JPH08127513A - Cosmetic - Google Patents

Abstract

PURPOSE: To prepare a cosmetic having high chroma, high opacifying properties, bleed resistance, dispersibility and stability of color tone with time, blended with an organic-inorganic complex pigment, by uniformly and firmly sticking aluminum lake of yellow no.4 to the surface of an inorganic white pigment having a high refractive index to make a composite material. CONSTITUTION: This cosmetic is mixed with an organic-inorganic pigment prepared by coating an inorganic white pigment having >=2 refractive index and 0.1-60μm average particle diameter with aluminum lake of yellow no.4. The pigment is obtained by dissolving aluminum chloride in purified water, dispersing an inorganic filler having a high refractive index, then heating the solution, adding metal aluminum powder, further continuing heating and stirring, then adding yellow no.4, adding a pH adjustor and finally adjusting the solution to pH5 to pH2. One of zinc oxide, zirconium oxide, titanium oxide (anatase type) and titanium oxide (rutile type), a combination of two or more of the compounds or a composite material of two or more of them is preferable as the inorganic white pigment. The cosmetic can substantially reduce the amount of yellow no.4 and is safe to skin.

Description

Detailed Description of the Invention

[0001]

BACKGROUND OF THE INVENTION 1. Field of the Invention The present invention relates to a cosmetic composition containing an organic-inorganic composite pigment having high saturation, high hiding power, and excellent bleeding resistance, dispersibility, and stability of color tone over time.

[0002]

2. Description of the Related Art Inorganic pigments and organic pigments are generally used as color pigments used in base makeup materials such as general cosmetics, powder foundations and emulsion foundations. Such a base make-up agent can naturally cover skin problems such as spots and freckles in order to improve the feeling of finish when applied to the skin, and has a uniform color development, It is important that the color does not become dull due to changes. However, in terms of color tone, red iron oxides such as red iron oxide have a problem in that they themselves have low saturation. Furthermore, red iron oxide changes its color to reddish black when it is wet with oil and water secreted from the skin. On the other hand, yellow hydrated iron oxide has a reduced refractive index when it is wet with sebum or water secreted from the skin. Therefore, a base make-up material using such a colored inorganic pigment has a drawback that the coating color becomes dull because it changes to a reddish black color tone over time or optically reflects the skin color of the base. Was.

On the other hand, in the emulsion type foundation, various organic pigments have been tried to be used in order to prevent such a dull phenomenon. However, Yellow No. 4, which is one of the organic pigments, has poor bleeding resistance, and it is difficult to select a surfactant and adjust the pH of the foundation, which makes it difficult to commercialize.

In terms of covering power for skin troubles such as spots and freckles, titanium dioxide having a refractive index of 2.5 to 2.75 is usually used as a white pigment having covering power. If you try to cover skin problems such as spots, freckles, etc. more beautifully, the amount of titanium dioxide in the formulation will increase, and if the hiding power of the colored inorganic pigment is exceeded as a result, the applied color will become too whitish, The result is a so-called bokeh finish, which defeats the purpose of the makeup fee. This phenomenon is particularly noticeable in a flesh color system having a high lightness and a light color tone.

Further, in the nail enamel, since there is a large difference in specific gravity between the organic pigment or pearl pigment used in the nail enamel and titanium dioxide, it causes color separation or caking and cannot be redispersed therein. In some cases, the product value is significantly impaired.

Techniques for improving the above-mentioned drawbacks of the prior art include (1) adding finely pulverized flaky substrates to a dye made into an aqueous solution by a chemical method, and then precipitating the dye on the surface of substrate particles,
A method of using a pigment having good colorability obtained by depositing (JP-A-62-91565). (2) A method of using a colored mica pigment obtained by depositing and coating a pigment on the surface of substrate particles in an aqueous system (JP-A-63-243168). (3) Flake-like substrate particles and pigments obtained by stirring pigments and / or dye particles on flake-like substrate particles such as mica, mica, sericite, kaolin and the like coated with metal oxide by a predetermined high speed stirring without using a liquid medium. A method of using a flaky composite pigment having excellent saturation and dispersibility, which is obtained by forming an ordered mixture with particles of a dye or a dye, and excellent adhesion stability of a pigment or a dye (JP-A-5-214257). Gazette) etc. have been proposed.

