improve the decrease in lightness, but suppress the change in hue. Had no effect on. For this reason, the hue of the makeup film was different due to the change with time after makeup. Such a change in hue has been a major problem in cosmetics.

[0003]

The problem to be solved by the present invention is to develop colored fine particles which do not change in hue even when they come into contact with oil or water, and cosmetics containing the same.

[0004]

SUMMARY OF THE INVENTION The present invention focuses on such a change in hue and encloses an organic and / or inorganic pigment having a hue in the Munsell symbol range of 2.5Y to 9R with an inorganic porous material. The problem can be solved by incorporating colored fine particles in contact with each other, which are almost completely spherical, or colored spherical fine particles treated with an oil agent or a fluorine-containing resin, into the cosmetic composition.

[0005]

BEST MODE FOR CARRYING OUT THE INVENTION The cosmetic of the present invention basically has the following constitution. (1) Organic and / or inorganic pigments in which one kind and / or two or more kinds are mixed or complexed, and the hue is Munsell symbol 2.
Colored fine particles in the range of 5Y to 9R are (2) Colored spherical fine particles having a nearly perfect sphere which are encapsulated with an inorganic porous material (3) If necessary, further treated with an oil agent or a fluorine-containing resin (4) This is to be contained in the cosmetic composition.

First, in the present invention, the colored spherical fine particles to be incorporated into the intended cosmetic composition will be described. The colored spherical fine particles of the present invention have a particle size of 0.1 which is a substantially perfect spherical shape in which an organic and / or inorganic pigment having a hue in the Munsell symbol range of 2.5Y to 9R is clathrated by an inorganic porous wall substance. ~
It is about 50 μm. As a method for producing the fine particles, any method capable of producing the above fine particles may be used. As a typical example thereof, the pigment disclosed in JP-A-6-47273 is used as a metal oxide sol and / or an alkoxy metal compound. Disperse in alcohol solution, add acidic substance or (or) basic substance or (or) electrolyte to this,
A hydrated metal oxide is deposited on the surface of the pigment, and at least one of inorganic compounds selected from alkali metal silicates, carbonates, phosphates, sulfates, alkaline earth metal halides and nitrates. Of the alkaline earth metal halide, the inorganic acid, the organic acid, the ammonium salt of the inorganic acid, the organic acid of the organic acid before or after being dispersed in an aqueous solution containing It is manufactured by adding and mixing an ammonium salt and an aqueous solution of a compound which is at least one kind of an alkali metal carbonate and which can form a water-insoluble precipitate by an aqueous solution reaction with the above-mentioned inorganic compound.

The manufacturing method will be described in more detail below. The inorganic pigment / organic pigment included in the colored spherical fine particles to be incorporated into the cosmetic of the present invention includes titanium oxide, zinc oxide, zirconium oxide, magnesium oxide, red iron oxide, red ultramarine, and yellow iron oxide, which are commonly used in cosmetics. ,
Ultramarine, navy blue, manganese violet, ultramarine violet, black iron oxide, titanium black, carbon black, aluminum powder, titanium mica, bismuth oxychloride, iron oxide treated mica titanium, navy blue treated mica titanium, carmine treated mica titanium, silica, calcium carbonate Inorganic pigments such as magnesium carbonate, barium sulfate, precipitated barium sulfate, alumina, talc, mica, bentonite, kaolin and sericite, red 202
No., Red No. 203, Red No. 204, Red No. 205, Red No. 207, Red No. 208, Red No. 219, Red No. 220
No., Red 221, Red 226, Red 228, Orange 203, Orange 204, Yellow 205, Blue 201
No. 2, blue No. 204, red No. 404, red No. 405, orange No. 401, yellow No. 401, blue No. 404 and the like, and one kind or two or more kinds selected from them.

In the present invention, such a pigment is used in a so-called known interfacial reaction method or, for example, in Japanese Patent Laid-Open No.
The method of forming a gel from the sol described in No. -103904 makes it possible to produce colored spherical fine particles in which the pigment is clathrated with an inorganic porous substance. In addition, inorganic non-porous fine particles are encapsulated in an inorganic porous material layer in which a coloring material is contained in an amount of 1% by weight to 80% by weight or less. Those having a coating of hydrated metal oxide (JP-A-6-47273) can also be used.

When the interfacial reaction method is used, it is manufactured, for example, as follows. The above coated pigment is dispersed in an aqueous solution containing at least one inorganic compound selected from alkali metal silicates, carbonates, phosphates, sulfates, alkaline earth metal halides and nitrates, (ii) Before or after adding and mixing an organic solvent having a solubility in water of 8% or less to form a W / O type emulsion, (iii) an alkaline earth metal halide, an inorganic acid, an organic acid, an ammonium salt of an inorganic acid, Method for producing inorganic microspheres by adding and mixing an aqueous solution of a compound that is at least one of an ammonium salt of an organic acid and a carbonate of an alkali metal and is capable of forming a water-insoluble precipitate by the aqueous solution reaction with the inorganic compound Is.

