JPH07145021A - Colored globular fine particle-containing cosmetic - Google Patents

Abstract

PURPOSE:To obtain a make-up cosmetic having bright color, free from unevenness of color, having both of cosmetic effect such as proper coloring force or hiding power and good slip in application, and excellent in long acting property of cosmetic, e.g. not causing penetration of color with the passage of time. CONSTITUTION:This cosmetic contains colored globular fine particles having nearly completely globular shape and obtained by enclosing an organic and/or inorganic pigment, coated with a hydrated metal oxide, with an inorganic porous wall substance.

Description

Detailed Description of the Invention

[0001]

BACKGROUND OF THE INVENTION 1. Field of the Invention The present invention relates to a makeup cosmetic composition which is vivid in color, has no color unevenness, has a cosmetic effect such as coloring power and hiding power, spreads upon application, and suppresses the bulkiness of the skin. In this regard, the present invention relates to a cosmetic material containing colored spherical fine particles, which has a natural finished cosmetic film and which is excellent in makeup durability such that the color does not sink over time.

[0002]

2. Description of the Related Art The makeup effect of makeup cosmetics is mainly a skin color correction effect for covering defects such as spots and bruises on the skin, and a coloring effect for giving an attractive appearance. In order to have these effects, titanium oxide,
Pigments such as white pigments such as zinc oxide, red iron oxide, yellow iron oxide, black iron oxide, inorganic coloring pigments such as ultramarine blue and dark blue, and organic coloring pigments such as tar dyes have been used. However, these pigments are generally granular or acicular, have different surface properties, and have a particle size of 0.001-1.
Although it has a coloring power and a hiding power sufficiently, it has a large cohesive force and adhesive power of particles, and therefore, when incorporated into makeup cosmetics or the like, it causes color unevenness, There were times when it was difficult to spread and the finish was unnatural. To improve these problems,
Spherical or plate-like extender pigments are used together as a component of makeup cosmetics, and recently, these pigments and so-called extender pigments such as mica, talc, silica gel, nylon powder are combined to adjust the feeling of use. I am still not satisfied with my work.

On the other hand, there has been proposed a colored fine spherical silica gel in which 1 to 40% by weight of a water-insoluble coloring material is enclosed in the voids of porous spherical silica gel in order to improve the coloring effect and the feeling of use such as spreading. (Japanese Patent Publication No. 61-28605), it is not sufficiently satisfactory in terms of hiding power, and when it is blended with cosmetics including basic cosmetics, it absorbs too much sebum on the skin, so the skin becomes bulky. There were problems such as sticking.

Further, as a method for producing a pigment-inclusion capsule powder, those obtained by a conventionally known method (Japanese Patent Publication No. 54-6251 and Japanese Patent Publication No. 57-55454) do not have a sufficient pigment inclusion rate. Because the clathrate pigment is agglomerated,
The vividness of the color is lost, the hiding power is not sufficient, and the particle size of the pigment-encapsulating capsule powder is relatively large. There were problems such as inferiority and roughness. Further, an organic pigment such as a tar dye cannot be included.

[0005]

The problem to be solved by the present invention is to solve the above-mentioned drawbacks of the conventional cosmetics of this kind. More specifically, the coloring is colorful and the color unevenness is caused. It is an object of the present invention to provide a make-up cosmetic having an excellent makeup effect such as proper coloring power and hiding power and good spreadability at the time of application, and having excellent makeup lasting property such as no color fading over time.

[0006]

This object is to provide colored spherical fine particles in which an organic and / or inorganic pigment coated with a hydrated metal oxide is clathrated with an inorganic porous wall substance, or an oil agent or fluorine. The problem can be solved by incorporating colored spherical fine particles treated with a containing resin into a cosmetic composition.

[0007]

The function and structure of the present invention The cosmetic of the present invention basically has the following structure.

(1) Organic and / or inorganic pigments coated with hydrated metal oxides

(2) Colored spherical fine particles having an almost perfect spherical shape which are included in an inorganic porous wall substance.

(3) If necessary, further treat with an oil agent or a fluorine-containing resin.

(4) Constituting this in a cosmetic composition.

First, in the present invention, the colored spherical fine particles to be incorporated in the intended cosmetic composition will be described.

The colored spherical fine particles of the present invention have an almost perfect spherical particle size in which an organic and / or inorganic pigment coated with a hydrated metal oxide is clathrated by an inorganic porous wall substance and has a particle size of 0.5 to 0.5.
It is about 50 μm. The method for producing the fine particles may be any method as long as the fine particles can be produced. As a typical example thereof, a pigment is used as a metal oxide sol and / or
Or dispersed in an alcohol solution of an alkoxy metal compound,
An acidic substance or / and a basic substance or / and an electrolyte is added thereto to deposit a hydrated metal oxide on the surface of the pigment, which is further treated with an alkali metal silicate, carbonate, phosphate,
Alkaline earth is prepared by dispersing it in an aqueous solution containing at least one inorganic compound selected from sulfates, halides of alkaline earth metals and nitrates, and adding and mixing an organic solvent to form a W / O type emulsion. At least one of a halide of a group metal, an inorganic acid, an organic acid, an ammonium salt of an inorganic acid, an ammonium salt of an organic acid, and a carbonate of an alkali metal, and a water-insoluble precipitate due to an aqueous solution reaction with the inorganic compound. It is manufactured by adding and mixing an aqueous solution of a compound capable of forming.

The manufacturing method will be described in more detail below.

