JPS6372620A - Cosmetic - Google Patents

Abstract

PURPOSE:To provide a cosmetic having excellent ultraviolet-shielding capability and transparent natural color, by using a compound oxide of a specific metal and zinc having an average particle diameter falling within a specific range as a component. CONSTITUTION:A compound oxide powder of Zn and a metal selected from Al, Fe, Cr, Ce, Zr and Ti and having an average particle diameter of 0.001-0.5mum, especially 0.005-0.2mum is used as a component of the cosmetic at an amount of 0.1-40wt%, especially 0.5-30wt%. All Zn atoms in the compound oxide are preferably bonded to the other metals via oxygen atom. The ratio of Zn to the other metal depends upon the kind of the metal and is 0.001-0.5 for Al and 0.01-0.25 for Ti per 1pt. of Zn. The compound oxide powder has an ultraviolet-shielding capability of >=90% to ultraviolet ray of <=400nm wavelength and a transmittance of >=60% for visible light and near infrared radiation (400-3,000nm wavelength) and does not deteriorate organic materials contacting the oxide.

Description

DETAILED DESCRIPTION OF THE INVENTION <Industrial Application Field> The present invention relates to a cosmetic having excellent ultraviolet yXX performance, transparency, and natural color tone.

More specifically, the average particle diameter is 0.001 μm to 0.5 μm.
The present invention relates to a cosmetic containing 0.1 to 40% by weight of a composite oxide powder of zinc and a metal selected from aluminum, iron, chromium, cerium, zirconium, and titanium.

<Prior Art> It is generally well known today that excessive ultraviolet irradiation is extremely harmful to the skin.

Approximately 280 nm to approximately 32 nm of ultraviolet rays included in sunlight
Mid-wavelength ultraviolet light of 0 nm causes acute inflammation and burns on human skin, while long-wavelength ultraviolet light of about 320 nm to about 400 nm oxidizes reduced melanin in the epidermis, directly causing sunburn and darkening the skin. Furthermore, UV light reflected from the snow surface can cause sunburn and darken the skin.

Recently, in order to protect the skin from these harmful ultraviolet rays, various types of ultraviolet shielding agents have been added to products ranging from basic cosmetics such as day creams, foundations, white powders, lipsticks, and eye shadows to make-up cosmetics.

In particular, cosmetics known as sunscreen cosmetics and sunscreen cosmetics have been carefully considered to take into account the effects of ultraviolet rays on the skin. be.

) are mixed.

In other words, sunburn cosmetics contain ultraviolet absorbers that easily pass long-wavelength ultraviolet rays that directly promote sunburn, but absorb mid-wavelength ultraviolet rays that cause skin irritation, and even long-term sunbathing can cause skin irritation. It is a cosmetic used for the purpose of creating a healthy tan according to your preference without sunburn, and sunscreen cosmetics increase the amount of UV absorbers and also absorb irradiation energy in the low wavelength range. Designed to prevent sunburn.

As such ultraviolet absorbers, organic substances such as salicylic acid, para-aminobenzoic acid, cinnamic acid, esters thereof, or benzophenones are used.

These organic substances have a maximum absorption wavelength of approximately 290 nm ~
It selectively absorbs ultraviolet rays in the medium wavelength range, which is approximately 310 nm and is especially harmful to the skin, but when sweating or bathing,
It has the disadvantage that it is difficult to maintain its ultraviolet absorbing ability because it is washed away or absorbed into the skin.

In addition, due to concerns about side effects on the skin and the human body, the amount of these ingredients is regulated, and at present no sunscreen cosmetics or sunscreen cosmetics with sufficient UV-shielding ability have been obtained. It is.

On the other hand, metal oxide powders such as zinc oxide, titanium oxide, and iron oxide have a good ability to absorb and scatter ultraviolet rays with a wavelength of about 400 nm or less, so they are used in cosmetics as ultraviolet screening agents. It is blended into food and used.

However, these metal oxide powders have a high refractive index and absorb and scatter ultraviolet rays, while also strongly scattering visible light, making the cosmetic film applied to the skin whitish, creating a thick makeup, and making it look opaque and natural. The disadvantage is that the sense of humor is lost.

