JPH08175949A - Ultravoilet light controlling agent and cosmetic containing the same - Google Patents

Abstract

PURPOSE: To obtain an ultraviolet light controlling agent having excellent ultraviolet light screening effect, comprising a swelling lamellar silicate mineral containing a specific amount of iron in a crystal structure and between layers and to provide a cosmetic containing the ultraviolet light controlling agent. CONSTITUTION: This ultraviolet light controlling agent comprises a swelling lamellar silicate mineral which contains at least 7wt.%, preferably >=10wt.% calculated as ferric oxide of iron in a crystal structure and between layers and has <=50μm particle diameter alone or a mixture of two or more of swelling lamellar silicate minerals. The swelling lamellar silicate mineral is obtained by sieving a natural swelling lamellar silicate mineral with water and bentonite may be cited as the swelling lamellar silicate mineral. The ultraviolet light controlling agent comprising the swelling lamellar silicate mineral is used an active ingredient and an anti-suntan cosmetic containing 0.05-50wt.% of the ultraviolet light controlling agent can be prepared. The ultraviolet light controlling agent is fine particles, has excellent dispersibility, has chemical stability, is hardly denatured, has swelling properties and thickening action. The ultraviolet light controlling agent having uniform particle diameters and shapes of particles is obtained at a low cost.

Description

Detailed Description of the Invention

[0001]

BACKGROUND OF THE INVENTION 1. Field of the Invention The present invention relates to an ultraviolet protective agent having a swellable layered silicate mineral, and a cosmetic containing the ultraviolet protective agent, which is excellent in the protective effect against ultraviolet rays which adversely affects the skin.

[0002]

2. Description of the Related Art Ultraviolet rays have an adverse effect on human skin such as suntan, sunburn, photosensitivity dermatitis, acceleration of skin aging, and skin cancer. In recent years, such things have been generally recognized widely, and it has been attempted to impart an ultraviolet ray preventing function to various things such as cosmetics and clothes. Conventionally, sunscreen cosmetics have been prepared by adding an inorganic UV scattering agent made of inorganic powder such as titanium oxide or iron oxide or an organic UV absorber made of phenolic substance having a conjugated double bond. It is performed to give an ultraviolet ray protection effect.

[0003]

However, the conventional sunscreen cosmetics are not sufficiently effective against strong ultraviolet rays,
Inorganic powder is being made into fine particles in order to enhance the UV protection effect.However, as the above-mentioned inorganic powder becomes finer, the elongation becomes heavier, which deteriorates the usability of cosmetics and makes the particles finer. It causes problems such as later re-aggregation and reduction of light resistance due to photocatalytic activity. Further, in the case of an organic ultraviolet absorber, there is a problem in that the amount that can be dispersed is limited in terms of formulation. Further, conventionally used organic and inorganic UV protection agents have problems that the manufacturing process is generally complicated and costly. For this reason, the cost is relatively low, the raw materials are easily available, the anti-UV effect is excellent, it is chemically stable, and it is compounded in various types and forms of materials to prevent formulation restrictions. The development of a new UV protection agent that is difficult to receive has been desired. Further, it has been desired to develop a sunscreen cosmetic having an excellent effect of preventing ultraviolet rays as well as excellent usability and dispersion stability and having the above-mentioned conventional ultraviolet protective effect.

[0004]

Means for Solving the Problems As a result of intensive studies conducted by the present inventors in order to overcome the drawbacks of the conventional UV protectants, the swellable layered structure containing a predetermined amount of iron in the crystal structure and between the layers. Silicate minerals show high UV protection,
And, it is stable as a compound having an iron content in the crystal structure or between the layers, and further, the dispersibility in the medium, the dispersion stability is also excellent, it was found that the above objects can be achieved, the present invention based on this finding I arrived.

