JPH0655664B2 - Beautiful skin cosmetics - Google Patents

Description

DETAILED DESCRIPTION OF THE INVENTION The present invention relates to cosmetics containing isoferulic acid and / or its derivatives.

More specifically, the present invention, by the action of isoferulic acid or a derivative thereof, prevents whitening due to ultraviolet rays, has a whitening effect by inhibiting thyrodinase activity and an effect of reducing stains and freckles, and further suppresses the acceleration of skin aging by light. The present invention is intended to provide a new skin cosmetic composition that can be used.

In general, when the skin is exposed to excessive ultraviolet rays in the open air, sunburn occurs within a few hours after exposure to sunlight and causes blistering when it becomes severe. Furthermore, pigmentation subsequently occurs. Thus, excessive UV exposure is extremely harmful from the aesthetic point of view and the health of the skin.

And, so far, as the main cause of the above-mentioned symptoms, among the ultraviolet rays reaching the ground, medium wavelength ultraviolet rays of 290 to 320 nm (hereinafter referred to as UV-B), particularly ultraviolet rays in the vicinity of 305 to 310 nm which are most involved in "erythema inducing". The emphasis has been placed on how to prevent this.

However, recently, the harmful effects of long-wavelength ultraviolet rays of 320 to 400 nm (hereinafter referred to as UV-A) have been clarified. For example, irradiation with UV-A before and after irradiation with UV-B causes erythema of UV-B. Noh promotion, UV-
Since A reaches the inside of the dermis, aging of the skin due to a long-term effect on the intradermal components (collagen, glycosaminoglycan, etc.) has become known.

Many ultraviolet absorbers have been developed in order to prevent the ultraviolet rays, but in reality, few of them have the effects and safety as well as the stability and solubility as a cosmetic raw material. That is, the ultraviolet absorbers that have been used before in Japan are roughly classified into benzophenone type, urocanic acid type, p-aminobenzoic acid type, cinnamic acid type, and others (salicylic acid type, benzotriazole type, etc.). However, for example, benzophenone type has a wavelength of 280 to 290 nm and 3
It has an absorption maximum around 20 to 330 nm and is one of the widely used raw materials, but on the other hand, it is most involved in the induction of erythema.
It has a characteristic that the absorption power in the vicinity of 05 to 310 nm is relatively low. Further, the urocanic acid type is a biological component and is highly safe, but its absorption maximum is around 280 to 290 nm, so that it has a low practical effect particularly for UV-A. p
-Aminobenzoic acid type and cinnamic acid type have maximum absorption of 300-
It is around 310 nm and has a high absorption effect, but it was said to have a safety problem such as contact photosensitivity. Further, the benzotriazole type has a drawback that it is not allowed to be incorporated into cosmetics from the viewpoint of safety, and the salicylic acid type has a weak absorption effect, and it is difficult to maintain the function as a sunscreen unless a large amount is incorporated.

In this way, since the safety of the ultraviolet absorber is emphasized in Japan, the actual amount of the ultraviolet absorber used is regulated to 4 to 5% or less.

Therefore, for high SPF products desired by consumers, inorganic powder such as titanium oxide which physically reflects and scatters ultraviolet rays is often used in combination, but in this case, the dosage form that can be blended is limited, Moreover, it may be unsuitable for lotion type or oil type products, since the feeling of use during application may deteriorate.

Therefore, in view of the above-mentioned conventional problems, the present inventor is truly safe and excellent in the effect side, and as a cosmetic raw material, to find a material having both stability and solubility, as a result of repeating various exploratory experimental studies, An isoferulic acid-based compound, which has never been used practically in cosmetics and was not known for its effect on the skin, is 290-330 nm.
The present invention has been completed by finding that it has a large ultraviolet ray absorbing effect in the vicinity and is optimal as an ultraviolet ray absorbent for cosmetics, and that it has a large thyrodinase activity inhibitory effect in the skin and is excellent in whitening effect. Came to.

That is, the present invention, as an active ingredient, the general formula (I) (In the formula, R represents hydrogen or a linear, branched, cyclic, or polycyclic alkyl group, alkenyl group, aryl group, and alkali metal, alkaline earth metal, or quaternary amine.) The present invention relates to a cosmetic for beautiful skin, which comprises an acid and / or a derivative thereof.

The present invention will be described in detail below.

