JP2003321343A - Composite for removing pigment adsorption - Google Patents

Abstract

<P>PROBLEM TO BE SOLVED: To provide a cosmetic material for removing pigments whose highly concentrated particle is dispersed as a completely single particle when dispersed in a basic cosmetic material and globular particles of highly purified silicon oxide that can be adsorbed on an electrically strongly negative-charged surface of the particle to which pigment molecules are fixed. <P>SOLUTION: The particle of silicon dioxide for removing pigment adsorption is either amorphous silica or micro crystalline silica of high temperature series whose electrically charged globular shape is strongly negative and does not have a silanol group on the particle surface in a juvenile stage. The particles are characterized in that they are not coagulative but extremely fluid and completely dispersed in water and can be manufactured with the reaction of non-polluted high-frequency thermal plasma when highly purified silicon is used as a material and are also characterized in that the particle of silicon dioxide is a strongly adsorptive cosmetic material whose dispersed condition in a cream is extremely favorable when the particles of silicon dioxide are combined in high concentration. <P>COPYRIGHT: (C)2004,JPO

Description

Detailed Description of the Invention

[0001]

BACKGROUND OF THE INVENTION 1. Field of the Invention The present invention relates to a composition for removing dye adsorption, and more particularly to a composition in which high-purity spherical silicon dioxide ultrafine particles which are effective in the field of cosmetics are uniformly dispersed.

[0002]

2. Description of the Related Art Silicon dioxide has long been recognized as a very safe substance for living bodies, and has been used in medicines, cosmetics and foods.

However, a method or material for monodispersing silicon dioxide without aggregation has not been easily found. In particular,
In the submicron to nanometer range of the claims of the present invention, the charge balance is often collapsed by a large number of silanol groups to form a strong aggregate.

In particular, in silicon dioxide obtained by the sol-gel method or the Aerosil method, a large number of silanol groups are bonded to the surface and air is included between the particles, so that a difficult dispersion of about several μm to 10 μm is formed. Will be formed.

When the aggregate is formed, the composition becomes very sticky. Therefore, even when the silicon dioxide is simply dispersed in pure water, the content of the ultrafine particles is 3 to.
If it is less than 5%, the composition will solidify into a paste.

Further, many silanol groups are present on the surface of the silicon dioxide particles, hydrogen bonds are formed between the particles, and ROH which is not completely hydrolyzed exists in the C-axis direction of the silicon dioxide tetrahedron. Therefore, a strong hydrogen bond is generated at the end of these functional groups, and the electric adsorption force that should be present in each particle itself is extremely reduced.

Further, even when the silicon dioxide particle agglomerates produced by these methods are dispersed into a cosmetic material by some method, the stability is poor and the fluidity is impaired in most cases.

Therefore, for the purpose of the present invention, the development of cosmetics that make the most of the adsorptive power of high-purity silica is
It was not found other than the application of the ultra thin silica film of another application filed by the present inventor.

Here, the silicon dioxide monodisperse particles used in protein adsorption type analysis systems such as liquid chromatography are mainly used for the adsorbing action by utilizing the space of the particles of a certain size. ,
Homogeneous dispersion of silicon dioxide was not a problem except for critical chromatography.

In general, a pigment molecule having a binding state that is stronger than that of melamine pigment that constitutes a stain is a protein dimer that forms age spots, and once the age spots have been produced in the body or on the skin surface, It is common knowledge in the medical community that it is extremely difficult to remove this.

In recent years, laser scalpels and the like have been increasingly used as a surgical treatment method for removing these pigments. However, there are technical problems for complete treatment, success rate, progress treatment until complete cure, etc. There are various problems. Another problem is that the treatment unit price is considerably high.

[0012]

The present invention has been made in order to solve the above-mentioned problems, and comprises a high-purity spherical silicon dioxide fine particle or ultrafine particle synthesized by thermal plasma synthesis that does not initially have a silanol group. The strong negative charge state developed on the surface should not be consumed for the mutual aggregation of the particles, and the hydrogen bond force and / or van der Waals force and electric adsorption force, which are close to the limit, should be exhibited in the complete dispersion. The present invention is characterized in that the silicon dioxide particles of the present invention are uniformly dispersed in a cosmetic at a high concentration so as to adsorb and remove pigment molecules or / and their precursors and promote their adsorption. There is.