(Problems to be Solved by the Invention) For this reason, a method is known in which a metal oxide powder is made into an ultrafine powder and incorporated into a cosmetic base as an ultraviolet shielding agent. (For example, JP-A No. 60-231607 However, this method can provide a transparent and natural cosmetic film with no noticeable whiteness when applied, and since the particles are fine, when incorporated into cosmetics, it has good dispersibility and improves the feeling of use (spreadiness, texture, etc.). etc.) Although it has the effect of improving 1. tia particle powder,
It has a very strong oxidation catalytic ability and has the problem of altering and coloring oils and fats, higher alcohols, preservatives, organic ultraviolet absorbers, etc. that coexist in cosmetics.

In view of these circumstances, the present inventors have been able to obtain a natural cosmetic film that has an excellent ultraviolet shielding effect, has no activity or catalytic ability, has no noticeable whiteness, and has a transparent feel when used. Moreover, as a result of intensive study to find a cosmetic that has an excellent feeling of use, we found a cosmetic that satisfies all of the above conditions.
The present invention has now been completed.

Means for Solving Problems〉 That is, the present invention has an average particle diameter of 0.001 μm to 0.01 μm.
5 μm, aluminum, iron, chromium, cerium,
To provide a cosmetic material containing 0.1 to 40% by weight of a composite oxide powder of zinc and a metal selected from zirconium and titanium.

The present invention will be explained in more detail below.

The composite oxide powder used in the present invention includes aluminum, iron, chromium, cerium, zirconium, and titanium (
Below, kl, Fe, Cr.

It may also be expressed as Ce, Zr, or Ti. ) and at least one metal selected from the group consisting of
Sometimes expressed as n. ), more specifically Zn-Af, Zn-Fez Zn-Cr, Z
Binary composite oxide consisting of n-Ce, Zn-Zr, Zn-Ti, Zn-Al-Fe5Zn-AI-Cr, Zn
-Al-Ce, Zn-Al-Zr, Zn-Aj! -T1
, Zn-Fe-Cr, Zn-Fe-Co.

Zn-Fe-Zr, Zn-Fe-Ti5Zn-Cr-C
e%Zn-Cr-Zr5 Zn-Cr-Tl, Zn-C
o-Zr, Zn-Ce-Tt.

Ternary composite oxide consisting of Zn-Zr-Tl, Zn-
AI-je-Cr, Zn-Affi-Fe-Ce,
Zn-Aj-Fe-Zr, Zn-A1-Fe-Tl, Z
n-Aj! -Cr-Ce, Zn-Al-Cr-Zr, Z
n-Al-Cr-Ti.

Zn-Al-Ce-Zr% Zn-Al-Ce-Ti
, Zn-Aj-Zr-Ti, Zn-Fe-Cr-Co
, Zn-Fe-Ce-Zr% Zn-Fe-Zr
-Ti, Zn-Fe-Cr-Zr.

Zn-Fe-Cr-Ti, Zn-Fe-Ce-T
iS Zn-Cr-Ce-Zr, Zn-Cr-Zr-
Ti, Zn-Ce-Zr-Tt, Zn-Cr-Co-T
A quaternary composite oxide consisting of Zn-Aj-Fe-C
r-Ce, Zn-Aj! -Fe-Cr-ZrSZn-A
j-Fe-Cr-Ti, Zn-Fe-Cr-Ce-Z
r, Zn-Fe-Cr-Co-Tl, Zn-Cr-Ce
-Zr-Ti, Zn-Aj-Co-Zr-Tt.

Zn-AJ-Fe-Ce-Zr, Zn-Al-Fe-C
o-Ti%Zn-Al-Fe-Zr-Ti5Zn-AI
-Cr-Co-Zr, Zn -Al-Cr-Ce-Ti
, Zn-Aj! -Cr-Zr-Tis Zn-Fe-C
e-Zr-Ti.

Five-component composite oxide consisting of Zn-Fe-Cr-Zr-Ti, Zn-Affi-Fe-Cr-Ce-Zrs
Zn-Al-Fe-Cr-Ce-Ti.

Zn-Al-Fe-Cr-Zr-Ti5 Zn-AI
-Fe-Ce-Zr-Ti, Zn-Al2-Cr-
Ca-Zr-Tl, Zn-Fe-Cr-Ce-Z
Six-component complex oxide consisting of r-Ti and Zn-Aj
A seven-component composite oxide consisting of -Fs-Cr-Ce-Zr-Tl and the like can be mentioned.

These composite oxides may be used alone or in combination of two or more.

