JPH072615B2 - Cosmetics - Google Patents

Description

DETAILED DESCRIPTION OF THE INVENTION [Field of Industrial Application] The present invention relates to a cosmetic composition containing monodisperse ultrafine particles.

In more detail, by mixing monodisperse and mature ultrafine particles (hereinafter referred to as monodisperse ultrafine particles) into a cosmetic base material,
The present invention relates to cosmetics having improved dispersibility, usability, and stability.

[Conventional technology]

It is said that when the skin is exposed to excessive ultraviolet rays, erythema, blisters and edema occur, and further, pigmented skin cancer occurs. In addition, it is said that ultraviolet rays are harmful to the hair and more hair is cut and extracted. It is also said that ultraviolet rays cause aging such as spots and wrinkles.

In the sun's rays, ultraviolet rays with a wavelength of 280-400 nm cause sunburn, causing skin to develop and blackening. Among these, the wavelength
It is said that mid-ultraviolet rays in the range of 290 to 320 nm have the strongest biological effect.

Conventionally, in order to prevent these problems, cosmetics containing an ultraviolet absorber and an infrared reflector have been developed.
For example, there are P-amino; benzoic acid derivatives, salicylic acid derivatives, benzotriazole derivatives and the like, and titanium oxide, zinc oxide, iron oxide and the like.

[Problems to be Solved by the Invention]

These cosmetics cause irritation, decrease in ultraviolet absorption, deterioration, and coloring, and titanium oxide and the like have a large particle size and have a particle size in a region that blocks visible light. The ultraviolet absorption was weak, and the shielding power was too strong to cause whitening or coloring, so that it could not be used for makeup cream such as foundation cream and lipstick. Further, these are dispersibility in a cosmetic base material, usability,
The stability was insufficient.

The present invention has been made to solve the problems associated with the above-mentioned conventional techniques, and the problems therefor are dispersibility, usability,
It is to provide a cosmetic material with improved stability.

[Means for Solving the Problems]

As a means for solving such a problem, the cosmetics according to the present invention, water in the hydrogel is replaced with an organic solvent,
Particles having a particle diameter of 0.1 μm, which is maintained at high temperature and high pressure in the range of the critical temperature or supercritical temperature and pressure specific to the organic solvent, and is separated from the organic solvent and matured by monodispersion.
In the following, at least a part of monodisperse ultrafine particles having a particle size distribution of 0.1 to 0.01 μm is blended.

The monodisperse ultrafine particles are composed of titania (TiO ₂ ), hematite (Fe ₂ O ₃ ), silica (SiO ₂ ), mullite (3Al ₂ O ₃ ).
₃ · 2SiO _2), zirconia (ZrO _2), titanium black (Ti
O) and magnetite (Fe ₃ O ₄ ) are desirable.

Further, the organic solvent is a water-soluble organic solvent such as ethanol or methanol, or a mixed organic solvent obtained by substituting a part of the water-soluble organic solvent with a slightly water-soluble higher alcohol, a polyhydric alcohol, or a water-insoluble organic solvent. It is desirable to use a solvent.

[Specific Description of the Invention]

In the present invention, the water in the hydrogel is replaced with an organic solvent, and held in a high-temperature and high-pressure container to be separated from the organic solvent and matured by monodispersion, a particle diameter of 0.1 μm or less,
The monodisperse ultrafine particles having a particle size distribution in the range of 0.1 μm to 0.01 μm are mixed preferably in an amount of 0.01 to 80 wt% with respect to the cosmetic base material.

The monodisperse ultrafine particles of the present invention are manufactured as follows.

(1) Hydrogels of water-insoluble and sparingly water-soluble hydrous oxides and hydrous hydroxides formed as fine or ultrafine particles,
After removing the coexisting water-soluble salts, replace the water in the hydrogel with a water-soluble organic solvent such as ethanol or methanol, or part of ethanol or methanol is a poorly water-soluble higher alcohol such as propanol or butanol, or glycerin. After replacing the water in the hydrogel with a mixed organic solvent substituted with a non-water-soluble organic solvent such as polyhydric alcohol or acetone and ether or benzene and hexane, put it in a high temperature and high pressure container and use the single organic solvent or mixture used. Before and after the critical temperature peculiar to the organic solvent, or in the range of supercritical temperature and pressure, the mixture is matured by monodispersion to separate the organic solvent and the solid to obtain a dry powder of monodisperse ultrafine particles.

