JPS62198608A - Cosmetic - Google Patents

Abstract

PURPOSE:To provide a cosmetic containing monodispersed ultrafine crystal particles having specific particle diameter and particle size distribution as at least a part of the component, having excellent spreadability on the skin, giving durable makeup, capable of protecting skin from sunburn and having potential to decrease cause of aging such as spots and wrinkles. CONSTITUTION:A cosmetic base is compounded with at least one kind of ultrafine monodispersed crystalline particles having particle diameter of <=0.1mum and particle size distribution of 0.1-0.01mum and preferably selected from titania (TiO2), hematite (Fe2O3), silica (SiO2), mullite (3Al2O3.2SiO2), zirconia (ZrO2), titanium black (TiO) and magnetite (Fe3O4). The cosmetic produced by this process transmits visible light, reflects and scatters harmful ultraviolet ray causing sunburn, has potential to reflect infrared ray and reduce the cause of aging such as spots and wrinkles, affords durable makeup and is easily spreadable on the skin.

Description

DETAILED DESCRIPTION OF THE INVENTION [Technical Field of the Invention] The present invention relates to a cosmetic containing at least a portion of monodispersed ultrafine crystal particles.

In other words, the particle size is 0.1 gra or less and the particle size distribution is 0.
．． By mixing monodispersed ultrafine particle crystals in the range of 1 to 0.01 ALm into a cosmetic base material, they transmit visible light and reflect and scatter harmful ultraviolet rays that cause sunburn, thereby protecting the skin from sunburn. It reflects infrared rays and causes stains,
This invention relates to cosmetics that have good long-lasting makeup and have the potential to reduce causes of aging such as wrinkles.

[Technical background of the invention and its problems] Excessive ultraviolet rays on the skin cause erythema.

Blisters and edema occur, and it is said that pigmented skin cancer may occur. It is also said that ultraviolet rays are harmful to the hair of one head, leading to hair breakage and hair loss. or.

It is also said that infrared rays cause age spots and wrinkles. Ultraviolet rays with a wavelength of 295 to 40 hm in sunlight cause sunburn, which causes the skin to develop and darken.Among these, the middle rays with a wavelength of 290 to 320 hm are said to have the strongest biological effects. There is.

Conventionally, cosmetics containing ultraviolet absorbers and infrared reflectors have been developed to prevent these problems. Others and titanium oxide,
There are zinc oxide, iron oxide, etc. These can cause irritation, decrease in UV absorption power, and change in quality and color.Also, titanium oxide etc. have large particle sizes that are in the region that blocks visible light, so they have weak absorption in the ultraviolet region, but they do not. It's too strong and doesn't whiten, and it's too pigmented so I couldn't use products intended for makeup like Foundation Cream 1 lipstick.

In addition, these have excellent dispersibility and usability in cosmetic base materials.

Stability was insufficient.

[Purpose of the invention]

The present invention aims to solve the problems associated with the prior art as described above, and is to produce monodispersed ultrafine particles with a particle size of 0.1 μL or less and a particle size distribution in the range of 0.1 to 0.01 pm. An object of the present invention is to provide a cosmetic characterized by containing at least a portion of crystals.

[Detailed description of the invention]

First, the particle size of the present invention is 0. I" or less, the particle size distribution is 0.
Monodisperse ultrafine particle crystals having a size in the range of 1 to 0.01 JLm are produced as follows.

(1) Hydrogels of water-insoluble and poorly water-soluble hydrated oxides and hydrated hydroxides produced as fine or ultrafine particles,
After removing coexisting water-soluble salts, the water in the hydrogel is replaced with a water-soluble organic solvent such as ethanol or methanol, or a portion of the ethanol or methanol is converted into a propatool.

After replacing the water in the hydrogel with a mixed organic solvent such as poorly water-soluble higher alcohols such as butanol, polyhydric alcohols such as glycerin, or water-insoluble organic solvents such as acetone and ether, benzene and hexane, etc., After holding the single organic solvent or mixed organic solvent used within the range of the critical temperature or supercritical temperature and pressure range specific to each, the organic solvent and the solid are separated.

A dry powder of monodisperse mature solid microparticle crystals can be obtained.

(2) When using the above-mentioned water-soluble organic solvent such as ethanol or methanol, after replacing the water in the hydrogel of hydrated oxide or hydrated hydroxide with the water-soluble organic solvent, The particle size of the particulate crystals can be changed by changing the specific critical temperature, pressure range, and holding time.