When implementing the present invention, zinc and 'r constituting the composite oxide
i, Aj, Fes The composition ratio of other metals selected from the group of Cr, Co, and Zr varies depending on the metal. For example, in a combination of zinc and titanium, the atomic ratio of titanium to 1 zinc is 0.01 to 0.0. 25, preferably 0.05-0.1
, zinc and aluminum have a ratio of 1 zinc to 1 aluminum
, oot ~ 0.5, preferably 0.01 to 0.4, iron to zinc l is 0.0001 to 0.5, preferably 0.0001 to 0°2, zinc and chromium are zinc chromium is 0°0005 to 0.5, preferably o, oo
os~0.3, zinc and cerium are 01oooos~2 for 1 zinc, preferably 0.00005~0
．． 5. Regarding zinc and zirconium, the ratio of zirconium to 1 part of zinc is 0.0005 to 0.5, preferably 0.0005 to 0.
．． It is 3.

If the ratio of metal to 1 atomic ratio of zinc is outside the above range, the UV shielding ability will be poor, and in the case of iron, if the ratio of metal to 1 atomic ratio of zinc exceeds 0.5, the transmittance of visible light and near infrared rays will decrease. Therefore, it is not desirable.

In addition, the amount of metal added in a composite oxide consisting of zinc and multiple metals is within the range of each addition amount of zinc and other metals in a binary system, preferably in a binary system of zinc and other metals. The preferred ranges for each metal in .

In the present invention, the composite oxide is composed of zinc used as a starting material and A1, Fe-, Cr%Ce%Zr.
−.

It is not necessary that all of the one or more metals selected from Ti react to form a composite oxide, but the reaction product must constitute at least a composite oxide and the product has an ultraviolet shielding ability of 90% or more. A composite oxide partially containing a metal oxide or the like may be used as long as it has visible light and near-infrared transmittance of 60% or more.

The composite oxide for an ultraviolet screening agent used in the present invention has a structure in which metals are bonded via oxygen atoms.

For example, a zinc atom interacts with another metal via an oxygen atom -Zn-
0-Ti(-1-Zn-0-81,>Al-0-Zn
-0-Ti(-1-Zn-0-Fe, -Zn-0-C
e←, >Fe-0-Z'n-0-Ce←, -Zn-0-
Zr←, -Zn-Q-(:, r<, >Cr-0-Zn-
It contains bonds such as 0-Zr(-), and preferably all Zn atoms are bonded to other metals via oxygen as described above.

Such a structure can be confirmed by an infrared spectrum as shown in JISKO117.

Zn atoms are AR-0-Zn-0-RA, -Zn-0
- Those that do not contain a bond such as RA (R is a metal atom selected from Al, Fe5ZrSTisCe, Cr, A is a bond, indicating the valence of R -1) are simply oxidation of zinc oxide and the above metals. This is a mixture of different powders, and the powder used in the present invention, which has excellent ultraviolet shielding ability and excellent visible light and near-infrared vAi3 performance, cannot be obtained.

The average particle size of the composite oxide used in the present invention is approximately 0.5
It is not more than μm, preferably not more than 0.2 μm.

Large particle sizes are not preferred because they have a slightly low ultraviolet shielding ability, have a poor texture when used as cosmetics, and have poor dispersibility.

On the other hand, particles with a fine particle size have an average particle size of about 0.00 Lum or more, more preferably 0.005 μm or more, because although they have sufficient ultraviolet shielding ability, they become difficult to handle and develop oxidation catalytic ability. be.

As a method for producing such a composite oxide, zinc salt and
One or more metal salts selected from aluminum salts, iron salts, chromium salts, cerium salts, zirconium salts, and titanium salts, and at least one metal salt selected from urea and hexamethylenetetramine in an alcohol aqueous solution. Examples include a method of performing hydrolysis in the presence of a hydrolysis precipitant and then calcining the hydrolysis product.

Here, the raw materials zinc salt, aluminum salt, iron salt, chromium salt, cerium salt, zirconium salt, and titanium salt are water-soluble inorganic acid salts, organic acid salts, such as chlorides, sulfates, nitrates, Acetate, etc.

As for the aluminum salt, polyaluminum chloride and the like can also be used.

Moreover, titanium alkoxide can also be suitably used in place of titanium salt.

Next, the alcohol aqueous solution has an alcohol concentration of approximately 5% by volume.
Above, preferably 10% by volume or more is used.

If the alcohol concentration is less than about 5% by volume, it will be difficult to reduce the average particle size of the composite oxide to 0.5 μm or less, and the particle size distribution will expand and large particles will be mixed together. Undesirable.