That is, the present invention provides (1) an ultraviolet protective agent comprising a swellable layered silicate mineral having at least 7% by weight of ferric oxide in terms of iron structure in the crystal structure and between layers, (2) The swellable layered silicate mineral contains 10% by weight or more of iron in terms of ferric oxide, and the ultraviolet protection agent according to item (1), (3) the swellable layered silicate mineral is natural The ultraviolet protective agent according to (1) or (2), which is obtained by elutriating a swelling layered silicate mineral, and (4) a swelling layered silicate in which the swelling layered silicate mineral is natural. The ultraviolet protection agent according to item (1) or (2), which is obtained by pulverizing and refining a salt mineral, and (5) the swellable layered silicate mineral has a particle size of 50 μm or less ( The ultraviolet protector according to item 4), and (6) the swellable layered silicate mineral is bentonite (1 , (2), (3), (4) or (5) item, the ultraviolet protective agent, (7) at least 7% by weight of ferric oxide in terms of iron content in the crystal structure and between layers having a swellable layer (8) A swellable layered silicate mineral containing 10% by weight or more of iron content in terms of ferric oxide (8) A cosmetic for protecting ultraviolet rays characterized by containing a silicate mineral. The cosmetic for ultraviolet protection according to item 7), wherein the swellable layered silicate mineral of (9) is obtained by elutriating a natural swellable silicate mineral, (7) or (8) The cosmetic for ultraviolet protection according to (10), wherein the swellable layered silicate mineral is obtained by pulverizing and refining a natural swelling layered silicate mineral, followed by refining (7) or (8). (11) The cosmetic for ultraviolet protection according to (11), wherein the swellable layered silicate mineral has a particle size of 50 μm or less. UV protective cosmetic composition according, and (12) swellable layered silicate mineral is bentonite (7), (8), (9), (1
The object of the present invention is to provide the ultraviolet protective cosmetic composition according to item (0) or (11).

In the present specification, the content in terms of ferric oxide is the content of iron in the ore analyzed as ferric oxide by the pyroxene analysis method according to JIS M8855. Therefore, not only the content of iron ore contained from the beginning as ferric oxide, but also the content of all other iron converted to ferric oxide and analyzed. In the ultraviolet protection agent of the present invention, the content of iron in the swelling layered silicate mineral in terms of ferric oxide (Fe ₂ O ₃ ) (hereinafter, simply referred to as the content of ferric oxide) is at least 7 weight. %, And if the content of ferric oxide is less than 7% by weight, the scattering of ultraviolet rays is insufficient and it cannot be used as an ultraviolet protective agent. The content of ferric oxide is preferably 10% by weight or more, more preferably 11% by weight or more. There is no particular upper limit, and it may be contained up to the maximum amount that can be contained in the crystal structure or between layers, but if it is contained in too much amount, the ultraviolet scattering action will be saturated and will not change, so it is set to 20% by weight or less. Is preferred. In the ultraviolet protective agent of the present invention, the swellable layered silicate mineral may be used alone or in combination of two or more. When two or more kinds are mixed, the content of ferric oxide as a whole average may be within the above-specified range. For example, even if the content of ferric oxide is less than 7% by weight, the total average is 7% by weight. It should be at least%. Swellable layered silicate mineral containing such iron content in the crystal structure and between layers is preferably a purified product of natural swellable layered silicate mineral,
As a production method thereof, for example, bentonite ore, particularly bentonite ore produced in Gujarat, India, can be obtained by elutriation. Examples of such natural swellable layered silicate minerals include montmorillonite containing iron, saponite, hectorite, nontronite, and the like.

In the case of purifying this with elutriation, after swelling the raw ore of the swelling layered silicate mineral with water, quartz,
Shale, slate, etc. are removed by natural precipitation separation and further operations such as centrifugation are performed to separate foreign particles such as finely divided silica and iron oxide mixed from the obtained slurry, and the obtained slurry is dried and then Crush to obtain a purified swellable layered silicate mineral. The conditions for elutriation are not particularly limited, but the pH of water is 8 to 11, and the temperature is 1 to 40 ° C.
Done in.

