JPH01190626A - Cosmetic composition - Google Patents

Abstract

PURPOSE:To provide a cosmetic composition compounded with cerium oxide or hydrated cerium oxide, having excellent ultraviolet-shielding effect especially against the ultraviolet ray of UV-A region, effective in protecting the skin and having high dispersibility in cosmetic base and applicability to the skin. CONSTITUTION:The objective cosmetic composition can be prepared by compounding >=0.1wt.%, preferably 1.0-50wt.% (in terms of CeO2) of fine particles surface-coated with cerium oxide and/or hydrated cerium oxide together with conventional cosmetic base to a cosmetic. The composition can be formed in the form of powder, cake, pencil, stick, ointment, liquid, etc., and is applied as a cream, face lotion, milky lotion, lipstick, rouge, face powder and hair-dressing. The cosmetic has extremely high shielding effect against the ultraviolet ray of 340-380nm wavelength or thereabout which is liable to cause the melanization of the skin.

Description

DETAILED DESCRIPTION OF THE INVENTION The present invention relates to a cosmetic composition, and more particularly to a cosmetic composition having an excellent ultraviolet shielding effect.

Since ancient times, many cosmetics have been used mainly by women.These cosmetics include, for example, creams, lotions,
They are broadly classified into basic cosmetics such as milky lotions, finishing cosmetics such as lipsticks, rouges, and powders, and hair cosmetics such as hair styling products, and various ingredients are used depending on the purpose.

By the way, sunlight contains ultraviolet rays with a wavelength of 100 to 400 nm, of which about 280 to 320 nm
1UV-B region) In particular, ultraviolet rays having a wavelength of 297°6 nm are called Dorneau radiation and have the effect of causing erythema and burns, which are acute inflammations, on the skin. This erythema clears up after a certain period of time and later causes the deposition of melanin pigment, which causes sunburn. Also 320-400nl
(UV-A region) It is known that ultraviolet rays having a wavelength of 340 to 380 nm, in particular, oxidize reduced melanin in the epidermis, causing melanin pigmentation in the skin.

Sunscreen cosmetics are used as cosmetics to prevent sunburn caused by such melanin pigmentation. This sunscreen cosmetic contains various ultraviolet absorbers or ultraviolet shielding agents, which prevent the formation of erythema or blisters caused by excessive ultraviolet irradiation on the skin, and suppress the formation of melanin in pigment cells. It has been used to prevent pigmentation. UV absorbers used in sunscreen cosmetics include quinine salts such as quinine hydrochloride and quinine sulfate, para-aminobenzoic acid derivatives such as ethyl para-aminobenzoate and isopropyl para-aminobenzoate, salicylic acid derivatives such as phenyl salicylate, and cinnamic acid. Pencil, cinnamic acid derivatives such as homomenthyl cinnamic acid, acetanilide, etc. are used.

Inorganic compounds such as titanium oxide, talc, kaolin, zinc oxide, and iron oxide are used as ultraviolet shielding agents.

However, the above-mentioned ultraviolet absorbers have the problem that when the amount added to the cosmetic base material increases, they do not dissolve uniformly.
In addition, there are concerns about side effects such as irritation to the skin, and there is also the problem of lack of stability, such as deterioration due to absorption of ultraviolet rays, resulting in decreased ultraviolet absorption ability or coloration. On the other hand, the UV-screening agents made of the above-mentioned inorganic compounds have little deterioration due to UV-induced deterioration and are not absorbed through the skin, so there are no problems with side effects such as skin irritation.However, titanium oxide and iron oxide are UV-screening agents that cause erythema Although it is effective in blocking ultraviolet rays in the UV-A region, it is not sufficiently effective in blocking ultraviolet rays with wavelengths in the UV-A region.On the other hand, suboxide 59 is effective in blocking ultraviolet rays in the UV-A region, but The effect of blocking ultraviolet rays with wavelengths in the UV-B region is weak, and furthermore, the dispersibility in cosmetic base materials is poor, and when mixed in multiple layers to achieve the effect, the usability is poor, and the result is a cosmetic with no transparency, which is unsatisfactory. It's not a thing.