On the other hand, it is possible to use too much alcohol, but even if there is too much alcohol, the effect will not be as great.

The type of alcohol only needs to have a solubility in water of 1% by volume or more, such as monohydric alcohols such as methanol, ethanol, isopropanol, normal propazol, ethylene glycol, diethylene glycol, propylene glycol, and glycerin. Polyhydric alcohols such as

As the hydrolysis precipitant, it is desirable to use either urea or hexamethylenetetramine, or a mixture of both in the form of an aqueous solution.

The amount of the hydrolysis precipitant is at least twice the theoretical amount necessary to neutralize the acid generated by hydrolysis of the metal salt, preferably 3 times or more.
Use twice to 5 times the amount.

The hydrolysis reaction is carried out under stirring at a temperature ranging from room temperature to 100°C.
More preferably, it is carried out at a temperature of 70°C or higher for about 3 to 6 hours.

The completion of the reaction can be confirmed when the pH of the reaction solution increases to around 7.

The hydrolyzed product is then removed by conventional solid-liquid separation operations such as filtering and decantation, washed with water, thoroughly dried at room temperature to about 200°C, and heated to 350°C to 1100°C.
Firing is performed at a temperature of approximately 1 to 3 hours.

It is desirable to crush (disintegrate) the secondary agglomerated particles before and after firing, and the crushing may be carried out by a conventional means such as a hammer mill, mulch mill, ball mill, or vibration mill.

The average particle size obtained in this way is 0.001 μm to 0.
．． The 5 μm composite oxide has an excellent UV shielding ability of 90% or more for wavelengths of 400 nm or less, and has 60% transparency for visible light and near-infrared rays (wavelengths of 400 nm to 3000 nm).
In addition to the above, since they have almost no catalytic activity and do not alter the coexisting organic substances, cosmetics containing these ingredients have extremely excellent ultraviolet shielding effects, and also have good visible light transmission.
When applied, the cosmetic film is white (you can obtain a natural cosmetic film with a sense of transparency).

The amount of zinc-based composite oxide used in the present invention is approximately 0.
1% to about 40% by weight, preferably 0.5% to
It is added in an amount of 30% by weight.

If the content of the zinc-based composite oxide in the cosmetic is less than 0.1% by weight, the ultraviolet shielding ability will be poor, while if it exceeds 40% by weight, the cosmetic will become whitish and a transparent and natural cosmetic film cannot be obtained, which is not preferable.

In addition, for the purpose of improving the UV shielding effect, salicylic acid derivatives, benzoic acid derivatives, cinnamic acid derivatives, benzophenone derivatives, titanium oxide, zinc oxide, kaolin,
Known ultraviolet shielding agents such as aluminum oxide and calcium carbonate can also be added and used in combination with the zinc-based composite oxide.

Furthermore, in the present invention, when blending an ultraviolet shielding agent made of a zinc-based composite oxide, surface coating treatment with oil and fat raw materials, surfactant treatment, zinc stearate, etc., which are commonly used for the purpose of improving dispersibility and usability, may be applied. It may be blended after surface treatment such as metal soap treatment.

(Effects of the Invention) The cosmetics obtained by the present invention as detailed above not only have excellent texture and spreadability when used, but also have extremely excellent ultraviolet shielding ability and a natural color tone with transparency. ,
In addition, because of its low activity and catalytic ability, it does not alter the quality of cosmetics, making it excellent as a sunscreen cosmetic or a sunscreen cosmetic.

(Example) Hereinafter, the present invention will be explained in more detail with reference to Examples.
The present invention is not limited by these examples.

In addition, although the expression "trace" was used in the examples, this is o, os weight% with respect to the cosmetic composition.

Example 1 Cream (formulation) (wt%) Complex oxide 10.0 Oil phase (1)
Stearic acid 2.0 (2) Stearyl alcohol 7.0 (3) Reduced lanolin
2.0(4) Squalane 5
．． 0(5) Octadodecanol 6.0(
6) Polyoxyethylene 3.0 Cetyl ether (25E, O,) (7) Lipophilic monostearic acid 2.0 Glycerin (8) Fragrance 0. 3
(9) Preservative Trace amount of water Phase αe Propylene glycol 5.000 Purified water 57.7 (Production method) Mix the aqueous phase Qlαυ and add the complex oxide to it and 70°C
Heat to.