The inorganic pigments / organic pigments included in the colored spherical fine particles to be incorporated into the cosmetics of the present invention include titanium oxide, zinc oxide, zirconium oxide, magnesium oxide, red iron oxide, and red ultramarine which are commonly used in cosmetics. Yellow iron oxide, ultramarine blue, 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,
Inorganic pigments such as calcium carbonate, magnesium carbonate, precipitated barium sulfate, alumina, talc, mica, bentonite, kaolin and sericite, Red No. 202, Red 20
No. 3, Red 204, Red 205, Red 207, Red 208, Red 219, Red 220, Red 221
No., Red 226, Red 228, Orange 203, Orange 204, Yellow 205, Blue 201, Blue 204
No. 1, Red 404, Red 405, Orange 401, Yellow 401, Blue 404, and other organic pigments.

In the present invention, a coating of hydrated metal oxide is formed on such a pigment. The hydrated metal oxide at this time, silica, alumina, zirconia, titanium oxide, barium oxide, refers to iron oxide, preferably silica,
Alumina. As a general rule, this hydrated metal oxide film is preferably formed almost uniformly over the entire surface of the pigment, but 30% or more, preferably 80% or more of the minimum pigment surface may be coated.

The means for forming the film of hydrated metal oxide on the pigment itself is not particularly limited, and the point is that the above-mentioned film can be formed in a predetermined manner. The typical means is as follows.

The (A) pigment is added to an alkoxy metal compound or an alcohol solution thereof and stirred with a stirrer such as an ultrasonic disperser or a high-speed stirrer to form a uniform dispersion, to which water and a hydrolysis catalyst are added. A method of adding and hydrolyzing an alkoxy metal compound to deposit a hydrated metal oxide on the surface of a pigment.

A typical example of the alkoxy metal compound in this method is represented by the general formula M (OR) _n (where M is a metal element, R is an alkyl group, and n is a formula weight). M is preferably Si, Al, Zr, B
a, Ti, etc. R is usually an alkyl group having 1 to 8 carbon atoms, and particularly preferably an alkyl group having 1 to 3 carbon atoms.

As the alcohol, one capable of dissolving the above-mentioned alkoxy metal compound is used, and not only monohydric alcohol but also dihydric or trihydric alcohol may be used. Preferred specific examples thereof are methanol, ethanol, isopropylate alcohol, Glycerin and the like. Usually, it is used as an alcohol solution of about 5 to 30%. The hydrolysis catalyst may be an ordinary one, for example, HCl, NH ₄ OH, etc., and the amount used is about 0.1 to 1%.

(B) The pigment is added to alcohol and stirred to wet the surface of the pigment, and a uniform dispersion is prepared with a suitable stirrer such as an ultrasonic disperser or a high speed stirrer, and the metal oxide sol is added to this. Of the metal oxide sol is mixed with an acidic substance, a basic substance or an electrolyte to gelate the metal oxide sol.
A method of depositing a hydrated metal oxide on the surface of a pigment and coating the surface of the pigment with the hydrated metal oxide.

As the alcohol used in this method, those in the same range as the alcohol of the above method (A) can be used, and the acidic substance is usually hydrochloric acid, sulfuric acid, phosphoric acid or the like, or a basic substance. As such, sodium hydroxide, potassium hydroxide, ammonia or the like is usually used.

(C) The pigment is added to an alcohol solution of a mixture of a metal oxide sol and an alkoxy metal compound, and the mixture is stirred to wet the surface of the pigment, and then uniformly dispersed with an appropriate agitator such as an ultrasonic disperser or a high speed agitator. A dispersion liquid is prepared, and an acidic substance, a basic substance or an electrolyte is added to this to cause the metal oxide sol to gel, deposit hydrated metal oxides on the pigment surface, and hydrate the metal surface on the pigment surface. A method of covering with an oxide film.

Metal oxide sol, alkoxy metal compound, alcohol, acidic substance, basic substance,
As the electrolyte and the electrolyte, those of the above (A) and (B) can be used.

In the present invention, a so-called known interfacial reaction method is used by using a pigment coated with such a hydrated metal compound.
Alternatively, for example, a colored spherical fine particle in which the pigment is clathrated by a porous inorganic wall substance can be produced by a method of forming a gel from a sol described in JP-A-1-103904.

When the interfacial reaction method is used, it is manufactured, for example, as follows.

The above coated pigment is treated with an alkali metal silicate,
At least one of inorganic compounds selected from carbonates, phosphates, sulfates, halides of alkaline earth metals, and nitrates
(Iii) Alkaline earth metal halide or inorganic, before or after being dispersed in an aqueous solution containing seeds, and (ii) adding and mixing an organic solvent having a water solubility of 8% or less to form a W / O type emulsion. An aqueous solution of a compound which is at least one of an acid, an organic acid, an ammonium salt of an inorganic acid, an ammonium salt of an organic acid and a carbonate of an alkali metal and which can form a water-insoluble precipitate by the aqueous solution reaction with the above-mentioned inorganic compound. This is a method for producing inorganic microspheres by adding and mixing.

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 / l. ~ Prepare a saturated aqueous solution.

Next, the solubility in water is preferably 8%
The following organic solvents are 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:
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 preferred examples of the organic solvent 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, especially 0.1 to 3
About wt% is preferable.

As the surfactant used, a nonionic surfactant is used.

