JPS62138422A - Ultraviolet light absorber of long wavelength (2354/20)uv-a absorber) - Google Patents

Abstract

PURPOSE:A UV-A absorber, containing a specific benzophenone derivative as an active ingredient, showing a maximum absorption within the UV-A region and high molar extinction coefficient, capable of protecting the skin against UV-A and useful as a cosmetic for preventing promotion of aging. CONSTITUTION:A UV-A absorber containing a benzophenone derivative expressed by the formula (X is alkali metal ion, ammonium ion, etc.; n Y and m Z are OH, 1-24C alkyl, alkoxy, etc.; n and m are integers 0-3; k+l is an integer 1-4). The compound expressed by the formula which is a phenolate salt of the benzophenone derivative shows a maximum absorption on the side of a longer wavelength, i.e. within the UV-A region than a simple benzophenone derivative and is excellent as a UV-A absorber. A salt of the hydroxyl group at the 4-position having a molar extinction coefficient of twice based on that of the derivative which is not a salt is preferred. The absorber is preferably used in combination with a UV-B absorber and used as an actisuntan cosmetic.

Description

DETAILED DESCRIPTION OF THE INVENTION [Industrial Application Field] The present invention relates to long wavelength ultraviolet absorbers, specifically, benzophenones having 1 to 4 hydroxyl groups on two benzene stages. The present invention relates to a long-wavelength ultraviolet absorber (hereinafter referred to as a UV-A absorber) containing a benzophenone-bound conductor in the form of a salt.

[Conventional technology and its problems]

Ultraviolet rays are known to cause various changes in the skin. Dermatologically, the wavelength of action is 400 to 320.
Divided into long wavelength ultraviolet rays of am, medium wavelength ultraviolet rays of 320 to 290 nrn, and short wavelength ultraviolet rays of 290 nrn or less,
They are called UV-A% UV-H and UV-C, respectively.

Normally, most of the ultraviolet ω that humans are exposed to comes from sunlight, but the ultraviolet rays that reach the ground are UV-A and UV-B, and UV-C is absorbed by the ozone layer and almost never reaches the ground. . Among the ultraviolet rays that reach the ground, UV-B
When the skin is exposed to more than a certain amount of light, it forms erythema and water capsules, and melanin formation is reversed, causing changes in the skin such as pigmentation. On the other hand, it was conventionally believed that UV-A does 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, UV-
Unlike UV-B, its energy reaches even the dermis, causing chronic changes by imitating the elastic fibers in blood vessel walls and the skin, and these changes are thought to lead to accelerated skin aging. There is. In addition, it is known that UV-A has the effect of darkening the skin immediately after irradiation (immediate blackening) and that it enhances the degenerative effect of UV-B on the skin.
UV-A is considered to be a factor in the occurrence and aggravation of age spots and freckles.

As is clear from these facts, 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 effects of UV-A on the skin has a short history, and when applied to the skin, UV-A
A substance that absorbs A is not well known, but it is pointed. At present, only a few dibenzoylmethane and cinnamon are known to be active substances, but the inugun are fat-soluble (Seikoku Tokushu Publications No. 2728241, 27).
No. 28243, Japanese Patent Application Publication No. 51-61641, Publication No. 52-46056, Publication No. 57-197209), and there are few Peking Opera-like ones (Japanese Patent Publication No. 57-59840).

Therefore, when attempting to cold-blend these LIV-A absorbers into cosmetics, restrictions are placed on the properties of the cosmetic base;
It has been desired to develop a more versatile UV-A absorber. JvT's UV-A absorber must satisfy the following neutrality.

■Has maximum absorption wavelength near wavelength 35 Q ntn.

(2) The molar absorption number (ε) is sufficiently large at the above wavelength.

■ Since coloring is desirable and undesirable in cosmetic compositions,
The absorption in the visible region should be small, that is, ε' should be 0 at 400 nrn or more.

■ Must be stable against heat and light.

■ No toxicity, irritation, or other harmful effects on the skin.

■ Excellent compatibility with cosmetic bases.

■ When dropped onto the skin, it is difficult to be absorbed through the skin and difficult to be removed by sweating, etc. Therefore, the effect becomes more effective.
to do.

