JPH0717911A - 3-naphthylpropenoic acid ester derivative, ultraviolet rays absorber and skin external preparation containing the same blended therein - Google Patents

Abstract

PURPOSE:To obtain a novel 3-naphthylpropenoic acid ester derivative, having excellent UV-A absorptivity and usability and useful as a UV rays absorber and a skin external preparation. CONSTITUTION:This 3-naphthylpropenoic acid ester derivative is expressed by the formula (R<1> and R<2> are H, OH or 1-8C alkoxy; R<3> is 2-18C alkyl or alkenyl), e.g. 2-ethylhexyl 3-(1-naphthyl)propenoate. The exemplified compound in the compound expressed by the formula is obtained by reacting 3-(1-naphthyl) propenoic acid with 2-ethylhexanol.

Description

Detailed Description of the Invention

[0001]

BACKGROUND OF THE INVENTION 1. Field of the Invention The present invention relates to a 3-naphthylpropenoic acid ester derivative and a skin external preparation, and more particularly to a substance having an ultraviolet absorbing ability in the UV-A region and a skin external preparation.

[0002]

2. Description of the Related Art Ultraviolet rays contained in sunlight are dermatologically long wavelength ultraviolet rays (UV-) of 320 nm to 400 nm.
A) Medium wavelength ultraviolet rays (UV-
B), and short wavelength ultraviolet rays (UV-C) of 290 nm or less
are categorized. Of these, UV-C is almost absorbed by the ozone layer before it reaches the surface of the earth, so most of the ultraviolet rays that reach the ground are UV-A and UV-B. Although UV-A and UV-B have various effects on human skin, the sunburn phenomenon is most prominent.

UV-B sunburn is generally a sunbu
It is called rn and causes inflammatory symptoms such as erythema and blisters mainly on the skin, whereas UV-A sunburn is a browning of the skin generally called suntan, which reduces the elasticity of the skin and reduces wrinkles. Accelerates the occurrence and causes a rapid aging phenomenon. UV-A is also known to accelerate the initiation of the erythema reaction, but it may enhance the erythema reaction in some patients, which causes phototoxicity or photoallergic reaction. Sometimes.

In order to prevent such harmful effects of ultraviolet rays, it is effective to appropriately select and use an ultraviolet absorber suitable for the purpose, and various ultraviolet absorbers have been developed so far. However, the UV-A absorber is U
The number is very small compared to V-B absorbents, for example,
Only benzophenone derivatives, dibenzoylmethane derivatives, benzotriazole derivatives and the like are known.

On the other hand, in order to maintain the effect of the ultraviolet absorber in the skin external preparation, it is important to make the skin external preparation excellent in water resistance and not easily washed off by sweat or water bath. Therefore, in recent years, non-polar oils such as liquid paraffin, squalane and silicone oil have been widely used as a base for external preparations for skin such as cosmetics for preventing ultraviolet rays. These bases have not only a water-resistant function, but also have a great use feeling such as good spreadability, a refreshing feeling, and non-stickiness.

[0006]

However, since the existing UV-A absorbers have extremely low solubility in non-polar oils, they are based on skin external preparations, especially non-polar oils which have been widely used in recent years. In the external preparation for skin, the amount used is limited, and there is a problem that the function of the UV-A absorber is not sufficiently exhibited. In addition, it is generally a dark-colored crystal, crystallization at low temperature in products, coloring clothes, etc.,
There was also a problem that when metal ions were present, they reacted and discolored. The present invention has been made in view of the above-mentioned problems of the prior art, and an object thereof is a UV-A absorber which exhibits high solubility in a nonpolar oil base and does not discolor even in the presence of metal ions. It is to provide a skin external preparation containing

[0007]

Means for Solving the Problems As a result of intensive studies to achieve the above-mentioned object, the present inventors have found that the 3-naphthylpropenoic acid ester derivative has excellent UV-A absorption ability and usability. Therefore, the present invention has been completed. That is, the 3-naphthylpropenoic acid ester derivative and the ultraviolet absorber according to the present invention are represented by the following general formula 2.