Next, oil phases 1) to (9) were mixed and heated to 70°C, the previously prepared aqueous phase was added and homogeneously emulsified using a homomixer, and then cooled to room temperature to obtain cream.

Example 2 Emulsion (formulation) (wt%) Complex oxide 12.0 Oil phase (11
Stearic acid 2.4 (2) Monostearic acid 2.0 Propylene glycol (3) Cetostearyl alcohol 0. 2(4) Liquid lanolin 2. 0 (5) Liquid paraffin 3.0 (6) Isopropyl myristate 8.5 (7) Preservative Trace aqueous phase (8) Purified water 64.1 (9) Carboxymethyl 0. 2 Cellulose Sodium Bentonite 0. 5Qυ Propylene Glycol 4.0 (2) Triethanolamine 1. 1 Pigment α1 Colored pigment
Amount α (Minor amount of fragrance (manufacturing method) Sodium carboxymethylcellulose in which propylene glycol was dispersed, triethanolamine, and bentonite were added to purified water heated to 70°C to prepare an aqueous phase.

Next, the pigment and composite oxide were pulverized and mixed in a small ball mill, added to the previously prepared aqueous phase, stirred, and passed through a colloid mill.

The solution thus obtained was heated to 75°C, then added to an oil phase consisting of (1) to (8) prepared by heating to 80°C while stirring, and allowed to cool naturally.

When the temperature of the solution reached 45°C, a fragrance was added, and the solution was cooled to room temperature while stirring to obtain a milky lotion.

Example 3 Foundation cream (formulation) (wt%) Complex oxide 15.0 Oil phase (11
Stearic acid 5.0 (2) Lipophilic monostearic acid 2.5 Glycerin (3) Cetostearyl alcohol 1.0 (4) Monolauric acid 3.0-Propylene glycol (5) Liquid paraffin 7.0 (6) Myristic acid Isopropyl 8.0 (7) Preservative
Trace aqueous phase (8) Purified water 53.3 (9) Triethanolamine 1. 2. Sorbitol 3.0 Material αD bentonite 1.0 Subcolor pigment
Minor flavoring
A small amount (manufacturing method) Add and disperse the pigment and composite oxide that have been mixed and ground in advance to the aqueous phase prepared by mixing (8) to Q@, and after heating to 75°C, separately prepare (1) to (7). An oil phase prepared by mixing and heated to 80° C. was added to the aqueous phase, stirred, emulsified, and allowed to cool naturally.

When the temperature of the sample reached 45° C., a fragrance was added to the sample, and the sample was cooled to room temperature while stirring to obtain a foundation cream.

Example 4 0-silon (formulation) (wt%) Composite oxide 10.0 (11 ethanol 15.0 (2) glycerin
5. 0 (3) Purified water 68.0 Pigment (4) Colloidal kaolin 1.85 Others (5) Camphor 0.15 (6) Fragrance Small amount (manufacturing method) Add and dissolve the fragrance in ethanol and glycerin and pre-preparation. The pigment and complex oxide were added to purified water in which camphor was dissolved with stirring, dispersed, and filtered through a 325 mesh sieve to obtain a lotion.

Example 5 Compact foundation Silin (formulation) (wt%) Complex oxide 40.0 Pigment (1)
Tarri 45.0 (2) Titanium oxide 5.0 (3) Rice starch
2. 0(4) Magnesium stearate
3.0 (5) Colored pigments Trace amounts of binders (6) Liquid paraffin 3.0 (7)
Isopropyl myristate 2. 0 Others (8) Preservatives Trace amounts (9) Flavorings
Small amount (manufacturing method) Pigment ill ~ (5) and composite oxide were mixed in a blender, and a mixture of binders (6) and (7) and other +81 tel mixed in advance was added to this and mixed uniformly. Thereafter, the mixture was crushed and classified, left to stand for 3 days, and then compressed into a container to obtain a compact foundation silane.

Example 6 Lipstick (formulation) (% by weight) Complex oxide 10.0 Oil phase (11 Castor oil 40.0 (2) Hexadecyl alcohol 22.5 (3) Lanolin
4.0 (4) Beeswax (yellow) 5.0 (5) Osikelite 4.0 (6)
Candelilla wax 7.0 (7) Carnauba wax 2.0 (8) Preservative
Trace pigment (91 red No. 202
0.501 Red No. 204
2.5an red No. 227 A Ruki 2.5□□□
Fragrance: Trace amount (manufacturing method) An oil phase was prepared, heated and melted, and mixed uniformly.

