JP2000203834A - Ultrafine cerium oxide particle and ultrafine metal oxide.cerium oxide particle, its production and resin composition and cosmetic containing the same - Google Patents

Abstract

PROBLEM TO BE SOLVED: To provide a UV light-shielding agent having a high UV light-shielding effect and further having transparency. SOLUTION: The ultrafine cerium oxide particles and ultrafine metal oxide.cerium oxide particles have an average particle diameter of 2-4 nm. The ultrafine cerium oxide particles are produced by reacting a cerium salt aqueous solution with an alkali and then adding an oxidizing agent to the produced cerium hydroxide, or may be produced by simultaneously adding the alkali and the oxidizing agent to the cerium salt aqueous solution. The ultrafine metal oxide.cerium oxide particles are obtained by compounding the ultrafine cerium oxide particles with a metal oxide. A resin composition or cosmetic containing the ultrafine cerium oxide particles or the ultrafine metal oxide.cerium oxide particles has good transparency and a high UV light- shielding effect.

Description

DETAILED DESCRIPTION OF THE INVENTION

[0001]

The present invention relates to an ultrafine cerium oxide, an ultrafine metal oxide / cerium oxide composite, and a method for producing the same. In addition, the present invention relates to a resin composition having excellent ultraviolet light blocking effect and excellent light resistance or a cosmetic having an ultraviolet light blocking effect, which is blended with ultrafine cerium oxide and / or ultrafine metal oxide / cerium oxide composite.

[0002]

2. Description of the Related Art Various measures have been taken for ultraviolet rays to deteriorate plastics. As one of them,
Various ultraviolet ray blocking agents called various organic ultraviolet ray absorbing agents and inorganic ultraviolet ray scattering agents have been developed, and the influence of ultraviolet rays has been reduced by adding these to plastics. Organic UV absorbers include salicylic acid, benzophenone, benzotriazole, and cyanoacrylate. Recently, however, heat resistance, insufficient weather resistance, and the safety of decomposition products have been raised. ing. For the purpose of solving these problems, fine particles of titanium oxide and fine particle zinc oxide, which are inorganic ultraviolet scattering agents, have been developed, but these also have new problems in dispersibility and catalytic action.

[0003] Further, ultraviolet rays are known to have an adverse effect on living organisms. Ultraviolet rays in the UV-B region having a wavelength of 280 to 320 nm cause inflammation such as erythema vesicles on the skin and have a wavelength of 320 to 320 nm. Ultraviolet light in the UV-A region of 400 nm is known to promote melanin production and cause skin browning. As a countermeasure against such adverse effects of ultraviolet rays, various types of sunscreen cosmetics have been known. The UV blocking agents used in these cosmetics are roughly classified into UV absorbers such as cinnamic acid, benzophenone, and dibenzoylmethane, and UV scattering agents such as zinc oxide and titanium oxide. It can be divided into two types. However, these ultraviolet absorbers may have problems such as insufficient absorption of ultraviolet light and unfavorable safety in a large amount.
Furthermore, it has been difficult to increase the transparency of conventional UV scattering agents even if the dispersibility is improved, so that not only the feeling of use is deteriorated, but also an unnatural cosmetic finish is caused. Was.

Recently, techniques using a cerium compound as an ultraviolet scattering agent as disclosed in JP-A-6-145645 and JP-A-7-207251 have been proposed. Attempting to increase the level raises a problem in transparency, and it has been desired to develop a technology in which these factors are compatible. JP-A-9-1186
Although the technology of silica-cerium composite particles as disclosed in No. 10 is also disclosed, development of an ultraviolet ray blocking agent capable of obtaining higher ultraviolet ray blocking ability has been desired.

[0005]

SUMMARY OF THE INVENTION The present invention has been made in view of the above circumstances, and an object of the present invention is to provide an ultraviolet scattering agent having a high ultraviolet blocking effect and having transparency. It is. It is another object of the present invention to provide a resin composition having extremely high transparency, excellent stability and safety, and a high light-blocking effect having a high ultraviolet-blocking effect, in which the ultraviolet light scattering agent is blended. It is another object of the present invention to provide a cosmetic composition which has a high ultraviolet blocking effect, is excellent in transparency and safety, and has a good feeling in use, in which the above-mentioned ultraviolet scattering agent is blended.

[0006]

That is, the present invention relates to ultrafine cerium oxide having an average particle diameter of 2 to 4 nm. This ultra-fine cerium oxide has a temperature of 40 ° C.
Hereinafter, under the condition of pH 9 or more, an aqueous cerium salt solution is reacted with an alkali to produce cerium hydroxide, and thereafter, 6
It can be produced by adding an oxidizing agent at a temperature of 0 ° C. or lower and a pH of 5 or higher. The ultrafine cerium oxide is 4
It can also be produced by simultaneously dropping and mixing an aqueous cerium salt solution, an alkali and an oxidizing agent under the conditions of 0 ° C. or lower and pH 5 or higher.