[Chemical 2] (In the formula, R ¹ and R ² are each a hydrogen atom, a hydroxyl group or C
_{1 to} C ₈ alkoxyl group, R ³ represents a C _{2 to} C ₁₈ alkyl group or alkenyl group. )

The external preparation for skin according to the present invention is characterized by containing one or more of the 3-naphthylpropenoic acid ester derivatives. The configuration of the present invention will be described in detail below. 3 represented by the general formula 2
In the naphthylpropenoic acid ester derivative, R ¹ and R ² are each a hydrogen atom, a hydroxyl group or a carbon number of 1-8.
Represents an alkoxyl group, and examples of the alkoxyl group include a methoxy group, an ethoxy group, a propoxy group, an isopropoxy group, a butoxy group, an isobutoxy group, a t-butoxy group, a pentyloxy group, a neopentyloxy group, a hexyloxy group, a heptoxyl group. , 2-ethylbutoxy group, 2-
An ethylhexyloxy group etc. are mentioned.

R ³ represents a linear alkyl group or alkenyl group having 2 to 18 carbon atoms, or a branched alkyl group, for example, ethyl group, propyl group, isopropyl group, butyl group, isobutyl group, t-butyl group. Group, pentyl group, neopentyl group, 2-ethylbutyl group, 2-ethylhexyl group, 2-hexyldecyl group, 2-heptylundecyl group, methyl-branched isostearyl, oleyl group and the like, but preferably branched alkyl group Is.

The 3-naphthylpropenoic acid ester derivative according to the present invention can be easily produced by a general esterification reaction. For example, 3 naphthyl propenoic acid,
A method of dehydrating an alkyl or alkenyl alcohol in a hydrocarbon solvent or aromatic solvent using an acid catalyst such as an organic acid or an inorganic acid, or a base catalyst such as an organic base or an inorganic base under heating, or 3-naphthyl. There is a method in which a halogenide of propenoic acid and an alkyl or alkenyl alcohol are reacted in the absence of a solvent or in a non-aqueous solvent in the presence of the base. By any of these methods, the target 3-naphthylpropenoic acid ester derivative can be obtained in high yield.

The 3-naphthylpropenoic acid ester derivatives of the present invention each have a maximum absorption in the UV-A region of 320 nm or more, and have extremely high solubility in nonpolar oils, and therefore, skin external preparations, In particular, it can be blended in a high concentration in a skin external preparation based on a non-polar oily agent, and it is possible to obtain a skin external preparation excellent in ultraviolet protection effect, water resistance and feeling of use. As the base used in the external preparation for skin of the present invention, there is no problem as long as it can dissolve the 3-naphthylpropenoic acid ester derivative, but liquid paraffin, squalane, a non-polar oil such as silicone oil is used. With this, it is possible to obtain excellent usability such as good spreadability, refreshing feeling, and non-greasiness, and water resistance that is hard to be washed away by water or sweat.

The silicone oil used as the above-mentioned base is not particularly limited, but for example, chain polysiloxanes such as dimethylpolysiloxane, methylpolysiloxane, methylhydrogenpolysiloxane, decamethylcyclopolysiloxane and dodecamethylcyclo. Examples include polysiloxane, cyclic polysiloxane such as tetramethylhydrogencyclopolysiloxane, polyether, fatty acid-modified polysiloxane, higher alcohol-modified polysiloxane, amino acid-modified polysiloxane, and the like.

The dosage form of the external preparation for skin of the present invention is arbitrary and may be any of powder, cream, paste, stick, liquid, spray, foundation and the like, and an emulsifier is used. It may be an emulsion. The compounding amount of the 3-naphthylpropenoic acid ester derivative in the external preparation for skin of the present invention is not particularly limited and varies depending on how much ultraviolet absorption effect is required. It is 1 to 20% by weight, preferably 0.5 to 10% by weight.

The 3-naphthylpropenoic acid ester derivative of the present invention exerts its effect sufficiently even if used alone, but if necessary, other UV-A absorber or UV-B can be used.
It is also possible to use together with an absorbent. In fact, in sunscreen cosmetics and the like, UV-B absorbers are often added together with UV-A absorbers. Examples of UV-B absorbers include p-aminobenzoic acid derivatives such as p-dimethylaminobenzoic acid 2-ethylhexyl ester and p-methoxycinnamic acid derivatives such as p-methoxycinnamic acid 2-ethylhexyl ester. , Salicylic acid derivatives, benzylidene camphor derivatives, urocanic acid or its derivatives, and inorganic pigments such as titanium dioxide and zinc oxide.

In addition to the above-mentioned components, the external preparation for skin of the present invention is a component usually used in medicines, cosmetics and the like, for example,
Oils, lubricating oils, antioxidants, surfactants, preservatives, sequestering agents, fragrances, water, alcohols, thickeners, agents and the like can be appropriately added within a range that does not impair the effects of the present invention.

