JPH0899838A - Colored cosmetic - Google Patents

Abstract

PURPOSE: To obtain the subject cosmetic containing a colored metal oxide gel produced by adding a coloring agent to a metal alkoxide and subsequently gelating the mixture, capable of being produced without producing by-products inconvenient for the treatment of a sodium salt, etc., and containing the gel capable of strongly carrying the coloring agent. CONSTITUTION: This cosmetic contains a colored metal oxide gel obtained by adding a coloring agent (preferably an organic pigment such as cochineal) to a metal alkoxide (preferably a silicone alkoxide such as tetraethoxysilane). The colored metal oxide gel is obtained e.g. by stirring a solution comprising a metal alkoxide, a coloring agent, water and an alcohol in the presence of a catalyst such as hydrochloric acid to subject the metal alkoxide to a hydrolysis reaction and a polycondensation reaction, and subsequently drying the obtained hydrogel, while raising the temperature of the hydrogel. The employment of an organic compound having amino groups or urethane groups, such as nylon, for the production of the gel is preferable, because the gel excellent in mechanical strengths and gas barrier property is obtained.

Description

Detailed Description of the Invention

[0001]

FIELD OF THE INVENTION The present invention relates to colored cosmetics,
In particular, the present invention relates to a cosmetic material in which a colored metal oxide gel that strongly supports a colorant and is easy to manufacture is blended.

[0002]

2. Description of the Related Art In recent years, the affinity between pigments and toning aids,
Due to the difference in surface activity, specific gravity, crystal form, particle size, etc., they are separated from each other at the time of production, transportation, storage or use, and color separation, segregation, color difference, etc. are prevented, in order to prevent the disadvantage that a colored metal oxide gel, Colored silica gel has been proposed.

This colored silica gel is obtained by dyeing silica gel with various water-soluble dyes. However, there are some problems in dyeing due to the unique physical properties of silica gel itself. That is, since the pore diameter of general silica gel is 2 to 20 nm, an organic dye having a large molecular weight cannot be sufficiently diffused inside the pores. For this reason,
Even when silica gel is dipped in a dye solution by a conventional dipping method, the dye only adheres to the surface of the silica gel particles and does not easily penetrate inside. Further, in the coloring method as described above, color unevenness is likely to occur, and the pigment is adhered to the surface. Therefore, when the pigment is mixed in a cosmetic containing a solvent capable of dissolving and dispersing the pigment, the pigment moves to the solvent phase. Then, there arises a problem that the silica gel and the dye are separated.

Further, JP-A-55-32775 discloses a method of uniformly blending a colorant with silica gel. In this method, the colorant is pre-dispersed in the raw material sodium silicate, the acid (dilute sulfuric acid) is added to form a dispersion, and this is stirred and poured into the dispersion medium in which the emulsifier is present. The silica gel is washed to remove the soda salt mixed in as a by-product (Glauber's salt when the acid is dilute sulfuric acid), and then dried. However, when a water-soluble dye is used in this method, when the soda salt is removed, the colorant dyed with care flows out together with the soda salt, the coloring concentration decreases, and it is difficult to waste the raw material and control the quality. In addition to the above, there is a disadvantage in that a troublesome post-treatment such as recovery of the coloring agent from the cleaning liquid and purification treatment of the coloring waste liquid is required.

[0005]

In order to solve the above drawbacks, Japanese Patent Publication No. 4-55972 discloses a silica hydrogel formed by reacting sodium silicate with an acid to form a silica sol and then gelling. Is washed with water to remove the soda salt mixed as a by-product, then hydrothermally treated, and then colored by adding a coloring agent, the colored mother liquor is separated and dried, and colored silica gel and a colored cosmetic containing the colored silica gel are mixed. A method of manufacturing is disclosed.

However, this colored cosmetic requires a step of removing soda salt in the manufacturing process thereof, and therefore, it takes time to manufacture the colored cosmetic, and it is inconvenient to dispose of the soda salt.