In the present invention, the average particle diameter is 2 to 4 nm.
An ultra-fine particle metal oxide / cerium oxide composite. The ultrafine metal oxide / cerium oxide composite is prepared by reacting an aqueous cerium salt solution with an alkali at a temperature of 40 ° C. or less and a pH of 9 or more to produce cerium hydroxide. And then compounding with a metal oxide. In addition, this ultrafine metal oxide / cerium oxide composite is added to a cerium salt aqueous solution at 40 ° C. or lower,
It can be produced by simultaneously adding an alkali and an oxidizing agent under conditions of pH 5 or more and further complexing with a metal oxide.

Further, the present invention is a resin composition or cosmetic containing the above-mentioned ultrafine cerium oxide and / or ultrafine metal oxide / cerium oxide composite. This resin composition has very high transparency, is excellent in stability and safety, and has a high ultraviolet blocking effect. In addition, the cosmetic has a high ultraviolet blocking effect, is excellent in transparency and safety, and has a good feeling upon use, and is particularly suitable for sunburn cosmetics.

[0009]

BEST MODE FOR CARRYING OUT THE INVENTION The ultrafine cerium oxide of the present invention has an average particle diameter of 2 to 4 nm. Such ultrafine cerium oxide is excellent in transparency and also excellent in dispersibility,
Moreover, it has a feature that the ultraviolet ray blocking effect is extremely high. The ultrafine cerium oxide of the present invention is prepared by reacting an aqueous cerium salt solution with an alkali to produce cerium hydroxide at a temperature of 40 ° C. or less and a pH of 9 or more. In addition, manufacture. The pH condition when the oxidizing agent is added is preferably 5 to 8, and ultrafine cerium oxide can be favorably produced. In this production, a cerium salt solution and an alkali solution each having a predetermined concentration are prepared in advance, and the alkali solution is first put into the reaction vessel to allow the alkali solution to exist, and then the cerium salt solution and the alkali solution are simultaneously dropped while stirring. Finally, it is preferable to employ a method of generating cerium hydroxide by dropping only the cerium salt solution. Next, an oxidizing agent is added to the resulting reaction solution. The obtained cerium oxide is filtered, dried and pulverized to obtain ultrafine cerium oxide. Here, ultrafine cerium oxide can be obtained by using the oxidizing agent.

The ultrafine cerium oxide is 40
It can also be produced by simultaneously dropping and mixing an aqueous cerium salt solution, an alkali and an oxidizing agent at a temperature of not higher than 5 ° C. and a pH of 5 or more, preferably a pH of 8 or more at the start of the reaction. Again,
A cerium salt, an alkali solution, and an oxidizing agent solution having a predetermined concentration are prepared in advance, and an alkali solution is first placed in a reaction vessel to allow the alkali solution to exist, and then the cerium salt solution, the alkali solution, and the oxidizing agent solution are stirred. At the same time, and finally, a cerium salt solution and an oxidizing agent solution are dropped to produce cerium oxide.

The cerium salt aqueous solution used here is prepared by, for example, dissolving cerium carbonate in an aqueous acid solution such as hydrochloric acid or nitric acid, or dissolving cerium chloride, cerium nitrate, cerium sulfate, cerium acetate or the like in water. The concentration of the cerium salt aqueous solution at this time may be appropriate, but a higher concentration is advantageous for the production of cerium oxide. In addition, pH of cerium salt aqueous solution
It is advantageous to increase the value of cerium hydroxide to such an extent that cerium hydroxide is not generated. As the alkaline solution, an aqueous solution of an alkali metal hydroxide such as sodium hydroxide or potassium hydroxide or aqueous ammonia can be used. As the oxidizing agent, hydrogen peroxide, hypochlorous acid, sodium hypochlorite, potassium hypochlorite, calcium hypochlorite, ozone, or the like can be used.