(2) Further, when the water-soluble organic solvent of ethanol or methanol is used, water in the hydrogel of the hydrous oxide or hydrous hydroxide is replaced with the water-soluble organic solvent, and then the water content in the mixed slurry The particle diameter of the monodisperse ultrafine particles can be changed by changing the temperature and the specific critical temperature, pressure range and holding time.

(3) Furthermore, with respect to the above water-soluble organic solvents such as ethanol and methanol, some of them are poorly water-soluble higher alcohols such as propanol and butanol, polyhydric alcohols such as glycerin, and further acetone, ether, benzene, cyclohexane, etc. It is possible to change the particle size of the monodisperse ultrafine particles by substituting the non-water-soluble organic solvent of 1) and changing the critical temperature, the range of pressure and the holding time peculiar to each.

The monodisperse ultrafine particles produced by the above method include (1) silicon dioxide (SiO ₂ ), (2) titanium dioxide (white) (TiO ₂ ), (3) titanium monoxide (black) (TiO) ( 4) Iron oxide (red) (Fe ₂ O ₃ ) (5) Zirconium dioxide (ZrO ₂ ) (6) Mullite (3Al ₂ O ₃ 2SiO ₂ ) (7) Magnetite (Fe ₃ O ₄ ) Among them, the monodisperse ultrafine particles (1) to (7) have the characteristics shown in Table 1.

Of these, the mullite is a flat plate with a width of 0.1 μm and a length of 0.5 μm.
m, thickness 100 Å ~ 200 Å are monodisperse ultrafine particles, so a cosmetic with good "spreading" can be obtained. For hematite (iron oxide), monodisperse ultrafine particles with a uniform particle size of 100 Å are obtained, and for titanium In addition, plate-like monodisperse ultrafine particles of 0.01 μm to 0.03 μm were obtained, which was the most suitable as a cosmetic.
Further, the other products (described in Table 1) were also excellent as cosmetic products. In addition, magnetite 0.03μm ~
0.1μm black ultrafine crystal, which is the best cosmetic for eyebrows, and titanium black (TiO)
Also, it is a black 0.03 μm to 0.05 μm ultrafine crystal, which is extremely good as a black cosmetic.

The features of the monodisperse ultrafine particles as described above are summarized as follows.

(1) Primary particles are ultrafine particles (0.1 μm or less) and monodisperse (m
onodisperse). And almost no secondary aggregation is observed.

(2) Obtained as dried ultrafine particles.

(3) Except for silica and mullite, it has a crystal form and has a beautiful and smooth crystal face (for example, titanium oxide, iron oxide, magnetite, etc.).

(4) The particle size distribution is concentrated in a very narrow range, which is often 0.1 to 0.01 μm.

(5) The particle size can be controlled by adjusting the manufacturing process.

(6) Surface hydrophilicity or hydrophobicity can be selected by adjusting the manufacturing process.

(7) The bulk does not aggregate even if left in the air.

(8) Each particle forms a particle shape unique to monodisperse ultrafine particles (Table 1).

(9) It exhibits extremely excellent performance as a cosmetic compounding material used for lipsticks, milky lotions, foundations, eyebrows, whitewashes, hair dyes, tics, manicures, pedicures, eye shadows, mascaras, creams, blushers, eye lines and the like.

〔The invention's effect〕

The cosmetics containing the monodisperse ultrafine particles have the following effects.

(1) By blending monodisperse ultrafine particles that are maintained around the critical temperature or supercritical temperature and pressure range peculiar to the organic solvent used, and matured by monodispersion and separated from the organic solvent, A dense and dry solid ultrafine particle crystal that does not cause aggregation can be blended, and a cosmetic having improved dispersibility, usability, and stability can be obtained.