Therefore, the present invention contains a colored metal oxide gel which can be produced without producing inconvenient by-products such as soda salt during the production process and which can firmly carry a colorant. The purpose is to provide colored cosmetics.

[0008]

In order to achieve the above objects, the present invention contains a colored metal oxide gel produced by gelling after adding a colorant to a metal alkoxide. Cosmetics. For more information,
The colored metal oxide gel to be blended in the present invention is prepared, for example, by first using a metal alkoxide, a colorant, water and an alcohol as a starting solution, and stirring the solution to cause the metal alkoxide to undergo a hydrolysis reaction, a polycondensation reaction and the like. It is prepared by converting the solution into a gel and then drying the resulting hydrogel at elevated temperature.

As the reaction catalyst, for example, an acid catalyst such as hydrochloric acid, sulfuric acid, nitric acid or acetic acid, or a basic catalyst such as ammonia can be used. Further, water is used for hydrolysis of the metal alkoxide, but when the hydrolysis rate is large and the reaction proceeds inhomogeneously, water in the air may be used.

The metal alkoxide is preferably a silicon alkoxide, such as Si (OR) ₄ . In addition to these, examples of the metal alkoxide used in the present invention include Zn, Ti, Al, Fe, Co, Ni and Z.
There are alkoxides such as r, which can be used alone or in combination depending on the purpose. For example, when it is desired to increase the reflectance, it is effective to mix Ti or Zn, Zr when it is necessary to improve the strength and alkali resistance, and Ni or the like when it is desired to further improve the weather resistance. Examples of the alkyl group of the metal alkoxide include a methyl group, an ethyl group and a propyl group.

The reaction solvent is used to make the starting solution a homogeneous solution, which includes methanol, ethanol,
There are alcohols such as propanol and butanol. Further, the alcohol produced by the progress of the reaction also acts to make the mixed solution a homogeneous solution, but if these reaction solvents are removed along with the progress of the reaction, the reaction proceeds rapidly.

The reaction temperature is such that the reaction proceeds at a constant temperature until a hydrogel is formed, and a gel dried product can be obtained by heating and heating the gel at the same time. You can also get The reaction temperature in the present invention controls the reaction rates of the hydrolysis reaction and the polycondensation reaction, and the reaction can proceed at room temperature or high temperature. Furthermore, regarding the temperature,
Although it is necessary to consider the heat resistance of the colorant used, the reaction rate can be further increased by heating up to about 150 ° C. as the reaction proceeds.

The organic polymer compound used in the present invention preferably has an amide group or a urethane group, and examples thereof include polyvinylpyrrolidone, nylon and polyurethane.

The colorant used in the present invention is preferably an organic dye. For example, as water-soluble organic colorants, red 2, 3, 10, 102 and 104 are used.
No. 105, 106, 201, 213, 214
No. 219, 227, 230, 231, 232
No. 401, 502, 503, 504, 506
No. 205, No. 205, No. 207, No. 402, Yellow No. 4, 5
No. 202, 402, 403, 406, 407
No. 3, Green No. 3, 204, 205, 401, 402
No. 1, Blue No. 1, No. 2, No. 202, No. 203, No. 205,
Red 202, 2 as water-insoluble or sparingly soluble organic dyes such as brown 201, purple 401, black 401, cochineal, carsamine, β-carotene, and chlorophyll
03, 204, 206, 219, 226, 4
04, 501, 505, orange 201, 203
No. 204, 206, 403, Yellow 201, 2
04, 205, 404, 405, blue 403
A book characterized by being able to prepare a colored metal oxide gel using almost all coloring agents that can be used in cosmetics, such as No. 4, yellow No. 4 aluminum lake, yellow No. 5 aluminum lake, etc. It is possible to make the colored metal oxide gel-containing cosmetics of the invention. However, when the colorant is insoluble or sparingly soluble in water or alcohol, it is effective to uniformly disperse the colorant under stirring or under irradiation of ultrasonic waves.