The ultrafine metal oxide / cerium oxide composite of the present invention has an average particle diameter of 2 to 4 nm. Such ultrafine metal oxide / cerium oxide composites have excellent transparency and extremely high ultraviolet blocking effect. Further, by forming cerium oxide into a composite, the oxidation catalyst activity is reduced, and the dispersibility in cosmetics and the like is improved. The content of cerium oxide in the composite is 40 to 98.
% By weight is preferred. The metal oxide in the composite is one or more selected from silicon oxide, zirconium oxide, alumina, and titanium oxide. By compounding the metal oxide, the oxidation catalyst activity is reduced and the dispersibility in cosmetics and the like is improved. The ultrafine metal oxide / cerium oxide composite is prepared by reacting an aqueous cerium salt solution with an alkali at a temperature of 40 ° C. or less and a pH of 9 or more to produce cerium hydroxide. To produce cerium oxide by adding an oxidizing agent and compounding with a metal oxide. The pH condition at the time of adding the oxidizing agent is preferably 5 to 8, and an ultrafine metal oxide / cerium oxide composite can be favorably produced. In addition, this ultrafine metal oxide / cerium oxide composite
It can be produced by simultaneously adding an alkali and an oxidizing agent to a cerium salt aqueous solution at a temperature of 40 ° C. or lower and a pH of 5 or higher to generate cerium oxide and further complexing with a metal oxide. In both of the above reactions, when the pH at the end of the dropping of the oxidizing agent is less than 8, it is possible to reduce the yellow tint of the ultrafine cerium oxide and the fine metal oxide / cerium oxide composite and increase the whiteness. it can. The compounding of cerium oxide with a metal oxide is usually carried out by adding a compound that forms a metal oxide to the cerium oxide obtained by the above method to form a metal oxide.

In producing the ultrafine metal oxide / cerium oxide composite of the present invention, the cerium salt, alkali and oxidizing agent described above can be used. The above-described method can be employed for the reaction. For example, when silicon oxide is used as the metal oxide, the cerium hydroxide formed by dropping a cerium salt aqueous solution and an alkali solution into water having a liquid temperature of 40 ° C. or less and a pH of 9 or more is reduced to 60 ° C. or less. The ultrafine cerium oxide obtained by heating and adding an oxidizing agent such as hydrogen peroxide is further heated to 80 ° C. or more, and while maintaining the pH at 9 or more, an aqueous solution of sodium silicate No. 3 and hydrochloric acid, nitric acid,
A complex is formed by dropping an aqueous solution of a mineral acid such as sulfuric acid,
Subsequently, this is washed with water, filtered, dried, and pulverized to obtain the desired ultrafine silica / cerium oxide composite. In this case, you may bake after drying and grinding. The amount of dripping sodium silicate, 2 to 60 of the complexes as SiO ₂
% Is appropriate. It is important to keep the above-mentioned temperature and pH conditions in the reaction for forming amorphous silica. If the temperature and pH conditions are not met, uniform ultrafine silica / cerium oxide composites cannot be obtained.

FIG. 1 shows the results of measuring the light transmittance of the ultrafine cerium oxide and the ultrafine silica / cerium oxide composite obtained by the above method with respect to the wavelength of light. The light transmittance was measured as follows. That is,
Each sample was taken in an amount such that the addition ratio became 3.0% by weight based on the solid content of the clear lacquer, and 0.4 ml of castor oil was added thereto, dispersed with a Hoover marler (50 rpm × 2), and the dispersion was cleared. After 6 ml of lacquer was added and kneaded, this solution was applied to a transparent quartz plate to a thickness of 30 μm, and measured with a spectrophotometer (UV-2200 manufactured by Shimadzu Corporation). In FIG. 1, the sample was not added, the sample was conventional silica / cerium oxide composite particles containing 30% by weight of SiO _{2 and having} an average particle size of 50 nm, and the sample was 2.6 nm having an average particle size of 30% by weight of SiO ₂ of the present invention. The ultrafine silica / cerium oxide composite of Example 1 is an ultrafine cerium oxide having an average particle diameter of 2.4 nm of the present invention, and the sample is commercially available high purity cerium oxide particles (average particle diameter of 10 μm).

As is clear from FIG. 1, the ultrafine silica / cerium oxide composite and the ultrafine cerium oxide of the present invention are 3 times smaller than commercially available high-purity cerium oxide.
The ultraviolet blocking effect in the range of 00 nm to 400 nm is very excellent, and the transparency in the visible region of 400 nm to 800 nm is high. Further, compared with the conventional silica / cerium oxide composite particles, the ultraviolet ray blocking effect in the 300 nm to 400 nm region is excellent. By making cerium oxide into ultrafine particles in this way, the ultraviolet blocking effect in the 300 nm to 400 nm region is further improved, and when this is combined with silica, high transparency is obtained in the visible region.

Next, the resin composition according to the present invention will be described. Generally, a resin composition is deteriorated by absorbing light in the ultraviolet region of sunlight. As a measure against ultraviolet rays therefor, by blending the ultrafine particle cerium oxide and / or the ultrafine particle metal oxide / cerium oxide composite of the present invention into a resin composition, light resistance is improved and light deterioration can be prevented or reduced. Further, it is possible to prevent or reduce the photodeterioration of the contents covered with the transparent resin composition due to ultraviolet rays. The resin composition referred to here is polyvinyl chloride, polypropylene,
Moldings of synthetic resins and natural resins such as polyethylene, polyamide, polyester and polycarbonate, and general resin compositions such as paints incorporating these resins.