Pigments and complex oxides were added thereto, and the mixture was uniformly kneaded and dispersed using a roll mill, then remelted, perfume added, defoamed, poured into molds, and rapidly cooled to solidify.

Comparative Example 1 In the formulation of Cream Example 1, composite oxide (Zn/Aj!-100
/10 atomic molar ratio, average particle size 0.01 μm) was replaced with commercially available cosmetic grade zinc oxide (average particle size 0.5 μm), and the same process as in Example 1 was performed to produce a cream.

Comparative Example 2 In the formulation of emulsion Example 2, composite oxide (Zn/Ti-100/
Example 2
A milky lotion was produced by processing in the same manner as in the production method.

Comparative Example 3 In the formulation of foundation cream Example 3, complex oxide (Zn/Zr-1001
0.5 atomic molar ratio, average particle size 0.018 m) was replaced with ultrafine zinc oxide (average particle size 0.01 μm), Example 3
A foundation silane cream was produced by processing in the same manner as in the production method.

(Application example 1) Examples 1 to 6 and comparative examples 1 to 6 obtained as above
Stability, ultraviolet ray shielding effect, and sensory evaluation were conducted for the product No. 3.

The results are shown in Table 1.

In addition, the measurement method was determined by the following method.

Stability: Cosmetics were stored in a room without temperature control for one year to check for deterioration.

Ultraviolet shielding effect: (SPF value, sun protection index) Apply 2mg 7cm of cosmetics evenly to the skin, or 2μj!
/cm'' The coated area and the uncoated area were treated with Toko Electric's medical ultraviolet irradiation device (M-DMR-1 type; light source Toshiba fluorescent lamp FL20S-E-30 (λmax 305 nm), FL20S/BLB (λ
max. 352 nm) and measured the respective minimum erythema generation energy using an ultraviolet intensity meter (UVR-305/365/D type) manufactured by Tokyo Kogaku Kikai ■. Shown as energy ratio.

Sensory test: 10 women used the product for two weeks, gave an absolute rating of good or bad, and recorded the number of people who answered that it was good.

Incidentally, the composite oxide used in the examples was manufactured by the following method.

Composite oxide 1 (used in Example 1) 44.7 g of industrial 97% aluminum nitrate nonahydrate and 362 g of industrial 95% zinc nitrate hexahydrate were mixed with 120 g of ethanol.
0mj! and stirred and mixed for 30 minutes to dissolve.

Subsequently, an aqueous solution of 283 g of 99% hexamethylenetetramine dissolved in 1,600 ml of water was added and further stirred.

This was heated and hydrolyzed at a temperature of about 80° C. for 5 hours with stirring, and then at a temperature of about 100° C. for 1 hour to obtain a hydrolyzed product.

This was defiltered, washed with 10,100O water, and heated to 150°C.
After drying, it was pulverized using a vibrating mill.

Then, it was fired at a temperature of about 700°C for 1 hour.

97.1 g of fine powder with an average particle size of about 0.01 μm was obtained.

The composition of this product powder was analyzed and the atomic ratio of Z/AI was 1.
It was 00/10.

When the atomic bonding state of the produced powder was measured, it was found that -Zn-0
-AI<binding (characteristic absorption 650 cm-1) was observed.

Composite oxide 2 (used in Example 2) 21.9 g of titanium tetrachloride and 36 g of 95% zinc nitrate hexahydrate
2g to 1200mj of ethanol! and stirred and mixed for 30 minutes to dissolve.

Next, an aqueous solution of 250 g of urea dissolved in 1,600 mff1 of water was added and mixed.

This was stirred at a temperature of about 80°C for 5 hours, followed by a temperature of about 10°C.
A hydrolysis reaction was carried out at 0°C for 1 hour to obtain a hydrolysis product.

This was defiltered, washed with 1000 mff1 of water, and heated to 15 ml.
After drying at 0°C, it was pulverized using a vibration mill.

The mixture was then calcined at a temperature of about 850° C. for 1 hour to obtain 101 g of fine powder having an average particle size of about 0.05 μm and containing no particles larger than about 1 μm.

As a result of analysis, the composition of this powder was found to be that the Zn/Ti atomic ratio was 10.
It was 0/10.

The atomic bonding state of this powder was confirmed to be -Zn-0-Ti (-(characteristic absorption 740 cm-')).