As another production method of the present invention, after the raw ore of the swellable layered silicate mineral is dried without being dispersed in water,
It is also possible to carry out crushing by impact crushing method, crushing crushing method, airflow crushing method, etc., and carrying out purification and crushing simultaneously. In this method, pulverization is performed, and classification is performed according to the particle size according to the difference in specific gravity of minerals for purification. To describe the preferred embodiment of this method, from the bottom to the top to the ground minerals, or
By sending the wind in the horizontal direction and adjusting the balance between the wind pressure and the difference in the specific gravity of the minerals by utilizing the difference in the specific gravity of the minerals, the particles having a particle size of 50 μm or less can be fractionated and purified. Drying is 80 ° C. or higher, preferably 100-
20% by weight or less of the layered silicate mineral at 200 ° C,
It is preferably performed until it becomes 10% by weight or less. This is crushed using an impact crusher, a grinding crusher, an airflow crusher, or the like. Upon pulverization, the particle size is preferably 50 μm or less, and particularly preferably 0.1 to 20 μm. By this pulverization, contaminants such as quartz, opal, feldspar, and mica can be removed by 10 to 40% by weight, but if the refining accuracy is lower than this, the particle size of the pulverized and refined product becomes large and the content of the contaminants increases, which is desirable. Absent. If the particle size of the pulverized and refined product obtained in this manner is too large, the effect of preventing ultraviolet rays deteriorates, and the feeling of use when blended in cosmetics and the like may deteriorate. According to this method, it is possible to easily obtain a fine powder of an ultraviolet protective agent having a uniform particle size and particle shape.

The UV protective agent of the present invention is excellent in UV blocking effect, fine particles, excellent in dispersibility (dispersion stability), and has iron content in the crystal structure and between layers, so that it is chemically stable and deteriorates. It has the property of being difficult. This UV protection agent can be used in various applications such as cosmetics, resins, paints and fibers. In addition, since the product purified by pulverization after drying is fine particles, the particle size and the particle shape are uniform, and therefore, in terms of the UV protection effect and in terms of feeling when used in cosmetics and the like. , Very good. The ultraviolet protection agent used in the present invention is particularly preferably used in cosmetics. The blending amount of the UV protective agent with respect to the cosmetic may be appropriately changed depending on the dosage form of the intended cosmetic and the expected amount of UV cut, and is not limited, but is usually 0.05 to 50% by weight in the total amount of the cosmetic. %, Preferably 0.5 to 30% by weight, particularly preferably 1 to 20% by weight.

Further, regarding the cosmetics containing the ultraviolet protective agent of the present invention, oil, wax, pigment, surfactant, preservative, dye, oxidative protective agent in addition to the ultraviolet protective agent of the present invention,
Ingredients generally used as cosmetics, such as fragrances, humectants, chelating agents, acids, alkalis, water-soluble polymers, oil-soluble polymers, clay minerals, and other UV protective agents can be added. The cosmetics of the present invention include sun oil, suntan lotion, sunscreen, sunscreen in stick form, sunscreen lip balm, suncalamine,
Widely applied as sun jelly, sunscreen cream, sunscreen lotion, sunscreen water white powder, foundation lotion, makeup base, hairnic, hair liquid, etc.

[0011]

EXAMPLES Next, the present invention will be described in more detail based on examples. Example 1 (Production of UV protection agent by elutriation refining) As a swellable layered silicate mineral, bentonite ore from Gujarat, India (ferric oxide content 14.3% by weight) (prepared by Kunimine Industries Co., Ltd.) 3 kg was placed in a 50-liter beaker, water was added to make the total amount 30 kg, and the mixture was left for 24 hours to swell the bentonite raw ore. Then, after stirring for 30 minutes using a stirrer, the mixture was allowed to stand for 20 hours, the precipitate was removed by decantation, the fine silica particles and foreign substances were removed by a centrifugation operation, and the obtained supernatant liquid was
The solid matter obtained was dried at 05 ± 5 ° C., and pulverized to obtain 95 g of elutriated purified bentonite having a particle size of 74 μm and a ferric oxide content of 11.6% by weight. This purified bentonite has a concentration of 0.125% and is suspended in water at a wavelength of 30.
The light transmittance at 0 to 500 nm is recorded by a self-recording spectrophotometer U-
It was measured with 3200 (manufactured by Hitachi Ltd.). The results are shown in Table 1.
It was shown to.