(2) When used on lipsticks, emulsions, foundations, eyebrows, powders, hair dyes, tics, manicures, pedicures, eye shadows, mascaras, creams, blushers, eye lines, etc., they are exposed to direct sunlight on the face, head, hands, etc. As a cosmetic for the affected part, it is possible to improve the makeup performance as well as the ultraviolet absorbing effect.

(3) Since the monodisperse ultrafine particles have a unique particle shape, the coating performance as a cosmetic can be improved.

(4) The "spreading", "stickiness", or "freshness" when applied is improved, the touch is improved, discomfort is reduced, and the product quality of cosmetics can be improved.

〔Example〕

Examples of the method for producing monodisperse ultrafine particles and cosmetics according to the present invention are shown below, but the present invention is not limited thereto.

[Example 1] 1.75 kg of water glass No. 3 (Na ₂ O ₃ 9.70%, SiO ₂ 28.69%) was taken, and 3.25 kg of pure water was added thereto and mixed well to make a uniform aqueous solution. This corresponds to about a 35% solution of water glass.

2.77 kg of 10% sulfuric acid is uniformly mixed with this solution for a short time.
After a while, the mixed solution gels and becomes agar-like as a homogeneous hydrogel. This hydrogel has a net 6.4 as SiO _2.
% Is included.

These agar particulate hydrogel penetrates into 10% sulfuric acid 4 liters for a NaSO ₄ residual NaOH was neutralized since gelation at position PH10, then it was acidified, washed with pure water.

After completely removing Na ⁺ and SO ₄ ⁼ , add 4 kg of methyl alcohol to 8 kg of the gel and let stand. This causes the water in the gel to be substantially replaced by methyl alcohol.

After repeating the same procedure, add 800 g of the gel to 16
The mixture was placed in 00 cc of methyl alcohol, placed in an autoclave having an internal volume of 5 liters, heated and kept at 300 ° C. and about 200 atm for 1 hour to remove methanol to obtain 50 g of monodispersed ultrafine particles of dry silica.

FIG. 5 (1) shows a gel-like ultra-fine particle silica.
(1) in the figure is a state after the treatment, showing clear ultrafine particle silica (particle size 100 × 300Å), which indicates that the particle group has an extremely narrow particle size distribution.

Since SiO ₂ (silica) is an amorphous substance and it is extremely difficult to crystallize up to ~ 500 ° C, hydrogel is not a broad crystal after treatment, as can be seen from its X-ray diffraction diagram (Fig. 2). The diffraction diagram is difficult to recognize.

Example 2 Ferric Sulfate Hydrous Salt (Fe ₂ (SO ₄ ) ₃ × H ₂ O, Solid Content 70%) 3.
Dissolve 57 kg in 5 kg of hot pure water (70-90 ° C), and blow in 0.765 kg of ammonia gas (NH ₃ ) while stirring.

The slurry containing the produced ferric hydroxide hydrogel is filtered, and 80 liters of hot pure water (70 to 90 ° C.) is washed in 12 to 13 times. The final filter cake is 20% solids
, And NH ₄ ⁺ and SO ₄ ⁼ ions are completely removed.

27 liters of 99.5% ethanol was added to 3 liters of the cake obtained after filtration and mixed well with a mixer to form a uniform slurry.

About 2.5 liters of this are sampled, placed in an autoclave with an internal volume of 5 liters, and heated to 300 ° C. The pressure at this time is 170 atm. After holding for 1 hour, the solid content and ethanol are separated, and the obtained solid content is ferric oxide, and 140 g of dried ultrafine powder of monodisperse ultrafine particles thereof is obtained.

Fig. 5 (2) shows amorphous ultrafine particles of ferric hydroxide hydrogel before autoclave treatment, and Fig. 6 (2) shows automorphic form of hematite (Fe ₂ O ₃ ) after treatment. ,
It shows monodisperse ultrafine particles with beautiful crystal planes.

FIG. 4 shows an X-ray diffraction diagram of ferric hydroxide hydrogel (Fe ₂ (OX) _x ), and the produced hematite crystals and magnetite crystals.

