JPH045223A - Cosmetic - Google Patents

Abstract

PURPOSE:To obtain a cosmetic, capable of sufficiently shielding ultraviolet light and having a natural color tone with transparency and suitable for preventing sunburn by blending compound oxide particles of cerium and zirconium with other ingredients. CONSTITUTION:The objective substance is obtained by mixing 0.1-50 wt.% compound oxide particles of cerium and zirconium with other cosmetic ingredients and preparing a cosmetic according to a conventional method. The cosmetic can be used in the form of particles, cake, pencil, stick, paste, jelly, sol, liquid, etc., as eye shadow, eye liner, mascara, lipstick, rouge, nail enamel, toilet water, foundation cream, cream, milky lotion, shampoo, rinse, etc. The oxide particles are obtained by adding a base such as aqueous ammonia to a mixture solution of a Ce salt and a Zr salt, neutralizing the resultant solution, heating and crystallizing the product. The aforementioned cosmetic is efficiently shielding ultraviolet light at 250-390 nm wavelength without being deteriorated by the ultraviolet light.

Description

DETAILED DESCRIPTION OF THE INVENTION <Industrial Application Field> The present invention relates to a cosmetic composition that has excellent ultraviolet shielding ability and a transparent and natural color tone, and is suitable for preventing sunburn.

<Conventional technology> Ultraviolet rays contained in sunlight, especially wavelengths of 280 to 32
Medium wavelength ultraviolet light (B wave) of 0 nm, especially wavelength 297.
6 nm ultraviolet rays are called Dornot radiation and cause acute inflammation in the form of erythema and burns on the skin. And the erythema is
It later disappears and causes the deposition of melanin pigment, which causes sunburn. In addition, long-wavelength ultraviolet rays (A waves) with a wavelength of 320 to 390 nm oxidize melanin and cause melanin pigmentation to occur on the skin, turning the skin black. Also called dermatitis, it is not only harmful in itself, but continued exposure to these UV rays over a long period of time can cause malignant diseases such as actinic keratosis and skin cancer.

Therefore, to protect your skin from these UV rays,
Cosmetics contain various types of UV-screening agents.

Cosmetics generally include basic cosmetics such as creams, lotions, and emulsions, finishing cosmetics such as lipstick, eye shadow, and powder, and hair cosmetics such as hair styling products. Various ingredients are blended into the skin, but sunscreen cosmetics and sunscreen cosmetics always contain an ultraviolet shielding agent. Cosmetics for sunburn are formulated with UV-screening agents that either transmit A-wave UV rays that promote sunburn or block B-wave UV rays that cause skin irritation, which can cause skin irritation even if you continue to be exposed to sunlight. It is used to get a healthy tan without causing any damage. On the other hand, sunscreen cosmetics block not only B-wave ultraviolet rays but also A-wave ultraviolet rays to prevent sunburn.

By the way, the UV-screening agents that are incorporated into such cosmetics include organic compounds such as para-aminobenzoic acids, salicylic acids, methoxycinnamic acids, and benzophenones;
Inorganic compounds made of metal oxides such as titanium oxide, zinc oxide, and iron oxide are known.

Most organic compounds have maximum absorption ability in the B-wave region and selectively absorb B-wave ultraviolet rays, but during use,
There is a problem that the ultraviolet shielding ability decreases due to being washed away due to sweating, bathing, etc., or absorbed through the skin.

In addition, it irritates the skin and deteriorates due to absorption of ultraviolet rays, and its usability and stability are not very good. Therefore, the blending amount is regulated, and it is difficult to obtain sunscreen cosmetics and sunscreen cosmetics with high ultraviolet shielding ability.

On the other hand, inorganic compounds are less susceptible to deterioration due to ultraviolet rays and are superior to organic compounds in terms of stability over time. However, titanium oxide and iron oxide are only effective at shielding B-wave ultraviolet rays, but are not sufficient at shielding A-wave ultraviolet rays. Zinc oxide, on the other hand, is effective in shielding ultraviolet A waves, but has a low ability to shield ultraviolet B waves. In addition, since titanium oxide, iron oxide, and zinc oxide are photo-oxidation catalysts, cosmetics containing these may be mixed with other ingredients, such as oils, fats, higher alcohols,
There is a problem that preservatives etc. are deteriorated and colored.