Next, the cosmetic according to the present invention will be described. The cosmetic of the present invention has transparency by blending the above-mentioned ultrafine particle cerium oxide and / or the ultrafine particle metal oxide / cerium oxide composite, and can provide an excellent ultraviolet blocking effect. As the dosage form of the cosmetic, it can be used for skin care cosmetics such as milky lotions and lotions, makeup cosmetics such as foundations and lipsticks, hair cosmetics and the like, and among them, sunscreen cosmetics are preferred.
The amount is not particularly limited, but is preferably 0.1 to 70.
% By weight.

When the ultrafine cerium oxide and / or the ultrafine metal oxide / cerium oxide composite is blended into a cosmetic, these ultrafine particles may be subjected to a surface treatment before use. Examples of the surface treatment include metal soap treatment, silicone treatment, dialkyl phosphoric acid treatment, treatment with a compound having a perfluoroalkyl group, amino acid treatment, lecithin treatment, collagen treatment and the like.

In the cosmetic according to the present invention, the effect is remarkable when it is combined with an ultraviolet absorber and / or an ultraviolet scattering agent which is an ultraviolet protective agent. As an ultraviolet absorber, oxybenzone, octyl methoxycinnamate,
One or more selected from 4-tert-butyl-4'-methoxydibenzoylmethane is preferred. The blending amount of the ultraviolet absorber is not particularly limited, but is preferably 0.1%.
1 to 40% by weight. As the ultraviolet scattering agent, titanium oxide and / or zinc oxide are preferable, and more preferably,
Fine particle titanium oxide and / or zinc oxide having an average particle diameter of 0.05 μm or less. The blending amount of the ultraviolet light scattering agent is preferably from 0.1 to 50% by weight.

Further, the cosmetics of the present invention include components usually used in cosmetics, for example, powders, surfactants, oils, gelling agents, polymers, cosmetics, humectants, pigments, preservatives, and fragrances. And the like can be used as long as the effects of the present invention are not impaired.

[0021]

EXAMPLE 1 488 g of cerium chloride (CeCl ₃ ) was dissolved in water to prepare 3.3 liter of cerium chloride aqueous solution. In addition, 237 g of sodium hydroxide was dissolved in water to prepare 3.3 liter of sodium hydroxide aqueous solution. An aqueous cerium chloride solution and an aqueous sodium hydroxide solution were added to 8.5 liters of water heated to 30 to 40 ° C. while stirring, and the pH of the reaction solution was adjusted to 9
-11, while dropping at the same time while maintaining the temperature at 40 ° C. or lower, cerium hydroxide was produced. After dropping, p
H was adjusted to 5 or more and the temperature was adjusted to 60 ° C., and 3.3 liters of an aqueous solution of hydrogen peroxide in which 118 g of 30% aqueous hydrogen peroxide was dissolved was added dropwise. The generated cerium oxide was washed by decantation five times with water, dried and pulverized. Average particle size 3.6
Ultrafine cerium oxide having a particle diameter of nm was obtained. The particle diameter was measured using a transmission electron microscope (manufactured by JEOL).
That is, the particle diameter of 100 particles was visually measured, and the average value was determined.

Example 2 488 g of cerium chloride (CeCl ₃ ) was dissolved in water to prepare 3.3 liter of cerium chloride aqueous solution. In addition, 237 g of sodium hydroxide was dissolved in water to prepare 3.3 liter of sodium hydroxide aqueous solution. Also, 118 g of a 30% hydrogen peroxide solution is dissolved in water to form a 3.3% aqueous hydrogen peroxide solution.
One liter was prepared. 8.5 heated to 30-40 ° C.
Liter, the above cerium chloride aqueous solution with stirring,
An aqueous solution of sodium hydroxide and an aqueous solution of hydrogen peroxide were simultaneously added dropwise while maintaining the pH of the reaction solution at 5 and the temperature at 40 ° C. or lower at the end of the reaction. After completion of the dropwise addition, the mixture was stirred for 30 minutes to readjust the pH of the reaction solution to 5 or more. The generated cerium oxide was washed by decantation five times with water, dried and pulverized. Ultrafine cerium oxide having an average particle size of 2.4 nm was obtained.

