JPH0786084B2 - Cosmetics - Google Patents

Description

DETAILED DESCRIPTION OF THE INVENTION <Industrial field of application> The present invention relates to a cosmetic composition having excellent ultraviolet ray shielding ability and transparent natural color tone, which is suitable for preventing sunburn.

<Prior art> Ultraviolet rays contained in sunlight, especially ultraviolet rays with a wavelength of 280 to 320 nm (B wave), especially ultraviolet rays with a wavelength of 297.6 nm, are called Dorno rays and are called erythema and burns on the skin. Causes acute inflammation. Then, the erythema later disappears and causes deposition of melanin pigment, which causes sunburn. In addition, long-wavelength ultraviolet light (A wave) having a wavelength of 320 to 390 nm oxidizes melanin to cause deposition of melanin pigment on the skin and darkens the skin. These diseases, which are also called acute actinic skin disorders and sunburn, are harmful in their own right,
If you continue to be exposed to these UV rays for a long time,
May cause malignant diseases such as actinic keratosis and skin cancer. Therefore, in order to protect the skin from these ultraviolet rays, various ultraviolet ray shielding agents are blended in the cosmetics.

Cosmetics generally include basic cosmetics such as creams, lotions, and emulsions, finishing cosmetics such as lipsticks, eye shadows, and white powders, and cosmetics for hair such as hair styling, depending on the purpose. Although various components are blended, an ultraviolet ray shielding agent is always blended in a sunscreen cosmetic and a sunscreen cosmetic. Sunscreen cosmetics contain a UV-blocking agent that transmits A-wave UV rays that promote sunburn but blocks B-wave UV rays that cause skin irritation, and causes skin irritation even when exposed to sunlight. It is intended to be used to tan without health. On the other hand, the sunscreen cosmetics are intended to block not only B-wave ultraviolet rays but also A-wave ultraviolet rays to prevent sunburn.

By the way, as an ultraviolet shielding agent to be mixed in such cosmetics, para-aminobenzoic acids, salicylic acids, methoxycinnamic acids, organic compounds such as benzophenones and the like,
Inorganic compounds composed of metal oxides such as titanium oxide, zinc oxide and iron oxide are known.

Most of the organic compounds have the maximum absorption ability in the liquid B region and selectively absorb B-wave ultraviolet light, but during use,
There is a problem that it is washed away by sweating, bathing with water, or is absorbed by the skin, resulting in a decrease in the ultraviolet shielding ability.
In addition, the skin feels irritated and is deteriorated by absorption of ultraviolet rays, so that the usability and stability are not so good. Therefore, it is difficult to obtain a sunscreen cosmetic and a sunscreen cosmetic having a high UV-shielding ability because the compounding amount is regulated.

On the other hand, the inorganic compounds are less deteriorated by ultraviolet rays and are superior to the organic compounds in terms of stability over time. However, although titanium oxide and iron oxide are effective for blocking B-wave ultraviolet rays, they are not sufficient for blocking A-wave ultraviolet rays. On the contrary, zinc oxide is effective in shielding A-wave ultraviolet rays, but has a low ability to block B-wave ultraviolet rays. Further, since titanium oxide, iron oxide, and zinc oxide are photooxidation catalysts, the cosmetics containing them are mixed with other components such as fats and oils, higher alcohols,
There is a problem in that the preservatives and the like are altered and colored.

In order to solve such a problem, Japanese Patent Laid-Open No. 63-72620 discloses a composite oxide of zinc oxide and at least one metal oxide selected from aluminum, iron, chromium, cerium, zirconium and titanium. We have proposed a cosmetic product that contains 0.1-40% by weight of particles. However, this conventional cosmetic has 90% of ultraviolet rays with a wavelength of 260 to 380 nm.
%, But the effect of blocking ultraviolet rays with a wavelength of 380 nm or more is not sufficient. The average particle size of zinc oxide is 0.00
Although the catalytic activity related to photooxidation is suppressed by setting the thickness in the range of 1 to 0.5 μm, it cannot be said to be sufficient.

Further, Japanese Patent Laid-Open No. 1-190626 discloses cerium oxide and / or
Alternatively, a cosmetic has been proposed in which hydrous cerium oxide is mixed as at least 0.1% by weight as cerium oxide.
However, this cosmetic also efficiently shields ultraviolet rays having a wavelength of 260 to 380 nm, but does not have sufficient ability to shield ultraviolet rays having a wavelength of 380 nm or more.

<Problems to be Solved by the Invention> The object of the present invention is to solve the above-mentioned problems of conventional cosmetics and not only to efficiently shield ultraviolet rays having a wavelength of 250 to 390 nm, but also to worry about deterioration by ultraviolet rays. It is to provide a cosmetic product which has almost no activity and has no activity or catalytic activity.