The present invention is an attempt to solve the above-mentioned problems, and has an excellent effect of shielding ultraviolet 41, particularly ultraviolet rays having wavelengths in the UV- region, and also reduces irritation to the skin. It has no side effects such as, and has excellent chemical stability.
Another object of the present invention is to provide a cosmetic composition that has excellent dispersibility in cosmetic base materials and has an excellent feel during use.

The first cosmetic composition according to the present invention is characterized by containing at least 0.1% by weight of cerium oxide and/or hydrous cerium oxide as CCO2.

Further, the second cosmetic composition according to the present invention is characterized in that at least 0.1% by weight of CeO2 is blended with fine particles whose surfaces are coated with cerium oxide and/or hydrous cerium oxide.

The cosmetic composition according to the present invention will be described in detail below.

The cerium oxide and hydrated cerium oxide used in the present invention may be sol or gel of cerium oxide or hydrated cerium oxide, or may be a fine powder obtained by drying or baking them, depending on the type of cosmetics to be blended. Used in any appropriate form.

There are no particular restrictions on the method for preparing these, and conventionally known methods can be applied. For example, an aqueous solution of inorganic or organic cerium salt, etc. is neutralized with an alkali to prepare a hydrous cerium oxide gel, which is then dehydrated, washed, dried as necessary, and optionally calcined to form a raw material for compounding. It can be done.

Alternatively, the above gel can be peptized with acid to produce a cerium oxide sol, which can be used as a raw material for formulation.

As a method for preparing fine particles coated with cerium oxide and/or hydrous cerium oxide (hereinafter referred to as cerium oxide-coated particles or hydrous cerium oxide-coated particles), the fine particles that are to become the core are suspended! A cerium salt aqueous solution is added to the gi suspension while maintaining a predetermined pH to deposit a predetermined amount of cerium oxide or hydrated cerium oxide on the surface of the implanter particles, and if necessary, this is then dehydrated, washed, It can be dried and optionally calcined to be used as a raw material for compounding.

As the core to be coated with cerium oxide and/or hydrous cerium oxide, any material can be used as long as the surface can be stably coated with cerium oxide. For example, iron oxide, zinc oxide, chromium oxide, zirconium oxide, aluminum oxide, titanium oxide, magnesium oxide, silica, silica/alumina, silica/magnea, etc. l oxide or talc, various mica, kaolin clay, montmorillonite clay, calcium carbonate,
Examples include one type or a mixture of 2M or more of magnesium carbonate.

Furthermore, titanates such as barium titanate, calcium phosphate, etc. can also be used, and depending on the application, navy blue,
Inorganic pigments such as manganese violet may also be used.

The amount of cerium oxide and/or hydrous cerium oxide to be coated depends on the particle size of the core fine particles, the type of cosmetics to be mixed, etc., but is at least about 0.1% by weight as CeO2 based on the total weight of the fine particles after coating. If so, the object of the present invention can be achieved.

Cerium oxide used in the present invention, hydrated cerium oxide,
The average particle size of these coated f6 particles when blended into cosmetics is preferably as small as about 80 mμ or less for cosmetics that require transparency, but when transparency is not required, , particle sizes larger than those mentioned above can also be used. However, as the particle size increases, problems such as poor dispersibility in cosmetic compositions occur, so the average particle size of the particles is preferably about 15 μm or less.

An example of the light transmittance of cerium oxide or the like used in the present invention is shown in FIG.

In addition, when the fine particles such as cerium oxide are sol, the method for measuring the light transmittance is as follows: CeO2'9 degree is 0.05
After adjusting to % by weight, it was placed in a quartz cell with a thickness of 1 inch, and measured using a spectrophotometer (Model 330, manufactured by Hitachi, Ltd.).

If the fine particles such as cerium oxide are in the form of a fine powder, add 90 parts by weight of liquid paraffin to 10 parts of the powder, disperse well with a homomixer, and then apply this dispersion to a transparent quartz plate with a thickness of 5 μm. and measured using the same spectrophotometer.

The above sample A is a sol obtained by adding aqueous ammonia to an aqueous cerium nitrate solution to obtain hydrous cerium oxide, and then peptizing this with an acid. In addition, sample B was prepared by washing the hydrated oxide obtained by adding ammonia water to the cerium nitrate aqueous solution.
It is dry.