(3) Furthermore, in addition to the above-mentioned water-soluble organic solvents such as ethanol and methanol, some of them are used as poorly water-soluble higher alcohols such as propatool and butanol.

The particle size of the microparticle crystals is changed by replacing polyhydric alcohol such as glycerin with a water-soluble organic solvent such as acetone, ether, benzene, or cyclohexane, and changing the specific critical temperature, pressure range, and holding time of each. be able to.

The following ultrafine particle groups produced by the above method include: (1) Silicon dioxide (S i07 ) (2) Titanium dioxide (white) (TiTo) (3)
-Titanium oxide (black) (Tie) (4) Iron oxide (red)
(Fe203) (5) Zirconium dioxide (Zr0
2) (8) Mullite (3AJL2032Si02) (7
) magnetite (FezOa), etc., and each of these ultrafine particle crystals has the characteristics shown in Table 1.

The features of the ultrafine crystal of the present invention as described above will be described in further detail as follows.

1. The primary particles are ultrafine (less than 0.1 l) and monodisperse (s
onodispero), and almost no secondary aggregation is observed.

2. Except for silica and mullite, ultrafine particles have an esomorphic structure (e.g., titanium oxide, iron oxide).

(magnetite, etc.) 3. The particle size distribution is concentrated in an extremely narrow range, which range is often from 0.1 to 0.014+w.

4. Monodisperse ultrafine particles can be obtained as dry ultrafine particles.

5. Particle size can be controlled by adjusting the manufacturing process.

6. Surface wood-philicity or hydrophobicity can be selected by adjusting the manufacturing process.

7. Bulk should not easily aggregate even if left in the air.

8. Crystalline ultrafine particles are euhedral and have beautiful and smooth crystal faces.

Next, the method for producing monodisperse ultrafine particle crystals according to the present invention will be described below, but the present invention is not limited thereto.

[Example 1] Water I Las 3% (Nazo 9.70L 5i02
28.89$) Take 1.75kg and add 3.5kg of pure water to it.
Add 25 kg and mix well to make a uniform aqueous solution. This corresponds to an approximately 35% solution of water glass. Add 2.77 g of 102 fE acid to this solution briefly and mix uniformly.

After some time, the mixture gels and becomes a homogeneous hydrogel agar-like. This hydrogel contains 6.4z net as 5i(h).

These agar-like hydrogels gel at a pH of about 10, so in order to neutralize the remaining NaOH and convert it into Na2SO4, they are soaked in 10ml of sulfuric acid to make them acidic, and then washed with pure water.

After completely removing Ha・, S04”, 8 kg of gel
Add 4 kg of methyl alcohol to the solution and let stand. As a result, a considerable portion of the water in the gel is replaced with methyl alcohol. After repeating the same process, 8 of the gels
00g into 1,800cc of methyl alcohol, contents! Place it in a 5fL autoclave and heat it.
After maintaining the temperature at 300° C. and about 200 atm for 1 hour, methanol was removed to obtain 50 g of monodisperse, dry ultrafine silica particles. Figure 5 (1) shows gel-like ultrafine particle silica, and Figure 6 (1) shows clear ultrafine particle silica (particle size 1
00×300A), indicating that the particle portion has an extremely narrow particle size distribution. 5i02 (silica) is an amorphous substance that is extremely difficult to crystallize up to ~500°C, so after treatment, the hydrogel also has a second X-ray diffraction pattern.
As can be seen from the figure, ``11 shows a diffraction pattern that is difficult to recognize as a wide crystal.

[Example 2] Ferric sulfate hydrate (Fe25Oa3X H2O, internal solid content 7(H) 3.57kg Hot pure water ripened water ~90°C
) Ammonia (NH3) is dissolved in 5 kg and stirred.
0.785 kg of gas is blown into the slurry containing the generated ferric hydroxide hydrogel.
°c) Divide 80 liters into 12 to 13 times and wash.

The final filter cake contains 20% solids and N
Ha and SOs ions are completely removed.