The colored spherical fine particles to be blended in the cosmetic of the present invention may have a particle size of 0.1 to 50 μm, preferably an average particle size of 1 to 5 μm is used 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 inclusions 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 invention, the above-mentioned colored spherical fine particles may be blended as they are, or 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 and a fluoroalkyl phosphate ethanolamine salt represented by the following formula. To be As a commercially available product of this fluoroalkyl phosphate ethanolamine salt, there is Asahi Guard AG530 (manufactured by Asahi Glass Co., Ltd.).

[0039]

[Chemical 1]

[0040]

[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 appropriate means can be optionally used, and representative 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 the treatment is not particularly limited, but sufficient agitation and mixing is possible even at a relatively high concentration of 5 to 20% by weight, and a large amount of treatment can be performed with a small apparatus. Also,
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 to be blended 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 the cosmetic of the present invention, in addition to the colored spherical fine particles, various bases usually used in cosmetics can be appropriately selected and blended 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.

[0045]

The colored spherical fine particle-containing cosmetic of the present invention is
The coloring is colorful and has no color unevenness, and it has a combination of makeup effects such as appropriate coloring power and hiding power and good spreadability at the time of application. Furthermore, it suppresses the bulkiness of the skin and, in addition, in makeup cosmetics. The finished makeup film is natural and has excellent makeup sustainability such as no color fading over time.

[0046]

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 part,% means% by weight.

[Production Example of Colored Spherical Fine Particles]

[0048]

[Reference Example 1] To a Teflon 100 ml Erlenmeyer flask, 11.2 g of tetraethoxysilane, 4.4 g of triisopropyl oxide aluminum and 30 g of isopropyl alcohol were added, and commercially available rutile titanium oxide (trade name "JR" manufactured by Teika). 28 g is added and dispersed and wet with an ultrasonic disperser. In addition to this, tetraethoxysilane and IN-
1 ml of ammonia water is added and heated in a constant temperature bath at 60 ° C. for 30 minutes while ultrasonically dispersing to deposit silica fine particles and alumina fine particles (3: 1) on the pigment surface. To the dispersion thus obtained, 80 ml of ion-exchanged water was added and stirred, and 4 mol / liter of JI was added to the dispersion of titanium oxide.
100 ml of S3 sodium silicate solution was added and mixed well, and this was added to a 15 g / l toluene solution of sorbitan monostearate and stirred at 11800 rpm for 1 time.
Perform for minutes to obtain a W / O emulsion. 2mo of this emulsion
It is added to 3000 ml of a 1 / l sodium sulfate aqueous solution and the reaction is carried out with stirring for 1 hour. Then, it is filtered, washed with water and washed with alcohol, and dried at 105 ° C. for 24 hours. Thus, about 54 g of white spherical silica fine particles having an average particle size of about 3 μm and containing about 50% of rutile type titanium oxide were obtained.

[0049]

Reference Example 2 100 parts by weight of the white spherical silica fine particles obtained in Reference Example 1 was dispersed in 100 parts by weight of isopropyl alcohol and 2 parts by weight of methylhydrogenpolysiloxane to form a slurry, which was heated. While drying under reduced pressure, baking treatment, and then crushing,
White spherical fine particles clathrating titanium oxide “(silicone oil treated) silica / alumina particle deposited titanium oxide clathrate silica capsules” were produced.

[0050]

Reference Example 3 To 50 parts by weight of the white 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 silica / alumina particle deposited titanium oxide inclusion silica capsule was obtained.

The colored spherical fine particles in the following examples are also
It was produced according to Reference Example 1 and Reference Example 2.

[0052]

[Example 1] The powder foundations shown in Table 1 were prepared, and their cosmetic effects, good spreadability during application, and cosmetic durability were evaluated.

[Evaluation Method] A sensory test was conducted by 20 specialist panels, and an average of 7-point evaluation was set as 7 points when the effect was very high and 1 point when the effect was very low, based on the following criteria. expressed.

(Standard) ◎ ・ ・ ・ ・ 6 points or more ○ ・ ・ ・ ・ 4 points or more and less than 6 points △ ・ ・ ・ ・ 2 points or more and less than 4 points × ・ ・ ・ ・ less than 2 points

(Manufacturing method) Nos. 1 to 11 were mixed and mixed, and Nos. 12 to 15 melted under heating were mixed and dispersed, then pulverized and homogenized, and press-molded into a predetermined container.

[0056]

[Table 1]

Remark 1: Reference example 2 (silicone oil treatment)
Silica particle deposition Titanium oxide inclusion silica capsule (inclusion rate 50%, average particle size 3 μm)

Remark 2: Titanium oxide inclusion silica capsule (inclusion rate 1 by the conventional interfacial sedimentation method (silicone oil treatment)
0%, average particle size 10 μm)

Remark 3: (Silicone oil treatment) Silica particle deposited titanium oxide inclusion silica capsule (inclusion rate 50%, average particle size 60 μm)

[0060]

Example 2 2-way foundation compounding amount (%) 1. Silica particle deposition Titanium oxide inclusion silica capsule (inclusion rate 45%, particle size 2 μm) ・ ・ ・ ・ ・ ・ ・ ・ ・ ・ ・ ・ ・ 10.0 2. Titanium oxide ... 8.0 3. Particulate titanium oxide (P-25) ・ ・ ・ ・ ・ ・ ・ ・ ・ ・ ・ ・ ・ 5.0 4. Mica ... 31.4 5. Talc ... 10.0 6. Mica Titanium ... 10.0 7. Bengala ・ ・ ・ ・ ・ ・ ・ ・ ・ ・ ・ ・ ・ 0.4 8. Yellow iron oxide ... 2.0 9. Black iron oxide ・ ・ ・ ・ ・ ・ ・ ・ 0.2 10． Spherical polystyrene powder ・ ・ ・ ・ ・ ・ 5.0