In samples C to F, an aqueous cerium nitrate solution and aqueous ammonia are added to the suspension water of each core material while maintaining a predetermined 1)H, and the core material is coated with hydrated cerium oxide. Thereafter, the sample was washed, dried, and fired.

Samples A to F of the present invention, compared to sample G, did not show an excellent shielding effect against ultraviolet rays of 340 to 380 μm that cause melanin pigmentation in the skin.

When blending these fine particles into cosmetics, they can be blended with other cosmetic base materials by a well-known method to obtain the desired cosmetic.

When the fine particles are in the form of a sol, they may be a sol with water as a dispersion medium, or depending on the type of cosmetics to be formulated, they may be a water-dispersed sol mixed with an organic solvent such as alcohol or glycerin, or a sol with water as a dispersion medium. It may also be used as an organic sol substituted with these organic solvents.

The blending ratio of these fine particles in cosmetics varies depending on the type of cosmetics, but is at least 0.1% by weight or more, preferably 1.0 to 1.0% by weight as CeO2, based on the total weight of the cosmetics.
Selected from a range of 50% heavy indigo. If the amount is less than 0.1%, the ultraviolet shielding effect will not be sufficient, which is not preferable.

The cosmetics according to the present invention can be in the form of powder, cake, pencil, snack, ointment, liquid, etc., and specifically include lotions, foundations, creams, milky lotions, eye shadows, and makeup bases. , nail enamel, eyeliner, mascara-2 lipstick, pack, shampoo, conditioner, hair cosmetics, etc.

The cosmetics of the present invention have an excellent effect of shielding ultraviolet rays, and are particularly effective for UV rays of 340 to 380 nm, which tend to cause melanin pigmentation on the skin.
It very well blocks Q ultraviolet MA around II (tJV-A region), provides excellent protection of the skin from ultraviolet rays, and has excellent dispersibility even when added to cosmetic base materials in large quantities.
In addition, it has excellent light resistance, usability, and finish feel for cosmetics. In addition, cosmetics containing cerium oxide or hydrous cerium oxide with an average particle size of about 80 mμ or less do not lose their transparency even when added in relatively large amounts, so cosmetics that require transparency can be used in cosmetics that require transparency. It is suitable as such.

EXAMPLES The present invention will be explained below with reference to Examples, but the present invention is not limited to these Examples.

1 kyu (Preparation method of cerium oxide sol) Dissolve cerium nitrate in pure water to obtain 0.23 as CeO2.
An aqueous solution containing % by weight was obtained. While stirring this aqueous solution, 15% aqueous ammonia was gradually added to obtain a white-yellow slurry of 11H6,0. After filtering and washing, a cake of hydrous cerium oxide having a solid content concentration of 22% by weight was obtained. 435 g of this cake was dispersed in 2000 ml of pure water, a small amount of nitric acid was added thereto, and the mixture was heated at 98° C. for 5 hours to obtain a yellow translucent water-dispersed cerium oxide sol. After concentrating this to make a cerium oxide sol with a solid content concentration of 10% by weight, glycerin was added and water was distilled off by heating to obtain a glycerin-dispersed cerium oxide colloidal solution with a Ce content of 10% by weight. The average particle size of the particles was 5 mμ.

(Manufacture of lotion) A lotion having the following composition was manufactured according to the following procedure.

Glycerin dispersion colloidal solution 5.0% by weight propylene glycol 4. On oleyl alcohol 0.1 l Polyoxyethylene lauryl ether 0.5 II Ethanol 11.5 77 Fragrance 0.11 I pure
Water 78.
8H dye
Mix an appropriate amount of pure water with the glycerin-dispersed colloidal solution obtained as above and propylene glycol. Separately, a mixture of ethanol, oleyl alcohol, polyoxyethylene lauryl needle, and fragrance is prepared, and the pure water mixture is added thereto.

After adding dye to adjust the color, it is filtered and used as a product.

A portion of this lotion was taken and placed in a quartz cell with a thickness of III+, and the light transmittance from visible light to ultraviolet light was measured using a spectrophotometer (model 330, manufactured by Hitachi). The results are shown in Figure 2 ( Shown in curve a).