Conventional methods can be applied to the above means, for example, Japanese Patent Publication Nos. 54-6251 and 57.
The method disclosed in No. 55454 can be exemplified. More specifically, the concentration of at least one inorganic compound selected from alkali metal silicates, carbonates, phosphates, sulfates, alkaline earth metal halides and nitrates is 0.3 mol / min.
1. Prepare a 1-saturated aqueous solution. Next, an organic solvent having a solubility in water of preferably 8% or less is mixed to obtain a W / O type emulsion.

Then an alkaline earth metal halide,
At least one of inorganic acid, organic acid, ammonium salt of inorganic acid, ammonium salt of organic acid and carbonate of alkali metal
An aqueous solution of a compound which is a seed and is capable of forming a water-insoluble precipitate by an aqueous solution reaction with the above-mentioned inorganic compound (concentration: 0.
05mol / l) ~ saturated concentration, preferably 0.1-2.0mol
/ L) is mixed in the latter equivalent amount to 20 times the amount with respect to 100 parts by weight of the W / O type emulsion.

Specific examples of preferred organic solvents having a solubility in water of 8% or less include aliphatic hydrocarbons such as n-hexane, alicyclic hydrocarbons such as cyclopentane,
Examples thereof include aromatic hydrocarbons such as benzene, ethers such as propyl ether, halogenated hydrocarbons such as methylene chloride, and esters such as ethyl acetate.

These organic solvents may be used either individually or in combination of two or more. When this W / O type emulsion is prepared, the W / O ratio of the obtained emulsion is 4/1 to 1/5, preferably about 2/1 to 1/2. The amount of the surfactant used is preferably about 10% by weight or less of the organic solvent, and particularly preferably about 0.1 to 3% by weight. As the surfactant used, a nonionic surfactant is used.

The colored spherical fine particles to be blended in the cosmetics of the present invention can have a particle size of 0.1 to 50 μm, and preferably have an average particle size of 1 to 5 μm to obtain a sufficient coloring power. It is preferable because it can obtain the hiding power. Further, the inclusion rate of the inorganic pigment / organic pigment needs to be 10% by weight to 60% by weight based on the total weight of the colored spherical fine particles. When the inclusion rate is less than 10% by weight, the concentration of the included pigment is too low, and the coloring power and the hiding power are not sufficient, which is not preferable. Further, it is difficult to include the inorganic pigment / organic pigment in the inclusion rate of more than 60% by weight. In the present cosmetic composition, the hue of the colored spherical fine particles having a Munsell symbol in the range of 2.5Y to 9R can be used.
When the ratio is larger, the yellowness becomes too strong, and when it is smaller than 9R, the redness becomes strong, and when the wetting of the cosmetic material progresses with time, the change in the makeup hue becomes large and the natural makeup film cannot be maintained.

In the present invention, the above-mentioned colored spherical fine particles may be blended as they are, and further, they may be blended by treating with an oil agent or a fluorine-containing resin. By this treatment, the intended cosmetic composition can more effectively suppress the makeup lasting such as no color sinking over time and the bulkiness of the skin.
As the oil agent to be treated, any oil agent usually used in cosmetics can be used without any limitation. For example,
Liquid paraffin, squalane, petrolatum, paraffin wax, microcrystalline wax, beeswax, candelilla wax, rosin acid pentaerythritol ester, dimethylpolysiloxane, methylhydrogenpolysiloxane and the like.

On the other hand, other components for treating the colored spherical fine particles to be added to the cosmetic of the present invention include fluorine-containing resins such as Teflon (registered trademark) and fluoroalkyl phosphate ester ethanolamine represented by the following formula. Salt etc. are mentioned. As a commercially available product of this fluoroalkyl phosphate ethanolamine salt, Asahi Guard A
G530 (manufactured by Asahi Glass Co., Ltd.) and the like.

[0017]

[Chemical 1]

[0018]

[Chemical 2]

(However, in the above formula, n is an integer of 6 to 18) The processing means itself is not limited in any way, and any suitable means can be optionally used. Typical examples thereof are colored spherical fine particles. To water or a mixture of two or more of them to make a slurry, while adding water to a compound having a fluoroalkyl group and stirring to make an emulsion state of 0.1 to 5% by weight. Gradually pour, mix and acidify, break the emulsion by standing at room temperature or high temperature, coat the surface of the powder with a continuous layer of a compound having a fluoroalkyl group, then wash, filter and dry. Good. The concentration of the powder during treatment is not particularly limited,
For example, sufficient stirring and mixing is possible even at a relatively high concentration of 5 to 20% by weight, and large-scale processing is possible with a small device. Further, the compound having a fluoroalkyl group is preferably used in an amount of 0.1 to 10% by weight, more preferably 0.5 to 5% by weight, based on the powder. Incidentally, these treatments can be carried out at an atmospheric temperature of 10 to 35 ° C.