11. Methyl hydrogen polysilixane (Shin-Etsu Silicone KF-99) ... Dimethylpolysiloxane (Shin-Etsu Silicone KF-96 (100CS)) ... 5.0 13. Microcrystalline wax ・ ・ ・ ・ ・ ・ ・ ・ ・ ・ ・ 1.0 14． Liquid paraffin 5.0.15. Beeswax .............. 0.5 16. Glyceryl trioctanoate 3.0 17. Ultraviolet absorber ・ ・ ・ ・ ・ ・ ・ ・ ・ ・ ・ ・ ・ 18 18. Antioxidant ・ ・ ・ ・ ・ ・ ・ ・ ・ 0.1 19． Preservative ・ ・ ・ ・ ・ ・ ・ ・ ・ ・ ・ ・ ・ 0.3 20. Perfume ・ ・ ・ ・ ・ ・ ・ ・ ・ 0.1

(Production Method) 1. Mix and grind No. 1 to No. 9. 2. No. 11 and No. 12 are dissolved in isopropyl alcohol, 1 is added to form a slurry, dried under reduced pressure while heating, further baked and then pulverized.

3.2 and No. 10 are mixed, to which No. 13 to No. 20 heated and dissolved are added and mixed, and pulverized to homogenize. 4. Press-mold 4.3 into a predetermined gold plate.

(Evaluation) The way foundation of Example 2 can be used with either a dry sponge or a sponge moistened with water, has good spreadability upon application, has a uniform finish, and has an appropriate skin color correcting effect, and further has a aging effect. There was no color bleeding and the makeup was long-lasting.

[0065]

Example 3 Oily solid foundation compounding amount (%) 1. (Treatment with rosin acid pentaerythritol ester) Silica particle deposited titanium oxide, red iron oxide inclusion silica capsule (titanium oxide = 48%, red iron oxide = 2%, particle size 3 μm) ... 30.0 2. Titanium oxide ... 5.0 3. Mica titanium ・ ・ ・ ・ ・ ・ ・ ・ ・ ・ ・ ・ ・ 3.0 4. Sericite ・ ・ ・ ・ ・ ・ ・ ・ 3.0 5. Talc ・ ・ ・ ・ ・ ・ ・ ・ ・ ・ ・ ・ ・ 3.9 6. Nylon powder (SP-500) ・ ・ ・ ・ ・ ・ ・ ・ ・ ・ ・ 8.0 7. Bengara ・ ・ ・ ・ ・ ・ ・ ・ ・ ・ ・ ・ ・ 0.3 8. Yellow iron oxide ・ ・ ・ ・ ・ ・ ・ ・ ・ ・ ・ ・ ・ 3.5 9. Black iron oxide ... 0.3 10. Dextrin fatty acid ester: 2.5

11. Carnauba wax ... 12.12. Paraffin wax ・ ・ ・ ・ ・ ・ 3.5 13． Dimethylpolysiloxane (Shin-Etsu Silicone KF-96 (6CS)) ... 10.0 14. Methylphenyl polysiloxane (Shin-Etsu Silicone KF-56) ・ ・ ・ ・ ・ ・ ・ ・ ・ ・ 5.0 15. Liquid paraffin 8.5 16． Glyceryl trioctanoate ・ ・ ・ 10.0 17． Ultraviolet absorber ・ ・ ・ ・ ・ ・ ・ ・ ・ ・ ・ ・ ・ 18 18. Antioxidant ・ ・ ・ ・ ・ ・ ・ ・ ・ 0.1 19． Preservative ・ ・ ・ ・ ・ ・ ・ ・ ・ ・ ・ ・ ・ 0.3 20. Perfume ・ ・ ・ ・ ・ ・ ・ ・ ・ 0.1

(Manufacturing method) 1. Mix and grind No. 1 to No. 9. 2. No. 10 to No. 20 are dissolved by heating, 1 is added and homogenized with a roll mill. 3.2 is dissolved by heating and defoaming under reduced pressure. 4.3 is melted by heating, poured into a predetermined gold plate, covered with a cloth while being soft, press-molded, cooled and solidified, and then the cloth is peeled off.

(Evaluation) The oily solid foundation of Example 3 spread well during application, had a uniform finish, had an appropriate skin color correcting effect, and was excellent in makeup durability.

[0069]

Example 4 Makeup Base Component Blending Amount (%)

1. Stearic acid ... 2.0 2. Cetanol ・ ・ ・ ・ ・ ・ ・ ・ ・ ・ ・ ・ ・ 1.0 3. Glycerin fatty acid ester ... 1.0 4. Sorbitan sesquioleate: 0.6 5. Polyoxyethylene sorbitan trioleate (20 EO) 1.0 6. Liquid paraffin ・ ・ ・ 5.0 7. Paraffin wax ・ ・ ・ ・ ・ ・ 5.0 8. Decamethylpentacyclosiloxane ... 3.0 9. Triethanolamine ..... 10. Glycerin ... 3.0