[0012]

[Table 1]

From the results shown in Table 1, it can be seen that the ultraviolet protection effect of the present invention exhibits a remarkably high ultraviolet protection effect.

Example 2 (Production of UV protection agent by mixture of elutriation refining) Purified bentonite obtained in Example 1 (ferric oxide content 1
1.6% by weight) and the elutriated product of bentonite from Wyoming, USA (ferric oxide content 3.1% by weight) were mixed at a ratio of 1: 1 to obtain a mixture. The content of ferric oxide in this mixed product was measured to be 7.1% by weight. The light transmittance of this mixed product was measured in the same manner as in Example 1. The results are shown in Table 2.

[0015]

[Table 2]

From the results shown in Table 2, it can be seen that even a mixed product can be made to have an excellent ultraviolet protection effect by setting the ferric oxide content to 7% by weight or more.

Example 3 (Production of UV protection agent by impact crushing purification) 1 kg of bentonite ore from Gujarat, India, which was the same as that used in Example 1, was blown by a blower dryer at 105 ±.
Dry at 5 ° C until the water content becomes 8%, crush this with an impact crusher KII-1 (manufactured by Fuji Paudal Co., Ltd.), and at the same time the mineral comes into contact with the rotating hammer, at the same time contaminants are generated by the wind pressure of the rotating hammer. And bentonite 910 having a particle size of 48 μm and a ferric oxide content of 11.8% by weight
g was obtained (purity was 95% by removing 15% of impurities such as quartz, gypsum, mica, and feldspar). The light transmittance of this purified bentonite was measured in the same manner as in Example 1. Table 3 shows the results.

Example 4 (Production of UV protection agent by air flow crushing and refining) 100 g of the purified bentonite obtained in Example 3 was further crushed and purified by an air flow crusher FS-4 (manufactured by Seishin Enterprise Co., Ltd.) to have a particle size of 1 92 g of purified bentonite having a ferric oxide content of 11.8% by weight of 0.5 μm were obtained. The light transmittance of this purified bentonite was measured in the same manner as in Example 1.
Table 3 shows the results.

[0019]

[Table 3]

From the results shown in Table 3, it can be seen that the purified bentonite obtained by pulverizing after drying according to the present invention also has a remarkably high ultraviolet protection effect. Further, it can be seen that the ultraviolet protection effect of the product of the present invention when purified by pulverization after drying increases as the particle size decreases.

Example 5 (Production of UV protection agent by grinding and refining the mixture) The same bentonite ore from Gujarat, India as used in Example 1 and bentonite ore from Wyoming, USA (second oxide) Iron content (6.1% by weight) was mixed at a ratio of 1: 1 to obtain 1 kg of a mixed product, and the mixture was heated to 105 ± 5 using a blower dryer.
Dry at ℃ until the water content becomes 7.5%, crush it with a grinding mill cup mill (made by FRITSH), and crush the minerals between the wall of the crushing chamber and the rollers and pass through a sieve. 835 g of purified bentonite having a particle size of 22.8 μm and a ferric oxide content of 7.1% by weight (12% of impurities such as quartz, gypsum and cristobalite are removed, and a purity of 90) %Met.). The light transmittance of this purified bentonite was measured in the same manner as in Example 1. The results are shown in Table 4.