■ It must be inexpensive.

Among conventionally known ultraviolet absorbers, benzophene and non-derivatives are known to have absorption in the UV-A region.
, ■ did not fully satisfy.

That is, as shown in Table 1, for example, the longest extremely thick absorption wavelength is generally on the considerably shorter wavelength side than 350 nm;
There are very few that exhibit absorption in the vicinity of r1m, and even those that exhibit absorption cannot be said to have a sufficiently large molar extinction coefficient (ε).

Table 1 1) Abbreviations of compounds in the table are the same as in Example 1 below.

U.S. DDBSS cannot be measured because it is almost untainted by ethanol.

[Means for solving problems]

What did the inventor intend to do to solve the above problems? As a result of conducting research, we found that a benzophenone derivative, which is a phenolate salt of a benzophenone having 1 to 4 hydroxyl groups at the top of two benzenes, satisfies the conditions (1) and (2) for the UV-A absorber. The present invention has been developed.

That is, the present invention provides the following general formula (where X represents an alkali metal ion, ammonium ion, or amino acid organic cation.
2 are the same or different, hydroxyl group, carbon number 1-
24 alkyl or alkoxy groups or sulfonic acids or alkali metal salts thereof. n and “n is 0 to 3
is an integer of 1 to 4, and k+t is an integer of 1 to 4. ) A long wavelength ultraviolet absorber containing a benzophenone derivative represented by:

The benzophenone derivative used in the present invention is a compound represented by the MiJ formula (1), and is a phenolate salt of benzophenones having 1 to 4 hydroxyl groups on two benzene rings. As such benzophenones,
2,2'-dihydroxy-4-methoxybenzophenone, 2-hydroxy-4-methoxybenzophenone, 2-
Hydroxy-4-methoxybenzophenone-5-sulfonerm, 2゜2'-dihydroxy-4,4'-dimethoxybenzophenone, 2.2',4.4'-tetrahydroxybenzophenone, 2,2'-dihydroxy-4, 4
Sodium '-dimethoxybenzophenone-5-sulfonate, 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,
Examples include 2.5-dihydroxybenzophenone and 2-hydroxy-5-methoxybenzophenone.

Examples of cations that form phenolate salts include alkali metal cations such as sodium and potassium; ammonium ions such as triethanolamine, triethylamine, and ammonia; and amino acid organic cations such as arginine and lysine.

The benzophenone derivative represented by formula (1) used in the present invention can be produced by converting benzophenones having a hydroxyl group as described above into a phenolate salt according to a conventional method. For example, ■Hatabe with hydroxyl group/
A method of dissolving cyphenones in methanol, adding an appropriate number of methanol solutions of sodium methoxide, and distilling off the solvent;
A method for obtaining a benzophenone derivative of the general formula N) by distilling off the solvent; It is produced by filtering out the salt, but the simplest method is: ① Bath dissolving an appropriate number of equivalents of a base (alkali metal hydroxide, amines, amino acids, etc.) in water or alcohol to obtain a hydroxyl group. It can be obtained by adding and reacting benzophenones, and then distilling off the solvent. Also, if necessary, the IAI can be used as is.

The UV-A absorber of the present invention is a benzophenone derivative (
It is produced by adding 1) to a carrier and mixing. The carrier may be any carrier as long as it is inert to the benzophenone derivative (1) V, and may be solid, liquid, emulsion, foam, gel, or the like. Typical examples of these include water, alcohol, fats and oils (e.g. hydrocarbon oils, fat UJD esters, long chain alcohols, silicone oils), fine powders of starch or talc, and low-boiling carbonized materials used as aerosol propellants. Examples include hydrogen and halogen hydrocarbons. The UV-A absorber of the present invention further includes, as long as it does not impair the UV-A absorbing effect of the benzophenone derivative.
Other ingredients such as preservatives, fragrances, colorants, surfactants, etc. can be added and blended.

The thus obtained long-wavelength ultraviolet absorber of the present invention can be suitably added to cosmetics, medical agents, etc. and used in order to prevent the harmful effects of ultraviolet rays on the skin.