In addition, in order to evaluate light resistance, this lotion was sealed in a quartz cell, and the degree of discoloration of the lotion after being left exposed to sunlight for 30 days was observed. Similarly, the degree of discoloration was examined after irradiation with carbon arc light for 300 hours and after irradiation with xenon lamp for 300 hours.

The results are shown in Table 1 (sample a).

In place of the glycerin-dispersed cerium oxide colloidal solution in Example 1, a glycerin dispersion (Ti 0□10
All compositions were the same as in Example 1, except that % by weight) was used.
The light transmittance and light resistance of the lotion produced by the same method were evaluated in the same manner as in Example 1.

The results are shown in FIG. 2 (curve b) and Table 1 (sample b).

Table 1 The light resistance in Table 1 was evaluated by visually observing the degree of discoloration of the lotion, with no discoloration and O2 discoloration being evaluated as ×.

As can be seen from FIG. 2 and Table 1, it can be seen that the lotion of the present invention is significantly superior in ultraviolet shielding effect, particularly in the UV-A region, as well as in transparency and light resistance.

(Preparation method of cerium oxide coated fine powder) Cerium nitrate is dissolved in pure water and 5% by weight as CeO□
Next, add titanium oxide fine powder (Aerosil, P25, manufactured by Degussa Corporation) for 1 h to 100 ml of pure water and heat to 60°C while stirring well. Aqueous solution and 15% ammonia water at pH 8,
5 and was added until it reached 60% by weight as CeO□. After dehydrating, washing, and drying the shell, 60
It was fired at 0°C for 3 hours to obtain a cerium oxide-coated fine powder with an average particle size of 35 mμ.

(Manufacture of cream) Cerium oxide coated titanium oxide 5.8% by weight Pure water 52
．． 2n stearyl alcohol 5.
0 No I stearic acid 8.
0)1 Squalane 9.
5 No? Propylene glycol monostearate 3. Onol Polyoxyethylene Cetyl Ether 1. Q II Propylene Glycol 8.0 11 Glycerin 4.0 No I Triethanolamine 1.0 Heavy Plate% Beeswax 2. On fragrance
0.5 r-preservative After dispersing an appropriate amount of cerium oxide-coated fine powder in pure water, propylene glycol, glycerin, and triethanolamine are added and heated to 70°C (aqueous phase).

Separately, components other than the above are mixed and heated and melted at 70°C. This extracted phase was added to the aqueous phase, uniformly emulsified with a homomixer, and then cooled to 30°C to obtain cream (Sample C).

The obtained cream was applied to a thickness of 5 μm on a quartz plate.
After drying the soot for 15 minutes, use a spectrophotometer (Hitachi Model 330).
The absorbance in the ultraviolet region was measured.

The results are shown in Figure 3 (curve C).

In place of the cerium oxide coated fine powder of Example 2, 5.8% titanium oxide fine powder (Aerosil, p-25, manufactured by Degussa) was used.
Absorbance was measured using a cream (sample d) manufactured in the same manner and with the same composition as in Example 2, except that the weight percent was used. The results are shown in Figure 3 (curve d).

As is clear from Figure 3, cosmetics containing fine powder whose surface is coated with cerium oxide have a lower melanin pigmentation under ultraviolet light, especially on the skin, compared to cosmetics containing conventional fine powder of titanium oxide. It exhibits a significantly high absorbance value in the UV- region, which causes irradiation, and has an excellent UV-shielding effect even in the LJ V-B region. That is, it can be seen that the cosmetic composition of the present invention is excellent in both suntan prevention and sunburn prevention.

(Preparation method of cerium oxide-coated fine powder) Cerium whose surface was coated with 50 layers of CeO2 was prepared using the same method except that sericite was used instead of the titanium oxide fine powder of Example 2. Cyto fine powder was prepared. The average particle size was 10 μm.

(Manufacture of solid white powder) Cerium oxide-coated sericite 45.0% heavy weight
35. OB titanium oxide pigment
10.0 t+oxidized pigment (red)
1.4 Jr. I (black)
0.2
No I horn (yellow)
2,9 n stearyl alcohol 2. On lanolin
2.0 sorbitan fatty acid ester 0.5 u triethanolamine 1.0 t fragrance
Appropriate amounts of lanolin, sorbitan fatty acid ester, l-heliethanolamine, and fragrance are first heated and mixed at 70'C, and the remaining powder, which has been thoroughly mixed in advance, is added thereto and thoroughly mixed. This is press-molded to obtain a solid white powder sample e).

