JPH0455972B2 - - Google Patents

Description

DETAILED DESCRIPTION OF THE INVENTION The present invention relates to colored silica gel and colored cosmetics, and provides a colored silica gel that firmly holds a coloring agent inside and a colored cosmetic that is characterized in that the colored silica gel is blended as a pigment. It is.

Conventionally, as colorants for cosmetics, paints, pharmaceuticals, etc., for example, Red No. 202, No. 203, No. 204, No. 205,
No. 206, No. 207, No. 208, No. 215, No. 218, No. 221,
No. 223, No. 225, Orange No. 201, No. 203, No. 206, 401
No. 403, Yellow No. 201, No. 204, No. 205, No. 401,
No. 404, No. 405, Green No. 202, Blue No. 201, No. 204,
Organic pigments such as No. 403, No. 404, and Purple No. 201, titanium oxide, zinc white, iron sesquioxide, yellow iron hydroxide, chromium oxide, chromium hydroxide, ultramarine, deep blue, purple ultramarine,
Colors can be obtained by mixing inorganic pigments such as triiron tetroxide and carbon black with toning aids such as talc, kaolin, titanium dioxide, and microcrystalline cellulose. Due to differences in affinity, surface activity, specific gravity, crystal form, particle size, etc., they have the disadvantage that they separate from each other during production, transportation, storage, or use, resulting in color separation, segregation, color difference, etc. Colored silica gel has been proposed as an alternative to conventional coloring materials having such drawbacks. This colored silica gel is obtained by dyeing silica gel with various water-soluble dyes, but due to the unique physical properties of silica gel itself, there are several problems in dyeing it. The pore diameter of general silica gel is 2 to 20 nm.
Organic dyes with large molecular weights cannot diffuse sufficiently into the pores, so even if silica gel is immersed in a dye solution using the conventional immersion method, the dyes will only adhere to the surface of the silica gel particles and will not be absorbed inside. Difficult to penetrate. In addition, the coloring method described above tends to cause color unevenness, and since the pigment is attached to the surface, if it is blended into a cosmetic that contains a solvent that dissolves and disperses the pigment, the pigment will migrate to the solvent phase. As a result, the silica gel and the dye separate. On the other hand, when colored silica gel is specially treated to enlarge the internal pore diameter so that dye molecules can penetrate, the dye is uniformly dispersed and permeated into the pores, but the pores are 10 nm thick.
If the temperature exceeds the limit, light will be refracted within the pores, causing the silica gel to become cloudy and the color saturation of the dye to be lost. In addition, since the pore diameter is large, if a solvent that dissolves and disperses the dye is used, the dye that has penetrated into the pores will easily escape from the pore and transfer to the solvent phase, causing the silica gel and the dye to separate. I end up doing it. As another conventional example, Japanese Patent Application Laid-Open No. 55-32775 discloses a method in which a dye is uniformly blended into silica gel.
This method involves pre-dispersing the pigment in the raw material sodium silicate, adding acid (dilute sulfuric acid) to form a dispersion liquid, stirring and pouring this into a dispersion medium containing an emulsifier, and gelling it by heating. Wash the generated silica gel and
After removing the soda salt (or glauber's salt if the acid is dilute sulfuric acid) mixed as a by-product, it is dried. However, when using this method with water-soluble dyes, when removing the soda salt, The dyed pigment flows out together with the soda salt, reducing the color concentration, which not only causes wasted raw materials and makes quality control difficult, but also requires troublesome post-processing, such as recovering the pigment from the cleaning solution and purifying the colored waste liquid. There are drawbacks that require processing. On the other hand, cosmetics manufactured by blending pigments or colored silica gel using conventional techniques as described above have problems such as irritation to the skin due to free pigments, problems with light resistance, problems with mixing stability, and problems with low chroma. This has resulted in restrictions on its formulation, making it highly safe and difficult to freely incorporate coloring. Particularly in recent years, the safety of tar-based pigments and the like has become an issue, and coloring, which is the lifeblood of cosmetics, has been severely restricted due to restrictions on use such as guidance from the Ministry of Health and Welfare and industry voluntary regulations.