<Means for Solving the Problems> In order to achieve the above object, the present invention provides a composite oxide particle containing a solid solution of cerium and zirconium in an amount of 0.1 to 5
Provided is a cosmetic composition containing 0% by weight. The average particle size of the composite oxide particles is preferably 1.0 μm or less.

In the composite oxide particles of cerium and zirconium used in the present invention, cerium oxide and / or cerium oxide (hereinafter collectively referred to as cerium oxide) and zirconium oxide form a solid solution. is doing. However, cosmetics may contain particles of a compound of cerium oxide and zirconium oxide in addition to such composite oxide particles. That is, the composite oxide particles referred to in the present invention are not a mixture of cerium oxide particles and zirconium oxide particles. However, a part of the composite oxide may be cerium oxide and / or zirconium oxide. Further, the composite oxide is preferably crystalline, but may be amorphous (amorphous). Some may be crystalline and the other may be amorphous. Further, part of the cerium oxide or zirconium oxide may be hydrous cerium oxide or hydrous zirconium oxide.

The ratio of cerium oxide and zirconium oxide constituting the composite oxide is the atomic ratio of cerium and zirconium (Ce / Z
r) is preferably 0.25 or more, and more preferably 0.3 or more.

As the composite oxide particles, those having an average particle diameter of 1.0 μm or less are usually used. Preference is given to using composite oxide particles of 0.5 μm or less, more preferably 0.2 μm or less. The larger the particle size, the lower the ultraviolet ray shielding ability, the poorer the dispersibility in cosmetics, the lower the transparency to visible rays and near infrared rays, and the lower the transparency.

The composite oxide particles can, of course, be used in a dry form, but can also be used in the form of a slurry, a sol, a gel or a paste.

The compounding amount of the composite oxide particles in the cosmetic is 0.1 to 50% by weight.
Is the range. The preferred range is 0.5 to 40% by weight. When the content of the composite oxide particles is less than 0.1% by weight, the ultraviolet ray shielding ability is hardly obtained. On the contrary, if it exceeds 50% by weight,
It becomes yellowish and the makeup film does not have a natural color tone.

The composite oxide particles used in the present invention can be manufactured by various methods. For example, it is produced by a hydrothermal crystallization method in which a base such as aqueous ammonia is added to a mixed aqueous solution of a cerium salt and a zirconium salt for neutralization, and the neutralized product is heated and crystallized in a pressure vessel. be able to. Further, the above-mentioned neutralized product may be dehydrated, washed, dried if necessary, and further fired if necessary. Further, a method of hydrolyzing an alcohol solution of a mixture of cerium alkoxide and zirconium alkoxide with water can be used.

The composite oxide particles are mixed with other cosmetic ingredients,
Used as cosmetics. At this time, it is also possible to use other ultraviolet shielding agents together. In addition, in order to improve the dispersibility of the composite oxide particles and the usability as a cosmetic, after the surface treatment of the composite oxide particles with oils and fats, surface treatment such as surfactant treatment or metal soap treatment is performed. It can also be blended.

The cosmetics of the present invention include particles, cakes, pencils,
In the form of stick, paste, jelly, sol, liquid, etc., eye shadow, eyeliner, mascara,
It can be used as a lipstick, blusher, nail enamel, makeup base, pack, lotion, foundation, cream, emulsion, shampoo, conditioner, hair cosmetic, and the like.

<Examples and Comparative Examples> Example 1 Ce / Zr was set to 30/70, and ceric oxide (CeO ₂ ) was added.
Converted 1.614mol / l cerium chloride (CeCl ₃ ) aqueous solution 44.61
ml and 96.89 g of a zirconium oxychloride (ZrOCl ₂ ) aqueous solution of 21.37% by weight in terms of zirconium oxide (ZrO ₂ ) are mixed, and 1.15 g of hydrogen peroxide solution is added to and mixed with the mixture.
Pure water was added to make 200 ml. Hereinafter, this is referred to as raw material A.

On the other hand, ammonia water (ammonia content: 25% by weight)
In Aminonia (NH ₃ ) conversion in CeCl ₃ and ZrOCl ₂ .
46.55 ml of NH ₃ / Cl was adjusted to 1.5, and pure water was added to this to make 200 ml. Hereinafter, this is referred to as raw material B.

Next, the above raw material A and raw material B are added to 50 ml of pure water which is being stirred.
And were simultaneously dropped to obtain a coprecipitated gel of hydrous cerium hydroxide and hydrous zirconium oxide.

Next, the coprecipitated gel was heat-treated in a pressure vessel at 150 ° C. for 24 hours, the obtained slurry was filtered 5 times using pure water, washed with water, further stirred with acetone 3 times, and filtered. I got a cake.