[0022]

[Table 4]

Comparative Example 1 Kunipia (trade name, ferric oxide content 1.9, which is a bentonite elutriated product containing montmorillonite as a main component)
% By weight, manufactured by Kunimine Industry Co., Ltd. and bentonite from Wyoming (purified according to Example 1. Ferric oxide content 3.1% by weight). Measured. The results are shown in Table 5.

[0024]

[Table 5]

From Table 5, it can be seen that this product has a low ultraviolet protection effect.

Example 6 (Addition of UV protection agent to cream foundation by elutriation refining) The elutriation-refined bentonite (ferric oxide content 11.6% by weight) obtained in Example 1 was used in the following composition. According to the method, it was kneaded with a roll mill to obtain a uniformly dispersed foundation. (Wt%) Elutriation purified bentonite prepared in Example 1 5.2 Liquid paraffin 15.0 Propylene glycol monostearate 6.0 Stearic acid 2.5 Sodium lauryl sulphate 1.1 Triethanolamine 1.3 Pigment 11. 0 Purified water 53.1 Bentonite 4.7 Methyl paraoxybenzoate 0.1 Perfume Appropriate amount The amount of foundation obtained was 0.07% and 0.
The UV transmittance of a suspension of 17% in water was measured at a wavelength of 300 nm. For comparison, the ultraviolet transmittance of a commercially available sunscreen emulsion (containing oxybenzone) was also measured in the same manner. Table 6 shows the results. Further, since the foundation had a soft feel and light weight, it had a uniform color tone and was stable without aggregation or sedimentation of the pigment or dispersed particles.

[0027]

[Table 6]

From Table 6, it can be seen that the product of the present invention is remarkably excellent in the ultraviolet protection effect as compared with the commercially available product.

Example 7 (Blending of UV protection agent to cake-like foundation by elutriation refining mixture) After mixing the components in the following formulation with a Henschel mixer, 3
The mixture was kneaded by this roll mill to prepare a foundation containing the elutriated bentonite obtained in Example 2 (ferric oxide content: 7.1% by weight). (% By weight) Elutriation purified bentonite prepared in Example 2 25.0 Liquid paraffin 10.0 Sorbitan sesquistearate 3.5 Bengala 0.8 Yellow iron oxide 2.5 Black iron oxide 0.1 Talc 45.1 Oxidation Titanium 10.0 Dipropylene glycol 3.0 Fragrance Appropriate amount The ultraviolet transmittance of the obtained foundation was measured in the same manner as in Example 6. The results are shown in Table 7. Also,
The foundation was non-greasy, had a smooth, light spread, could be smoothly spread, and had a smooth feel.

Example 8 (Composition of UV protection agent in cake-like foundation by elutriation purification) After mixing each component in the following composition with a Henschel mixer, 3
The mixture was kneaded with this roll mill to prepare a foundation containing the elutriated refining bentonite obtained in Example 1 (ferric oxide content: 11.6% by weight). (Wt%) Elutriation purified bentonite prepared in Example 1 25.0 Titanium oxide 10.0 Talc 45.1 Red iron oxide 0.8 Yellow iron oxide 2.5 Black iron oxide 0.1 Liquid paraffin 10.0 Sesquioleic acid Sorbitan 3.5 Glycerin 3.0 Fragrance Appropriate amount The UV transmittance of the obtained foundation was measured in the same manner as in Example 6. The results are shown in Table 7. Also,
This foundation had a light feel and a smooth feel even when it was not used in the sponge when it was used.

Example 9 (blending of UV protective agent into cream-like foundation by air flow pulverization and refinement) The pulverized and refined bentonite obtained in Example 4 (ferric oxide content: 11.8% by weight, particle size: 1.5 μm) Was kneaded by a roll mill with the following composition by a conventional method to obtain a uniformly dispersed foundation. (Wt%) Pulverized bentonite prepared in Example 4 5.2 Liquid paraffin 15.0 Propylene glycol monostearate 6.0 Stearic acid 2.5 Sodium lauryl sulphate 1.1 Triethanolamine 1.3 Pigment 11.0 Purified water 53.1 Bentonite 4.7 Methyl paraoxybenzoate 0.1 Perfume A suitable amount The ultraviolet transmittance of the obtained foundation was measured in the same manner as in Example 6. The results are shown in Table 7. Also,
Since the foundation had a soft and light feel, it had a uniform color tone and was stable without aggregation or sedimentation of the pigment or dispersed particles.