The colored spherical fine particles used in the present invention are used in an amount of 0.1 to 50% by weight based on the total weight of the cosmetic. If it is less than 0.1% by weight, a sufficient effect cannot be obtained. In addition, the effect is not changed even if it is blended in an amount of 50% by weight or more, and the range of use as a cosmetic is narrowed,
Powder press-molded products and the like are not preferable because they may weaken the impact strength of the product.

The cosmetics of the present invention are provided in various forms such as powders, liquids, solids, gels, and the like, and are used for basic cosmetics such as packs, sun care milks, marlin lotions, body powders, and white powders. , Foundation, control color, makeup base, eye shadow,
Makeup cosmetics such as cheek color, lipstick, eyeliner, and eyebrow.

In addition to the colored spherical fine particles, various bases usually used in cosmetics can be appropriately selected and blended in the cosmetic of the present invention within a range that does not impair the effects of the present invention. . Examples of such a base include inorganic pigments, organic pigments, oils, gelling agents, surfactants, lower alcohols, polyhydric alcohols, purified water, preservatives, antioxidants,
Examples include ultraviolet absorbers, moisturizers, hydrolyzing agents, cosmetic ingredients, and fragrances.

[0023]

The colored spherical fine particle-containing cosmetic of the present invention is
In particular, in order to selectively use a specific one having a hue in the Munsell symbol range of 2.5Y to 9R, even when the colored fine particles, or the cosmetic containing the fine particles, comes into contact with water or an oily substance. , Exerts an extremely unique effect that the hue is unlikely to change. Therefore, the cosmetic of the present invention has a great feature that it has a stable hue forever even if it comes into contact with water or an oily substance. In addition, the coloring is colorful and has no color unevenness, and it has a combination of makeup effects such as moderate coloring power and concealing power, and good spreadability when applied. Furthermore, it suppresses the bulkiness of the skin, and is also a makeup cosmetic product. In addition, the finished makeup film is natural, and the makeup is excellent in that the color does not fade over time.

[0024]

EXAMPLES Next, reference examples, examples and comparative examples which are production examples of colored fine particles will be described in more detail, but these do not limit the present invention at all. In the following parts, "part or%" means "part by weight" or "% by weight".

[Production Example of Colored Spherical Fine Particles]

[Reference Example 1] Commercially available rutile titanium oxide (trade name "J
R ”Teika Co., Ltd. 111.6 g, hydrated iron oxide (trade name“ LEMON ”Titanium Industry Co., Ltd. 7.2 g) and red iron oxide (trade name“ 100ED ”Toda Kogyo Co., Ltd.) 1.2 g JIS A of 4 mol / liter
Add 500 ml of sodium silicate solution, mix and disperse well, add this to a toluene solution of sorbitan monolaurate at 15 g / liter, and stir at 11,000 rpm for 1 minute to obtain a W / O type emulsion. 2 mol of this emulsion
Per liter of ammonium sulfate aqueous solution (1500 ml) and stirred for 1 hour. Then, it is filtered, washed with water and washed with alcohol, and dried at 105 ° C. for 24 hours. Thus, about 24 skin-colored spherical silica fine particles having a Munsell hue of 5.4YR and having an average particle size of about 1 μm and containing about 50% of A are about 24.
0 g was obtained.

[0026]

Reference Example 2 100 parts by weight of the skin-colored spherical silica fine particles obtained in Reference Example 1 were dispersed in 100 parts by weight of isopropyl alcohol and 2 parts by weight of methylhydrogenpolysiloxane to form a slurry, and the mixture was heated. While drying under reduced pressure, baking treatment, and then crushing,
Skin-colored spherical fine particles enclosing A “(Silicone oil treated) A
Inclusion silica capsule "was manufactured.

[0027]

Reference Example 3 To 50 parts by weight of the skin-colored spherical silica fine particles obtained in Reference Example 1, 1000 ml of water was added to form a slurry. On the other hand, fluoroalkyl phosphate diethanolamine salt (Asahi Guard AG530, manufactured by Asahi Glass Co., Ltd.)
350 ml of water was added to 9 g and stirred to obtain an emulsion. This emulsion was gradually added to the above slurry, mixed, and then allowed to stand at room temperature (Asahi Guard AG5
30 treatment) A clathrate silica capsules were obtained.