[0007]

[Problems to be Solved by the Invention] However,
According to the techniques (1) and (2), it is difficult to obtain a satisfactory color because the fine particles and the dispersion of the pigment or dye are not yet sufficient.
Furthermore, pigments or dyes that did not adhere to the surface of the substrate particles in the treatment process or were weakly adhered were separated and dropped during the filtration process or washing process, and the expected color development was found for the amount of pigment or dye used. In some cases, no bleeding resistance is obtained when applied to Yellow No. 4 aluminum lake. .

Further, in the technique (3), since the particles are fixed by physical means such as impact force, compression force, shearing force, etc., not all the pigments and dyes are necessarily fixed stably and uniformly on the substrate surface. Bleed resistance cannot be expected when applied to Yellow No. 4 aluminum lake. In addition, as a result of the substrate being crushed by the high-speed stirring, the particle size distribution width of the substrate is widened, which does not have a favorable effect on the high saturation.

Furthermore, since a flaky material having a low refractive index is used as the substrate, it has high transparency and is unlikely to have high saturation due to the influence of the underlying color. Therefore, particularly in the field of cosmetics, the use as a coloring agent is greatly limited in combination with the fact that the morphology of the underlying skin is easily visible.

SUMMARY OF THE INVENTION It is therefore an object of the present invention to solve the above-mentioned problems of the prior art, and to provide a cosmetic having high saturation, high hiding power, bleeding resistance, dispersibility and stability of color tone over time. .

[0011]

In order to solve the above-mentioned problems, the present inventors have conducted extensive studies on changes in saturation and hiding power when an organic pigment and a high-refractive-index inorganic white pigment are combined. When the yellow No. 4 aluminum lake is uniformly and firmly attached to the surface of the high-refractive-index inorganic white pigment to form a composite, it is much more than when the high-refractive-index inorganic white pigment is mixed with the yellow No. 4 aluminum lake. The inventors have found that they have high saturation and high hiding power, as well as excellent dispersibility in the formulation and stability of color tone over time, and have completed the present invention.

That is, the present invention provides a cosmetic having high saturation, high hiding power, bleeding resistance, dispersibility and stability of color tone over time.

The present invention will be described in detail below.

The organic-inorganic composite pigment applied to the present invention by coating the inorganic white pigment with yellow No. 4 aluminum lake includes (1) a step of dissolving aluminum chloride in purified water and dispersing the high refractive index inorganic white pigment. (2) a step of heating this dispersion solution, adding metallic aluminum powder, and further continuing heating and stirring; (3) a step of adding yellow No. 4; and (4) adding a pH adjuster, and finally PH between 5 and 2
It is manufactured by the following process.

In the step (1) of dissolving aluminum chloride in purified water to disperse the high-refractive-index inorganic white pigment, the high-refractive-index inorganic white pigment may be dispersed as an aqueous solution of aluminum chloride. Aluminum chloride may be dissolved after dispersing the inorganic white pigment. It is also possible to add aluminum chloride and a high refractive index inorganic white pigment at the same time. As the aluminum chloride used,
Anhydrous aluminum chloride can also be used, but this one has the property of explosively reacting with water and releasing a large amount of heat, so from the viewpoint of safety, it is used in the form of hydrated salts such as aluminum chloride and hexahydrate. It is desirable to do.

The amount of aluminum chloride to be dissolved is not particularly limited, but in terms of work efficiency, the proportion is 6.5 to 20 parts by weight, preferably 6.7 to 11.4 parts by weight, relative to 100 parts by weight of purified water. preferable. The amount of the high-refractive-index inorganic white pigment to be dispersed is not particularly limited, but it is necessary to disperse it in a weight ratio of 2 to 4 times, especially about 2.5 to 3 times that of aluminum chloride. preferable.