Example 10 (Blending of UV-protective agent into cake-like foundation by impact crushing and refining) After mixing the components in the following formulation with a Henschel mixer, 3
The mixture was kneaded with this roll mill to prepare a foundation containing the pulverized and refined bentonite obtained in Example 3 (ferric oxide content 11.8% by weight, particle size 48 μm). (Wt%) Milled and purified bentonite prepared in Example 3 25.0 Titanium oxide 10.0 Talc 45.1 Red iron oxide 0.8 Yellow iron oxide 2.5 Black iron oxide 0.1 Liquid paraffin 10.0 Sorbitan sesquioleate 3.5 Dipropylene glycol 3.0 Fragrance An appropriate amount of the obtained foundation was measured for ultraviolet transmittance in the same manner as in Example 6. The results are shown in Table 7. Also,
This foundation had no sticky feeling, could be smoothly spread with a light, light spread, and had a smooth feel.

[0033]

[Table 7]

From Table 7, the ultraviolet protection cosmetic composition of the present invention is
It can be seen that both have excellent UV protection effects.

[0035]

The UV protective agent of the present invention is excellent in UV blocking effect, fine particles, excellent in dispersibility (dispersion stability), and has an iron content in the crystal structure and between layers, so that it is chemically stable and hardly deteriorates. It has the property of Furthermore, since it is composed of a swellable layered silicate mineral, it exhibits excellent effects such as fine particles having a swelling property and also having a thickening property.
Moreover, according to the method of the present invention, it is possible to obtain a fine powder of an ultraviolet protective agent having a uniform particle size and particle shape at a low cost. In addition, the cosmetic of the present invention is excellent in UV protection effect as well as usability and dispersion stability.

Claims (12)

[Claims] 1. An ultraviolet protection agent comprising a swellable layered silicate mineral having an iron content of at least 7% by weight in terms of ferric oxide in and between crystal structures. 2. The ultraviolet protection agent according to claim 1, wherein the swellable layered silicate mineral contains 10% by weight or more of iron as calculated as ferric oxide. 3. The ultraviolet protection agent according to claim 1, wherein the swellable layered silicate mineral is obtained by elutriating a natural swellable layered silicate mineral. 4. The ultraviolet protective agent according to claim 1, wherein the swellable layered silicate mineral is obtained by drying and then pulverizing and refining a natural swellable layered silicate mineral. 5. The swellable layered silicate mineral has a particle size of 50 μm.
The ultraviolet protective agent according to claim 4, which is as follows. 6. The ultraviolet protection agent according to claim 1, wherein the swellable layered silicate mineral is bentonite. 7. A cosmetic composition for protecting ultraviolet rays, which comprises a swellable layered silicate mineral having an iron content of at least 7% by weight in terms of ferric oxide in the crystal structure and between layers. 8. The ultraviolet protection cosmetic composition according to claim 7, wherein the swellable layered silicate mineral contains an iron content of 10% by weight or more in terms of ferric oxide. 9. The swellable layered silicate mineral is obtained by elutriation of a natural swellable silicate mineral.
The cosmetic for protection against ultraviolet rays according to. 10. The cosmetic composition for protecting ultraviolet rays according to claim 7, wherein the swelling layered silicate mineral is obtained by drying and pulverizing and refining a natural swelling layered silicate mineral. 11. The particle diameter of the swellable layered silicate mineral is 50 μm.
The ultraviolet protection cosmetic composition according to claim 10, which has a thickness of m or less. 12. The ultraviolet protective cosmetic composition according to claim 7, wherein the swellable layered silicate mineral is bentonite.