11. Purified water ... 54.2 12. Carboxyvinyl polymer 0.2 13.1, 3-butylene glycol 14.0 14. (Glyceryl trioctanoate treatment) Silica particle deposited titanium oxide ・ Blue 404 inclusion silica capsule (inclusion rate, titanium oxide = 54% blue 404 = 6%, average particle size 5 μm) 1.0 15. Yellow iron oxide ・ ・ ・ ・ ・ ・ ・ ・ 0.2 16． Talc ・ ・ ・ ・ ・ ・ ・ ・ ・ ・ ・ ・ ・ 3.8 17． Soybean lecithin 0.2 18． Polyoxyethylene sorbitan monooleate (20 EO) · 0.8 19. Ethyl alcohol ... 18 20. Preservative ・ ・ ・ ・ ・ ・ ・ ・ ・ ・ ・ ・ ・ 21 21. Perfume ・ ・ ・ ・ ・ ・ ・ ・ ・ 0.1

(Production Method) 1. No. 13 to 18 are dispersed by a roll mill and homogenized. 2. No. 12 was added to No. 11 to swell, and No. 12 was added here.
Add 9, 10 and [1] and mix and disperse.

3. Heat-dissolved Nos. 1 to 8 were adjusted to 70 ° C., and [2] which was also adjusted to 70 ° C. was gradually added with stirring to emulsify and cooled to 40 ° C. 4. Nos. 19 to 21 dissolved in advance in [3] are added and mixed. 5. The tube was filled with [4] to obtain a makeup base.

(Evaluation) The makeup base of the present invention had a colorful color, had an appropriate control effect and spreadability at the time of application, and did not cause the skin to be bulky, and improved the duration of makeup.

[0075]

[Example 5] cheek color component blending amount (%)

1. Talc ... 30.0 2. Mica titanium ・ ・ ・ ・ ・ ・ ・ ・ ・ ・ ・ ・ ・ 10.0 3. Mica ... 43.4 4. Silica Particle Deposition Red No. 226 Inclusion Calcium Silicate Capsule (inclusion rate 10%, average particle size 3 μm) ... 5.0 5. Ultramarine ................................ 2.0 6. Microcrystalline wax ... 0.5 7. Squalane ・ ・ ・ ・ ・ ・ ・ ・ ・ ・ ・ ・ ・ 5.0 8. Vaseline ・ ・ ・ ・ ・ ・ ・ ・ 1.0 9. Dimethyl polysiloxane (Shin-Etsu Chemical Co., Ltd. Silicone KF-96 (100CS)) ··· 3.0 10. Perfume ・ ・ ・ ・ ・ ・ ・ ・ ・ 0.1

(Manufacturing method) 1. No. 1 to 5 are mixed and ground. 2. Add and mix No. 6 to 10 dissolved in [1] with heating,
Grind and homogenize. 3. [2] was press-molded into a predetermined gold plate to obtain a cheek color.

(Evaluation) The cheek color of the present invention has an appropriate coloring power and spreadability at the time of application, has a colorful color development, has a natural finish, and has no color sinking with time and is excellent in makeup durability. It was a thing.

[0079]

Example 6 Pack Component Blending Amount (%)

1. Vinyl acetate resin emulsion ... 15.0 2. Polyvinyl alcohol ... 10.0 3. Glycerin ..................... 5.0 4. (Teflon treatment) Silica / alumina particle deposited titanium oxide clathrate silica capsules (inclusion rate 45%, average particle size 30 μm) ・ ・ ・ ・ ・ ・ ・ ・ ・ ・ 14.0 5. (Teflon treatment) Silica / alumina particle deposition Yellow 205 / Red 226 inclusion silica capsule (inclusion rate, yellow 205 = 6%, red 226 = 6%, average particle size 3 μm) ... 1.0 6. Zinc flower ... 5.0 7. Kaolin ・ ・ ・ ・ ・ ・ ・ ・ 5.0 8. Ethyl alcohol ... 5.0 9. Purified water ... 39.7 10. Fragrance ・ ・ ・ ・ ・ ・ ・ ・ ・ ・ ・ ・ ・ 0.2 11. Preservative ・ ・ ・ ・ ・ ・ ・ ・ ・ 0.1

(Production Method) 1. Mix Nos. 1 to 3 and Nos. 8 to 11 and stir to homogenize. 2. Nos. 4 to 7 were added to [1] and kneaded to obtain a pack cosmetic.

(Evaluation) The pack cosmetic of the present invention was excellent in color, spreadability at application was good, and did not cause skin roughness.

[0083]

Example 7 Lipstick component blending amount (%)

1. Cesylene wax ... 4.0 2. Beeswax ・ ・ ・ ・ ・ ・ ・ ・ ・ ・ ・ ・ ・ 5.0 3. Candelilla Row ... 7.0 4. Carnauba Row 2.0 5. Castor oil ... 49.2 6. Hexadecyl alcohol 25.0 7. Titanium oxide ... 2.0 8. Silica particle deposition Red No. 226 inclusion silica capsule (inclusion rate 22%, average particle size 2 μm) ... 5.0 9. Silica Particle Deposition Yellow No. 401 Inclusion Silica Capsule (inclusion rate 17%, average particle size 2 μm) ... Perfume ・ ・ ・ ・ ・ ・ ・ ・ ・ 0.1

(Manufacturing method) 1. No. 1 to 6 are dissolved by heating. 2. Add Nos. 7 to 9 to [1] and uniformly disperse with a roll mill. 3. [2] was melted by heating, No. 10 was added, and then defoamed and poured into a mold, and solidified by cooling to obtain lipstick.

(Evaluation) The lipstick of the present invention has an appropriate coloring power and spreadability at the time of application, and the coloring is brilliant, there is no color unevenness, there is no color sinking with time, and the makeup is long-lasting. there were.