[Example 3] In Example 2, 3 liters of the cake obtained after filtration was added.
Add 25 liters of 99.5% ethanol and 2 liters of acetone and mix well with a mixer to make a uniform slurry.

About 2.5 liters of this are sampled, placed in an autoclave with an internal volume of 5 liters, and heated to 280 ° C. The pressure at this time is about 140 atm. Hold for 1 hour to separate solids and ethanol / acetone mixed solvent. The solid content thus obtained is monodisperse ultrafine particles of ferric oxide, and 140 g of dried ultrafine powder thereof is obtained.

The difference between the results of Example 3 and the results of Example 2 is that the particle size is smaller than that of (2) in FIG. 6, as shown in (3) of FIG. This shows the effect of the added acetone. The monodisperse ultrafine particles of hematite (Fe ₂ O ₃ ) show an automorphic shape and have a beautiful crystal face.

Example 4 Ferrous crystalline sulfate _{(FeSO 4 · 7H 2 O)} 333.6g and, ferric crystals sulphate _{(Fe 2 (SO 4) 3} · 17H 2 O) 348g and heat purified water (70 to 90 ℃) 2.4
Dissolve in liters. A solution prepared by dissolving 720 g of cargo soda in 3 liters of pure water is added with good stirring to form a gel containing ultrafine particles of magnetite (FeO · Fe ₂ O ₃ ) (shown in Fig. 5 (3)). .

This was filtered NetsuJun water (70 to 90 ° C.) with 40 l Na ^+, SO ₄
⁼ Wash until almost all the ions are gone. The water content of the cake obtained after washing is around 25%. 7 liters of ethanol is added to this cake and mixed well with a mixer to uniformly disperse the magnetite gel ultra-fine particles in ethanol. This gives 8 liters of alcohol slurry.

3 liters of this alcohol slurry is taken and placed in an autoclave having an internal volume of 5 liters, and heated to 280 ° C. The pressure is 150 atm. After holding for 1 hour to remove ethanol, 170 g of dry ultrafine powder containing monodisperse ultrafine particles of magnetite (shown in FIG. 6 (4)) is obtained.

The Example 5 Zirconium oxychloride crystals _{(ZrOCl 2 · 8H 2 O)} 2.615kg dissolved in hot pure water 5 liters. While thoroughly stirring the obtained solution, blow 0.276 kg of ammonia gas (NH ₃ ). The slurry containing the obtained zirconium hydroxide gel was filtered, and then 80 liters of hot pure water was divided into 12 times to wash the cake,
Completely remove NH ₄ ⁺ , CL ⁻ ions in the cake.

To 2 liters of the washed gel (containing 500 g of zirconium dioxide ZrO ₂ ) was added 6 liters of methanol containing 10% propanol, and the gel was completely dispersed in methanol with a mixer.

From this, 3 liters of the mixed slurry is taken and placed in an autoclave having an internal volume of 5 liters and heated to 300 ° C.
The pressure becomes 190 atm, and by holding for 1 hour to separate methanol, 187 g of dry ultrafine powder of monodisperse ultrafine particles of zirconium dioxide (ZrO ₂ ) is obtained.

The particle size of ultrafine zirconium dioxide is 100 Å or less as shown in Fig. 6 (5). However, the zirconium dioxide hydrogel particles shown in FIG.

An X-ray diffraction diagram of the zirconium dioxide hydrogel is shown in FIG. 1, showing only a dull halo. However, the X-ray diffraction pattern of zirconium dioxide ultrafine particles having a particle size of 100 Å or less shows extremely clear crystals.

Example 6 950 g of titanium tetrachloride (TiCl ₄ ) is dissolved in 5 liters of pure water. Obtained titanium oxychloride (TiOCl ₂ )
While stirring the solution, blow 340 g of ammonia gas (NH ₃ ). Slurry containing titanium hydroxide gel (titanium dioxide gel may be generated) generated at the end of blowing is filtered and washed. Hot water (70 to 90 ° C) 40 is used as the washing water, and most of NH ₄ ⁺ and Cl ^- are removed. Finally on the cake 7
1 liter of ethyl alcohol (containing 5% ether) is added and the cake is thoroughly dispersed in ethyl alcohol with a mixer.