To the 3 pieces of cake obtained after filtration, add 27 pieces of 913.5 dollar ethanol and mix well with a mixer.
Make a uniform slurry. About 2.51 of these were collected,
Place in an autoclave with an internal volume of 5°C and heat to 30G'c. The pressure at this time is 170 atmospheres. After holding for 1 hour, the solid content and ethanol are separated, and the solid content obtained exceeds 140 g of dry fine particles monodispersed with ultrafine particles of ferric oxide.

(2) in Figure 5 shows amorphous ultra-superfine particles of ferric hydroxide hydrogel before autoclaving, and (2) in Figure 6 shows the amorphous ultra-fine particles of ferric hydroxide hydrogel before autoclaving.
) indicates the euhedral shape of hematite (Fe20s) after treatment,
FIG. 2 shows the X-ray diffraction patterns of the iron hydroxide hydrogel and FIG. 3 shows the produced hematite crystals, showing monodispersed ultrafine crystals with beautiful crystal faces.

[Example 3] In Example 2, for 3 cakes obtained after filtration, 9
9.5X Tanol 25 sentences and acetone 2! Add L and mix well with a mixer to make a homogeneous slurry.

Collect about 2.5 sentences from this, place them in an autoclave with an internal volume of 5 cm, and heat to 280'c. The pressure at this time is approximately 140 atmospheres.

After holding for 1 hour, the solid content and ethanol and acetone mixed medium were separated. The solid content obtained is 140 g of dry ultrafine powder monodispersed with ultrafine particles of ferric oxide.

The difference between the results of Example 3 and the results of Example 2 is that, as shown in (3) of FIG. 6, the particle size is smaller than that of (2) of FIG. This is monodispersed hematite CFe that shows the effect of added acetone.
The a-fine particles of 20z) exhibit euhedral shape and still have beautiful crystal faces.

[Example 4] Ferrous sulfate crystal (Fl!s047H20) 333. E
! g! : Ferric sulfate crystal (F[45O4317H20)
348g hot pure water (70-90'c) 2.4
Dissolve into a sentence. To this was added a solution of 720 g of carbonated soda dissolved in 3 parts of pure water with good stirring, and magnetite (
Gel (PH
(shown in (2) of OTO3). This was filtered and washed with hot pure water (70 to 90'C) for 40 minutes until almost all Na and SOs ions were removed.

The moisture content of the cake obtained after washing is about 25z.

Add 7 grams of ethanol to this cake and mix well with a mixer to uniformly disperse the magnetite gel ultra-fine particles in the ethanol. Here you can get 8 father's alcohol slurry.

This alcohol slurry 3! 1 is placed in an autoclave with a five-pronged internal volume, and heated to 280'C.

The utility power will be 150 atm. After holding for 1 hour, the ethanol was removed and 170 g of dry ultrafine powder containing monodispersed ultrafine particles of magnetite (shown in FIG. 6 (4)) was returned.

[Example 5] Zirconium oxychloride crystal (ZrOGi 28H20
) 2. Dissolve 1315 kg in 5 cups of hot pure water. Add 0.0% ammonia gas (NH3) to the Erareta solution while stirring well.
Inject 278 kg of the slurry containing the purified zirconium hydroxide gel, followed by 80 g of hot pure water.
Wash the cake twice to remove NH4° in the cake,
CI- ions are completely removed.

Washed gel 2! 6 methanol containing 10% propatool is added to L (which contains 2500 g of zirconium dioxide ZrO), and the gel is completely dispersed in methanol using a mixer. Take a 3-mix slurry from this and put it in an autoclave with a content of 1A31.
Heat to 0°C. The pressure becomes 190 atm and methanol is separated after 1 hour. As a result, 187 g of dry ultrafine powder of monodispersed zirconium dioxide (Z ra2) Mi particles was obtained. The particle size of the ultrafine zirconia particles is 100A or less, as shown in FIG. 6 (5). However, the zirconium dioxide hydrogel shown in FIG. 5 (4) is so ultrafine that it cannot be called a particle.

FIG. 1 shows an X-ray diffraction diagram of zirconium dioxide hydrogel, which shows only a dull halo, whereas the X-ray diffraction diagram of ultrafine particles of zirconium dioxide of 100 A or less shows extremely clear crystals.