In the step (2) of adding the metallic aluminum powder, the temperature of the solution is heated to 70 to 85 ° C., preferably around 80 ° C. at the time of addition, and further heated and stirred. If the metal aluminum powder is added at a temperature lower than 70 ° C., the reaction between the metal aluminum powder and the aluminum chloride aqueous solution becomes slow, which is not preferable. On the other hand, if the metallic aluminum powder is added at a temperature exceeding 85 ° C., the metallic aluminum powder and the aqueous solution of aluminum chloride react rapidly, which is not preferable.

The metallic aluminum powder is available in the form of aluminum fine foil pieces and may be added as it is. However, in order to suppress the reactivity of metallic aluminum, the surface of the metallic aluminum powder is coated with an oil agent or the like. Therefore, in this case, it is desirable to remove these coating agents with an appropriate solvent before adding them.

After the addition, basic polymerized aluminum is produced by the reaction of aluminum metal with an aqueous solution of aluminum chloride, and the mixture is heated and stirred until it is sufficiently adhered to the surface of the high refractive index inorganic white pigment. The reaction conditions therefor are: 80 ~
A temperature of 100 ° C., preferably 95 to 100 ° C., is suitable for 2 to 8 hours, preferably 3 to 4 hours.

In the step (3), Yellow No. 4 is added to the solution after the reaction as it is or as an aqueous solution.
The addition amount of Yellow No. 4 is appropriately selected according to the amount to be finally coated.

In the step (4), the pH of the solution is adjusted to 2 to 5 by adding the pH adjuster as it is or as an aqueous solution.
In the range of 3 to 4, preferably in the range of 3 to 4. As such a pH adjuster, it is preferable to use an alkali metal carbonate such as sodium carbonate, potassium carbonate or lithium carbonate in consideration of ease of subsequent washing.

The obtained high-refractive-index inorganic white pigment coated with yellow No. 4 aluminum lake is thoroughly washed with deionized water by a method such as decantation, and then a water-soluble organic solvent such as methanol, It is washed with ethanol, isopropyl alcohol, acetone, tetrahydrofuran or a mixture thereof to remove salts generated during the reaction and residual chemicals.

When the finally obtained high-refractive-index inorganic white pigment coated with Yellow No. 4 aluminum lake is dried, it is desirable to dry it at a temperature of 100 ° C. or lower.
Drying at a temperature of more than 100 ° C. is not preferable because the particles may be strongly aggregated, resulting in poor dispersibility or discoloration.

The inorganic white pigment to be coated preferably has a refractive index of 2 or more. When a material having a refractive index of less than 2 is used, the transparency becomes strong, and the morphology of the base is easily visible, and it is affected by the tint of the undertone of the base, so a pigment with high saturation and high hiding power cannot be obtained. Such white inorganic pigments having a refractive index of 2 or more include zinc oxide (refractive index 2.0), zirconium oxide (refractive index 2.4), anatase type titanium oxide (refractive index 2.5) rutile type titanium oxide. (Refractive index 2.7
5) or a mixture or a mixture of two or more of these can be preferably used.

The average particle size of the inorganic white pigment is 0.1 to 60.
It is desirable to be in the range of μm. Average particle size is 0.1μ
If it is less than m, the hiding power of the pigment is lowered, and it is difficult to obtain an optically sufficient pigment dispersion state. If it exceeds 60 μm, not only sufficient coloring power is not obtained, but also a feeling of particles is felt. It is not preferable.

The amount of Yellow No. 4 coated on the inorganic white pigment is
It can be selected according to the desired tint, and if the amount of Yellow No. 4 is increased, a dark yellow organic-inorganic composite pigment can be obtained, but the ratio of the inorganic white pigment and Yellow No. 4 is 1: 1 by weight. If it exceeds 1, the yellow color does not actually become dark, so it is desirable to select it appropriately within this range.

The high-refractive-index inorganic white pigment coated with yellow No. 4 aluminum lake applied to the present invention will be described in more detail below with reference to production examples.