In order to solve the above-mentioned problems, the high-purity silicon dioxide fine particles are made of silicon powder having a purity of at least 99.9% or more as a raw material, and the raw material is cut to a particle size of 44 μm or more and then placed in an argon stream. 350
It is blown into argon / oxygen plasma at 0 ° C. or higher to instantly vaporize the silicon powder into an atomic state and to rapidly terminate the oxidation reaction to obtain a desired spherical silicon dioxide powder.
This plasma reaction is due to a gas / solid reaction, and is characterized in that silanol groups are not initially bound to the particle surface.

To completely disperse the silicon dioxide fine particles, an ultrasonic homogenizer having a longitudinal amplitude of 30 μm or more is used. When the solid content of the present silicon dioxide is within 35% by weight, this dispersion device can easily and completely produce a dispersion in pure water. Particularly, when the solid content is 20% by weight or less, the viscosity of the dispersion is extremely low.

The above dispersion is well dispersed in an oil-in-water type or water-in-oil type cosmetic base. In particular, during the production of cosmetics, it does not aggregate even when heated at about 80 ° C. in the emulsification step, so that it is characterized in that a complete emulsion can be produced by using a general high-speed vacuum mixer.

[0016]

BEST MODE FOR CARRYING OUT THE INVENTION In the practice of the present invention, the high-frequency thermal plasma device has an output of 13.56 MHz and 40 KW, and the torch portion has a diameter of 80 mm. The raw material powder is finely moved by ultrasonic vibration, continuously carried on an argon stream, and blown into the lower part of the torch. At this time, the plasma gas is a mixed gas of argon and oxygen,
Has a strong oxidizing power. When the raw material silicon powder reacts with this plasma, silicon is immediately gasified and combined with the oxygen plasma to produce amorphous silicon dioxide powder. The particles are almost perfect spheres, the particle size belongs to the range of 10 nm to 1.5 μm, and the center diameter is approximately 150 to 200 nm.

Among the above particles, the size with a particularly large negative charge is usually considered to be 500 nm or less. However, considering the fluidity of the cosmetic, it is desirable to cut the oversize to 1 μm or less, so the longitudinal amplitude is reduced. Disperse all the powders obtained by the above plasma equipment in pure water with a powerful homogenizer equipped with an ultrasonic horn of 50 μm, and force particles of 1000 nm or more from the dispersion slurry in a 1000 rpm centrifuge. To remove by sedimentation.

The solid content concentration of the resulting slurry was measured and pure water was adjusted to obtain 20% of the silicon dioxide of the present invention.
A weight percent complete dispersion is obtained.

Next, in the production of oil-in-water type cosmetics, the dispersion containing 20% by weight of silicon dioxide is
Aqueous phase, that is, purified water, a mixture of 1.3 butylene glycol or a single phase, and uniformly dispersed, and an oil phase selected from the group of siliconoyl, squalane, liquid paraffin, surfactants and the like, and a vacuum high speed mixer at about 60 to 80 ° C. After mixing and cooling, a complete emulsion is obtained. At this time, the content of silicon oxide in the cosmetic is 15% or less.

[0020]

Example of the present invention (Example 1 of fine particles of silicon dioxide of the present invention) 4N (99.99%) metallic silicon (25 μm or less) was used as a starting material, and metallic silicon was vaporized and vaporized in the high frequency plasma apparatus. Instantly, silicon dioxide powder was obtained. At this time, relatively large particles were concentrated in the chamber bottom of the plasma device, but fine particles (maximum diameter of 1.4
(μm) was only captured.

The above particles were dispersed using the ultrasonic homogenizer (manufactured by Ginsen Co., Ltd.) according to the following formulation.

The above dispersion was placed in a continuous low-speed centrifuge and processed at 1000 rpm. As a result, particles of 1 μm or larger were completely removed.

Further, the solid content concentration in the obtained slurry was measured to be 24.0%. Therefore, ultrapure water was added so that the solid content was accurately adjusted to 20.0%.

When the particles of this dispersion were observed with a transmission electron microscope, they exhibited a very good dispersion state, and a strong drift due to static electricity was noted.