Solid white powder was prepared using the same composition and method as Sample e, except that sericite was used instead of the cerium oxide-coated sericite in Example 3 (Sample f).

These e, f and sample C of Example 2 and sample d of Comparative Example 2 were used as samples for the panel test. The results are shown in Table 2.

Table 2 shows that in Cream C and Solid White Powder E, which use fine titanium oxide powder and sericite powder and whose surfaces are coated with cerium oxide, no melanin pigmentation was observed, and they were excellent in erythema. In addition, it was found that the creams and solid white powders were excellent in lightness, spreadability, adhesion, and transparency, and compared with samples d and f, samples C and e were particularly superior in terms of ultraviolet shielding ability.

Kori■1 <Preparation method of hydrous cerium oxide fine powder> Dissolve cerium nitrate in pure water and add 5% by weight as CeO□.
An aqueous solution was obtained. While stirring this aqueous solution, 5% ammonia water was gradually added to obtain 1) a white-yellow slurry of H9.0. .3% by weight of hydrous cerium oxide was obtained.

This was added to pure water and well dispersed with a homomixer to obtain a slurry with a solid content concentration of 3.1% by weight. Spray this onto liquid nitrogen so that the average particle size of the droplets becomes 7 μm, and immediately freeze the sprayed droplets.

This was collected and freeze-dried to obtain hydrous cerium oxide with an average particle size of 70 mμ.

(Method for producing milky lotion foundation) A foundation having the following composition was produced according to the following procedure.

Hydrous cerium oxide fine powder 6.8% pure by weight
Water 61.
3 Nor triethanolamine 1,
1% by weight methyl paraoxybenzoate as appropriate Carboxymethylcellulose 0.2% by weight bentonite 0.5 Tunostearic acid 2.4 Propylene glycol Tunostearate 2. On Cetostearyl alcohol 0.2 Liquid paraffin 3.0 Liquid lanolin 2.0 Isopropyl myristate 8.5 71 Propyl paraoxybenzoate i Quantity Titanium oxide pigment 1.0% by weight Tal
the law of nature
11.0 Horn fragrance
Suitable: After dispersing hydrated cerium oxide fine powder in pure water, carboxymethyl cellulose is dispersed therein. Bentonite is added to this and heated to 70°C while stirring well to swell the bentonite well.

Next, to this liquid, triethanolamine, oxyammonium,! Add methyl disozate. Add the pigment and pulverized mixture of Yuruk to this, disperse well with a colloid mill, and heat to 75°C.

Separately, prepare a mixture of stearic acid, propylene glycol monostearate, cetostearyl alcohol, liquid paraffin, in-10-bill myristate, and propyl paroxybenzoate, heat to 80°C, mix with the above dispersion mixture, and stir thoroughly. . Thereafter, the mixture is cooled, a fragrance is added at 45°C, and the mixture is stirred and cooled to room temperature.

The obtained milky lotion foundation (sample g) was used by a female panelist, and its feeling of use, melanin pigmentation, and light resistance were evaluated.

The results are not shown in Table 3.

Arashitsuketsu A A milky lotion foundation (sample h ) was produced and evaluated for feel on use, melanin pigmentation, and light resistance.

The results are not shown in Table 3.

Table 1 (Preparation method of cerium oxide coated fine powder) An average of 5% by weight of CeO2 coated on silica using the same method except that commercially available silica fine powder was used instead of the titanium oxide fine powder of Example 2. A fine powder with a particle size of 8 mμ was prepared.

(Production of solid white powder) In place of the cerium oxide-coated sericite of Example 3, the amount of fine powder added in this example was 15% by weight, 30% by weight of talc, and 35% by weight of sericite. Other than that, solid white powder was made using the same composition and method.

As in Example 3, the obtained white powder had excellent effects on erythema and melanin pigmentation, and was also excellent in spreadability and feel on use.