In an attempt to solve such problems, Japanese Patent Application Laid-Open No. 63-72
No. 620 discloses composite oxide particles of zinc oxide and at least one metal oxide selected from aluminum, iron, chromium, cerium, zirconium, and titanium.
We are proposing cosmetics containing 1 to 40% by weight. However, this conventional cosmetic has a wavelength of 260~
Although 90% or more of ultraviolet rays with a wavelength of 380 nm are blocked, the effect of blocking ultraviolet rays with a wavelength of 38 Qnm or more is not sufficient. Further, although the catalytic activity related to photo-oxidation is suppressed by setting the average particle size of zinc oxide to a range of 0.001 to 0.5 μm, this is still not sufficient.

Furthermore, JP-A-1-190626 proposes a cosmetic composition containing at least 0.1% by weight of ceric oxide and/or hydrous cerium oxide as ceric oxide. However, this cosmetic also has a wavelength of 26
Although it efficiently blocks ultraviolet rays with a wavelength of 0 to 380 nm, its ability to block ultraviolet rays with a wavelength of 380 nm or more is not sufficient.

<Problems to be Solved by the Invention> The purpose of the present invention is to solve the above-mentioned problems of conventional cosmetics, to not only efficiently block ultraviolet rays with a wavelength of 250 to 390 nm, but also to eliminate concerns about deterioration due to ultraviolet rays. The purpose of the present invention is to provide a cosmetic that has almost no active or catalytic ability.

Means for Solving the Problems> In order to achieve the above object, the present invention provides composite oxide particles of cerium and zirconium in a 0. 1-50% by weight
To provide a cosmetic containing the following ingredients.

The composite oxide particles of cerium and zirconium used in this invention form an isocontainer such as cerium oxide and/or ceric oxide (hereinafter collectively referred to as cerium oxide) and zirconium oxide. Alternatively, the particles are particles in which cerium oxide and zirconium oxide form a compound, and are not a mixture of cerium oxide particles and zirconium oxide particles. However, part of the composite oxide may be cerium oxide and/or zirconium oxide. Further, the composite oxide is preferably crystalline, or may be amorphous. Some parts may be crystalline and other parts may be amorphous. Furthermore, cerium oxide and zirconium oxide may partially be hydrated cerium oxide or hydrated zirconium oxide.

The ratio of cerium oxide and zirconium oxide constituting the composite oxide is determined by the atomic ratio of cerium and zirconium (Ce
/Zr), preferably 0.25 or more, more preferably 0. It is better if it is 3 or more.

The composite oxide particles used usually have an average particle diameter of 1.0 μm or less. Preferably it is 0.5 μm or less, more preferably 0.5 μm or less. The purpose is to use composite oxide particles of 2 μm or less. The larger the particle size, the lower the ultraviolet shielding ability, and the worse the dispersibility in cosmetics, the lower the transparency of visible light and near infrared rays, and the lower the sense of transparency.

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

The amount of composite oxide particles added to the cosmetic is in the range of 0.1 to 50% by weight. Preferably, it is in the range of 0.5 to 40% by weight. When the composite oxide particles are less than 0.1% by weight,
Almost no UV shielding ability is obtained. Conversely, 50% by weight
If it exceeds this range, the makeup film will become yellowish and lose its natural color tone.

The composite oxide particles used in this invention can be produced by various methods. For example, it is produced by a hydrothermal crystallization method in which a mixed aqueous solution of cerium salt and zirconium salt is neutralized by adding a base such as aqueous ammonia, and the neutralized product is heated and crystallized in a pressure-resistant container. I can do something.

In addition, the above-mentioned neutralized product can be dehydrated, washed, and
It can be dried and further fired if necessary. Furthermore, a method can be used in which an alcohol solution of a mixture of cerium alkoxide and zirconium alkoxide is hydrolyzed with water.

The composite oxide particles are mixed with other cosmetic ingredients,
It is considered a cosmetic. At this time, it is also possible to use other known ultraviolet shielding agents. In addition, in order to improve the dispersibility of composite oxide particles and their usability as cosmetics, we have applied surface coating treatments using well-known oils and fats to composite oxide particles.
It can also be blended after surface treatment such as surfactant treatment or metal soap treatment.

The cosmetics of this invention can be in the form of particles, cakes, pencils,
Eyeshadow, eyeliner, mascara in stick, paste, jelly, sol, liquid, etc.
It can be used as lipstick, rouge, nail enamel, makeup base, pack, lotion, foundation, cream, milky lotion, shampoo conditioner, hair cosmetic, etc.