Production Example 1. 40 ml of aluminum chloride / hexahydrate in 320 ml of purified water placed in a 1000 ml flask.
Was dissolved and 120 g of titanium oxide (titanium oxide A-100, manufactured by Ishihara Sangyo) was dispersed. This solution was heated to 80 ° C. in an oil bath and washed with acetone to obtain metallic aluminum powder (Alpaste 1100, Toyo Aluminum Co., Ltd.).
10 g) was gradually added with stirring, a cooling tube was attached, and the mixture was heated to 100 ° C. and refluxed for 4 hours. Then 80
After the temperature was lowered to 0 ° C., a dye solution in which 33 g of Yellow No. 4 was dissolved in 200 g of purified water was slowly added dropwise with stirring, and the mixture was stirred for 30 minutes after completion of the addition. Further, a 5 wt% aqueous solution of sodium carbonate was added dropwise to finally adjust the pH to 3.6. After this, it was left to stand at room temperature for 1 hour for aging. The obtained yellow No. 4 aluminum lake-coated titanium oxide dispersion was washed 3 times with 500 ml of purified water by decantation, and then 500 m of a 2: 1 mixture of acetone-ethanol.
It was washed twice with 1 and dried at 60 ° C. for 24 hours to obtain 147.6 g of yellow No. 4 aluminum lake-coated titanium oxide.

Preparation Example 2. 40 g of aluminum chloride hexahydrate in 600 ml of purified water placed in a 1000 ml flask.
Was dissolved and 360 g of titanium oxide (titanium oxide A-100, manufactured by Ishihara Sangyo) and zinc oxide (zinc flower No. 1, manufactured by Honjo Chemical) were dispersed. This solution was heated to 80 ° C. in an oil bath and washed with ethanol. Metal aluminum powder (Alpaste 1100, manufactured by Toyo Aluminum Co., Ltd.) 10 g
Is gradually added with stirring, and a cooling pipe is attached to
Heat to 0 ° C. and reflux for 4 hours. Then, after lowering the temperature to 80 ° C., a dye solution in which 33 g of Yellow No. 4 was dissolved in 200 g of purified water was slowly added dropwise with stirring, and after the completion of dropping, the mixture was stirred for 60 minutes. Furthermore, a 5 wt% sodium carbonate aqueous solution was added dropwise to finally set the pH to 3.4. Then, the mixture was left at room temperature for 2 hours for aging. The obtained yellow No. 4 aluminum lake-coated titanium oxide / zinc oxide dispersion was washed three times with 500 ml of purified water by decantation,
Further, twice with 500 ml of ethanol, 500 ml of acetone
Repeatedly wash twice with and dried at 60 ℃ for 16 hours,
267.9 g of yellow No. 4 aluminum lake-coated titanium oxide / zinc oxide was obtained.

The organic-inorganic composite pigment used in the present invention is usually 0.01 to 10% by weight, preferably 0.1 to 5% by weight in cosmetics, although it varies depending on the dosage form and the required appearance color. Be compounded.

Further, since the organic-inorganic composite pigment used in the present invention is excellent in saturation and hiding power, it is possible to mix yellow 4 with yellow 4 as compared with the case where yellow 4 is simply used in combination.
It is also preferable from the standpoint of skin safety, since the amount of particles can be substantially reduced.

Hereinafter, the present invention will be described in more detail with reference to examples.

[0033]

EXAMPLES The cosmetics of Examples 1 to 5 were produced by using the high refractive index inorganic white pigments coated with Yellow No. 4 of Production Examples 1 and 2.

Example 1. Emulsion type foundation (prescription) 1. Composite pigment 2.0% compounded pigment paste of Production Example 1 25.6 2. Stearic acid 1.75 3. Nonionic surfactant 5.0 4. Glycerin tri-2-ethylhexanoate 3.0 5. Butylparaben 0.1 6. PEG-200 1.0 7. Carboxymethyl cellulose sodium salt 0.1 8. Methylparaben 0.2 9. Triethanolamine 0.7 10. Aluminum magnesium silicate 1.0 11. Purified water 61.55 (Production method) Components 1 to 5 were dissolved and dispersed at 85 ° C to obtain an oil phase composition. Separately, 6 to 10 components were dissolved and mixed in 11 purified water and heated to 85 ° C. to obtain an aqueous phase composition. The aqueous phase composition was added to the oil phase composition to emulsify and then cooled to obtain an emulsified foundation.

