JPS62138423A - Ultraviolet light absorber of long wavelength (2354/20)uv-a absorber) - Google Patents

Abstract

PURPOSE:A UV-A absorber, obtained by adsorbing a specific benzophenone derivative on the surface of a solid base and capable of shifting the maximum absorption to a longer wavelength region, selectively and effectively absorbing rays within the UV-A region and protecting the skin against damage by UV-A. CONSTITUTION:A UV-A absorber obtained by dissolving a benzophenone derivative expressed by the formula (m X and n Y are 1-24C alkyl, alkoxy, etc.; n and m are integers 0-3; k+l is an integer 1-4). e.g. in 0.1-50wt% concentration in a solvent, dripping the resultant solution in a dispersion of a solid base, e.g. alpha-Al2O3, CuO, alpha-Fe2O3, etc., while stirring, filtering the above-mentioned solid base, washing the solid base with water and drying the washed base so as to adsorb the compound expressed by the formula on the solid base. Although the maximum absorption wavelength of the compound expressed by the formula is present in a shorter wavelength side than 350nm, the maximum absorption shifts to a longer wavelength side. The absorber is safe without percutaneous absorption and has lasting property.

Description

Detailed Description of the Invention [Industrial Field of Application] The present invention is a long-wavelength ultraviolet absorber, more specifically, a benzophenone derivative having 1 to 4 water groups on two benzene tops is plated on the surface of a solid base. The present invention relates to a layered long wavelength ultraviolet (hereinafter referred to as "UV-AJ") absorber.

[Conventional technology and its problems]

Ultraviolet rays are known to cause various changes in the skin. In dermatology, the wavelength of action is 400 to 3201.
Ultraviolet rays are divided into long-wavelength ultraviolet rays of 320 to 290 nm, medium-wavelength ultraviolet rays of 320 to 290 nm, and short-wavelength ultraviolet rays of 290 nm or less, and are called UV-A, UV-B, and UV-C, respectively.

Normally, most of the sources of ultraviolet radiation that humans are exposed to are sunlight, but the ultraviolet rays that reach the ground are UV-A and UV-B.
However, UV-C is absorbed in the ozone layer and almost never reaches the ground. Among the ultraviolet rays that reach the ground, UV
-B causes changes in the skin, such as the formation of erythema and blisters when the skin is irradiated with a certain amount of light or more, and melanin formation is advanced, resulting in pigmentation. On the other hand,
Previously, it was thought that UV-A did not cause much change in the skin. However, in recent years, it has been revealed through electron microscopy and histochemical techniques that the skin is also subject to changes due to UV-A irradiation. In particular, U
VA-A [Unlike JV-B, its energy reaches even the dermis, causing microchronic changes in the elastic fibers in blood vessel walls and connective tissue, and these changes are thought to lead to accelerated skin aging. ing. In addition, UV-A has the effect of blackening the skin immediately after irradiation (immediate blackening), and
It is known that V-H enhances the degenerative effect on the skin, and UV-A is considered to be a factor in the occurrence and aggravation of age spots and freckles.

These things are clear that not only UV-B (U
Protecting the skin from VA is also important in terms of preventing accelerated aging of the skin and preventing the occurrence and aggravation of age spots and freckles.

However, research on the effect of UV-A on the skin has a short history, and when applied to the skin, UV-A
The reality is that not much is known about substances that absorb A. Currently, only a few dibenzoylmethane derivatives and cinnamic acid derivatives are known, but most of them are fat-soluble (West German Patent Publication No. 2728241, West German Patent Publication No. 27
28243, JP-A-51-61641, JP-A-52-46056, JP-A-57-197209), and there are few water-soluble ones (JP-A-57-59840). Therefore, when attempting to add and blend these UV-A absorbers into cosmetics, there are restrictions on the properties of the base of the cosmetics.

In addition, in the case of organic ultraviolet absorbers, problems remain with respect to safety such as irritation to the skin, transdermal absorption, sustainability due to diffusion on the skin, etc.

- It is also possible to reflect and scatter ultraviolet rays using inorganic pigments, which have the advantage of not being absorbed through the skin, being safe and non-irritating to the skin, but it is also possible to selectively absorb specific ultraviolet rays. It is impossible to defend against it. That is, although inorganic pigments have high suitability for visible light, they have a drawback in that they cannot selectively and effectively absorb only the UV-A region.

[Means for solving problems]

Under such circumstances, the present inventor conducted various studies and found that the longest maximum absorption wavelength of the benzophenone derivative represented by the general formula (I) below is on the considerably shorter wavelength side than 35Qnrn. The present invention was completed based on the discovery that the maximum absorption shifts to longer wavelengths, allowing selective and effective absorption and protection of light in the UV-A region.