The inventors of the present invention have conducted various studies in order to solve the problems encountered with known pigments and cosmetics as described above. As a result, if coloring is applied during the process of silica hydrosol, which is an intermediate of silica gel, the coloring efficiency is high, and the coloring is strongly retained during the subsequent drying process, and the dye does not fall off, and the color fades due to light, especially ultraviolet light. He came up with the invention of colored silica gel without
Furthermore, due to its combination of colored silica gel, it has low skin irritation, high light stability and mixing stability,
We have achieved the invention of colored cosmetics that can be colored with any hue, saturation, and brightness. That is, in the present invention, a silica hydrosol is formed by reacting sodium silicate with an acid, and then the silica hydrogel produced by gelation is washed with water to remove the by-product soda salt, and then subjected to hydrothermal treatment. The gist of the present invention is to provide a colored silica gel which is then colored by adding a coloring agent, and a colored mother liquor is separated and dried, and a colored cosmetic containing the colored silica gel.

Hereinafter, the first invention will be explained in more detail.
An example of the sodium silicate used in the production of the colored silica gel of the invention is the commercially available sodium silicate 1.
No. 2, No. 3 (JISK1048), etc.
In addition, as a coloring agent, for example, tar-based pigment red 2
No. 3, No. 10, No. 102, No. 104, No. 105, No. 106,
No. 201, No. 213, No. 214, No. 219, No. 227, No. 230,
No. 231, No. 232, No. 401, No. 502, No. 503, No. 504,
No. 506, Orange No. 205, No. 207, No. 402, Yellow No. 4, 5
No. 202, No. 402, No. 403, No. 406, No. 407, Green No. 3, No. 204, No. 205, No. 401, No. 402, Blue No. 1,
No. 2, No. 202, No. 203, No. 205, Brown No. 201, Purple
Examples include water-soluble organic dyes such as No. 401 and Black No. 401. In addition, organic dyes that are insoluble or poorly soluble in water can also be applied to coloring if the water that has penetrated into the pores of the silica hydrogel can be replaced with an organic solvent that can dissolve the above dyes. Specific examples of colorants include tar-based pigments Red No. 501 and 505.
No., orange No. 201, 206, 403, yellow No. 201, 204
No. 404, No. 405, blue No. 403, etc.

The colored silica gel of the present invention is produced by applying the above-mentioned coloring agent to the silica hydrogel, which has been thoroughly washed with water to remove the soda salt that is produced as a by-product when forming silica hydrosol through the reaction of sodium silicate and acid. Coloring is performed using one or more types. By adopting such a method, when removing soda salt mixed with by-products by washing with water, as in the conventional method,
It is possible to prevent the dyed coloring material from falling off together. In addition, the pore diameter inside the silica hydrogel can be freely adjusted by subjecting it to hydrothermal treatment for a certain period of time at a controlled pH during the silica hydrogel stage. In the present invention, this method is used to adjust the pore diameter and color the silica gel, which is then dried. This is a major feature of the colored silica gel of the first invention, as it is occluded, that is, sealed and immobilized, and there is no elution, resulting in a strongly colored colored silica gel.

Hydrothermal treatment here means heating and keeping the silica hydrogel at a constant temperature for a certain period of time.

The colored silica gel of the first invention can be produced, for example, as follows. That is, an aqueous solution of a demetalized sodium silicate salt is mixed and stirred in an acid such as dilute sulfuric acid to form a silica hydrosol, which is then gelled at elevated temperature to obtain a silica hydrogel. Next, this silica hydrogel is separated by filtration and thoroughly washed with water to remove by-products such as sodium sulfate such as sodium sulfate. Next, the silica hydrogel is suspended in water, adjusted to a certain pH by adding alkali such as aqueous ammonia or sodium hydroxide, and then kept at a certain temperature in a closed container and subjected to hydrothermal treatment for a predetermined time to dye. The silica hydrogel is transformed into a silica hydrogel having a desired pore size depending on the molecular size of the colorant to be used.