From the obtained ethyl alcohol slurry, 3 liters are sampled and placed in an autoclave having an internal volume of 5 liters, and the temperature is raised to 350 ° C. The pressure is 300 atm. By keeping it for 1 hour to remove ethyl alcohol, dry ultrafine powder of monodispersed ultrafine particles of titanium dioxide (TiO ₂ ) 15
You can get 0g.

As shown in Fig. 6 (6), these ultrafine particles are 0.01-0.04μ.
m. FIG. 5 (5) shows titanium hydroxide hydrogel, which is ultrafine particles whose shape is unknown. Also, X of titanium hydroxide hydrogel (TiO ₂ gel in FIG. ₂ )
The line diffraction diagram shows a dull halo that is not a crystal.
X-ray diffraction diagram (Fig. 3) of ultrafine O ₂ particles is clear anatase
The diffraction diagram of TiO ₂ is shown.

[Example 7] 565 g of aluminum trichloride (AlCl ₃ ) was dissolved in 10 liters of pure water, and the obtained solution was stirred to obtain silicon tetrachloride (Si
Dissolve by adding 240 g of Cl ₄ ). While stirring 168 g of ammonia gas (NH ₃ ) into the obtained solution, stir well. When the blowing is completed, a slurry containing mullite hydrogel consisting of ultra-fine particles as shown in Fig. 5 (6) is obtained. This is filtered, washed with 50 liters of hot pure water (70 to 90 ° C), and N
Completely remove H ₄ ⁺ and Cl ⁻ ions. 6 liters of methyl alcohol (containing 5% butyl alcohol) was added to the mullide hydrogel in which water was filtered by suction as much as possible, and the gel was completely dispersed in the methyl alcohol with a mixer.

3 liters of the obtained methyl alcohol slurry is sampled, put into an autoclave having an internal volume of 5 liters, and heated to 350 ° C. The pressure reaches 300 atm and is maintained for 6 hours to remove methyl alcohol.

As a result, as shown in Fig. 6 (7), the monodisperse ultrafine particles of mullite (the shape is a leaf-shaped plate with a major axis of 1 μm and a minor axis of 0.2).
~ 0.8μm, thickness 0.03μm), 113g as dry ultrafine powder
available.

[Example (1)] Of the monodisperse ultrafine particles obtained as described above, an example in which mullite (width 0.1 μm, length 0.5 μm, thickness 100 Å to 200 Å, plate-like) is blended in a cosmetic composition Examples of application to food are shown below, but the present invention is not limited thereto.

(1) UV absorption effect measurement To 40 g of mullite (3Al ₂ O ₃ · 2SiO ₂ ) was added 60 parts of castor oil,
Thoroughly knead with three rollers to make a slurry. Take 25 parts of the slurry, add 75 parts of castor oil, and further disperse the mullite using a stirrer. The dispersion was applied to a transparent quartz plate to form a film thickness of 5 μm, and the absorbance in the wavelength region of 280 to 380 nm was measured using a spectrophotometer. The results are shown in Fig. 1 (wavelength (nm) on the horizontal axis and absorbance on the vertical axis).

As is clear from FIG. 1, in the present invention, the maximum absorption wavelength region of the ultraviolet absorption effect is 295 to 3 which has the strongest biological action.
It was in the range of 20 nm, which was a good result.

(2) Actual Usability Test for Cosmetics The mullite of the present invention was blended as described below to prepare an emulsion.

(Composition) Mullite 6.0wt% Stearic acid 2.0wt% Cetyl alcohol 1.0wt% Vaseline 5.0wt% Silicone oil 2.0wt% Liquid paraffin 11.0wt% Glyceryl monostearate 1.0wt% Polyoxyethylene (25mol) Monooleate
1.0 wt% Polyethylene glycol 1500 5.0 wt% Veegum 0.5 wt% Purified water 65.5 wt% Perfume preservative Suitable amount To prepare emulsion, add polyethylene glycol with purified water, heat and dissolve it, and add mullite ultrafine beakum, polyoxyethylene (25 Mol) monooleic acid ester was added, and the mixture was uniformly dispersed with a homomixer and kept at 70 ° C (aqueous phase).
Other ingredients are mixed, dissolved by heating and kept at 70 ° C (oil phase).
Add the oil phase to the water phase, homogenize and disperse with a homomixer,
After emulsification, the mixture was cooled to 35 ° C. with stirring and adjusted.