─────────────────────────────────────────────────── ───

[Procedure amendment]

[Submission date] September 16, 1993

[Procedure Amendment 1]

[Document name to be amended] Statement

[Name of item to be corrected] 0015

[Correction method] Change

[Correction content]

The inorganic pigments and / or organic pigments included in the colored spherical fine particles to be incorporated in the cosmetic of the present invention are titanium oxide, zinc oxide, zirconium oxide, magnesium oxide, red iron oxide, and red pigment which are usually used in cosmetics. Ultramarine, yellow iron oxide,
Ultramarine, Navy Blue, Manganese Violet, Ultramarine Violet, Black Iron Oxide, Titanium Black, Carbon Black, Aluminum Powder, Mica Titanium, Bismuth Oxychloride, Iron Oxide Mica Titanium, Navy Blue Mica Titanium, Carmine 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.

[Procedure Amendment 2]

[Document name to be amended] Statement

[Correction target item name] 0016

[Correction method] Change

[Correction content]

In the present invention, a coating of hydrated metal oxide is formed on such a pigment. The hydrated metal oxide at this time, silica, alumina, zirconia, titanium oxide, barium oxide, refers to iron oxide, preferably silica,
Alumina. As a general rule, this hydrated metal oxide film is preferably formed almost uniformly over the entire surface of the pigment, but 30% or more, preferably 80% or more of the minimum pigment surface may be coated. Also as the thickness of the coating
Does not aggregate primary particles in at least one molecular layer
It is preferably about 2-3 molecular layers.

[Procedure 3]

[Document name to be amended] Statement

[Name of item to be corrected] 0022

[Correction method] Change

[Correction content]

As the alcohol used in this method, those in the same range as the alcohol of the above method (A) can be used, and the acidic substance is usually hydrochloric acid, sulfuric acid, phosphoric acid or the like, or a basic substance. As such, sodium hydroxide, potassium hydroxide, ammonia or the like is usually used. electrolytic
The quality and metal oxide sols are already listed in the pigment section.
The same ones used are all used.

[Procedure amendment 4]

[Document name to be amended] Statement

[Name of item to be corrected] 0027

[Correction method] Change

[Correction content]

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

[Procedure Amendment 5]

[Document name to be amended] Statement

[Correction target item name] 0036

[Correction method] Change

[Correction content]

The colored spherical fine particles to be blended in the cosmetic of the present invention may have a particle size of 0.1 to 50 μm, preferably an average particle size of 1 to 5 μm is used to obtain a sufficient coloring power. It is preferable because it can obtain the hiding power. Furthermore, the inclusion rate of the inorganic pigment and / or the organic pigment is
10% to 60% by weight based on the total weight of the colored spherical fine particles
It is necessary to be. 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. Moreover, beyond the inclusion of 60 wt%, to the inclusion of inorganic pigments and / or organic pigments Engineering
It is hard to say that it is industrially advantageous.

[Procedure correction 6]

[Document name to be amended] Statement

[Name of item to be corrected] 0045

[Correction method] Change

[Correction content]

[0045]

The colored spherical fine particle-containing cosmetic of the present invention is
The coloring is colorful and has no unevenness in color, and it has a makeup effect such as appropriate coloring power and hiding power , an ultraviolet ray blocking effect such as sun protection and good spreadability at the time of application, and further suppresses the bulkiness of the skin. In the case of the above makeup cosmetics, the finished makeup film is natural, and the makeup durability is excellent such that the color does not fade over time.

[Procedure Amendment 7]

[Document name to be amended] Statement

[Correction target item name] 0048

[Correction method] Change

[Correction content]

[0048]

Reference Example 1 In a Teflon 100 ml Erlenmeyer flask, 11.2 g of tetraethoxysilane, 4.4 g of aluminum triisopropyl oxide and 3 of isopropyl alcohol were added.
In addition to 0 g, commercially available rutile titanium oxide (trade name "J
28 g of "R" manufactured by Teika Co., Ltd.) is added and dispersed and wetted by an ultrasonic disperser. This tetraethoxysilane and added 1ml of IN- aqueous ammonia as hydrolytic agents triisopropyl oxide aluminum, 60 ° C. in a constant temperature bath heated 30 minutes with an ultrasonic dispersing silica fine particles and alumina on the surface of the pigment Deposit fine particles (3: 1).
80 m of ion-exchanged water was added to the dispersion liquid thus obtained.
1 mol and stirred, 4 mol / l in the titanium oxide dispersion liquid
100 ml of JIS No. 3 sodium silicate solution was added and mixed well, and 15 g of sorbitan monostearate was added.
It is added to a toluene solution of 1 / l and stirred at 11800 rpm for 1 minute to obtain a W / O type emulsion. 2 this emulsion
It is added to 3000 ml of a mol / l sodium sulfate aqueous solution, and the reaction is carried out with stirring for 1 hour. Then, it is filtered, washed with water and washed with alcohol, and dried at 105 ° C. for 24 hours. In this way, about 54 g of white spherical silica fine particles having an average particle size of about 3 μm and containing about 50% of rutile type titanium oxide were obtained.

[Procedure Amendment 8]

[Document name to be amended] Statement

[Correction target item name] 0050

[Correction method] Change

[Correction content]

[0050]

Reference Example 3 To 50 parts by weight of the white spherical silica fine particles obtained in Reference Example 1, 1000 ml of water was added to form a slurry. Meanwhile, fluoroalkyl phosphate diethanolamine salt (Asahi Guard AG530, Asahi Glass Co., Ltd.)
350 g of water was added to 9 g of the product) 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 AG)
530 treatment) A silica / alumina particle deposited titanium oxide inclusion silica capsule was obtained.

