JPS6351318A - Ultraviolet absorber and cosmetic containing same - Google Patents

Abstract

PURPOSE:To produce a cosmetic enabling practically complete absorption of ultraviolet radiation in sunlight and having excellent anti-suntan effect, by using a specific isocoumarin derivative as an ultraviolet absorber. CONSTITUTION:The objective cosmetic contains the compound of formula (R is 1-4C alkyl, 1-4C alkoxy, methylenedioxy or phenoxy; n is 1 or 2) [e.g. 3-(4'-methoxypenyl)isocoumarin] at an amount of 0.5-10wt%, preferably 0.5-5wt% based on the cosmetic. The compound of formula is stable to ultraviolet radiation, free from skin irritation and allergic activity and gives a cosmetic having extremely high safety to skin.

Description

Detailed Description of the Invention [Industrial Application Field] The present invention contains an "isocoumarin" derivative that has an absorption effect on harmful ultraviolet rays of 290 to 400 nm, and contains it, and has an excellent sunburn prevention effect. related to the provision of cosmetics.

[Prior Art] Ultraviolet rays in sunlight are known to have harmful effects on human skin. That is, 290-320nn1 (UVI
Ultraviolet rays (abbreviated as 3 ultraviolet rays) pass through the cornea yit1[1] to the milk UJ[f, are the main cause of solar erythema, and also exhibit melanin-producing effects.

In addition, ultraviolet rays (UVA) with longer wavelengths between 320 and 400
Ultraviolet rays (abbreviated as ultraviolet rays) penetrate into the dermis and have a melanin-producing effect, causing skin darkening.

Furthermore, chronic irradiation with UVA and UVB ultraviolet rays
It is also said that it accelerates skin aging and causes Form 9, such as the appearance of age spots and wrinkles.

As the effects on human skin become clearer, the development of compounds that protect skin H from these ultraviolet rays has become more desirable than ever.

[Problems to be Solved by the Invention] Methods for protecting against solar erythema have been intensively researched, and many compounds have been developed and known as UVB absorbers. However, the OV of these compounds
The absorption effect for ultraviolet A radiation is very low, and only a portion of the ultraviolet radiation in sunlight is absorbed. In addition to UVB absorbers, in order to protect the skin from ultraviolet rays in the sun,
A UVA absorber is required, and the development of this UVA absorber is also being considered.

By using a UVB absorber and a UVA absorber in combination, it is possible to completely absorb ultraviolet rays in sunlight. However, the combination of these multiple active ingredients may cause safety problems because unexpected photoreactions may proceed due to sunlight and the total amount of ultraviolet absorber increases. Among the UV absorbers commonly used today, those that absorb a wide range of UV rays include:
Although 2-hydroxy-4-methoxybenzophenone exists, its absorption effect on both UVA and UVB ultraviolet rays is weak, and it is difficult to expect a sufficient effect.

As described above, although there is a desire for a compound that absorbs ultraviolet rays in sunlight and protects the skin, there is currently no compound that satisfies this demand.

The desired compound must absorb as much of the ultraviolet rays in sunlight as possible, be harmless, and have excellent stability against light. As a result of intensive research from these viewpoints, the present inventors found that "isocoumarin" derivatives are particularly suitable, and completed the present invention.

[Means for Solving the Problems] That is, the present invention provides "isocoumarin" derivatives that practically completely absorb UVA and UVB ultraviolet rays and are highly stable against ultraviolet rays, and one or more of them. The present invention relates to a sunscreen cosmetic characterized by containing two or more types.

Hereinafter, the configuration of the present invention will be explained in detail.

The ultraviolet absorber of the present invention is represented by the following general formula (1).

(However, R is an alkyl group having 1 to 4 carbon atoms,
represents an alkoxy group, methylenedioxy group, or phenoxy group, and n represents an integer of 1 or 2. ) As a method for synthesizing the compound applicable to the present invention, a generally known method (R. K., K., Knox, J.).

Org, Chem, 16, 1064 (1951
) ), for example, can be easily obtained by performing a Friedel-Crafts reaction of homofucric anhydride and alkyl-substituted benzene or alkoxy-substituted benzene in anhydrous benzene or anhydrous nitrobenzene using anhydrous aluminum chloride as a catalyst.