Example 3 488 g of cerium chloride (CeCl ₃ ) was dissolved in water to prepare 3.3 liter of cerium chloride aqueous solution. In addition, 237 g of sodium hydroxide was dissolved in water to prepare 3.3 liter of sodium hydroxide aqueous solution. Further, 118 g of a 30% aqueous hydrogen peroxide solution was dissolved in water to obtain a 3.3% aqueous hydrogen peroxide solution.
One liter was prepared. 8.5 heated to 30-40 ° C.
The cerium chloride aqueous solution and the sodium hydroxide aqueous solution were added to the liter while stirring, and the pH of the reaction solution was adjusted to 9-1.
1. Simultaneously, the temperature was kept at 40 ° C. or lower while dropping to produce cerium hydroxide. After completion of the dropwise addition, the pH of the reaction solution was adjusted to 5 or more, and the temperature was adjusted to 60 ° C. The aqueous hydrogen peroxide solution was added dropwise to the reaction solution. The generated cerium oxide was decanted and washed five times with water to prepare cerium oxide.

[0024] Aluminum chloride (AlCl ₃ · 6H ₂ O)
692 g was dissolved in water to prepare 3 liters of an aluminum chloride aqueous solution. 378 g of sodium hydroxide was dissolved in water to prepare 3 liter of sodium hydroxide aqueous solution. After the whole amount of the aluminum chloride aqueous solution was added dropwise to the above cerium oxide while stirring, an aqueous solution of sodium hydroxide was added dropwise until the pH became 7 to 8. Thereafter, stirring was continued for 30 minutes, followed by filtering, washing with water, drying and pulverizing to obtain an ultrafine alumina / cerium oxide composite containing 30% by weight of Al ₂ O ₃ . The average particle size of the composite is 3.
It was 8 nm.

Example 4 488 g of cerium chloride (CeCl ₃ ) was dissolved in water to prepare 3.3 liter of cerium chloride aqueous solution. In addition, 237 g of sodium hydroxide was dissolved in water to prepare 3.3 liter of sodium hydroxide aqueous solution. Further, 118 g of a 30% aqueous hydrogen peroxide solution was dissolved in water to obtain a 3.3% aqueous hydrogen peroxide solution.
One liter was prepared. 8.5 heated to 30-40 ° C.
An aqueous cerium chloride solution, an aqueous sodium hydroxide solution and an aqueous hydrogen peroxide solution were simultaneously added dropwise to the liter while maintaining the pH of the reaction solution at the end of the reaction at 5 and the temperature at 40 ° C. or lower while stirring. After the completion of the dropwise addition, the mixture was stirred for 30 minutes, and the pH of the reaction solution was readjusted to 5 or more. The generated cerium oxide was decanted and washed five times with water to prepare cerium oxide.

Sodium silicate solution (SiO ₂ content 2
562 g (8.5% by weight) was dissolved in water to prepare 2 liters of an aqueous solution of sodium silicate. 95% by weight sulfuric acid
8 g was diluted with water to prepare 2 liter of diluted sulfuric acid. While heating and stirring the above cerium oxide at 80 ° C. or higher, the sodium silicate solution prepared above and dilute sulfuric acid were mixed at pH of the reaction solution.
Was simultaneously dropped so as to be able to maintain 9 or more. The mixture was stirred for 30 minutes after the completion of the dropping of both solutions, and adjusted with diluted sulfuric acid so that the pH of the reaction solution became 7 to 8. This is filtered, washed with water, dried and crushed to obtain S
An ultrafine silica / cerium oxide composite containing 30% by weight of iO ₂ was obtained. The average particle size of the composite was 2.6 nm.

Example 5 The ultrafine silica / cerium oxide composite containing 30% by weight of SiO ₂ obtained in Example 4 was mixed with 0% by weight, 0.5% by weight and 1.0% by weight of soft polyvinyl chloride. Into a sheet having a thickness of 0.24 mm with a heating roll. The light transmittance of these sheets was measured using a spectrophotometer (UV-220 manufactured by Shimadzu Corporation).
0), the result of FIG. 2 was obtained. Sample A thing of no addition Sample B SiO ₂ 30 wt% containing ultrafine silica cerium oxide complex 0.5 wt% blending sheet, Sample C SiO ₂ 30 wt% containing ultrafine silica
A sheet containing 1.0% by weight of a cerium oxide composite. From this figure, it was found that the ultrafine silica / cerium oxide composite of the present invention was able to obtain an excellent ultraviolet blocking effect with a small amount of blending and to maintain high transparency even in the visible region.