A desired colorant aqueous solution is added to the silica hydrogel thus obtained in a slurry state, for example,
After leaving it in the sun, the colored silica hydrogel and the colorant aqueous solution are separated by filtration, and the colored silica hydrogel is heated at 100° C. or higher for several hours and dried to obtain a silica gel colored to a desired color tone, that is, a colored silica gel. The colored mother liquor after filtration has the advantage of not containing by-product soda salt, and can be recovered and reused for coloring.

On the other hand, the colored cosmetics of the second invention are produced by blending the colored silica gel of the first invention into cosmetics as a pigment, and the applicable cosmetics include all types of cosmetics that require coloring. . For example, it can be applied to whitening powder, foundation, lipstick, eye shadow, eyeliner, mascara, blusher, nose shadow, manicure or pedicure. The blending ratio of colored silica gel in cosmetics can be adjusted as appropriate depending on the desired color, but in general, from the viewpoint of color development, spreadability, adhesion, feel, etc. of cosmetics, it is generally 1 to 40% in the basic formulation of cosmetics. (The same percentages by weight and below) are preferred. The compounding method is the usual method of blending pigments into cosmetics, and no special steps are required.

As described above, the colored silica gel of the first invention is produced by reacting sodium silicate with an acid to form a silica hydrosol, and then washing the silica hydrogel produced by gelation with water to form a by-product of soda salt. It is obtained by performing hydrothermal treatment after removing , then adding a coloring agent for coloring, separating the colored mother liquor and drying it. This colored silica gel strongly retains the coloring agent inside, making it suitable for coloring cosmetics and pharmaceuticals, and does not cause pigment separation or fading when added to cosmetics or pharmaceuticals, unlike conventional organic pigments. In terms of color development, it has performance equivalent to or better than that of conventional coloring materials. Moreover, since the separated mother liquor after coloring does not contain impurities such as sodium sulfate such as sodium sulfate, it can be used again to color silica hydrogel without being discarded, and can be purified for disposal. It has the advantage of not requiring any processing. Furthermore, the colored cosmetics of the present invention can realize brightly formulated cosmetics with a high degree of freedom in formulation due to the high safety and mixing stability of the colored silica gel and the faithful color development and stability of the dyeing pigments.

Next, typical examples based on the present invention will be described, but the content of the present invention is not limited to these examples. Here, Examples 1 and 2 relate to the invention of colored silica gel,
Examples 3 to 6 relate to the invention of colored cosmetics using this colored silica gel.

Example 1 Commercially available sodium silicate No. 3 (molar ratio 3.3)
A silica hydrosol was obtained by mixing 1000 ml of a demetalized salt aqueous solution with a SiO ₂ concentration of 18% and 500 ml of dilute sulfuric acid (8N), and further gelled and molded to obtain a spherical silica hydrogel (1000 gr) with an average particle size of 50 μ. .This silica hydrogel was washed with 5000 ml of demetalized brine,
Remove the Glauber's salt and prepare the spherical silica hydrogel (SiO ₂ 22
%, _H2O 78%). Add 500ml of demetalized salt water to 500g of washed spherical silica hydrogel and adjust the pH.
7.2, the temperature was maintained at 50°C and hydrothermal treatment was performed on a hot water bath for 12 hours in a closed container. After hydrothermal treatment, a sample was taken, dried, and measured using the nitrogen adsorption method.
A surface area of 560 m ² /g was obtained. From this result, it was found that the average pore diameter of the silica hydrogel was 25.3 nm.