[Example 6] 950 g of titanium tetrachloride (TiC14) is dissolved in 5 volumes of pure water. The obtained titanium oxychloride (Ti
e(fL7) While stirring the solution, ammonia gas (NH
3) Blow in 340 g. Once the blowing is finished, filter and wash the slurry containing titanium hydroxide gel (titanium dioxide gel may also be used). Washing water is hot pure water (70-906C), NHa', C
Most of L is removed. Finally, as much residual water as possible is filtered off with suction from the cake, 7 parts of ethyl alcohol (containing 5% ether) is added to the cake, and the cake is completely dispersed in the ethyl alcohol using a mixer.

Three sentences were collected from the resulting ethyl alcohol slurry,
Place in a 5-pronged autoclave and maintain temperature at 350°C.
to rise to. The pressure will be 300 atmospheres. After holding for 1 hour, ethyl alcohol was removed and titanium dioxide (TiO
150g of the monodispersed dry ultrafine powder of 2) can be used. These ultrafine particles are 0.0 mm as shown in Figure 6 (6). O2N2.
It is 04gts.

FIG. 5 (5) shows titanium hydroxide hydrogel, which has ultrafine particles whose shape is difficult to discern.

In addition, titanium hydroxide hydrogel in Figure 1 (Ti in Figure 2)
The X-ray diffraction pattern of TiO2 gel) shows a dull halo that cannot be called a crystal, but the X-ray diffraction pattern of Tioz ultrafine particles shows a clear diffraction pattern of anatase TiO2.

[Example 7] 5 g of aluminum trioxide (AfLC13) was dissolved in 10 g of pure water, and while stirring the resulting solution, 240 g of silicon tetrachloride (5iC1s) was added and dissolved. While blowing 168 g of ammonia gas (NH3) into the resulting solution, stir well. When the blowing is completed, Figure 5 (
A slurry containing mullite hydrogel consisting of ultra-fine particles shown in 6) is obtained. Filter this and heat pure water (70~
90°C) Wash for 50 fL to completely remove NH4. and CI- ions. 651 methyl alcohol (containing 5% butyl alcohol) is added to the mullite vitrogel from which as much water as possible has been sucked and discharged, and the gel is completely dispersed in the methyl alcohol using a mixer. Of the obtained methyl alcohol slurry, 3IL was collected and added to the content f1.
Place in a 51 autoclave and heat to 350°C.

The pressure reached 300 atm and was maintained for 6 hours.

Remove methyl alcohol. This results in Figure 6 (7
), 113 g of ultrafine mullite (leaf-shaped, tabular shape, !i diameter IJLm, short axis 0.2 to 0.8IL layer, thickness 0.03m) was obtained as a dry ultrafine powder.

The magnetite of the present invention is a black ultrafine crystal with a thickness of 0.03 JL to 0.1 JL, and is the best cosmetic for eyebrows. Furthermore, titanium black (Tie) is also black in a thickness of 0.03 JL to 0. It was an ultrafine crystal of .05 #L, -, and was extremely good as a black cosmetic.

The mullite of the present invention is 1110, IIL, whose crystals are tabular.
*Length 0.5 pm Thickness 10 QA ~ 200 A (7) a Since it is a fine particle, a cosmetic with good "spreadability" can be obtained. For hematite, crystals with a uniform particle size of 100 A can be obtained,
As for titanium, plate-like ultrafine particle crystals of 0.01 #L to 0.03 g were obtained, making them ideal for cosmetics. Furthermore, other products (listed in Table 1) were also obtained which were excellent as cosmetics.

In the present invention, the particle size is 0.11L1 or less and the particle distribution is 0.1
pL Peng~0.01. Preferably, monodispersed ultrafine particle crystals in a range of 0.01 to 80% are applied to the cosmetic base material.
! Among the monodisperse ultrafine particle crystals of the present invention obtained by mixing 0 or more to form the cosmetic composition of the present invention, examples include mullite (width: 0.IJLII, length: 0.5, thickness: 10
Examples of the use of magnetite as a cosmetic are shown below, but the present invention is not limited thereto.The monodisperse ultrafine particle crystals of the present invention can be used in lipsticks, milky lotions, foundations, eyebrows, Powder 9 hair dye.

It exhibits extremely excellent performance as an ultrafine crystal for cosmetics such as nail polish, manicure, pedicure, eye shadow, mascara, cream, blusher, and eyeliner, and is used in these cosmetics.