Example 6 Using the ultrafine cerium oxide obtained in Example 2 or the ultrafine silica / cerium oxide composite containing 30% by weight of SiO ₂ obtained in Example 4, a cream foundation was prepared by the following composition and preparation method. Manufactured. Composition: (1) 5.0% by weight of stearic acid (2) Lipophilic glyceryl monostearate 2.5 (3) Cetanol 1.5 (4) Isopropylene glycol monolaurate 2.5 (5) Liquid paraffin 8 0.0 (6) Isopropyl myristate 7.0 (7) Propyl parahydroxybenzoate 0.1 (8) Residual water residue (9) Triethanolamine 1.2 (10) Sorbitol 3.0 (11) Paraoxybenzoic acid Methyl 0.2 (12) Titanium oxide 8.0 (13) Kaolin 5.0 (14) Ultrafine powder obtained in Example 2 or Example 3.0 (15) Bentonite 1.0 (16) Bengala 2 .5 (17) Yellow iron oxide 2.0 (18) Black iron oxide 0.2

Preparation method: (12)-(14) and (16)-(18) are mixed well. B. Add (15) to (8) at 80 ° C and swell well. Next, (9) to (11) are added and dissolved. The mixture of A is added to this and dissolved at 80 ° C. (aqueous phase). C. (1) to (7) are dissolved at 80 ° C. (oil phase). D. The oil phase is added to the above water phase to emulsify, then cooled and cooled.
Stir and cool to 5 ° C. Each of the cream foundations obtained as described above had a transparent feeling, extended well, and had an excellent ultraviolet blocking effect.

Example 7 The ultrafine cerium oxide 150 obtained in Example 1 was placed in a flask.
g and 200 g of purified water are added and heated to 70 ° C. while mixing to form a slurry. 6 g of a perfluoroalkyl phosphate diethanolamine salt (manufactured by Asahi Glass Co., Ltd., trade name: Asahigard AG530) and 150 g of purified water
Was gradually added to the slurry, and after 1 hour mixing, the liquid was made acidic and washed.
After filtration and drying, 154 g of ultrafine cerium oxide treated with a fluorine compound (hereinafter referred to as fluorine-treated particles) was obtained.

Example 8 150 g of the ultrafine silica / cerium oxide composite obtained in Example 4 and 150 g of isopropyl alcohol were added to a flask and heated to 70 ° C. while mixing. 3 g of methyl hydrogen polysiloxane (manufactured by Shin-Etsu Chemical Co., Ltd.) was added thereto, mixed for 1 hour, heated under reduced pressure to remove isopropyl alcohol, and then treated with a silicon-treated ultrafine silica-cerium oxide composite (hereinafter, silicone-treated composite). 152 g).

Example 9 Using the fluorinated composite obtained in Example 7, a sunscreen emulsion was prepared according to the following composition and preparation method. Composition: (1) Fluorine-treated particles 10.0% by weight (2) Microcrystalline wax 1.0 (3) Beeswax 2.0 (4) Squalane 10.0 (5) Methylpolysiloxane (10CS) 10.0 (6) ) Decamethylcyclopentacyclosiloxane 10.0 (7) Sorbitan sesquioleate 4.0 (8) Polyoxyethylene / methylpolysiloxane copolymer 1.0 (9) Oxybenzone 0.1 (10) 1,3 -Butylene glycol 9.0 (11) Preservative appropriate amount (12) Remaining purified water (13) Perfume appropriate amount

Preparation method: (2) to (9) were dissolved by heating, and (1) was added to
0 ° C. B. (10) to (12) are heated and dissolved to 70 ° C., added to (1) and emulsified and mixed. C. (2) After cooling, add (13) and mix to obtain a sunscreen emulsion.

Comparative Example 1 Comparative Example 1 was the same as Example 9 except that (1) was replaced with commercially available high-purity cerium oxide particles (average particle size: 10 μm).
Was similarly prepared. In Comparative Example 1, a natural finish feeling could not be obtained because the dispersibility was poor and a uniform decorative film could not be obtained. On the other hand, Example 9 according to the present invention was transparent, had a good finish, and was excellent in the effect of blocking ultraviolet rays.

Example 10 Using the silicone-treated composite obtained in Example 8, a powder foundation was produced by the following composition and preparation method. Composition: (1) Silicone-treated talc 20.0% by weight (2) Silicone-treated mica residue (3) Silicone-treated titanium oxide 12.0 (4) Silicone-treated Bengala 1.0 (5) Silicone-treated yellow iron oxide 0 (6) Silicone-treated black iron oxide 0.1 (7) Silicone-treated complex 20.0 (8) Silicone-treated zinc oxide 1.0 (9) Squalane 5.0 (10) Glyceryl tri-2-ethylhexanoate 2 0.0 (11) White petrolatum 1.0 (12) Preservatives appropriate amount (13) Fragrance appropriate amount

Preparation method: (1) to (8) are mixed with a Henschel mixer. B. (9) to (11), which were mixed by heating, were added to (a) and mixed.
2) and (13) are added. C. After pulverizing b, press molding is performed to obtain a powder foundation.