Next, 300 ml of acetone was added to the cake and crushed by a ball mill for 24 hours, and the obtained organic solvent sol was dried at 60 ° C. using a rotary evaporator. The average particle size was 0.01 μm and the Ce / Zr Is 30/70, composite oxide particles in which cerium and zirconium are in solid solution were obtained.

Next, the above complex oxide particles were blended in the following formulation to produce a cream. The unit is% by weight.

Composite oxide particles 10.0 Stearyl alcohol 6.3 Stearic acid 1.8 Hydrogenated lanolin 1.8 Squalane 4.5 2-Octyldodecyl alcohol 5.4 Polyoxyethylene cetyl alcohol ether 2.7 Glycerin monostearate ester 1.8 Propylene glycol 4.5 Purified water 60.9 Perfume 0.3 Preservatives are purified. Propylene glycol was added to water, further composite oxide particles were added, and an aqueous phase obtained by heating to 70 ° C. and the remaining components were mixed, and an oil phase at 70 ° C. obtained by heating and melting,
The oil phase was added to the aqueous phase to carry out preliminary emulsification, then uniformly emulsified with a homomixer, and after emulsification, stirring was performed while cooling.

With respect to the cream thus obtained, the stability, the ultraviolet ray shielding ability, and the functionality were evaluated by the following methods. The evaluation results are shown in the table.

Evaluation of stability: The cream was left indoors for one year and evaluated for the presence or absence of alteration.

Evaluation of UV blocking ability: M-DMR-1 manufactured by Toko Denki Co., Ltd. was applied to the area where the cream was applied to the skin at a rate of ² mg / cm ² and the area where it was not applied.
Type medical UV irradiator with maximum wavelength 305nm and 352nm
Ultraviolet rays of nm were irradiated, the minimum erythema formation energy was measured for the application site and the non-application site with a DM-N type digital UV intensity meter manufactured by Irie Shokai Co., Ltd., and evaluated by the SPF value. Here, the SPF value is SPF value = minimum erythema formation energy of application site / minimum erythema formation energy of non-application site.

Evaluation of sensuality: Let 20 female monitors use for 2 weeks, and feel
For the four items of growth and transparency, the questionnaire answered "good" and "bad". In addition, they also received a comprehensive evaluation. The numbers in the table are the number of people who answered "good" for these items.

Example As 2 Ce / Zr is 40/60, and 59.48ml of CeCl ₂ aqueous solution, in addition to the 83.04g of ZrOCl ₂ aqueous solution to obtain a raw material A in the same manner as in Example 1. A raw material B was obtained in the same manner as in Example 1 except that the amount of ammonia water was changed to 48.57 ml so that NH ₃ / Cl was 1.5. Further, filtration with pure water and washing with water were performed in the same manner as in Example 1 to obtain a wet cake of composite oxide particles.

Next, the wet cake of the composite oxide particles was blended in the following formulation to produce a lotion. The unit is% by weight.

Complex oxide particles 1.5 Glycerin 3.0 Propylene glycol 4.0 Dipropylene glycol 4.0 Oleyl alcohol 0.1 Polyoxyethylene sorbidan monolanophosphate
1.5 Polyoxyethylene lauryl alcohol ether 0.5 Ethyl alcohol 15.0 Purified water 70.3 Perfume 0.1 Dye preservative The production is as follows: Wet cake of complex oxide particles is added to purified water and mixed, and then glycerin, propylene glycol and dipropylene glycol are added. , The water part obtained by dissolving at room temperature, and the alcohol part obtained by mixing and dissolving the other components at room temperature, the alcohol part is added to the water part, mixed, solubilized, and further dyed. It was done by coloring.

The lotion thus obtained was evaluated in the same manner as in Example 1. However, the coating amount was 2 μl / cm ² . The evaluation results are shown in the table.

Example 3 As Ce / Zr is 50/50, and 77.35ml of CeCl ₂ aqueous solution, in addition to the 69.20g of ZrOCl ₂ aqueous solution to obtain a raw material A in the same manner as in Example 1. A raw material B was obtained in the same manner as in Example 1 except that the amount of ammonia water was changed to 50.60 ml so that NH ₃ / Cl was 1.5. Further, composite oxide particles were obtained in the same manner as in Example 1.

Next, the above composite oxide particles were blended in the following formulation to obtain an emulsion. The unit is% by weight.

Complex oxide particles 14.0 Stearic acid 2.5 Cetyl alcohol 1.5 Vaseline 5.0 Liquid paraffin 10.0 Polyoxyethylene monooleate 2.0 Polyethylene glycol 3.0 Triethynolamine 1.0 Purified water 70.5 Perfume 0.5 Preservative For manufacturing, add complex oxide particles to purified water. After mixing,
Polyethylene glycol and triethanolamine were added, heated and dissolved to obtain a 70 ° C aqueous phase, and the other components were mixed, heated and dissolved to obtain an 70 ° C oil phase After adding the oil phase and pre-emulsifying, homogenize with a homomixer,
After emulsification, cooling was performed with stirring.