Example 2. Blusher (prescription) 1. Talc 66.75 2. Sericite 13.0 3. Kaolin 10.0 4. Zinc myristate 2.0 5. Magnesium carbonate 1.0 6. 7. Composite pigment of Production Example 8.0 7. Red No. 226 0.5 8. Red iron oxide 0.4 9. Stearic acid 2.5 10. Liquid paraffin 2.2 11. Lanolin 0.6 12. Nonionic surfactant 0.3 13. Vitamin E 0.01 (Manufacturing method) After crushing the components of 1 to 8 with a crusher, they were transferred to a Henschel mixer and the temperature was adjusted to 60 ° C. 9 separately
The components (13) to (13) were dissolved and mixed at 85 ° C., poured into a Henschel mixer, coated on the powder portion, cooled, taken out, pulverized with a pulverizer, and press-molded to obtain a blusher.

Example 3. Lip color (prescription) 1. Isostearic acid diglyceride 14.7 2. Glycerin tri-2-ethylhexanoate 6.8 3. Glycerin fatty acid ester 10.8 4. Microcrystalline wax 15.6 5. Bead wax 1.5 6. Candelilla wax 6.4 7. Carnauba wax 0.5 8. 8. Dye paste containing 2% of the composite pigment of Production Example 38.7. Red No. 226 3.8 10. Red iron oxide 1.2 (Manufacturing method) After mixing and dissolving the components 1 to 7 at 90 ° C., 8
The dye paste and ingredients 9 and 10 were added, stirred and uniformly dispersed, and decompressed under reduced pressure. It was filled in a lip mold while maintaining at 90 ° C. and cooled to obtain a lip color.

Example 4. Nails (prescription) 1. Nitrocellulose 15.0 2. Alkyd resin 12.0 3. Dibutyl phthalate 6.0 4. Butyl acetate 23.7 5. Ethyl acetate 9.0 6. Ethanol 7.0 7. Toluene 25.0 8. Composite Pigment of Production Example 2.8 9. Red No. 202 0.1 10. Carbon black 0.03 (Manufacturing method) Components 1 to 7 were mixed and dissolved, and then composite pigment 8 and components 9 and 10 were added and uniformly dispersed in a ball mill to obtain a nail enamel.

Example 5. Aqueous nail color (prescription) 1. Acrylic polymer emulsion 77.7 2. Carbitol 7.7 3. Diethyl phthalate 3.9 4. Purified water 8.4 5. Composite pigment of Production Example 1 1.6 6. Red No. 202 0.03 7. Bentonite 0.4 8. Preservative 0.1 9. Silicone antifoaming agent 0.1 (Production method) Carbitol and diethyl phthalate are added to purified water, the composite pigment is dispersed therein, and then an acrylic polymer emulsion and 6 to 9 components are added to make the mixture uniform. Stir mixing was performed. After mixing, deaeration treatment was performed to obtain an aqueous nail color.

With respect to the organic-inorganic composite pigments of Production Examples 1 and 2, the bleeding resistance of the coated yellow No. 4 and the hiding power and saturation of the organic-inorganic composite pigments were evaluated for the cosmetics of Examples 1-5. The dispersibility and the stability of color tone were evaluated.

<Bleed resistance evaluation test of organic-inorganic composite pigment> 4 g of the organic-inorganic composite pigment of Production Example was put in 100 g of purified water, and the mixture was stirred with a magnetic stirrer for 1 hour. Filter with a 5c filter paper and use an ultraviolet absorptiometer to
The absorbance of the filtrate at 11 nm was measured. 2. Into 100 g of 95% ethanol, 1.5 g of the organic-inorganic composite pigment of the production example was put, and 1
After stirring for 30 hours, centrifuge at 3,000 rpm, 30
After treatment for minutes, the supernatant was filtered through a Teflon filter membrane (0.5 μm), and the absorbance of the filtrate at 411 nm was measured with an ultraviolet absorptiometer. The results are shown in Table 1.