Silica hydrogel obtained as above
0.05% red No. 213 aqueous solution as a coloring agent in 100gr
After adding 100gr and leaving it in a slurry state for one day,
The colored mother liquor was separated by filtration and dried at 120°C for 6 hours to obtain 22 gr of red silica gel. In addition, its physical properties are as follows: BET surface area is 550m ² /gr by nitrogen adsorption method.
The pore volume was 0.88 ml/gr, and the average pore diameter was 6.4 nm.
Further, when the particle size distribution was analyzed by the Coulter Counter method, the average particle size was 30μ. 20 gr of red silica gel obtained in this example was washed with 500 ml of demetalized salt water, but there was almost no coloration in the washing solution.The red silica gel after washing was dried and compared with that before washing, but the coloring concentration decreased. was not recognized. Moreover, no elution of the coloring material was observed even when the water slurry was used again.

For comparison, 100g of silica hydrogel after hydrothermal treatment obtained in this example was dried at 120°C for 6 hours, and the BET surface area, pore volume, and average pore diameter were 560 m ² /gr, respectively. 0.05g as a colorant to 22gr of uncolored silica gel showing 0.86ml/gr, 6.1nm.
Add 100g of % Red No. 213 aqueous solution, leave it in slurry form for 1 day, filter it to separate it from the colored mother liquor, dry it at 120℃ for 6 hours, and mix the resulting colored silica gel with demetalized salt water.
Washed with 550ml. As a result, most of the colored pigment was eluted and fell off. That is, this shows that in the case of the comparative example, the coloring material only adheres to the surface and the dye does not penetrate into the pores.

Example 2 To 100g of the polymerized silica hydrogel obtained in Example 1, 100g of a 0.05% Yellow No. 402 aqueous solution was added as a coloring agent, and after leaving it in a slurry state for one day, it was filtered to separate it from the colored mother liquor. , and dried at 120°C for 6 hours to obtain 22 gr of yellow silica gel. In addition, its physical properties include a BET surface area of 550 m ² /gr by nitrogen adsorption method.
The pore volume was 0.88 ml/gr, and the average pore diameter was 6.4 nm.
Further, when the particle size distribution was analyzed by the Coulter Counter method, the average particle size was 30μ. 20g of yellow silica gel obtained in this example was washed with 500ml of demetalized salt water, but almost no coloration was observed in the washing solution.The yellow gel after washing was dried and compared with that before washing, but the coloring concentration was No decrease was observed. Moreover, even when the water slurry was used again, no elution of the colorant was observed. The size of the pores formed in this example was estimated as follows. That is, take a part of the sample from the silica hydrogel, dry it to form silica gel, find the nitrogen adsorption isotherm, find out the BET surface area SA (m ² /g) from this, and approximate the average pore diameter of the silica hydrogel using the following formula. presume.

Calculation formula for average pore diameter of silica hydrogel: D _H = 4 (100-a)/a・SA×10 ³ (nm) However, D _H = pore diameter of silica hydrogel (nm) a = SiO ₂ content (%) In addition, the final product silica gel (colored silica gel)
The average pore diameter of can be determined as an approximate value from the following equation.

D _X = 4P _V / ^SA ×10 ³ (nm) However _{, D} Obtained pore volume (cm ³ /g) Example 3 White powder was obtained using the following ingredients and production method.

(A) Ingredients Talc 70.0% Mica 20.0% Titanium oxide 5.0% Iron oxide 1.0% Colored silica gel 2.0% (B) Ingredients Liquid paraffin 2.0% Fragrance Appropriate amount Production method After thoroughly stirring and mixing (A) ingredients, (B) The ingredients were added and sieved to obtain a product.

Example 4 A powder foundation was obtained using the following ingredients and manufacturing method.

(A) Ingredients Talc 23.0% Mica 50.0% Zinc stearate 4.0% Iron oxide 1.0% Colored silica gel 10.0% (B) Ingredients Liquid paraffin 5.0% Lanolin 4.0% Sorbitan monooleate 2.0% Preservatives Appropriate amount Fragrance Appropriate amount Manufacturing method (A) Components () are thoroughly stirred and mixed, and separately, component (B) is dissolved and mixed by heating at 70°C. Next, a heated and dissolved mixture of component (B) was added to the mixture of component (A), mixed, passed through a sieve, and press-molded into a metal plate to obtain a product.