The cosmetic composition according to the present invention may contain components other than those mentioned above, for example, an ultraviolet absorber.

[0016]

The colored metal oxide gel according to the present invention does not require treatment such as washing with water to remove soda salts in the manufacturing process thereof, and since the coloring agent is added before gelation, Stronger than when a treatment such as washing is required, or when a coloring agent is added after gelling,
In addition, the colorant can be uniformly supported.

Further, since the difficult treatment of removing such soda salt and the like is not required, the production is easy. That is, the by-products produced in the reaction of the colored metal oxide gel blended in the present invention are only water and alcohol, and in order to remove these by-products, only the produced colored metal oxide gel is dried. Good.

Furthermore, by using an organic compound having an amino group or a urethane group, the amino group or the urethane group forms a hydrogen bond with the surface hydroxyl group of the metal oxide, and therefore the colored metal oxide gel according to the present invention. Has excellent mechanical strength and gas barrier properties.

[0019]

EXAMPLES Next, the examples of the present invention will be compared with the comparative examples.
It will be explained together with the ratio test. Examples of the present invention include metal alcohols.
Tetraethoxysilane [Si (C ₂H_FiveO)
_Four] Is used as a coloring agent (pigment)
Chinyl (main component: carminic acid) was used. First,
Ethanol 1.33 to 36.47 g of traethoxysilane
5 g was added and the solution was stirred. Then ethanol
1.335 g, 0.035 M aqueous cochineal solution 2.5
ml, and 2.06 ml of water and 1.75 m of 0.1N hydrochloric acid.
The water-soluble component mixed with 1 was slowly dropped into the solution,
Then stirring was continued until the solution became clear (mol
Ratio: cochineal / tetraethoxysilane = 5.0 × 10
^-Four). After adjusting the solution to be transparent, a pinhole was opened.
Cover with a luminium film to increase the viscosity of the solution.
The solution was left at room temperature until it gelled. Gelation of solution
Then, the gel was allowed to stand at room temperature for 2 months to mature.
Then, the gel body is allowed to stand at 50 ° C. for 60 hours,
The temperature is raised to 80 ° C over 60 hours, and the temperature is increased to 24 hours.
It was dried under reduced pressure at 80 ° C. using diphosphorus oxide. Dried
The gel body thus prepared is crushed in advance using an automatic mortar and
It was crushed by a bar type muller. After grinding, the powder is pentoxide.
It was dried under reduced pressure using phosphorus to obtain colored silica gel.

Next, as a comparative example, the following coloring agent
A silica gel mixture was obtained. That is, a metal oxide gel containing no colorant was produced by the same method as described above, and the two were mixed so that the weight ratio of the metal compound gel and the colorant was the same as in the above example, and this mixture was mixed. Thorough mixing was carried out using a Hover type muller to obtain a colorant-metal oxide gel mixture. Here, cochineal and carmine (cochineal calcium-aluminum lake) are used as colorants, the former is used as Comparative Example 1, and the latter is used as Comparative Example 2.

Next, a colorant dissolution test was carried out on the colored silica gel of Example and the colorant-silica gel mixture of Comparative Example 2. In the dissolution test, the colored metal oxide gel of Example 1 or the carmine used in Comparative Example 2 was dispersed in a 1 wt% sodium chloride aqueous solution so as to be 2 wt% and stirred. Then, after 24 hours, stirring was stopped, the dispersion was centrifuged, the supernatant was filtered, and the amount of the colorant dissolved in the filtrate was measured using a spectrophotometer to calculate the elution rate. The results are shown in Table 1.

[0022]

[Table 1]

From Table 1, it can be seen that the colored silica gel of the example has a lower dye elution rate than the carmine used in Comparative Example 2, and the colorant is firmly supported in the silica gel.

Next, using the colored silica gel of the example and the colorant-silica gel mixtures of Comparative Example 1 and Comparative Example 2 and the compounding amounts shown in Table 2, eye shadows were prepared by the same preparation method.