Cosmetics containing benzophenone derivative (1) (hereinafter referred to as
The cosmetic composition of the present invention is prepared by appropriately selecting a benzophenone derivative (referred to as the cosmetic composition of the present invention) that has an affinity for the cosmetic base.
It is prepared by blending this into a known cosmetic base by a conventional method and making it into a dosage form such as cream, fδ liquid, oil spray, stick, milky lotion, foundation ointment, etc.

That is, by selectively using benzophenone derivative (1) according to the cosmetic base, oil-based cosmetic oil,
From basic cosmetics such as oil-based creams and emulsions that contain large amounts of oil, weakly oily creams and emulsions that contain large amounts of water, and water-based lotions, to makeup such as oil-based foundations and lipsticks. It is possible to produce all types of cosmetics, including cosmetics, that have UV-A absorbing properties. Suitable bases and solvents include solid or liquid paraffin, crystal oil, hydrocarbons such as ceresin, osikelite or montan wax; olive, earth wax, carnauba wax,
Vegetable oils or animal fats or waxes such as lanolin or glandular wax; also stearic acid, palmitic acid, oleic acid, glycerin monostearate, glycerin distearate, chrycerin monooleic ester, inpropyl myristate, inpropyl Fatty acids and their esters such as stearate or butyl stearate; alcohols such as ethyl alcohol, inpropyl alcohol, cetyl alcohol, stearyl alcohol, palmityl alcohol or hexyldodecyl alcohol; and the like. In addition, polyhydric alcohols having a moisturizing effect such as glycol, glycerin or sorbitol can also be used.1 The composition of the benzophenone derivative in the cosmetic of the present invention is not particularly limited as it may vary depending on the form of use. Although it is sufficient if it is present in an effective amount, it is generally advisable to blend it into the composition in an amount of 0.1 to 20% by weight (hereinafter referred to as H), preferably 0.5 to 10%.

The cosmetic of the present invention may only contain benzophenone derivatives, but may also be combined with other UV-B absorbers,
It is more preferable to use it as a regular sunscreen cosmetic. As this stronger UV-B absorber, for example, p-
Methylbenzylidene-D, L-camphor or its sulfonic acid sodium salt; 2-phenylbenzimidazole-5-sulfone sodium salt; 3,4-dimethylphenylglyoxylic acid sodium salt; 4-phenylbenzophenone; Examples include phenylbenzophenone-21-carboxylic acid octyl ester, p-methoxycinnamic acid ester, 2-phenyl-5-methylbenzoxazole, and p-dimethylaminobenzoic acid ester: JA.

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, W2
O-type and O/W-type emulsifiers may be mentioned. As the emulsifier, commercially available emulsifiers can be used. Thickeners such as methylcellulose, ethylcellulose or carboxymethylcellulose, polyacrylic acid, tragacanth, spherules or gelatin can also be added as additives. Furthermore, if necessary, fragrances, preservatives, humectants, emulsion stabilizers, medicinal ingredients, and physiologically acceptable colorants may be added.

[Action and effect of invention]

As shown in Examples below, the benzophenone derivative (1) according to the present invention has maximum absorption in the long wavelength ultraviolet region, the so-called UV-A region, and is useful as a long wavelength ultraviolet absorber.

Furthermore, the salt of the hydroxyl group at the 4-position of the benzophenone derivative (1) has a molar extinction coefficient approximately twice that of a non-salt, making it an excellent long-wavelength ultraviolet absorber.

Therefore, by using the long-wavelength ultraviolet absorber of the present invention, cosmetics and the like having excellent ultraviolet protection effects can be obtained.

〔Example〕

Next, an example will be given and explained.

Example 1 The UV protection effect of the benzophenone derivative according to the present invention was investigated based on its absorption spectrum.

That is, the benzophenone derivative according to the present invention is dissolved in water or alcohol, its absorbance is measured with a self-recording spectrophotometer, and the longest maximum absorption wavelength and its molar extinction coefficient (
ε) was calculated. The results are shown in Table 2.

In addition, the abbreviations of compounds in the table indicate the following (the same applies hereinafter).