Further, according to the FTIR data, even if the silicon dioxide is completely immersed in water, OH is
Very few group bonds, less than T (%) = 5%,
Furthermore, the infrared absorption position shift that is not found in ordinary silicon dioxide, that is, the maximum absorption is 9.2μ for ordinary products.
m was 8.95 μm for the particles of the present invention.

(Examples of Cosmetics of the Present Invention) Next, the cosmetics of the present invention will be described. A cosmetic was produced by changing the content of silicon dioxide.

[0027]

In the above examples, the comparative examples are base creams of the present invention which do not contain silicon dioxide.
Lightly mix (a) and heat to 80 ℃, (b)
Was mixed and emulsified to form an emulsion, which was cooled to room temperature to obtain a cream.

In Example 1 above, 4% by weight of the silicon dioxide of the present invention was added, and the manufacturing method is the same as that of Comparative Example. The cream is fairly homogeneous, milky white and very smooth.

In Example 2 above, 8% by weight of the silicon dioxide of the present invention was blended, and the manufacturing method was the same as that of Comparative Example. The cream is slightly viscous but very smooth with few agglomerates.

Using the above Examples / and 2, the dye adsorption test was carried out by using 20 expert samples having a lot of spots and freckles. Test Results of Example 1 Expert Sample 1: Using cream under right eye. The color of freckles became lighter a month later. Expert Sample 2: Using a cream spot under the right eye. The color of freckles became distinctly lighter after 3 weeks. Expert Sample 3: Used with cream spread under the right eye. After two weeks the freckles were clearly lighter. Test Results of Example 2 Expert Sample 1: Use a slightly thick cream under the left eye. After a week the color of freckles became light and after a month barely spotted. Expert Sample 2: Apply cream under the left eye. Two weeks later I couldn't understand the freckles. Expert Sample 3: Thickly moistened cream under the left eye. The color of freckles became pale in a week and disappeared in 3 weeks.

It was used in Example 2 of the present invention and 5 expert samples with age spots. The results are as follows. It should be noted that only one oval-shaped senile was targeted, 1/3 of which was applied as a comparative example, an unused band was made in the middle portion, and the rest was applied as in Example 2.

(Examples of Hydrogen Cosmetics Containing 20% Silicon Dioxide Fine Particles of the Present Invention) The silicon dioxide fine particles of the present invention were added to 30% by weight of ultrapure water and completely dispersed by the ultrasonic homogenizer. The coarse particles that were centrifugally classified at 1000 rpm were removed, and then the slurry portion was evaporated to dryness to obtain particles of 300 nm or less. The average particle size of this solid component was 160 nm. Further, using this, a hydrogen cosmetic having the following composition was obtained. (A) Silicon dioxide of the present invention 20.0% by weight (b) Pure water 79.0% by weight (c) Sodium hyaluronate 1% 1.0% by weight Aqueous solution In the above formulation, after grinding (a), (b) , Then completely dispersed with an ultrasonic homogenizer, mixed with (c) and mixed, the water-based cosmetic obtained by this formulation was contaminated with a gardening paint mixed with an organochlorine insecticide It was applied to one expert sample that became.

(Results of Monitoring 20% Silicon Dioxide-Containing Water-Based Cosmetics of the Present Invention on Expert Samples of Skin Black Matter) Here, the paint causing the contamination is Takeda Pharmaceutical Co., Ltd.
Xyladecol sold, which contains three kinds of organochlorine insecticides such as cyfluthrin and azaconazole. Since the expert sample used this paint without permission, it showed a strong immune antibody reaction and allergic reaction, and many spots of skin melanosis occurred. Therefore, 1 after getting sick
After a week, the above cosmetic of the present invention was applied to the entire affected area to try to eliminate the causative substance. The results were as follows.

[0035]

The high-purity silicon dioxide fine particles of the present invention have extremely high monodispersity and fluidity particles as in the above-mentioned examples, and the charged state of the particle surface is strongly negatively charged.
A counter charge acts between the particles, and even if this silicon dioxide is incorporated into the cosmetic, it still has remarkably excellent dispersion characteristics and fluidity. It was also found that melamine pigments in skin cells and strong protein dimers forming senile cells, such as electroadsorption and hydrogen bonding, were also extracted through ceramide as a passage route. Therefore, the high-purity plasma-synthesized silicon dioxide of the present invention provides a cosmetic amount for adsorbing and removing pigment molecules such as stains having a high probability, which has been heretofore impossible.