The isoferulic acid used in the cosmetic for beautiful skin of the present invention is a substance represented by the general formula (I) (R is hydrogen), and as its name implies, is a structural isomer of ferulic acid. Ferulic acid has been used in cosmetics so far, and is a useful substance having an antioxidant effect on oils and fats, an ultraviolet absorbing effect, and the like. However, ferulic acid is also shown in its ultraviolet absorption property in, for example, handbook, cosmetics / pharmaceutical raw material, revised edition (edited by Nikko Chemicals Co., Ltd., Nippon Surfactant Industry Co., Ltd., published February 1, 1977), page 496. As described above, the absorption maximums in the cis form are 316 to 317 nm (in ethanol), and the absorption maximums in the trans form are 236 nm and 322 nm (in ethanol), which are effective as UV absorbers for UV-A. However, it had a relatively weak effect on UV-B.

On the other hand, isoferulic acid has never been practically used in cosmetics until now, but as shown in the ultraviolet absorption spectrum (see FIG. 1) described later, 295 nm and 3
It has an absorption maximum around 20 nm (in ethanol) and shows an absorption pattern similar to that of benzophenone-based UV absorbers, and moreover, the absorption capacity in the "erythema-inducing" region (305-310 nm) like benzophenone-based UV absorbers. From the fact that there was almost no decrease, it was revealed by the experiments of the present inventor that the erythema-suppressing effect and the increase in the number of melanocytes when irradiated with ultraviolet rays are excellent.

Similarly, the experiments conducted by the present inventor also revealed that isoferulic acid has a tyrosinase activity inhibitory action, and was also proved to be useful for the whitening effect as well as the reduction of spots and freckles.

Isoferulic acid is generally a pale yellow to white needle-like or powdery crystal, is easy to handle, has no odor, and is hardly soluble in cold water, vegetable oil such as olive oil and soybean oil, and esters. Since it is slightly soluble in alcohol, it is soluble in alcohols and polyhydric alcohols, so that it can be applied to a wide range of dosage forms when used as a cosmetic ingredient.

On the other hand, in the cosmetic for beautiful skin of the present invention, isoferulic acid may be used as its salt. When used as a salt, the solubility in water is increased, which is particularly preferable for use in lotion and the like. When using isoferulic acid as a salt, the basic substance for forming the salt, lithium hydroxide, sodium hydroxide, potassium hydroxide, magnesium hydroxide, calcium hydroxide, inorganic bases such as ammonium hydroxide, arginine, lysine, Basic amino acids such as histidine and ornithine, and organic bases such as monoethanolamine, diethanolamine and triethanolamine are used. The above-mentioned salt may be prepared in advance and then added, or the salt-forming components may be added separately and reacted in the formulation system to form a salt.

Furthermore, isoferulic acid can also be used as its ester. By using it as an ester, the solubility in oily components is improved, and it becomes suitable for use in cosmetic oils and the like. The method itself for esterifying isoferulic acid can be produced by a known method such as an acid halide method, an acid anhydride method, a direct method, or a DCC method. The properties of the isoferric acid ester derivative vary depending on the type of alcohol used for esterification.
A wide range of transition from viscous oil to oil. In addition, the ultraviolet absorption characteristics of these isoferric acid ester derivatives generally shift the absorption maximum toward the longer wavelength side (red shift) by 3 to 4 nm as compared with that of isoferric acid.

Specific examples of such an isoferric acid ester derivative include:
Isoferulic acid such as ethyl isoferric acid, 2-ethylhexyl isoferric acid, allyl isoferric acid, cetyl isoferric acid, oleyl isoferric acid, phenyl isoferric acid, menthyl isoferric acid, cholesteryl isoferric acid and linear, branched, cyclic, polycyclic Ester compounds with alkyl, alkenyl, and aryl alcohols.

In the cosmetic for beautiful skin of the present invention, any one kind or two or more kinds can be selected and used from the group consisting of isoferulic acid and its derivatives. The blending ratio is selected to be 0.01% by weight or more, and a particularly preferable amount is 0.5% by weight or more based on the whole cosmetic. Even if the amount is more than 10% by weight, there is almost no change in the effect, so it is not necessary to exceed 10% by weight.

The cosmetic base used in the skin-care cosmetic of the present invention may be any base as long as it is a base normally used in skin-care cosmetics, and is not particularly limited. Specific dosage forms include cream, ointment, emulsion, lotion, oil, pack and the like. For example, as a cream base, beeswax,
As a lotion base such as cetyl alcohol, stearic acid, glycerin, propylene glycol, propylene glycol monostearate, polyoxyethylene cetyl ether, oleyl alcohol, ethanol, propylene glycol, glycerin, lauryl ether, sorbitan monolaurate ester, etc. Can be mentioned.

The skin-care cosmetic of the present invention may be prepared as a cosmetic in a suitable form such as cream, emulsion or lotion by a conventional method using these raw materials appropriately. Incidentally, in the cosmetic for beautiful skin of the present invention,
In contrast to the above-mentioned usual cosmetic bases, if necessary, ultraviolet absorbers other than isoferulic acid and its derivatives, ultraviolet scattering agents typified by particulate titanium oxide, allantoin, various medicinal ingredients such as placenta extract, and other thickeners , Plasticizers, calamines, pigments, antioxidants, chelating agents, fragrances and the like can be added.