Example 5 Lipsticks were obtained using the following ingredients and manufacturing method.

(A) Ingredients Carnauba wax 2.5% Ozokerite 8.5% Lanolin 20.0% Liquid paraffin 10.0% Squalane 10.0% Castor oil 39.0% Antioxidant Appropriate amount Preservative Appropriate amount (B) Ingredient Titanium oxide 2.0% Iron oxide 2.0% Colored silica gel 6.0% (C) Ingredient Fragrance Appropriate amount manufacturing method (A) Ingredients were heated at 80°C and were already stirred.
Add component (B) little by little and disperse well, then add 70%
After cooling to ℃, component (C) was added and mixed, and the mixture was filled into a container, molded, and taken out to give a product.

Example 6 An emulsion type foundation was obtained using the following ingredients and manufacturing method.

(A) Ingredients Liquid paraffin 28.0% Setanol 2.0% Paraffin wax 5.0% Glyceryl monostearate 2.4% POE(20) sorbitan trioleate 2.6% Preservative appropriate amount Ingredient (B) PG 10.0% Purified water 35.0% Titanium oxide 8.0% Iron oxide 2.0% Preservative Appropriate amount (C) ingredient Fragrance Appropriate amount (D) ingredient Colored silica gel 5.0% Manufacturing method Mix and dissolve ingredients (A) and hold at 70℃, while heating and mixing ingredient (B) at 75℃ Gradually add to component (A) at the same temperature to emulsify, then cool to 50℃.
Components (C) and (D) were added, and the mixture was further cooled to 30°C and then filled into containers to obtain a product.

A comparative test was conducted between the above Examples 3 to 6 and cosmetics formulated using conventionally used organic pigments (hereinafter referred to as conventional products). The results are shown below.

Stability test: Hardness test, specific volume test, and color difference measurement test on items stored in a refrigerator room (0°C), insulated room (40°C), and cycle room (-5°C to 40°C) for 6 months each. and a dye elution test.

As a result, no difference was observed between the example and the conventional product in the hardness test and specific volume test.

In the color difference measurement test and pigment elution test, no change was observed in the cosmetics of the examples, whereas dullness or bleeding of color was observed in the conventional products.

Light resistance test Observation was performed by irradiating ultraviolet light with a wavelength of 300 to 400 nm for 100 hours.

As a result, the cosmetics of the examples showed no discoloration at all, whereas the conventional products were found to have some discoloration.

Outdoor exposure test After being left outdoors for one month, observations were made.

As a result, the cosmetics of Examples showed no discoloration, whereas the conventional products were found to have discoloration.

Skin irritation test Primary skin irritation and cumulative irritation tests were conducted using mice and rabbits.

As a result, the cosmetics of the examples showed significantly higher safety than conventional products.

Claims (1)

[Claims] 1. Sodium silicate and acid are reacted to form a silica hydrosol, and then the silica hydrogel produced by gelation is washed with water to remove the by-product soda salt, and then subjected to hydrothermal treatment. colored silica gel, which is then colored by adding a coloring agent, and the colored mother liquor is separated and dried. 2. The pore size of the silica hydrogel after hydrothermal treatment is large enough to allow the colorant to penetrate, and the pore size of the colored silica gel after drying is large enough to prevent the colorant from detaching and seal it. Colored silica gel according to item 1. 3 Sodium silicate and acid are reacted to form a silica hydrosol, then the silica hydrosol produced by gelation is washed with water to remove the by-product soda salt, and then subjected to hydrothermal treatment, followed by coloring. 1. A colored cosmetic, characterized in that the cosmetic is blended with a colored silica gel obtained by adding a coloring agent to the cosmetic, separating the colored mother liquor, and drying the colored silica gel. 4 Claim 3, characterized in that the cosmetic contains 1 to 40% by weight of colored silica gel.
Colored cosmetics as described in section.