[0028]

Example 1 Powder foundations shown in Table 1 were prepared and their characteristics were measured. The hue is shown in Table 2 and the cosmetic properties are shown in Table 3. However, in Tables 1 to 3, for comparison, as Comparative Examples 1 to 4, colored spherical fine particles other than the present invention,
Also, the results of using the colored particles of the present invention in a predetermined amount or more are shown together.

[0029]

[Comparative Example 1] To 500 ml of a JIS No. 3 sodium silicate solution of 4 mol / liter, a toluene solution of sorbitan monolaurate of 15 g / liter was added, and 11,000 was added.
Stir at rpm for 1 minute to obtain a W / O emulsion. This emulsion is added to 1500 ml of a 2 mol / liter ammonium sulfate aqueous solution, and the reaction is carried out with stirring for 1 hour. Then, it is separated by filtration, washed with water and washed with alcohol, and dried at 105 ° C. for 24 hours. Thus, porous fine particles made of silica are obtained. In addition, commercially available rutile type titanium oxide (trade name "JR" Teika Co., Ltd.) 111.6 g, iron oxide hydrate (trade name "LEMON" Titanium Industry Co., Ltd.) 7.2 g and red iron oxide (trade name "100ED" Toda) A mixture of 1.2 g (manufactured by a technician) (hereinafter referred to as A) was added, and a cosmetic product was prepared according to the composition shown in Table 1.

[0030]

[Comparative Examples 2 to 4] Cosmetics were prepared according to the composition shown in Table 1.

[0031]

[Table 1]

However, all the colorants used in Table 1 were treated with 2% methylhydrogen, and the two kinds of encapsulated silica were all pigments treated with 5% methylhydrogen. .

[0033]

[Table 2]

However, this hue measurement was carried out by measuring the hues after the oil was added to each sample cosmetic and when it was not added.
This is a change in hue after addition of oil.

It was found that the hue changes were large in Comparative Examples 1 and 4, but extremely small in Example 1.

[0036]

[Table 3]

[0037]

Example 2 The hues of the colored fine particles of Reference Example 1 and the other four types of colored fine particles A to D were measured. The results are shown in Table 4.
As shown in. However, as the four kinds of colored particles A to D, the pigments used in Reference Example 1 were the same as those shown in Table 4, and the other pigments were treated in the same manner as in Reference Example 1. All of the colored particles A to D are out of the hue range of the present invention. In addition, the measurement of the wet state in the hue measurement in Tables 2 and 4 was carried out using liquid paraffin (High Coal K-350 manufactured by Kaneda).

[0038]

[Table 4]

[0039]

Example 3 Example 1 was carried out using the predetermined components shown in Table 5.
A cosmetic was prepared in the same manner as in (1) and its properties were measured. The results are also shown in Table 5. For comparison, the results of the cosmetic of Comparative Example 5 in which the particles of the present invention are not used are also shown.

[0040]

[Table 5]

─────────────────────────────────────────────────── ─── Continuation of front page (51) Int.Cl. ⁷ Identification code FI theme code (reference) C09C 3/06 C09C 3/06 3/10 3/10 (72) Inventor Osamu Kuroki Higashiyodogawa-ku, Osaka-shi, Osaka 2- 1-37 Itakano Suzuki Resin Industry Co., Ltd. (72) Inventor Masayasu Noguchi 2- 1-37 Itakano, Higashiyodogawa-ku, Osaka City Osaka Prefecture (72) Inventor Minoru Ueda Osaka City, Osaka Prefecture 2 1-37 Itakano, Higashiyodogawa-ku F-term (Reference) at Suzuki Jushi Kogyo Co., Ltd. (reference) 4C083 AB172 AB232 AB242 AB432 AB442 AC022 AC242 AC332 AC342 AC422 AC482 AC542 AC912 AD021 AD022 AD072 AD152 AD162 AD492 AD512 BB11 BB23 BB24 BB25 CC01 CC11 CC12 4J037 A02 AA05 AA09 AA10 AA15 AA16 AA17 AA18 AA22 AA25 AA26 CA05 CA15 CA16 CA18 CB22 CC03 CC14 CC28 EE03 EE04 EE14 EE43

Claims (4)

[Claims] 1. A colored organic and / or inorganic pigment is clathrated by an inorganic porous material, and the hue is Munsell symbol 2.5Y-9.
Colored spherical fine particles in the range of R. 2. A hue in which a colored organic and / or inorganic pigment is clathrated with an inorganic porous material has a Munsell symbol of 2.5Y-9.
A cosmetic containing colored spherical fine particles in the range of R. 3. The cosmetic according to claim 2, which contains colored spherical fine particles having a particle size of 0.1 to 50 μm. 4. The cosmetic according to claim 2, which contains colored spherical fine particles treated with an oil agent or a fluorine-containing resin.