Next, in order to explain the usefulness of the skin-care cosmetic of the present invention in more detail, with respect to the melanin-inhibiting action of isoferulic acid, the action of inhibiting tyrosinase activity known as its mechanism and the action of inhibiting melanin production by ultraviolet rays and Experimental Example 1 for suppressing erythema. ． The results of the experimental examples conducted for the following are shown below.

Tyrosinase activity inhibitory effect Regarding the tyrosinase activity inhibitory effect of isoferric acid,
It was investigated using the enzyme tyrosinase extracted from Harding-Passay mouse melanoma. The enzyme activity was determined by a photometric method in which the amount of dopachrome produced was measured by the absorbance at an absorption maximum of 475 nm using dopa as a substrate. The results are shown in Table 1 showing the thyrodinase activity inhibition rate after 10 minutes of reaction.

(Sample solution concentration) 5 × 10 ⁻³ M, 5 × 10 ⁻⁴ M, 1 × 10 ⁻⁴ M (reaction solution composition) enzyme solution 0.2 ml 5 mM dopa 1.0 0.1 M phosphate buffer (pH 6.8) 1.74 sample Solution 0.06 (total) 3.0 ml As shown in the results of Table-1, it was revealed that isoferulic acid has a remarkable tyrosinase activity inhibitory action, and it was proved that isoferulic acid is useful for the whitening action as well as the reduction of stains and freckles.

Experimental example 2. Inhibitory effect on melanin production by ultraviolet rays C57BL
A group of 6 mice was used as a test solution in the right auricle, that is, vehicle containing propylene glycol: ethanol = 1: 1 at a ratio of 0.1 W / V% and 0.5 W / V% of isoferric acid and 2-hydroxy. -4-methoxybenzophenone-5
10 μl of each solution of sulfonic acid was applied, and the same amount of vehicle was applied to the left auricle of the mouse.

Then, the FL20SE30 lamp was used as a light source, the auricle was placed directly under the light source, and ultraviolet rays of 33 μw / sec · mm ² were irradiated for 20 seconds (about 0.07 joule). The sample was applied to the auricle of the mouse once a day, and the ultraviolet irradiation was repeated once for three consecutive days after the application. After left for 1 week, the left and right auricles were collected, and then treated with NaBr to separate the epidermis. The epidermis was stained with Dopa to prepare a tissue sample, and the number of melanocytes was counted under a microscope. The results are shown in Table-2 (isoferulic acid) and Table-3 (2-hydroxy-4-methoxybenzophenone-5-sulfonic acid).

As shown in the comparison of Table-2 and Table-3, isoferulic acid is a conventionally used 2-hydroxy-4-
It can be seen that methoxybenzophenone-5-sulfonic acid has an effect of suppressing melanin generation due to ultraviolet rays equivalent to or higher than that of methoxybenzophenone-5-sulfonic acid, and in particular, at 0.5 W / V% or more, generation of melanocytes is completely suppressed.

Experimental example 3. Suppressive effect on erythema and edema caused by UV rays Guinea pig 8
After shaving the back of a group of animals, apply 30 μl of the test solution to one site of the guinea pig fixed by applying a bandage with two small holes (circle of 1.5 cm in diameter) to the shaving area, 30μ of vehicle only (control) in one site
1 was applied. 1 hour later, about 4 times the minimum amount of erythema
0.8J / cm ² (using FL20SE30 lamp as the light source, 300
(irradiation with μW / cm ² for 28 minutes), and then allowed to stand for a certain period of time for evaluation. The determination method is irradiation 2.4.6.24.4.
After 8.72 hours, it was visually observed according to the criteria shown below. The test solution was a vehicle consisting of propylene glycol: isopropyl alcohol = 3: 7 (W / W) and wasoferuric acid at a ratio of 3 W / V% and 10 W / V%, and 2-at a ratio of 10 W / V%. Hydroxy-4-methoxybenzophenone was dissolved and adjusted. The obtained results (n = 8 for each test solution) were averaged and the final results are shown in FIG.

(Criteria) Mild erythema 0.5 (±) Erythema 1.0 (+) Erythema and weak swelling 1.5 (+ to ++) Erythema and obvious swelling 2.0 (++) Small blisters / vesicles 3.0 (+++) As shown in FIG. 2, isoferulic acid significantly suppresses erythema and edema due to ultraviolet rays at a concentration of 3 W / V%, which is significantly higher than that of conventional 2-hydroxy-4-methoxybenzophenone (10 W / V%). It is clear that it has an effect.