That is, in the present invention, in the following general formula (I) f, m X's and n Y's are the same or different and each has 1 to 1 carbon atoms.
24 alkyl or alkoxy groups or sulfonic acid groups or alkali metal salts thereof, where n and 1n are 0 to 1;
The object of the present invention is to provide a long-wavelength ultraviolet absorber characterized by adsorbing a benzophenone derivative represented by the formula (K+t is an integer of 3 and k+t is an integer of 1 to 4) on the surface of a solid base.

In the present invention, examples of the benzophenone derivative represented by m include 2,2'-dihydroxy-4-methoxybenzophenone, 2-hydroxy-4-methoxybenzophenone, 2-hydroxy-4-methoxybenzophenone-5-sulfonic acid, 2,2'-dihydroxy-
4,4'-dimethoxybenzophenone, 2,2'
, 4,4'-tetrahydroxybenzophenone,
2,2'-dihydroxy-4,4'-dimethoxybenzophenone-5-sulfonate sodium, 2,4-
Dihydroxybenzophenone, sodium 2-hydroxy-4-methoxybenzophenone-5-sulfonate, 2
-Hydroxy-4-octyloxybenzophenone, 2-
Hydroxy-4'-methoxybenzophenone, 2-hydroxybenzophenone, 4-hydroxybenzophenone, 2-hydroxy-4-methylbenzophenone, 2-hydroxy-5-methylbenzophenone, 2,5-dihydroxybenzophenone, 2-hydroxy-5-methoxy Examples include benzophenone.

Further, as the solid base, one that is suspended in anhydrous benzene, and when a few drops of an anhydrous benzene solution of bromothymol blue is added dropwise, the liquid turns green. Such solid bases include, for example, Q-At203, r
-At203, Q -At0OH1r -At
00H1γ-At(OH)3, BeO, CdO, C
uO.

Cr2O3, CaO, BaO, Fe(OH)2, a
-Fe2O3, γ-Fe2O3, Q -Fe0OH,
r -Fe0OH1MgO% MnO.

NiO, 5i02, ZnO% Y2O3, Na2C
O3, K2CO3, K)IC03, (MH)4C03,
CaCO3, 5rC03, BaCO3, KNaCOs
Metal oxides or (heavy) carbonates such as Azzo3゜5t0
2 and other metal oxides such as NaOH, KOH, alkali metals, alkaline earth metals, NH3, NFLs (R: hydrogen,
Anion exchange resins and the like are included. These solid bases are preferably in the form of fine particles with a diameter of 100 Pn or less, particularly 10 μrn or less, in terms of UV protection effect and usability.

The long wavelength ultraviolet absorber of the present invention can be prepared by adding, for example, a benzophenone derivative to water or an organic solvent at a concentration of, for example, 0.1 to
It is prepared by a method in which the solid base is dissolved to a concentration of 50%, added to a solid base dispersion under stirring, and then the solid base is filtered, washed with water and dried, or the solvent is distilled off.

The solvent for dispersing the base must be one that does not dissolve the solid base, and for example, water, alcohol, benzene, hexane, etc. are preferably used.

The amount of benzophenone derivative to treat the solid base varies depending on the number of basic sites and adsorption capacity, but generally the amount of benzophenone derivative to solid base is 0.01 to 1 (by weight), especially 0.1 to 1 (by weight). The case is preferred.

The long wavelength ultraviolet absorber of the present invention can be incorporated into cosmetics, pharmaceuticals, etc. for the purpose of preventing the harmful effects of ultraviolet rays on the skin.

The amount of the long-wavelength ultraviolet absorber of the present invention incorporated into cosmetics varies depending on the type (dosage form) of the cosmetic, but is generally 0.1 to 20% by weight as a benzophenone derivative, especially 0.5% by weight.
It is preferable that the thickness be 10 to 10 times.

The cosmetic of the present invention can be prepared by blending this long-wavelength ultraviolet absorber into a known cosmetic base by a conventional method and making it into a cream, solution, oil spray, stick, milky lotion, foundation, or soft gel. In other words, by selectively using benzophenone derivatives and solid bases in accordance with the cosmetic base, oil-based cosmetic oils, oil-based creams and oil-based emulsions containing a large amount of oil, and large amounts of water can be blended. From basic cosmetics such as weakly oily creams, weakly oily emulsions, and water-based lotions to makeup products such as oil-based foundations and lipsticks,
It is possible to produce cosmetics in all forms that have a VA-absorbing effect. Suitable bases and solvents include:
Hydrocarbons such as solid or liquid paraffin, crystal oil, ceresin, osichelite or montan wax; vegetable or animal fats and waxes such as olive, earth wax, carnauba wax, lanolin or spermaceti; also stearic acid, palmitic acid, Fatty acids and their esters such as oleic acid, glycerin monostearate, chrycerin distearate, chrycerin monooleate, inpropyl myristate, inpropyl stearate or butyl stearate; ethyl alcohol, propyl alcohol, cetyl alcohol, stearyl alcohol,
Examples include alcohols such as valmityl alcohol and hexyldodecyl alcohol.