The emulsion thus obtained was evaluated in the same manner as in Example 1.
However, the coating amount was 2 μl / cm ² . The evaluation results are shown in the table.

Example 4 As Ce / Zr is 70/30, and 104.10ml the CeCl ₂ aqueous solution, in addition to the 41.52g of ZrOCl ₂ aqueous solution to obtain a raw material A in the same manner as in Example 1. A raw material B was obtained in the same manner as in Example 1 except that the amount of ammonia water was 54.64 ml so that NH ₃ / Cl was 1.5. Further, composite oxide particles were obtained in the same manner as in Example 1.

Next, the above composite oxide particles were blended in the following formulation to obtain a compact powder. The unit is% by weight.

Complex oxide particles 45.0 Talc 30.0 Kaolin 9.0 Titanium dioxide 5.0 Liquid paraffin 3.0 Sorbitan sesquioleate ester 2.0 Sorbitol 4.0 Propylene glycol 2.0 Pigment Fragrances are produced by mixing complex oxide particles, talc, kaolin, titanium dioxide and pigments. While mixing with a blender, add a mixture of other ingredients uniformly, after crushing treatment,
It was performed by compression molding.

The emulsion thus obtained was evaluated in the same manner as in Example 1.
The evaluation results are shown in the table.

As Example 5 Ce / Zr is 90/10, and 133.80ml the CeCl ₂ aqueous solution, in addition to the 13.84g of ZrOCl ₂ aqueous solution to obtain a raw material A in the same manner as in Example 1. A raw material B was obtained in the same manner as in Example 1 except that the amount of ammonia water was 58.69 ml so that NH ₃ / Cl was 1.5. Further, composite oxide particles were obtained in the same manner as in Example 1.

Next, the above composite oxide particles were blended in the following formulation to obtain a foundation stick. The unit is% by weight.

Composite oxide particles 15.0 Titanium dioxide 15.0 Kaolin 7.0 Mica powder 7.0 Zinc white 4.5 Iron oxide (red) 1.4 Iron oxide (black) 0.1 Solid paraffin 5.0 Carnauba wax 3.0 Liquid paraffin 34.0 Isopropyl myristate 5.0 Sorbitan sesquioleate 3.0 Fragrance production , Mixed oxide particles, titanium dioxide, kaolin, mica powder, zinc white, and iron oxide were added to the particle portion obtained by blending with a half amount of liquid paraffin and sorbitan sesquioleate ester. And mix evenly with homomisaki, then heat, melt and add the other ingredients,
After mixing well, the mixture was poured into a container and cooled.

The emulsion thus obtained was evaluated in the same manner as in Example 1.
The evaluation results are shown in the table.

Comparative Example 1 A cream was obtained in the same manner as in Example 1 except that titanium oxide particles having an average particle diameter of 0.1 μm were used instead of the composite oxide particles.

The results of evaluations performed on this cream in the same manner as in Example 1 are shown in the table.

Comparative Example 2 An emulsion was obtained in the same manner as in Example 3 except that zinc oxide particles having an average particle diameter of 0.1 μm were used instead of the composite oxide particles.

The results of evaluations performed on this cream in the same manner as in Example 3 are shown in the table.

Comparative Example 3 A foundation stick was obtained in the same manner as in Example 5 except that cerium oxide particles having an average particle diameter of 0.3 μm were used instead of the composite oxide particles.

The results of evaluations performed on this foundation stick in the same manner as in Example 3 are shown in the table.

<Effects of the Invention> The cosmetic material of the present invention contains the composite oxide particles in which cerium and zirconium are solid-dissolved in the range of 0.1 to 50% by weight. It not only shields ultraviolet rays well, but also has excellent stability, texture, stickiness, elongation and transparency. When the composite oxide particles having an average particle size of 1.0 μm or less are used, the transparency is further improved by further increasing the transparency of visible light and near infrared rays, and the cosmetic film has a transparency. It becomes possible to obtain a makeup film having a natural color tone. Moreover, since the composite oxide in which cerium and zirconium are solid-dissolved has no photocatalytic activity or activity, there is no fear of irritating the skin, and the other coexisting organic components are not deteriorated.

Claims (2)

[Claims] 1. A cosmetic comprising a composite oxide particle comprising a solid solution of cerium and zirconium in an amount of 0.1 to 50% by weight. 2. The cosmetic material according to claim 1, wherein the average particle diameter of the composite oxide particles is 1.0 μm or less.