[0016]

The present invention will be described in more detail with reference to the following examples, but the present invention is not limited thereto. In the following description, all blending amounts are wt% unless otherwise specified. [Production of 3-naphthylpropenoic acid ester derivative] The production methods of the following compounds 1 and 2 will be described. Compound 1: 3- (1-naphthyl) propenoic acid 2-ethylhexyl ester Compound 2: 3- (6-Methoxy-2-naphthyl) propenoic acid 2-
Ethylhexyl ester

Production Example 1 (Production of Compound 1) A mixed solution of 5.0 g of 3- (1-naphthyl) propenoic acid, 6.0 g of thionyl chloride and 30 ml of benzene was refluxed for 3 hours, and then benzene and excess thionyl were added under reduced pressure. The chloride was completely distilled off. To the residue was added 60 ml of benzene and dissolved, 3.3 g of 2-ethylhexanol and 10 ml of pyridine.
The mixed solution of was added dropwise at room temperature with stirring. After completion of dropping, the reaction solution is heated at 70 to 80 ° C. for 3 hours, and the reaction solution is cooled to 200 ° C.
Injected into ml. Wash thoroughly with 2N-hydrochloric acid, followed by water,
After drying, the solvent was distilled off under reduced pressure. The residue was separated and purified by silica gel chromatography (eluted with a 15% ethyl acetate-hexane mixed solution) to obtain 6.4 g of the desired product as a colorless oil.

The maximum absorption wavelength (λma
x) and mass spectrum data were as follows. λmax (ethanol) 323 nm (ε = 13,3
00) Mass spectrum M ⁺ m / e 310

Production Example 2 (Production of Compound 2) A mixed solution of 5.3 g of 3- (6-methoxy-2-naphthyl) propenoic acid, 5.5 g of thionyl chloride and 30 ml of benzene was refluxed for 3 hours and then dried under reduced pressure to dryness. To the residue was added 60 ml of benzene to dissolve it, and a mixed solution of 3.02 g of 2-ethylhexanol and 10 ml of pyridine was added dropwise at room temperature with stirring. Thereafter, the same treatment as in Production Example 1 was carried out (however, a 20% ethyl acetate-hexane mixed solution was used as an eluent for silica gel chromatography) to obtain 5.2 g of the colorless oily target product.

The maximum absorption wavelength (λma
x) and mass spectrum data were as follows. λmax (ethanol) 325 nm (ε = 28.5
00) Mass spectrum M ⁺ m / e 340 [Solubility in non-polar oil] Compounds 1 and 2 as the 3-naphthylpropenoic acid ester derivative of the present invention, and 2-hydroxy-4-methoxybenzophenone (comparative compound) Using a), the solubility in non-polar oils was investigated. As the non-polar oil, silicone KF56 (10 cs, manufactured by Shin-Etsu Chemical Co., Ltd.) and squalane were used.

As a result, as shown in Table 1, the 3-naphthylpropenoic acid ester derivatives of Compounds 1 and 2 were dissolved by 10% or more in any nonpolar oil agent, while
The 2-hydroxy-4-methoxybenzophenone of Comparative Example a had low solubility in any nonpolar oil, and crystals were precipitated. As described above, it was revealed that the 3-naphthylpropenoic acid ester derivative according to the present invention has excellent solubility in nonpolar oils.

[Table 1] ───────────────────────────────── Samples Properties Solubility * Silicon KF56 Squalane ─── ────────────────────────────── Compound 1 colorless oil ○ ○ Compound 2 colorless oil ○ ○ ───────── ───────────────────────── Comparative compound a pale yellow crystal × × ───────────────── ──────────────── * Appearance of each sample dissolved in each non-polar oil at 10w / w%: ○ ・ ・ ・ Completely dissolved, × ・ ・ ・ Not dissolved (Crystal precipitation)

[Discoloration by Metal Ions] The compounds 1 and 2 as the 3-naphthylpropenoic acid ester derivative of the present invention and 2-hydroxy of the comparative compound a as a comparative example.
Using 4-methoxybenzophenone and 2-hydroxy-5-methylphenylbenzotriazole (comparative compound b) as samples, the discoloration by metal ions was examined.