<Examples and Comparative Examples> Example I In terms of ceric oxide (CeC)2), 1. 614 mol/44.61 ml of an aqueous solution of cerium chloride (CeCl3) and 96.6 ml of an aqueous solution of zirconium oxychloride (ZrOCl2) of 21.37% by weight in terms of zirconium oxide (zro2).
After adding and mixing 1.15 g of hydrogen peroxide solution, pure water was added to make 200 ml. Hereinafter, this will be referred to as raw material A.

On the other hand, ammonia water (ammonia content: 25% by weight)
, CeCl3 and Z in terms of ammonia (NH3)
r 46.55 ml was taken so that NH3/CI in OC12 was 1°5, and pure water was added to make 200 ml. Hereinafter, this will be referred to as raw material B.

Next, the above raw material A and raw material B were simultaneously dropped into 50 ml of pure water that was being stirred to obtain a co-precipitated gel of hydrous cerium oxide and hydrous zirconium oxide.

Next, the coprecipitated gel was heated at 150'C for 24 hours in a pressure vessel.
After heat treatment for 5 hours, the resulting slurry was heated for 5 hours using pure water.
Filtered twice, washed with water, stirred with acetone three times, filtered,
Got the cake.

Next, 300 ml of acetone was added to the cake and pulverized in a ball mill for 24 hours, and the resulting organic solvent sol was dried at 60°C using a rotary evaporator, and the average particle size was 0.01 μm. Z r is 30/
70, composite oxide particles of cerium and zirconium were obtained.

Next, the above composite oxide particles were blended according to the following formulation to produce a cream. Note that the unit is weighted percentage.

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 1.8 Propylene glycol 4.5 Purified water
60.9 fragrance
0.3 Preservative production involves adding propylene glycol to purified water, further adding composite oxide particles, and heating to 70°C to obtain an aqueous phase;
Mix the remaining ingredients and heat and melt the obtained oil phase at 70'C. Add the oil phase to the water phase and pre-emulsify it, then uniformly emulsify it with a homomixer, and after emulsification, stir while cooling. It was done by

The cream thus obtained was evaluated for stability, ultraviolet shielding ability, and sensory evaluation using the following methods. The evaluation results are shown in the table.

Stability evaluation: The cream was left indoors for one year and evaluated for the presence or absence of deterioration.

Evaluation of ultraviolet shielding ability: Toko Denki Co., Ltd.'s M
-DM R-1 type medical ultraviolet irradiation equipment is used to irradiate ultraviolet rays with maximum wavelengths of 305 nm and 352 nm, and a DM-N digital ultraviolet intensity meter manufactured by Irie Shokai Co., Ltd. is used to measure the minimum applied and uncoated areas. Erythema generation energy was measured and evaluated by SPF value. Here, the SPF value is as follows: SPF value=minimum erythema generation energy of applied area/minimum erythema generation energy of non-applied area.

Sensual evaluation: 20 female monitors used the product for two weeks and asked them to answer a questionnaire with 1 good or 1 bad for 4 items: texture, adhesion, stretchability, and transparency. We also asked them to give us an overall evaluation. The numbers in the table indicate the number of people who answered "good" for these items.

Example 2 The amount of CeC12 aqueous solution was 59.48 ml, and the amount of Zr0C1: aqueous solution was 83.0 ml so that the ratio of Ce/Zr was 40/60.
Raw material A was obtained in the same manner as in Example 1 except that the amount of raw material A was 0.4 g. Raw material B was also obtained in the same manner as in Example 1, except that 48.57 ml of ammonia water was used so that NH3,/CI was 1.5. Furthermore, in the same manner as in Example 1, filtration with pure water and washing were performed to obtain a wet cake of composite oxide particles.

Next, a wet cake of the composite oxide particles was blended according to the following formulation to produce a lotion. Note that the unit is weight %.

Composite oxide particles 1-05 Chrycerin 3.0 Propylene glycol 4,0 Dipropylene glycol
4. 0 oleyl alcohol 0
．． 1 Polyoxyethylene Solpidan Monolanolinate 1.5 Polyoxyethylene Lauryl Alcohol Ether
0. 5 ethyl alcohol
15.0 Purified water 70.3 Fragrance 0. 1. To produce a dye preservative, add and mix a wet cake of composite oxide particles to purified water, then add glycerin, propylene glycol, and dipropylene glycol, and dissolve at room temperature to obtain Suito, etc. The alcohol part obtained by mixing and dissolving the components at room temperature was mixed and solubilized by adding the alcohol part to Suito, and then colored with a dye.