[Example (1)] (1) Measurement of ultraviolet absorption effect 60 parts of mustard oil is added to 40 g of mullite C3Al2O3@2Si02, and thoroughly kneaded using a Miki roller to form a slurry. Take 25 parts of slurry and 75 parts of castor oil.
0 parts and use a stirrer to further disperse the mullite.
The dispersion was coated on a transparent quartz plate with a film thickness of 5 mm, and the absorbance in the wavelength range of 280 to 380 mm was measured using spectroscopy in Figure 1 (the horizontal axis shows the wavelength (2), and the vertical axis (showing absorbance).

As is clear from Figure 1, in the present invention, the maximum absorption wavelength for the ultraviolet absorption effect is 295-3, which has the strongest biological effect.
(2) Practical usability test on the cosmetic of the present invention The mullite of the present invention was blended as shown below to prepare an emulsion.

(Composition) Mullite 8.0wt%
Stearic acid 2.0ytl Cetyl alcohol 1.0wt$ Vaseline
5. Owt$ silicone oil
2.0wt1 liquid paraffin
11. Owt$ glyceryl monostearate 1, Ovt$ polyoxyethylene (25 mol) heptanooleate 1.0wtX polyethylene glycol 1,500 5. Owt$ Begum
0.5wH purified water G5
．． 5wH fragrance fat preservative suitable! ^ To adjust the emulsion, add polyethylene glycol with purified water,
After heating and dissolving the solution, add ultrafine mullite particle becam and polyoxyethylene (25 mol) monooleic acid ester and disperse uniformly with a homomixer. Mix the other ingredients, heat and dissolve and keep at 70°C (oil phase).

The oil phase was added to the water phase and uniformly emulsified and dispersed using a homomixer, and after emulsification, the mixture was cooled to 35°C while stirring.

Regarding the emulsion of the present invention prepared as described above, as follows:
The above-mentioned modified emulsion was used on the entire face of 20 female panelists who conducted a practical usability test, and the results showed "spreadability" and "stickiness" during use.
Evaluations were made on four items: ``light feeling,''``whiteness,'' and ``overall evaluation.'' The evaluation methods are “good”, “easy”, and “
Table 2 compares the number of people who answered "white buds" with that of another company (company A milky lotion).

As can be seen from Table 1, the emulsion of the present invention can be said to be a good emulsion with very good "spreadability" and "stickiness" when applied.

Since the emulsion of the present invention has good "spreadability" and "stickiness" as described above, it can be said that it is also good in blocking infrared rays.

[Brief Description of the Drawings] Figure 1 is a graph showing the ultraviolet absorption effect of cosmetics according to the present invention, and Figure 2 is a graph showing the ultraviolet absorption effect of the cosmetics according to the present invention.
Graph showing X-ray diffraction patterns of Zr02 gel) and zirconia (Zr07 gel). Figure 3 is an X-ray diffraction diagram of hematite (Fe203). Figure 4 is an X-ray diffraction diagram of magnetite (FexOa).
FIG. 5 is an electron microscope WL mirror photograph showing the structure of each fine particle according to the present invention in a gel state before autoclave treatment;
The figure is an electronic Ji1 microphotograph showing the structure of each fine particle according to the present invention after autoclave treatment. Patent applicant: Sumitomo Cement Co., Ltd. Agent
Patent attorney Hajime Tsuchihashi □ Engraving of drawings (V'': Yo (Nijo Banashi) Figure 1 Wavelength (2) m) 11!2 Figure □ IO [ Figure 5 ψ--Wataichi- ■ Part 1 1 unit [, 2 do r'q, % manbun hair 1) y u 4) -shito υ hand I 6th prisoner,...-sumi (3 ha 12032', E HO sword > r) ya Shaoyu Vx Raih (MnO7p O-fe2031 Threshold KukuΩ 10 A Procedure 7 City Official Book (Wa May 22, 1986)

Claims (2)

[Claims] (1) Particle size is 0.1 μm or less, particle size distribution is 0.1 to 0.
．． A cosmetic comprising at least a portion of monodispersed ultrafine crystal particles having a size in the range of 0.01 μm. (2) The ultrafine particle crystals are titania TiO_2, hematite Fe_2O_3, silica SiO_2, mullite 3Al
_2O_32, zirconia ZrO_2, titanium black TiO, and magnetite Fe_3O_4. The cosmetic according to claim 1, characterized in that it is an ultrafine particle crystal of at least one of magnetite Fe_3O_4.