As described above in detail, the skin-care cosmetic of the present invention containing isoferulic acid and its derivative is excellent in that it can reduce the whitening effect, stains and freckles, and prevent various harmful effects caused by ultraviolet rays. .

Examples of the skin-care cosmetic of the present invention are shown below. The mixing ratio is parts by weight.

Example 1. Lotion Propylene glycol 10.0 Ethyl alcohol 20.0 Liquid paraffin 2.0 Polyoxyethylene (30) Hydrogenated castor oil 1.0 Sodium isoferurate 8.0 Polyethylene glycol 5.0 Citric acid 0.2 Sodium phosphate 0.3 Allantoin 0.05 EDTA-2Na 0.05 Antioxidant 0.02 Perfume 0.2 Purified water 53.18 Implementation Example 2. Cream Solid paraffin 2.0 Stearyl alcohol 4.0 Squalane 2.0 Liquid paraffin 6.0 Glyceryl monostearate 2.5 Polyoxyethylene sorbitan monostearate 2.5 Ethyl alcohol 9.0 Propylene glycol 8.0 Ethyl isoferurate 4.0 2-Hydroxy-4-methoxybenzophenone 3.0 Hydrophobized fine particle oxidation Titanium 5.0 Purified water 52.0 Example 3. Foundation Hydrophobized fine particles Titanium oxide 7.0 Isostearic acid triglyceride 2.0 2-Octyldodecyl oleate 8.0 Liquid paraffin 3.0 Cetyl alcohol 5.0 Candelilla wax 2.0 Cetyl isoferurate 5.0 Polyoxyethylene (25) monostearate 2.0 Sorbitan monostearate 1.0 Yellow iron oxide 1.3 Rouge 0.8 Polyethylene glycol 4.0 Methylparaben 0.2 Perfume 0.2 Purified water 58.5 Example 4. Powder talc 80.0 Crystalline cellulose 5.0 Ultramarine 1.0 Spherical calcium silicate 3.0 Fine particle titanium oxide 3.5 Isoferulic acid 3.0 Squalane 4.5 Example 5. Lotion Propylene glycol 15.0 L-menthol 0.1 Ethanol 15.0 Polyoxyethylene (30) hydrogenated castor oil 0.5 Anti-inflammatory agent 1.0 Isoferulic acid 1.5 Isoferric acid triethanolamine 3.5 Perfume 0.3 Purified water 65.1 Example 6. Pack Polyvinyl alcohol 20.0 Ethanol 20.0 Isoferulic acid 1.0 Glycerin 5.0 Perfume 0.3 Water 53.7 Example 7. Oil Squalane 47.0 Castor oil 47.0-2-Ethylhexyl isoferrate 5.0 Cholesteryl isoferrate 0.79 Perfume 0.2 Antioxidant 0.01

[Brief description of drawings]

Figure 1 shows the ultraviolet absorption spectrum of isoferric acid (0.00
1% ethanol). FIG. 2 shows the relationship between erythema intensity (n = 8 average value) and time course after UV irradiation on guinea pigs. In the figure, (a) is control and (b) is 10 W / V. % 2
-Hydroxy-4-methoxybenzophenone solution is applied, (c) is applied 3 W / V% isoferric acid solution, and (d) is applied 10 W / V% isoferric acid solution.

 ─────────────────────────────────────────────────── ─── Continuation of the front page (72) Inventor Michio Matsukami 1 27 Takashimadai, Kanagawa-ku, Kanagawa-ku, Kanagawa Pref., Yokohama Research Laboratory, Pola Chemical Industry Co., Ltd. (72) Ichiro Koiso 27 Takashimadai, Kanagawa-ku, Yokohama, Kanagawa Address 1 Pola Kasei Kogyo Co., Ltd. Yokohama Laboratory (72) Inventor Toshimitsu Suzuki 27 Takashimadai, Kanagawa-ku, Yokohama, Kanagawa Prefecture Pola Kasei Kogyo Co., Ltd. Yokohama Laboratory (56) Reference JP-A-56-161315 (JP, A)

Claims (2)

[Claims] 1. A formula (I) based on a cosmetic base. (In the formula, R represents hydrogen or a linear, branched, cyclic, or polycyclic alkyl group, alkenyl group, aryl group, and alkali metal, alkaline earth metal, or quaternary amine.) A cosmetic for beautiful skin, comprising an acid and / or a derivative thereof as an active ingredient. 2. The cosmetic for beautiful skin according to claim 1, wherein the compounding amount of the isoferulic acid and / or its derivative is 0.01 to 10% by weight based on the total amount of the cosmetic.