Not only pigment molecules but also causative substances such as allergies and acute poisoning caused by the invasion of relics into human skin by insecticides and environmental hormones harmful to human beings are absorbed by the silicon dioxide. It is intended to provide a cosmetic that can be removed and removed from the body.

[Brief description of drawings]

FIG. 1 is an overall image observation of high-purity silicon dioxide by a scanning electron microscope.

FIG. 2 is a transmission electron microscope observation result of the centrifugal classification result of the high-purity silicon dioxide according to the present invention. A particle photograph of each rotation speed portion is shown as follows. (1) 1000 rpm An electron micrograph of particles precipitated at 1000 rpm or less. (2) 2000 rpm The silicon dioxide of the present invention obtained by removing the above (1) is 200
An electron micrograph of precipitated particles that were centrifugally classified at 0 rpm. (3) 3000 rpm The silicon dioxide of the present invention obtained by removing the above (2) is 300
An electron micrograph of precipitated particles that were centrifugally classified at 0 rpm. (4) 4000 rpm The silicon dioxide of the present invention obtained by removing the above (3) is 400
An electron micrograph of precipitated particles that were centrifugally classified at 0 rpm.

FIG. 3 is a transmission electron microscope observation result of a completely dispersed state of the silicon dioxide of the present invention in the cosmetic material according to Example 3 of the present invention. The white part is the cosmetic substrate, and the black shade is spherical thermal plasma synthetic high purity silicon oxide.

─────────────────────────────────────────────────── ─── Continuation of front page (51) Int.Cl. ⁷ Identification code FI theme code (reference) B01J 20/10 B01J 20/10 A 20/28 20/28 Z C01B 33/18 C01B 33/18 Z C08K 3 / 36 C08K 3/36 F Term (Reference) 4C083 AB171 AB172 AC022 AC101 AC122 AC352 AC422 AC442 AC482 AD152 AD331 CC05 DD32 DD33 EE07 EE16 4G066 AA02A AA22B BA09 BA20 BA33 BA38 CA10 CA20 EA20 FA31 4G072 AA25 BB23 HDR25 DD01 DD01 DD08 DD08 DD08 DD08 DD08 DD08 DD08 DD08 DD08 DD08 UU30 4G075 AA27 AA62 BA06 BD14 CA47 CA51 CA62 4J002 AA001 AE001 CP031 DJ016 FD016 HA07 HA08

Claims (4)

[Claims] 1. 99.9% by weight or more of silicon dioxide spherical ultrafine particles which are spherical and belong to a particle size distribution range of 5 nm or more and 2 μm or less, and the particles have a strong negative charge. A dye adsorption / removal composition, which is an adsorbent that is charged into a state and does not aggregate by counter charging. 2. The ultrafine particles are amorphous or / and microcrystalline crystals having an ultrafine structure obtained by evaporating and oxidizing high-purity metallic silicon in high-frequency thermal plasma, and silanol is originally formed. A dye adsorption-removing composition comprising silicon dioxide having almost no group and having an infrared absorption maximum at 8.9 to 9.0 μm. 3. The silicon dioxide spherical ultrafine particles according to claim 1 or 2 are homogeneous without aggregation in at least one medium selected from the group consisting of pure water, ethanol, isopropyl alcohol and sodium hyaluronate. A dye adsorption removal composition, characterized in that the particles have a low viscosity of 10 Stokes or less within 35% by weight, preferably 5 Stokes or less at a blending ratio of 25% by weight. 4. The particles according to claims 1 to 3 are oil-in-water (O / W) type or water-in-oil (W / W).
O) type cosmetic base completely mono-acidified and present in human skin cells or in the basal part of skin, a pigment molecule selected from the group of melamine or melanocytes, or a dimer protein pigment exhibiting senile spots. A dye adsorption / removal composition, which is capable of strongly adsorbing a negative charge to the body and forcibly adsorbing the dye through a ceramide as a passage while discharging the dye out of the body.