The compound of the present invention itself has the ability to completely absorb UVA ultraviolet rays and UVB ultraviolet rays, and exhibits sufficient effects as a sunscreen cosmetic. However, for people who are extremely sensitive to light, even a small amount of UV rays can be harmful, so it is also possible to use other UV absorbers in combination. Other absorbents such as 4.4″-dimethoxydibenzylmethane as a dibenzoylmethane derivative;
2-Hydroxy-4 as a benzophenone derivative such as 4-methoxy-4'-t-butyldibenzylmethane
-Methoxybenzophenone, 2-hydroxy-4-methoxyhensiphenone-5-sulfonic acid, etc., other urocanic acid, p-aminobenzoic acid, 2-ethylhexyl-P-dimethylaminobenzoate, 2-ethylhexyl-P -methoxycinnamate, mono-2-ethylhexanoyl-di-P-methoxycinnamoylpropane, 2
-Ethylhexyl salicylate, homomenthyl salicylate, etc.

The blending amount of the ultraviolet absorber of the present invention varies depending on the degree of prevention of sunburn and the season in which it is used, but it is generally 0.5 to 10% by weight, preferably 0.5 to 10% by weight.
5% by weight.

In addition to the compound represented by the above general formula (1), the cosmetic according to the present invention includes additives commonly used in cosmetics, such as solid or liquid paraffin, crystal oil, ceresin, ozkerite, Hydrocarbons such as monoclonal wax, silicone oils, vegetable or animal fats and waxes such as olive, earth's wax, carnauba wax, and lanolin, as well as stearic acid, valmitic acid, oleic acid, glycerin monostearate, and glycerin distearate. esters, fatty acids and their esters such as glycerin monooleate, isopropyl myristate, isopropyl stearate, monohydric or polyhydric alcohol esters of branched fatty acids, ethyl alcohol, isopropyl alcohol, cetyl alcohol, stearyl alcohol, Alcohols such as palmyl alcohol, polyhydric alcohols such as glycol, glycerin, and sorbitol, nonionic surfactants, anionic surfactants, cationic surfactants as emulsifiers or solubilizers, and preservatives as necessary. Coloring agents, fragrances, etc.

The properties of the cosmetics of the present invention include, for example, liquid, milky lotion, stickiness,
It may be in any shape as long as it can exhibit the effect.

The present invention will be described in more detail with reference to Examples.

Actual) fE example (o 3- (4°-methoxyphenyl)
Synthesis of isocoumarin 16 g of anhydrous aluminum chloride is added to a solution of 15 g of homophthalic anhydride and 80 d of anisole and stirred well. This mixed solution is gradually heated to 80° C. while stirring, and stirring is continued at this temperature for 3 hours. After cooling, 100 - of water is added, acidified with concentrated hydrochloric acid, benzene I○0 - is added and the organic layer is separated. After washing the organic layer with a 10% aqueous sodium carbonate solution and drying, benzene and anisole were distilled off under reduced pressure. Add 30% ethanol to the residue. When recrystallized by adding J, 2.3 g of pure 3-(4°-methoxyphenyl)isocoumarin is obtained.

mp 116-117°, 121-122°C (double melting point) Other compounds according to the present invention can also be synthesized by the same procedure as in Example (1).

Example (2) Ultraviolet absorption effect of the compound of the present invention Using 2-hydroxy-4-methoxybenzophenone as a comparison compound, L in 99.5% ethanol (reagent grade) solvent
Table 1 shows the ultraviolet absorption effect (light absorbance) at OP (W/V) concentration.

Table 1 Ultraviolet absorption effect 290 0.69 0.65 0.6
5300 0.97 0.92. 0.
39310 1.04 0.9B
0.35320 0.95 0.90
0.40330 0.55 0.52
0.42340 0.52 0.49
0.34350 0.53 (15
00,203600,460,430,11 3700,330,310,03 3800,180,170,00 *1 1-(4'-methoxyphenyl)isocoumarin*2 3-(4''-ethoxyphenyl)isocoumarin*32- Hydroxy-4-methoxybenzophenone These results demonstrate that the compound of the present invention
It has a stronger absorption effect on ultraviolet rays than the comparative compound 2-hydroxy-4-methoxybenzophenone, indicating that it has a high sun protection effect.