[0041]

[Table 1]

<Saturation and hiding power evaluation test of organic-inorganic composite pigment> (Preparation of evaluation sample) Organic-inorganic composite pigment of Production Example 1.0
g was precisely weighed and kneaded 150 times with 1.5 g of castor oil using a Hoover Mahler. Kneaded sample 0.
5 g was weighed in a polyethylene disposable cup having a capacity of 50 ml, and 10 g of transparent nail enamel lacquer was put therein and stirred until uniform. After the nail enamel lacquer volatilized during stirring was replenished and stirred, 1 was put on the hiding rate test paper (manufactured by Japan Test Panel Industry Co., Ltd.).
A 0 mil doctor blade was used to form a film as an evaluation sample.

(Evaluation of Saturation) The white part of the evaluation sample formed on the hiding ratio test paper was used as a CM-100 spectral color difference meter manufactured by Minolta.
0 was used to measure the spectral spectrum, and the L-a-b value was calculated.

(Evaluation of Concealment Power) Concealment Ratio The difference between the spectral portions of the white portion and the black portion of the test paper at 400 to 700 nm where the film is not formed is set to 100, and the white portion and the black portion of the film are formed at 400 to 700 nm. The difference in the spectrum was converted into a percentage to obtain the hiding rate.

The above results are shown in Table 2.

[0046]

[Table 2]

As is clear from the results of Tables 1 and 2, in the organic-inorganic composite pigment applied to the present invention, the white inorganic pigment and Yellow No. 4 are firmly fixed, and the coloring property is excellent, and the hiding property is high. Power and saturation were also high.

<Evaluation of Dispersibility of Organic-Inorganic Composite Pigment in Cosmetics> As a result of observing the cosmetics shown in Examples 1 to 5 with an optical microscope, all of the cosmetics have a median diameter of about 0.43 to 0. It showed a uniformly dispersed state in the range of 0.47 μm, and no aggregate was observed.

<Evaluation of stability of color tone of cosmetics over time> The cosmetics of Examples 1 to 3 were applied to the inner part of the upper arm in a size of 2 × 2 cm, and immediately after application and 3 hours after application. The change in color tone was examined with a spectrocolorimeter CM-2002 manufactured by Minolta.
The cosmetics of Examples 4 and 5 were applied to nails, and similarly, the change in color tone immediately after application and 3 hours after application was examined with a spectrocolorimeter CM-2002 manufactured by Minolta.

The results are shown in Table 3.

[0051]

[Table 3]

As is clear from the results of Tables 1 to 3, the cosmetics according to the present invention had high saturation and high hiding power, good dispersibility, and excellent stability of color tone over time.

[0053]

EFFECT OF THE INVENTION The cosmetic composition of the present invention provides a cosmetic composition having high color saturation and high hiding power, and excellent bleeding resistance, dispersibility, and color stability over time.

Claims (4)

[Claims] 1. A refractive index of 2 or more and an average particle size of 0.1 to 6
A cosmetic comprising an organic-inorganic composite pigment obtained by coating an inorganic white pigment having a size of 0 μm with a yellow No. 4 aluminum lake. 2. The inorganic white pigment in the organic-inorganic composite pigment is selected from zinc oxide, zirconium oxide, titanium oxide (anatase type) and titanium oxide (rutile type), or a combination of two or more thereof. Cosmetics described in. 3. The inorganic white pigment in the organic-inorganic composite pigment is selected from two or more composites of zinc oxide, zirconium oxide, titanium oxide (anatase type), and titanium oxide (rutile type). The listed cosmetics. 4. The organic-inorganic composite pigment comprises the steps of (1) dissolving aluminum chloride in purified water to disperse a high-refractive-index inorganic white pigment, and (2) heating the solution to add metallic aluminum powder. And a step of (3) adding yellow No. 4 and (4) further adding a pH adjuster to finally adjust the pH to 5 to 2. The cosmetic according to any one of claims 1 to 3, which is manufactured by.