COMPARATIVE EXAMPLE 2 Comparative Example 2 was prepared in the same manner as in Example 10, except that (7) was replaced with silica / cerium oxide composite particles (average particle size: 50 nm). In Example 10, compared with Comparative Example 2, the transparency was improved, the dispersibility in the cosmetic base material was good, the finish was good, and the ultraviolet ray blocking effect was further excellent.

Example 11 Using the silica / cerium oxide composite containing 30% by weight of ultrafine particles of SiO ₂ obtained in Example 4, a lipstick was produced by the following composition and preparation method. Composition: (1) Ethylene propylene copolymer 9.0% by weight (2) Microcrystalline wax 5.0 (3) Candelilla wax 3.0 (4) Celesin wax 3.0 (5) Lanolin 10.0 (6) Castor oil 20.0 (7) Isocetyl octoate residual amount (8) Red No. 201 2.0 (9) Red 202 No. 1.0 (10) Orange No. 201 0.1 (11) Ultrafine silica / cerium oxide composite 20 .0

Preparation method: (8) to (11) are mixed, added to part of (6), and mixed and dispersed by a roller. B. The remaining parts (1) to (5) and (6) and (7) are mixed and dissolved by heating. C. Fill the container with b and quench to obtain lipstick.

COMPARATIVE EXAMPLE 3 Comparative Example 3 was prepared in the same manner as in Example 11, except that (11) was replaced with fine particle titanium oxide. In Comparative Example 3, the color was pale and unnatural, and a healthy lip finish could not be obtained. On the other hand, Example 11 according to the present invention was transparent, had a healthy coloration, and was excellent in the ultraviolet ray blocking effect.

Example 12 Using the ultrafine alumina / cerium oxide composite obtained in Example 3, a white powder was produced by the following composition and preparation method. Composition: (1) Ultrafine alumina / cerium oxide composite 50.0% by weight (2) Talc 30.0 (3) Sericite 6.0 (4) Remaining kaolin (5) Titanium oxide 3.0 (6) Zinc myristate 2.0 (7) Bengala 0.2 (8) Yellow iron oxide 0.8 (9) Squalane 2.0 (10) Octyl methoxycinnamate 2.0 (11) Preservatives Appropriate amount (12) Appropriate amount of fragrance

Preparation method: (1) to (8) are mixed. B. (9) to (12) are mixed, and the mixture is added to (1) and uniformly mixed. C. After crushing b, press molding is performed to obtain a white powder.

Comparative Example 4 Comparative Example 4 was prepared in the same manner as in Example 12 except that (1) was replaced with fine particle titanium oxide. Comparative Example 4
However, a natural finish cannot be obtained due to bluishness or whitening of the decorative film. On the other hand, Example 12 according to the present invention was transparent, had a good finish, and was excellent in the effect of blocking ultraviolet rays.

[0044]

The ultrafine cerium oxide and the ultrafine metal oxide / cerium oxide composite of the present invention have excellent transparency,
It has excellent dispersibility and UV with high transparency in the visible region.
-Excellent UV blocking effect in A-region and UV-B region, safe and excellent in heat resistance and chemical resistance. In addition, the resin composition and the cosmetic containing the ultrafine cerium oxide and the ultrafine metal oxide / cerium oxide composite of the present invention have excellent ultraviolet blocking effect and high transparency.

[Brief description of the drawings]

FIG. 1 is a graph showing light transmittance of an ultrafine cerium oxide, an ultrafine metal oxide / cerium oxide composite of the present invention, and a conventional product.

FIG. 2: 30% by weight of SiO ₂ of the present invention in polyvinyl chloride
The figure which shows the light transmittance of the sheet | seat formed by mix | blending the containing ultrafine particle silica and cerium oxide composite.

──────────────────────────────────────────────────続 き Continued on the front page (51) Int.Cl. ⁷ Identification code FI Theme coat ゛ (Reference) C01B 33/12 C01B 33/12 A C01G 23/00 C01G 23/00 C 25/00 25/00 C09K 3 / 00 104 C09K 3/00 104Z (72) Inventor Kota Tofukuji, 48-18 Sakaemachi, Kita-ku, Tokyo Inside the Kose Research Institute (72) Inventor Shigetada Momose 48-18 Sakaemachi, Kita-ku, Tokyo Kose Corporation Inside the laboratory (72) Inventor Sakae Yoshida 3-14-1, Funatari, Itabashi-ku, Tokyo Nihonashi Machinery Chemical Industry Co., Ltd. (72) Inventor Kazuyuki Tabira 3-4-1-1, Funato, Itabashi-ku, Tokyo Nihonashiki Within Chemical Industry Co., Ltd. (72) Inventor Tsugio Sato 2-1-1 Katahira, Aoba-ku, Sendai, Miyagi Prefecture F-term in Tohoku University Research Institute for Reactive Chemistry 4C083 AA082 AA122 AB171 A B172 AB211 AB212 AB221 AB222 AB232 AB241 AB242 AB432 AB442 AC012 AC022 AC072 AC122 AC132 AC211 AC212 AC242 AC341 AC352 AC392 AC422 AC442 AC482 AC542 AC792 AC842 AD052 AD152 AD162 AD172 AD512 BB26 BB46 CC01 CC05 CC12 CC19 DD17 DD31 EE01 EE07 EE10 EE07 EE10 EE07 EE07 EE07 EE10 EE07 EE10 4G048 AA02 AC08 AD03 4G072 AA35 AA38 BB05 DD08 GG01 GG02 GG03 HH21 JJ15 LL06 LL07 MM01 MM02 MM21 MM22 MM26 MM31 RR06 RR12 TT01 UU30 4G076 AA02 AA24 AB04 AB07 BA08 DA03 BA02 BA03 DA03