[0025]

[Table 2]

The following tests were carried out on each of the eye shadows prepared as described above. First, a test for dye dispersibility in eye shadows was conducted by measuring the reflectance of each eye shadow. As a result, although the prepared eye shadows were each mixed with the same amount of dye, the reflectance of the eye shadow containing the colored silica gel of the example was the mixture of Comparative Example 1 or 2. It was lower than the eye shadow. From this, it can be seen that the eye shadow containing the colored silica gel of the example is superior in coloring property. This is because, in the preparation of colored silica gel, a uniform solution of the dye gels and contracts in a homogeneous state, so that the reaction proceeds all the time while the dye is dispersed in the bulk body of the gel at the molecular level. It is considered that the extremely good dispersion state of the dye in silica gel increased the dispersion efficiency of the dye in the eye shadow and improved the coloring power.

Next, 1 each of the prepared eye shadows was prepared.
Each eye shadow was subjected to a heat resistance test by allowing it to stand in a constant temperature bath at 20 ° C. for 50 hours and measuring the color difference (ΔE) before and after heating. Table 3 shows the results.

[0028]

[Table 3]

As can be seen from Table 3, the eye shadow containing the colored silica gel of the example has a smaller color difference (ΔE) than that of the comparative example. This is because most of the pigments in the colored metal oxide gel were embedded in the bulk body of silica gel due to the three-dimensional network structure of silica gel, and very few were exposed on the surface. It is considered that this is because the dye does not come into contact with oxygen in the air or the surface active part of the metal oxide and there is little discoloration caused by an oxidation reaction or the like.

From the above, the colored silica gel according to the present embodiment and the eye shadow containing the same can firmly support the coloring agent, and can improve the stability of the dye including heat resistance. . Further, according to this embodiment,
Even if it is a natural pigment, a sufficient coloring effect can be obtained,
As a result, when a natural pigment contained in insects or plants is carried, it is possible to solve the conventional problem that a vivid coloring effect cannot be obtained when contained in insects or plants. it can.

The colored metal oxide gel according to this embodiment may be blended not only with eye shadows but also with foundations, lipsticks and the like. Further, although tetraethoxysilane is used as the metal alkoxide in this embodiment, it is not necessary to limit to this, and tetramethoxysilane or the like may be used. Furthermore, although cochineal was used as the colorant in this example, it is not necessary to limit to this and, for example, carsamine, β-carotene, chlorophyll and the like may be used.

Further, an organic polymer compound such as polyvinylpyrrolidone, nylon or polyurethane may be mixed before gelling the metal alkoxide of this embodiment. Since these organic polymer compounds have an amide group or a urethane group, they form hydrogen bonds with the surface hydroxyl groups of the metal oxide. Therefore, the colored metal oxide gel containing these organic polymer compounds is excellent in mechanical strength and gas barrier property. As a result, cracking, discoloration, etc. can be reduced.

[0033]

As described above, according to the present invention, a colored metal oxide which can be produced without producing inconvenient by-products such as soda salt during the production process and which can firmly carry a coloring agent. It is possible to provide a colored cosmetic product containing the product gel.

Claims (7)

[Claims] 1. A cosmetic containing a colored metal oxide gel produced by gelling after adding a colorant to a metal alkoxide. 2. The cosmetic according to claim 1, wherein the metal alkoxide is a silicon alkoxide. 3. The cosmetic according to claim 1, wherein a colorant is added after the organic polymer compound is mixed with the metal alkoxide. 4. The cosmetic according to claim 1, wherein the organic polymer compound has an amide group. 5. The cosmetic according to claim 1, wherein the organic polymer compound has a urethane group. 6. The colorant is an organic dye.
The cosmetic according to any one of 1 to 5. 7. The composition according to claim 1, further comprising an ultraviolet absorber.
7. The cosmetic according to any one of 6 to 6.