Composite oxide 3 (used in Example 3) 2.01 g of zirconium oxychloride octahydrate and industrial grade 9
Add 392 g of 5% zinc nitrate hexahydrate to 500 ml of ethanol, stir and mix for 30 minutes, and prepare 225 g of industrial urea.
An aqueous solution of 2,300 ml of water was added and stirred, and this was subjected to a hydrolysis reaction at a temperature of about 80° C. for 5 hours and then at a temperature of about 100° C. for 1 hour to obtain a hydrolyzed product.

This was filtered and washed with 1000ml of water at a temperature of 150°C.
After drying, it was pulverized using a hammer mill and a vibration mill.

The mixture was then calcined at a temperature of 650° C. for 1 hour to obtain 98.1 g of fine powder having an average particle size of about 0.01 μm and containing no particles larger than about 0.5 μm.

As a result of analysis, the composition of this product powder is Z n / 7. r
The atomic ratio was 10010.5.

Composite oxide 4 (used in Example 4) 2.55 g of 99% ferric nitrate nonahydrate for industrial use and 9 for industrial use
392g of 5% zinc nitrate hexahydrate in normal propatool 1
200 ml, stirred and mixed for 30 minutes, added and stirred an aqueous solution of 265 g of industrial urea and 1600 mj of water, heated at a temperature of about 90°C for 4 hours, and then heated at a temperature of about 1
A hydrolysis reaction was carried out at 00°C for 1 hour to obtain a hydrolysis product.

This was defiltered, washed with 10,100O water, and heated to 150°C.
After drying, it was pulverized using a hammer mill and a vibration mill.

The mixture was then calcined at a temperature of 600° C. for 1 hour to obtain 97.4 g of fine powder having an average particle size of about 0.05 μm and containing no particles larger than about 1 μm.

As a result of analysis, the composition of this product powder was found to have a Z n /F6 atomic ratio of 10010.5.

Composite oxide 5 (used in Example 5) 308 g of industrial 95% zinc nitrate hexahydrate, 152 g of industrial 97% aluminum nitrate nonahydrate, 99% industrial nitric acid 2
Iron nonahydrate 2.01g, ceric nitrate hexahydrate 2.14
g and 18.7 g of industrial titanium tetrachloride with 40 g of glycerin.
0ml and stirred and mixed for 30 minutes.

Next, an aqueous solution of 322 g of industrial urea and 1600 ml of water was added and mixed.

While stirring, a hydrolysis reaction was carried out at a temperature of about 100° C. for 3 hours to obtain a hydrolyzed product.

This was filtered and washed with 1000ml of water at a temperature of 150°C.
After drying, it was pulverized using a hammer mill and a vibration mill.

The mixture was then calcined at a temperature of about 850° C. for 1 hour to obtain 109 g of fine powder with an average particle size of about 0.05 μm and no particles larger than about 1 μm.

The composition of this product powder is the result of analysis Z n/A 1/ F
The e/Ce/Ti atomic ratio was 100/4010°510.5/10.

The atomic bonding state of this powder is -11Ti-0-Zn-O
-AI<bond (characteristic absorption 650 e m-', 740
cm-').

Composite Oxide 6 (Used in Example 6) 18.7 g of quaternary titanium, 152 g of 97% aluminum nitrate nonahydrate, and 308 g of 95% zinc nitrate hexahydrate were dissolved in 200 ml of ethylene glycol.

An aqueous solution of 319 g of urea dissolved in 2,600 ml of water was added and mixed.

This was hydrolyzed at a temperature of about 100°C for 3 hours with stirring to obtain a hydrolyzed product.

This was filtered, washed with 1,000 ml of water, dried at a temperature of 150°C, and then pulverized with a vibration mill.

The mixture was then calcined at a temperature of 850° C. for 1 hour to obtain 108 g of fine powder containing no particles larger than about 1 μm and having an average particle size of about 0.1 μm.

As a result of analysis, the composition of this powder was found to have a Zn/Al/Ti atomic ratio of 100/40/10.

The atomic bonding state of this powder was measured → Ti -0
-Zn-0-AI<bond (characteristic absorption 650 cm-',
740 cm-').

Claims (1)

[Claims] A composite oxide powder of zinc and a metal selected from aluminum, iron, chromium, cerium, zirconium, and titanium having an average particle diameter of 0.001 μm to 0.5 μm is mixed with 0.0 μm.
A cosmetic containing 1 to 40% by weight.