Further, polyhydric alcohols having a moisturizing effect such as glycol, glycerin or norbitol can also be used.

It is preferable to further incorporate other UV-B absorbers into the non-inventive cosmetic composition. As a UV-B absorber,
For example, p-methylbenzylidene-D, L-camphor or its sulfonic acid sodium salt; 2-phenylbenzimidazole-5-sulfonic acid sodium salt, 3,4-
Dimethylphenylglyoxylic acid sodium salt, 4-phenylbenzophenone, 4-phenylbenzophenone-2'-carboxylic acid inoctyl ester, p-methoxycinnamic acid ester, 2-phenyl-5-methylbenzogisazole or p-dimethylaminobenzoin Examples include acid esters.

In addition to the above-mentioned components, various additives can be added to the cosmetic composition of the present invention. Suitable additives include, for example, W7.
Examples include type 10 and O/W type emulsifiers. As an emulsifier, use a commercially available emulsifier. J'1'7flIi agents such as matamethylcellulose, ethylcellulose or carboxymethylcellulose, polyacrylic silica, tragacanth, emulsion or gelatin can also be added as additives. Depending on the historical requirements, fragrances, anti-ag MIJ, humectants, emulsion stabilizers, medicinal ingredients, layer colorants, etc. may be added.

[Action and effect]

Since the long wavelength ultraviolet absorber of the present invention selectively and effectively absorbs UV-A, it can protect against skin damage caused by UV-A, and since it is insoluble in water, organic solvents, oils, sebum, etc. It has the excellent features of being safe, not absorbed through the skin, and lasting for a long time.

〔Example〕

Next, examples of the present invention and test sample 1] will be described.

Example 1 An amount corresponding to the saturated adsorption amount of a benzophenone derivative to a solid base was dissolved in 2 to 3 ml of ethanol, and this was added to a solid base dispersed in 20 ml of ethanol under stirring. After that, the ethanol was distilled off to obtain the long wavelength ultraviolet absorbers shown in Table 1 with a margin of 1° or less Test Example 1 Long wavelength ultraviolet rays of the UV absorbers (I) to (Io) obtained in Example 1 The absorption effect was investigated using absorption spectra.

The absorption spectrum shows the UV-absorbers (I) to (Io) at 1
It was suspended in diinstearyl malate at a density of 0% by weight, and applied to a quartz plate to a thickness of 30 μm, and the transmittance was measured.

The results are shown in Table 2.

Table 2 with blank space below Test Example 2 The transmittance (a) for each wavelength of the UV-A absorber (■) obtained in Example 1 is expressed as r -At20i (CI) and 2,4
-Measured in comparison with that of dihydroxybenzophenone (c). The results are shown in FIG. From Table 2 and FIG. 1, the long wavelength ultraviolet absorber of the present invention exhibits maximum absorption at longer wavelengths than the benzophenone derivative alone, so-called UV
It can be seen that -A is selectively and effectively protected.

Example 2 Oil: ■ Sodium absorbent (I) 30 (wt%
)■In-propyl myristate 1゜■Liquid lanolin 5■Mineral oil
The remaining amount of the above composition is kneaded using a roll mill to obtain an oil with uniform properties.

Example 3 Emulsion: ■UV-A absorber (7) 5 (
weight t%) ■ Stearic acid 1 ■ Setanol 2 ■ Vaseline
2.5 ■ Squalane
4 (wt%) (■ Hardened palm oil
2 ■ Polyoxyethylene (20) Rubitan monostearate 1.5 ■ Lipophilic monostearate Rubipan 1.2 ■ Glycerin
3 0 Potassium hydroxide 0.20 Carboxy vinyl polymer 0.2 OVJ preservative
Suitable O fragrance
A small amount @ Vt water was blended using a conventional method to obtain an emulsion.

Example 4 W10 type cream: ■UV-A absorber (3) 10 (wt%) ■Vaseline 6■Cholesterol 0.60 cetanol
0.5 ■ Rubitan sesquiolate 2 ■ Liquid lanolin 4 ■ Improvir palmitate) 8 (2%) ■
Squalane 10 ■ Solid paraffin 4 ■ Glycerin
3 ■ Preservatives Appropriate amount ■ Flavorings 0 traces Purified ice
A W10 type cream was obtained by blending in a conventional manner.