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 CeC12 so that Ce/Z r is 50.150
The aqueous solution was 77.35 ml, and the Zr0C]□ aqueous solution was 6
Raw material A was obtained in the same manner as in Example 1 except that the amount was 9.20 g. Raw material B was also obtained in the same manner as in Example 1, except that 50.60 ml of ammonia water was used so that the ratio of NH3/C1 was 1.5. Furthermore, 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 milky lotion. Note that the unit is weight %.

Composite 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 Triethanolamine 1.0 Purified water
70.5 Fragrance 0.
5 Preservative production involves adding and mixing composite oxide particles to purified water,
A 70°C aqueous phase obtained by adding, heating and dissolving polyethylene glycol and triethanolamine, and a 70°C oil phase obtained by mixing, heating and dissolving other components, The oil phase was added to the water phase, pre-emulsified, and then uniformly emulsified using a homomixer. After the emulsification, the mixture was cooled while 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 CeC1 so that Ce/Z r is 70/30
2 aqueous solution to 104.10 ml, Z r OC] 2
Raw material A was obtained in the same manner as in Example 1 except that the aqueous solution was changed to 41.52 g. Also, NH3/C1 is still 1.
Raw material B was obtained in the same manner as in Example 1, except that the amount of ammonia water was changed to 54.64 ml so that the amount of raw material B was 54.64 ml. Furthermore, 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. Note that the unit is weight %.

Composite oxide particles 45.0 talc
30.0 kaolin
9. 〇Titanium dioxide
5. 0 liquid paraffin
3.0 Sorbitan sesquioleate 2.0 Sorbitol 4. 0 propylene glycol 2. 0 Pigment fragrance production involves mixing composite oxide particles, talc, kaolin, titanium dioxide, and pigment in a blender, adding a uniform mixture of other ingredients, and pulverizing the mixture.
This was done by compression molding.

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

Example 5 CeC12 aqueous solution was 133.80ml and ZrOCl2 aqueous solution was 133.80ml so that Ce/Zr ratio was 90/10.
．． Raw material A was obtained in the same manner as in Example 1 except that the amount was changed to 84 g. Also, Example 1 except that the ammonia water was changed to 58.69n+l so that NH,,/CI was 1.5.
Raw material B was obtained in the same manner as above. Furthermore, composite oxide particles were obtained in the same manner as in Example 1.

Next, the above composite oxide particles were blended according to the following formulation to obtain a foundation stick. Note that the unit is 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 ester 5. 0 Sorbitan sesquioleate 3.0 Fragrance production involves blending composite oxide particles, titanium dioxide, kaolin, mica powder, zinc white, and iron oxide in a blender. Add half of the paraffin and sorbitan sesquioleic acid ester and mix uniformly with a homomixer, then heat and melt the other ingredients and add.
After mixing thoroughly, 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? ji=average particle diameter is 0. 1μ
A cream was obtained in the same manner as in Example 1 except that titanium oxide particles of m were used.

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

Comparative Example 2 Instead of composite oxide particles, the average particle diameter was 0. A milky lotion was obtained in the same manner as in Example 3 except that 18m zinc oxide particles were used.

The results of the evaluation of this cream performed 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 ceric oxide particles having an average particle diameter of 0.3 μm were used instead of the composite oxide particles.

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

<Effects of the Invention> Since the cosmetic of the present invention contains composite oxide particles of cerium and zirconium in a range of 0.1 to 50% by weight, as is clear from the examples, Not only does it block UV rays well, but it also has excellent stability, texture, adhesion, spreadability, and transparency. Transparency is achieved by an average particle size of 1
．． When using composite oxide particles of 0.011 m or less,
Transmittance of visible light and near-infrared rays is further improved, and the cosmetic film becomes transparent, making it possible to obtain a cosmetic film with a natural tone. Moreover, since the composite oxide of cerium and zirconium does not have photocatalytic ability or activity, there is no risk of irritation to the skin, and it will not alter the quality of other coexisting organic components.

Claims (1)

[Claims] Composite oxide particles of cerium and zirconium from 0.1 to
Cosmetics containing 50% by weight.