[Reference Example 4] Teflon was added to a 100 ml Erlenmeyer flask.
Laethoxysilane 18.7g and ethyl alcohol 20g
20g of ultrafine titanium oxide particles with an average particle size of 2 μm
Add and wet with an ultrasonic disperser. Tetrae
1N-ammonia water 1 as a hydrolyzing agent for toxysilane
Add ml and disperse ultrasonically in a constant temperature bath at 60 ° C.
Heat for 30 minutes to deposit silica particles on the pigment surface
It 80 g of ion-exchanged water was added to the dispersion liquid thus obtained.
Add 3 ml and stir to add 3m to the dispersion liquid of ultrafine titanium oxide.
90 ml of ol / l JIS No. 3 sodium silicate solution
Add and mix well, add this to the sorbitan monostearate
Add to 15g / l toluene solution at 11800rpm
Stir for 1 minute to obtain a W / O type emulsion. This emulsion
2000 mol of 1.5 mol / l sodium sulfate aqueous solution
Add to ml and stir for 1 hour. After that, the excess
Separated, washed with water, washed with alcohol and dried at 105 ° C for 24 hours
To dry. Thus, about 50% inclusion of ultrafine titanium oxide
Oxidation of deposited silica particles with an average particle size of about 2 μm
About 43 g of a titanium-encapsulated silica capsule was obtained.

[Procedure Amendment 9]

[Document name to be amended] Statement

[Correction target item name] 0055

[Correction method] Change

[Correction content]

(Production method) No. 1-No. 11 was mixed and pulverized , and No. 11 was dissolved by heating. 12-No. After 15 was mixed and dispersed, it was crushed and homogenized, and press-molded into a predetermined container.

[Procedure Amendment 10]

[Document name to be amended] Statement

[Correction target item name] 0076

[Correction method] Change

[Correction content]

1. Talc ... 30.0 2. Mica titanium ・ ・ ・ ・ ・ ・ ・ ・ 10.0 3. Mica ・ ・ ・ ・ ・ ・ ・ ・ ・ ・ ・ ・ ・ 43.4 4. Silica Particle Deposition Red No. 226 Inclusion Calcium Silicate Capsule (inclusion rate 10%, average particle size 3 μm) ... 5.0 5. Ultramarine ................................................ 2.0 6. Microcrystalline wax ... 0.5 7. Squalane ・ ・ ・ ・ ・ ・ ・ ・ ・ ・ ・ ・ ・ 5.0 8. Vaseline ... 1.0 9. Dimethylpolysiloxane (Shin-Etsu Silicone KF-96 (100CS)) ... 0 10. Fragrance ・ ・ ・ ・ ・ ・ ・ ・ ・ 0.1

[Procedure Amendment 11]

[Document name to be amended] Statement

[Correction target item name] 0086

[Correction method] Change

[Correction content]

(Evaluation) The lipstick of the present invention has an appropriate coloring power and spreadability at the time of application, and the coloring is brilliant, there is no color unevenness, there is no color sinking with time, and the makeup is long-lasting. there were.

[Embodiment 8] White powder mixture amount (%) 1. Silica particles Deposited fine particles Titanium oxide * 1 Inclusion silica capsule (inclusion rate 50%, particle size 2 μm) ... 50.0 2. Talc ... 35.9 3. Mica ・ ・ ・ ・ ・ ・ ・ ・ ・ ・ ・ ・ ・ 5.0 4. Bengara ・ ・ ・ ・ ・ ・ ・ ・ ・ ・ ・ ・ ・ 0.1 5. Noble iron oxide ..................... 0.4 6. Black iron oxide ... 0.1 7. Methyl hydrogen polysilotisant (Shin-Etsu Silicone KF-99) ... 1.0 8. Dimethyl polysiloxane (Shin-Etsu Silicone KF-96 (100CS)) ... 4.0 9. Ultraviolet absorber ... 3.0 10. Antioxidant ・ ・ ・ ・ ・ ・ ・ ・ 0.1 11． Preservative ・ ・ ・ ・ ・ ・ ・ ・ ・ ・ ・ ・ ・ 0.3 12. Fragrance ・ ・ ・ ・ ・ ・ ・ ・ 0.1 * 1 Fine particle titanium oxide MT-500B manufactured by TAYCA (manufacturing method) 1. No. 1 to 6 are mixed and ground. 2. No. 7, No. 8 is dissolved in n-hexane, 1 is added to form a slurry, dried under reduced pressure while heating, further baked, and then pulverized. 3.2 and No. Mix 9-12 and grind to homogenize. Fill the container with 4.3. (Evaluation) The white powder of the present invention has a high ultraviolet blocking effect (see FIG.
4) Good spread during application, uniform finish and natural
Has an eraser effect and covering power, and further color fades over time
It was excellent in the durability of makeup. ─────────────────────────────────────────────────── ───

[Procedure amendment]

[Submission date] December 2, 1993

[Procedure Amendment 1]

[Document name to be amended] Statement

[Correction target item name] 0086

[Correction method] Change

[Correction content]

(Evaluation) The lipstick of the present invention has an appropriate coloring power and spreadability at the time of application, and the coloring is brilliant, there is no color unevenness, there is no color sinking with time, and the makeup is long-lasting. there were.