Fire 1st discharge (preparation method of cerium oxide coated fine powder) CeO□ was applied to sabonite using the same method except that plate-shaped sabonite was used instead of the titanium oxide fine powder of Example 2.
A fine powder coated with 70% by weight was prepared. The fine powder had a thickness of 0.05 μm and a length of 1 μm.

(Manufacture of milky lotion foundation) Except that the fine powder of this example was used instead of the hydrous cerium oxide of Example 4, and the amount added was 10% by weight, and the amount of talc added was changed to 7.8% by weight. made a milky lotion foundation with exactly the same composition and method.

The obtained foundation had the same excellent feel as in Example 4, no melanin pigmentation, and excellent light resistance.

(Preparation method of cerium oxide coated fine powder) Zinc oxide was coated with carbon in the same manner except that the zinc oxide fine powder of Comparative Example 4 was used instead of the titanium oxide fine powder of Example 2.
A fine powder coated with 35% by weight of eO7 was prepared.

The particle size of the fine powder was 220 mμ.

(Manufacture of cream) A cream was made using the same composition and method as in Example 2, except that the cerium oxide powder of this example was used instead of the cerium oxide powder of Example 2. Obtained.

Apply this cream to a thickness of 5 μm on a quartz plate,
After drying for several minutes, the absorbance in the ultraviolet region was measured using a spectrophotometer (330J!
).

Hiei Example 5 Absorbance was measured using a cream manufactured in the same manner and with the same composition as in Example 7, except that zinc oxide (Comparative Example 4) was used instead of the cerium oxide coated VGI fine powder in Example 7. It was measured. The results are shown in Figure 4 (curve j).

(Preparation method of cerium oxide-coated fine powder) The surface was coated with CeO2 in the same manner as in Example 2, except that commercially available aluminum oxide was used instead of the titanium oxide fine powder in Example 2. A 60% by weight coated aluminum oxide powder was prepared and the average particle size of the powder was 100 mμ.

(Lipstick manufacturing method) A lipstick having the following composition was manufactured by the following procedure.

Base material Cerium dioxide coated alumina 3.0% by weight Castor oil 47.671 Hexadecyl alcohol 22.5 n Lanolin 3.
6 II Beehive
4.5 H Osigerite
3.6 77 Kyandelira Row
6.3〃Carnauba wax 1.8〃Antioxidant, preservative Suitable Indigo color material: Titanium oxide pigment 1.8% by weight Red No. 202
0.51fLj1% red No. 205
2.3 Horn red No. 227 A Ruki 2.3
TR Toiro No. 201 0.21 no incense
After heating and melting all of the refractory materials except for the cerium oxide-coated alumina and mixing them uniformly, the cerium oxide-coated alumina is mixed and stirred well. Pass through a colloid mill to further disperse. Add coloring material to this, knead with a roll mill,
After uniformly dispersing it, it is remelted, flavoring is added, it is redispersed in a colloid mill, it is defoamed, it is poured into a mold, and it is cooled and solidified. Remove the solidified material from the mold and load it into a container.

The obtained lipstick had an excellent finish, ultraviolet shielding effect, and light resistance.

[Brief explanation of the drawing]

FIG. 1 is a curve showing the light transmittance of fine particles (A to F) according to the present invention and the light transmittance of a conventionally known fine titanium oxide powder (G). FIG. 2 is a diagram showing the light transmittance of a lotion containing fine particles according to the present invention (curve a) and the light transmittance of a conventional lotion containing fine particles (curve b). FIG. 3 is a diagram showing the absorbance of a cream containing microparticles according to the present invention (curve C) and the absorbance of a cream containing conventionally known 81t'16 molecules (curve d). FIG. 4 is a diagram showing the absorbance (curve 1) of a cream containing RA particles according to the present invention and the absorbance (curve 1) containing conventionally known fine particles.
) 4 Figure 1 Figure 2 Wavelength (nm) Figure 3 Wavelength (nm)

Claims (2)

[Claims] (1) A cosmetic composition containing at least 0.1% by weight of cerium oxide and/or hydrous cerium oxide as CeO_2. (2) A cosmetic composition comprising at least 0.1% by weight of CeO_2 of fine particles whose surfaces are coated with cerium oxide and/or hydrous cerium oxide.