Claims (21)

[Claims] An ultrafine cerium oxide having an average particle diameter of 2 to 4 nm. 2. A method wherein cerium hydroxide is produced by reacting an aqueous cerium salt solution with an alkali at a temperature of 40 ° C. or lower and a pH of 9 or higher, and then an oxidizing agent is added at a temperature of 60 ° C. or lower and a pH of 5 or higher. The method for producing ultrafine cerium oxide according to claim 1. 3. The process for producing ultrafine cerium oxide according to claim 1, wherein the cerium salt aqueous solution, the alkali and the oxidizing agent are simultaneously dropped and mixed at a temperature of 40 ° C. or lower and a pH of 5 or higher. 4. The method for producing ultrafine cerium oxide according to claim 2, wherein the cerium salt is cerium nitrate, cerium chloride, cerium sulfate or cerium acetate. 5. The method according to claim 2, wherein the oxidizing agent is hydrogen peroxide, hypochlorous acid, sodium hypochlorite, potassium hypochlorite, calcium hypochlorite or ozone.
The method for producing ultrafine cerium oxide according to any one of the above. 6. An ultrafine metal oxide / cerium oxide composite having an average particle diameter of 2 to 4 nm. 7. The cerium oxide content in the composite is 40 to 40.
The composite according to claim 6, which is 98% by weight. 8. The metal oxide in the composite is one or more selected from silicon oxide, zirconium oxide, alumina and titanium oxide.
The complex according to any one of the above. 9. An cerium hydroxide is produced by reacting an aqueous cerium salt solution with an alkali at a temperature of 40 ° C. or less and a pH of 9 or more, and then adding an oxidizing agent at a temperature of 60 ° C. or less and a pH of 5 or more. The method for producing an ultrafine metal oxide / cerium oxide composite according to any one of claims 6 to 8, wherein the composite is composited with a metal oxide. 10. The ultrafine metal oxide according to claim 6, wherein an aqueous cerium salt solution, an alkali and an oxidizing agent are simultaneously dropped and mixed at a temperature of 40 ° C. or lower and a pH of 5 or higher. -A method for producing a cerium oxide composite. 11. The method for producing ultrafine cerium oxide according to claim 9, wherein the cerium salt is cerium nitrate, cerium chloride, cerium sulfate or cerium acetate. 12. The method according to claim 9, wherein the oxidizing agent is hydrogen peroxide, hypochlorous acid, sodium hypochlorite, potassium hypochlorite, calcium hypochlorite or ozone.
12. The method for producing ultrafine cerium oxide according to any one of 11. 13. A resin composition comprising the ultrafine cerium oxide and / or the ultrafine metal oxide / cerium oxide composite according to any one of claims 1 to 6. 14. A cosmetic comprising the ultrafine cerium oxide and / or the ultrafine metal oxide / cerium oxide composite according to claim 1. Description: 15. The cosmetic according to claim 14, wherein the ultrafine cerium oxide and / or the ultrafine metal oxide / cerium oxide composite is surface-treated. 16. The cosmetic according to claim 14, further comprising an ultraviolet absorber and / or an ultraviolet scattering agent. 17. An ultraviolet absorbent comprising oxybenzone, octyl methoxycinnamate, 4-tert-butyl-4'-
17. The cosmetic according to claim 16, wherein the cosmetic is one or more selected from methoxydibenzoylmethane. 18. The content of the ultraviolet absorbent is 0.1 to 40.
The cosmetic according to claim 16 or 17, which is in terms of% by weight. 19. The cosmetic according to claim 16, wherein the ultraviolet light scattering agent is titanium oxide and / or zinc oxide. 20. The content of the ultraviolet light scattering agent is 0.1 to 50.
20% by weight of the cosmetic according to any one of claims 16 to 19. 21. The cosmetic according to claim 14, which is a sunscreen cosmetic.