Example 8 White powder Powder content (%) 1. Silica particles Deposited fine particles Titanium oxide * 1 Inclusion silica capsule (inclusion rate 50%, particle size 2 μm) ... 50.0 2. Talc ... 35.9 3. Mica ・ ・ ・ ・ ・ ・ ・ ・ ・ ・ ・ ・ ・ 5.0 4. Bengara ・ ・ ・ ・ ・ ・ ・ ・ ・ ・ ・ ・ ・ 0.1 5. Noble iron oxide ..................... 0.4 6. Black iron oxide ... 0.1 7. Methyl hydrogen polysilotisant (Shin-Etsu Silicone KF-99) ... 1.0 8. Dimethyl polysiloxane (Shin-Etsu Silicone KF-96 (100CS)) ... 4.0 9. Ultraviolet absorber ... 3.0 10. Antioxidant ・ ・ ・ ・ ・ ・ ・ ・ 0.1 11． Preservative ・ ・ ・ ・ ・ ・ ・ ・ ・ ・ ・ ・ ・ 0.3 12. Fragrance ・ ・ ・ ・ ・ ・ ・ ・ 0.1 * 1 Fine particle titanium oxide MT-500B manufactured by TAYCA (manufacturing method) 1. No. 1 to 6 are mixed and ground. 2. No. 7, No. 8 is dissolved in n-hexane, 1 is added to form a slurry, dried under reduced pressure while heating, further baked, and then pulverized. 3.2 and No. Mix 9-12 and grind to homogenize. Fill the container with 4.3. (Evaluation) The white powder of the present invention has a high ultraviolet blocking effect (see FIG.
1 ) It spreads well during application, has a uniform finish, has a natural matting effect and covering power, and has no color bleeding over time and is excellent in makeup durability.

[Procedure Amendment 2]

[Document name to be amended] Statement

[Name of item to be corrected] Brief description of the drawing

[Correction method] Added

[Correction content]

[Brief description of drawings]

FIG. 1 is a drawing showing the ultraviolet blocking effect (ultraviolet ray transmission amount) of the cosmetic (white powder) of the present invention.

[Procedure 3]

[Document name to be corrected] Drawing

[Name of item to be corrected] Figure 1

[Correction method] Added

[Correction content]

[Figure 1] ─────────────────────────────────────────────────── ───

[Procedure amendment]

[Submission date] December 7, 1993

[Procedure Amendment 1]

[Document name to be amended] Statement

[Correction target item name] 0086

[Correction method] Change

[Correction content]

(Evaluation) The lipstick of the present invention has an appropriate coloring power and spreadability at the time of application, and the coloring is brilliant, there is no color unevenness, there is no color sinking with time, and the makeup is long-lasting. there were.

Example 8 White powder Powder content (%) 1. Silica particles Deposited fine particles Titanium oxide * 1 Inclusion silica capsule (inclusion rate 50%, particle size 2 μm) ... 50.0 2. Talc ... 35.9 3. Mica ・ ・ ・ ・ ・ ・ ・ ・ ・ ・ ・ ・ ・ 5.0 4. Bengara ・ ・ ・ ・ ・ ・ ・ ・ ・ ・ ・ ・ ・ 0.1 5. Yellow iron oxide ..................... 0.4 6. Black iron oxide ... 0.1 7. Methylhydrogenpolysiloxane white key Sun (Shin-Etsu Silicone KF-99) ············ 1.0 8. Dimethyl polysiloxane (Shin-Etsu Silicone KF-96 (100CS)) ... 4.0 9. Ultraviolet absorber ... 3.0 10. Antioxidant ・ ・ ・ ・ ・ ・ ・ ・ 0.1 11． Preservative ・ ・ ・ ・ ・ ・ ・ ・ ・ ・ ・ ・ ・ 0.3 12. Fragrance ・ ・ ・ ・ ・ ・ ・ ・ 0.1 * 1 Fine particle titanium oxide MT-500B manufactured by TAYCA (manufacturing method) 1. No. 1 to 6 are mixed and ground. 2. No. 7, No. 8 is dissolved in n-hexane, 1 is added to form a slurry, dried under reduced pressure while heating, further baked, and then pulverized. 3.2 and No. Mix 9-12 and grind to homogenize. Fill the container with 4.3. (Evaluation) The powdery white powder of the present invention has a high ultraviolet blocking effect (Fig. 1), spreads well during application, has a uniform finish, has a natural matting effect and covering power, and further has no color sinking over time. It was excellent in makeup lasting.

[Procedure Amendment 2]

[Document name to be amended] Statement

[Name of item to be corrected] Brief description of the drawing

[Correction method] Change

[Correction content]

[Brief description of drawings]

FIG. 1 is a drawing showing the ultraviolet blocking effect (ultraviolet transmittance (%) ) of the cosmetic (white powder) of the present invention.

[Procedure 3]

[Document name to be corrected] Drawing

[Name of item to be corrected] Figure 1

[Correction method] Change

[Correction content]

[Figure 1]

Claims (3)

[Claims] 1. A cosmetic composition comprising colored spherical fine particles, which are substantially perfect spheres in which an organic and / or inorganic pigment coated with a hydrated metal oxide is included in an inorganic porous wall substance. 2. The cosmetic according to claim 1, which contains colored spherical fine particles having a particle size of 0.1 to 50 μm. 3. The cosmetic according to claim 1, which contains colored spherical fine particles treated with an oil agent or a fluorine-containing resin.