Example 5 0/W type cream: ■UV-A absorber (9) 15 (
weight t%) @ stearic acid 2 (3
2, Setanol 4 ■ Vaseline 5 ■ Squalane
8 ■ Hydrogenated palm oil 4
■Polyoxyethylene (20) Nrubitan monostearate 2 ■Nrubitan monostearate 2 ■Glycerin
5 [F] Preservative
Appropriate amount ■Fragrance, ■Purified water The remaining amount was blended according to the usual method to make an O/W type mulberry cream.

Example 6 Oil-based foundation: ■UV-A absorber (4) 12 (shipping O
)■UV-A absorber (5) 10■
Liquid paraffin 15 ■ Impropyl palmitate 10 ■ Lanolin alcohol
3 ■ Microcrystalline wax 7 ■ Osikelite 8 ■ Candelilla wax 0.5 ■ Preservative
Appropriate amount [stock] Titanium oxide 80 Kaolin 180 Talc
6◎Red Gara
1.5■Black iron oxide 0.5
[Phase] Fragrance A small amount was blended in a conventional manner to obtain an oil-based foundation.

Example 7 Powder foundation: Naseta r -At203 ■ Mica Remaining amount ■ Talc
20(4) Titanium oxide
10■ Red Garla
0.8 ■ Yellow iron oxide 2.5 ■ Black iron oxide 0.1 ■ Liquid paraffin 8 ■ Beeswax
2.Applying preservative.•Fragrance, trace component (2) was prepared in the same manner as in Example 1, and mixed with other components in a conventional manner to obtain a powder foundation.

Actual example 8 Cream foundation: ■ Stearic acid 5 (movement 0) ■ Lipophilic glyceryl monostearate 2.5 ■ Cetostearyl alcohol 1 ■ Propylene glycol monolaurate 3 ■ Squalane
7 ■ Olive oil 8 ■ Butyl paraoxybenzoate appropriate amount ■ Purified water
Remaining amount ■ Triethanolamine 1,2
ri p7)'e t
3 ■ Methyl paraoxybenzoate appropriate amount @ titanium oxide 5 @ talc
100 colored pigments
Appropriate amount ◎Q-At00H11 [phase] fragrance with adsorbed 2-hydroxy-4-methoxybenzophenone
The minor component [phase] was prepared in the same manner as in Example 1 and mixed with other components in a conventional manner to obtain a creamy foundation.

[Brief explanation of drawings]

Figure 1 shows a long-wavelength ultraviolet absorber of the present invention in which 7''-Al2O5 is adsorbed with 2,4-dihydroxybenzophenone.
FIG. 3 is a diagram showing the transmittance of γ-At203 and 2,4-dihydroxybenzophenone at each wavelength. Ye 2,4-dihydroxybenzophenone adsorption γ-A
t203 0: r At203 C: 2,4-dihydroxybenzophenone and above r, Supplement II: 14F (I'1ffi) February 1986 711 #shi, 81 Agency Director General Uga Michibe 1, - Display of B items 1988 1960 Patent Application No. 278272 2 Title of the invention Long wavelength ultraviolet absorber 3 Person making the amendment/Relationship with the matter Applicant name (091) Kao Corporation 4 Agent address Nihonbashi, Chuo-ku, Tokyo Ningyocho 1-3-6 (〒
103)+1 (in place PI J2
1----2-) Name (
8632) Patent Attorney Nobuo Ono 1';1'・5, Date of amendment order
1; Ni, n-1 spontaneous 6, "Detailed explanation of the invention" column 7 of the specification to be amended 1B, contents of the amendment (I) Specification Yuchu, page 8, line 19, "After washing with water" Correct it to "after washing."

Claims (1)

[Claims] 1. The following general formula (I) ▲There are mathematical formulas, chemical formulas, tables, etc.▼(I) (In the formula, m X's and n Y's are each the same or different, and carbon Represents an alkyl or alkoxy group or a sulfonic acid group or an alkali metal salt thereof having a number of 1 to 24, and n
and m represents an integer of 0 to 3, and k+l represents an integer of 1 to 4. 2. The following general formula (I) ▲Mathematical formulas, chemical formulas, tables, etc.▼(I) or an alkoxy group, a sulfonic acid group, or an alkali metal salt thereof, and n
and m represents an integer of 0 to 3, and k+l represents an integer of 1 to 4.) A cosmetic containing a long wavelength ultraviolet absorber in which a benzophenone derivative represented by the following formula is adsorbed on the surface of a solid base.