THB: 2,2', 4,4'-tetrahydroxybenzophenone DHB: 2,4-dihydroxybenzophenone HMBS
S: Sodium 2-hydroxy-4-methoxybenzophenone sulfone DDBSS: 2,2'-dihydroxy-4,4'
- Sodium dimethoxybenzophenone-5-sulfonate HMB: 2-hydroxy-4-methoxybenzophenone HMBS: 2-hydroxy-4-methoxybenzophenone-5-sulfonic acid Table 2 As is clear from Table 2, the phenolic acid of benzophenone derivatives The product of the present invention, which is a rate salt, has a longer wavelength range than a simple benzophenone derivative, that is, the so-called U
It shows extremely thick absorption in the V-A region, indicating that it is an excellent long-wavelength ultraviolet absorber. In particular, the uninvented long-wavelength ultraviolet absorber produced from a benzophenone derivative having a hydroxyl group at the 4-position has an extremely thick absorption wavelength of Uy-A.
Not only was this observed in the @M range, but the molar extinction coefficient increased by about twice on average, and the effect of 2M was observed by using the phenolate salt.

Implementation row 2 Lotion: A lotion was prepared by blending the following composition according to a conventional method.

(Composition) ■T) (B di(triethanolamine) salt 2.0%
@Glycerin 2.0 (Q
Propylene glycol 5.0 ■ Ethanol 10.0 ■ Polyoxyethylene (20) hexadecyl ether 1.0
■Purified water 79. .

■Preservatives　　　　　　　　　　　　　　　■Fragrance ■Color element Trace amount Example 3 Gel: A gel was prepared by blending the following composition according to a conventional method.

(Composition) ■ THE lysine salt 4% ■ Inpropyl laurate 7 ■ Lecithin
0.5■Propylene glycol 8■Crystalline cellulose
7■Hydroxypropylcellulose
0.2■Purified water remaining amount Example 4 Emulsion: The following composition was blended according to a conventional method to prepare an emulsion.

(Composition) ■DHB triethanolamine salt 5.0%■
Stearin 21.5 ■Cetanol 1.0■
Oleic acid monoglyceride 0.5■Vaseline 2゜■Liquid paraffin 6.0■Squa2n 6.0■Purified water
. 9. .

■Triethanolamine 0.8 [
[Stock] Sifropyrene glycol 5.0■
Glycerin 2.0 [Co.] Carboxyvinyl Polymer 0.20 Preservative Appropriate amount [Phase] Fragrance Example 5 Cream: The following composition was blended according to a conventional method to prepare a cream.

(Composition) (υDHB disodium salt 4
Polyoxyethylene (20) Sorbitan Monooleate 2
．． O ■ Rubitan monooleate 2,0 ■ Inpropyl myristate ester 18.0 ■ Squalane 7,0 ■ 2-Ethylhexane cough triglyceride 12. O ■ Antioxidant appropriate amount ■ Purified water
51.00 Propylene glycol
5.0 ■ Preservative
Proper sound @Fragrance Example 5 Oil-based foundation: The following composition was blended in a conventional manner to prepare an oil-based foundation.

(Composition) ■2-Hydroxy-4-octyloxybenzophenone potassium salt 5 Ch ■p-
Methoxycinnamic acid 2-ethylhexyl ester 5.
0■Liquid paraffin 15.0
■Impropyl palmitate 160■Lanolin alcohol 3.00Microcrystalline wax 7.0■Osikelite 8.0■Candylla wax 0.5■Preservatives
Appropriate amount [Phase] Oxidized antifat agent ■Fragrance ■Titanium oxide 15.00 Kaolin 15.0■
Talc 60 [phase]
Red iron 1.50 yellow iron oxide 2. .

■Black iron oxide 0.5 or more

Claims (1)

[Claims] 1. The following general formula (I) ▲There are mathematical formulas, chemical formulas, tables, etc.▼(I) (In the formula, X represents an alkali metal ion, an ammonium ion, or an amino acid-based organic cation. n pieces Y and m Z's are each the same or different and represent a hydroxyl group, an alkyl or alkoxy group having 1 to 24 carbon atoms, or a sulfonic acid or an alkali metal salt thereof. n and m are integers of 0 to 3, and k+l is An integer of 1 to 4.) A long-wavelength ultraviolet absorber containing a benzophenone derivative represented by: 2. The long wavelength ultraviolet absorber according to claim 1, which is a cosmetic.