The emulsions prepared as described above were tested for their practical usability as follows. Twenty female panelists actually used the above adjusted emulsion on the entire face, and evaluated the four items of "spreading", "stickiness", "freshness", "whiteness" and "comprehensive evaluation" during use.

The evaluation method is summarized in Table 2 by comparing the number of people who answered “good”, “refreshing”, and “whitish” with the products of other companies (milk liquid of Company A).

As can be seen from Table 2, it can be said that the emulsion of the present invention has very good "spreading" and "stickiness" when applied, and is a good emulsion.

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

[Brief description of drawings]

FIG. 1 is a graph showing the ultraviolet absorbing effect of the cosmetic material according to the present invention. FIG. 2 is a graph showing an X-ray diffraction diagram of silica hydrogel (SiO ₂ gel), titania hydrogel (TiO ₂ gel), and zirconia hydrogel (ZrO ₂ gel). Figure 3 shows X of titania (TiO ₂ ) and zirconia (ZrO ₂ ).
It is a line diffraction diagram. FIG. 4 is an X-ray diffraction diagram of ferric hydroxide hydrogel (Fe ₂ (OX) _x ), hematite (Fe ₂ O ₃ ) and magnetite (Fe ₃ O ₄ ). FIG. 5 is an electron micrograph of each fine particle in a gel state before the autoclave treatment according to the present invention, where (1) is silica (SiO ₂ ) hydrogel and (2) is ferric hydroxide (Fe).
(OH) _x ) hydrogel, (3) magnetite gel,
(4) is zirconium dioxide human gel, (5) is titanium dioxide hydrogel, (6) is mullite hydrogel, (7) is cordierite hydrogel, and (8) is manganese zinc ferrite hydrogel. FIG. 6 is an electron micrograph of each fine particle after autoclave treatment according to the present invention. (1) is silicon dioxide (silica SiO ₂ ), (2) is ferric oxide (Fe ₂ O ₃ ), ( 3) is ferric oxide (Fe ₂ O ₃ ), (4) is magnetite (Fe)
₃ O ₄ ) and (5) are zirconium dioxide (ZrO ₂ ) and (6)
Is titanium dioxide (TiO ₂ ), (7) is mullite (3Al _{2
O 3 · 2SiO 2), (} 8) cordierite _{(2MgO · 2Al 2 O 3 ·} 5
SiO ₂ ) and (9) are manganese zinc ferrite (MnO ・ ZnO ・
Fe ₂ O ₃ ) is shown.

Claims (3)

[Claims] 1. Obtained by substituting water in a hydrogel with an organic solvent, maintaining it at a high temperature and high pressure in the range of a critical temperature peculiar to the organic solvent or supercritical temperature and pressure, and separating from the organic solvent. Monodispersed and mature, with a particle size of 0.1 μm or less,
A cosmetic comprising at least a part of monodispersed ultrafine particles having a particle size distribution in the range of 0.1 to 0.01 μm. 2. The monodisperse ultrafine particles are titania (Ti
O _2), hematite (Fe ₂ O _3), silica (SiO _2), mullite _{(3Al 2 O 3 · 2SiO 2} ), zirconia (ZrO _2), of the titanium black (TiO), magnetite (Fe ₃ O ₄₎ The cosmetic according to claim 1, wherein the cosmetic is at least one of 3. The water-soluble organic solvent such as ethanol or methanol, or a part of the water-soluble organic solvent is replaced with a slightly water-soluble higher alcohol, a polyhydric alcohol, or a water-insoluble organic solvent. The cosmetic material according to claim 1, which is a mixed organic solvent.