Example (3) Stability of the compound of the present invention against ultraviolet light (experimental method) The compound of the present invention and the comparative compound were dissolved in a 99.5% ethanol (reagent grade) solvent to a concentration of 0.1% (W/V). Then, using a xenon fade meter, ultraviolet rays were irradiated for 15 hours and 30 hours.

The UV absorption effect before and after UV irradiation was compared, and the stability was evaluated from the residual rate. The survival rate was calculated as follows.

(Margin below) The stability was evaluated based on the following criteria (Table 2).

Table 2 Stability Evaluation Criteria Evaluation Points Residual rate ○ Residual rate 95% or more Δ Residual rate 90% or more × Residual rate 90% or less Table 3 shows the stability evaluation results against ultraviolet rays measured as described above.

Table 3 (blank below) *I 3-(4"-methoxyphenyl)isocoumarin*2 3-(4'-ethoxyphenyl)isocoumarin*3 3-(3',4'-methylenedioxyphenyl)isocoumarin*42- Ethylhexyl-P-methoxycinnamate From the results in Table 3, 2 is frequently used as an ultraviolet absorber.
-Ethylhexyl-P-methoxycinnamate It is clear that the compounds of the present invention have superior stability against ultraviolet light.

The present invention will be further described below with reference to other examples, but the present invention is not limited thereby.

Compounding materials are shown in fffffi%.

Example (4) Clear liquid oil 3-(4'-ethoxyphenyl) 2.0% Isocoumarin Isopropyl myristate 15% Olive oil % Fragrance
Amount (!! method) While stirring the oil base at 50” to 60’, add 3-(4
′-ethoxyphenyl)isocoumarin was added and dissolved,
Cool naturally to room temperature.

Example (5) Cream 3-(4°-methoxyphenyl) 5% Ink Marine Diethylene Glycol Seven 2% Stearate Stearic Acid 1.5% Cetyl Alcohol 0.5% Benzyl Alcohol 6.0% Triethanolamine 1.0 %purified water
84.0% fragrance
Appropriate amount Antioxidant, preservative (appropriate amount)
! Method 1) Melt the oily part by heating to 65°C, add purified water heated to the same temperature, and when the temperature reaches 35°C without stirring, add fragrances, antioxidants, and preservatives, and let it cool to room temperature. Continue stirring until the mixture is mixed.

Example (6) Hair Cream 3-(3″, 4″-methylene dioxy 0.5% diphenyl) isocoumarin beeswax 1.0% liquid paraffin 50% stearic acid 3.09A sorbitan sesquiolate 2.2% polyoxyethylene sorbitan゛ 1.8% monourarate purified water 41.5% fragrance
Appropriate amounts of antioxidants and preservatives (Production method) Produced in the same manner as in Example (4).

Example (7) Sunscreen stick foundation 3-(4'-methoxyphenyl) 4.0% isocoumarin titanium dioxide 16.0 kaolin 10.0 mica powder
10.0 zinc white
4.5 Iron oxide (red) 1.4 Iron oxide (yellow) 4.0 Iron oxide (black) 0.1 Solid paraffin 5.0 Carnauba wax
3.0 liquid paraffin
34.0 Isopropyl myristate ester
5.0 Sorbitan sesquioleic acid 3.0 Ester fragrance Appropriate amount (manufacturing method) Mix titanium dioxide, kaolin, mica powder, and iron oxide thoroughly in a blender (powder part). Add a portion of liquid paraffin and sorbitan sesquioleic acid ester to the powder portion, disperse uniformly with a homomixer, heat and melt the other components, add to this, and stir well. Pour this into a container and cool it.

In addition, the cosmetics according to the present invention had no skin irritation, no allergic properties, and was extremely safe for the skin.

Claims (1)

[Claims] 1. An ultraviolet absorber represented by the following general formula (1). ▲There are mathematical formulas, chemical formulas, tables, etc.▼...(1) (However, R is an alkyl group having 1 to 4 carbon atoms, and 1 to 4 carbon atoms.
represents an alkoxy group, methylenedioxy group, or phenoxy group, and n represents an integer of 1 or 2. ) 2 A cosmetic material containing one or more types of ultraviolet absorbers represented by the above general formula (1).