That is, 0.1 g of each sample was added to 1 part of ethanol.
Dissolve in 0 ml, ferric chloride (FeCl ₃ ) 0.02%
After adding 2 ml of the contained ethanol solution and stirring well, the change in color tone of the solution was observed. All the ethanol used in this test had a purity of 99.5% (special grade reagent). As a result, as shown in Table 2, no change in the color tone of the test liquid was observed for the 3-naphthylpropenoic acid ester derivatives of Compounds 1 and 2, but 2-hydroxy-4 of Comparative Compound a.
-Methoxybenzophenone and 2-hydroxy-5-methylphenylbenzotriazole of Comparative Compound b are Fe ³⁺
The addition of each caused discoloration from pale yellow to brown and pale yellow to blue, respectively.

As described above, it is clear that the 3-naphthylpropenoic acid ester derivative of the present invention is an excellent UV-A absorber which does not react with metal ions and does not discolor even in the presence of metal ions. became.

[Table 2] ────────────────────────────── specimen FeCl ₃ addition before FeCl ₃ after the addition ────── ──────────────────────── Compound 1 Colorless No change Compound 2 Colorless No change ──────────────── ────────────── Comparative compound a Light yellow brown Comparative compound b Light yellow blue ──────────────────────── ──────

[UV Protection Effect Test] Formulation Example 1 (Sunscreen Oil) The UV protection effect of the 3-naphthylpropenoic acid ester derivative of the present invention was actually examined using a human body panel as follows.

<Preparation of sunscreen oil> As a sample,
Using the 3-naphthylpropenoic acid ester derivative of Compound 2 described above, each component was sufficiently dissolved according to the following formulation and then filtered to prepare a sunscreen oil (Formulation Example 1). In addition, as a comparative example, a sunscreen oil using p-dimethylaminobenzoic acid 2-ethylhexyl ester instead of the 3-naphthylpropenoic acid ester derivative of Compound 2 (the total content of the sunscreen oil is 5.0% by weight) Was also prepared in the same manner. Decamethylcyclopentasiloxane 47.0 wt% Dimethylpolysiloxane (10cs / 25 ° C) 20.0 Methylphenylpolysiloxane (20cs / 25 ° C) 22.0 Silicone resin 5.0 p-Dimethylaminobenzoic acid 2-ethylhexyl ester 3 0.0 sample 2.0

<Test Method> The sunscreen oils of Formulation Example 1 and Comparative Example were applied to the left and right half of each body of 10 panelists, and the degree of sunburn on the beach was evaluated according to the following criteria. ○: Almost no sunburn was observed △: Mild sunburn was observed ×: Strong sunburn was observed

<Results> As shown in Table 3, when the oil of the blending example 1 was applied, 90% of the panelists showed almost no sunburn, and the remaining 10% of the panelists had mild sunburn symptoms. It was only observed and none of the panelists had severe sunburn symptoms. On the other hand, in the oil of Comparative Example, 80% of panelists complained of severe or mild sunburn symptoms, and 40% of the panelists had severe sunburn symptoms. Further, no skin trouble was observed at the sunscreen oil application part of the formulation example 1, but troubles such as skin tightness, itchiness and rash occurred at the application part of the comparative example.

From the above, it has been clarified that the external preparation for skin containing the 3-naphthylpropenoic acid ester derivative of the present invention has an excellent UV protection effect and prevents sunburn and skin troubles caused by UV rays.

[Table 3] ─────────────────────────────── Panel Suntan Evaluation Formulation Example 1 Comparative Example ─────── ───────────────────────── A ○ ○ B ○ × C ○ × D ○ ○ E ○ × F ○ △ G ○ △ H △ × I ○ △ J ○ △ ──────────────────────────────── No skin troubles 4 withdrawals 4 with itching 1 with rash 2 ───────────────────────────────── The following external preparations for skin were prepared, and When the ultraviolet protection effect was tested in the same manner as in Example 1, all had excellent effects and were able to prevent sunburn and skin troubles caused by ultraviolet rays.

Formulation Example 2 (W / O cream) A W / O cream was prepared according to the following formulation. As for the preparation method, the oil phase part and the water phase part were each melted by heating and kept at 70 ° C., the water phase part was added to the oil phase part, and the mixture was sufficiently emulsified by an emulsifying machine. After emulsification, the mixture was cooled to 35 ° C. or lower with stirring, poured into a container, allowed to cool and solidified to obtain a W / O cream. <Oil phase part> Octamethylcyclotetrasiloxane 10.5 wt% Dimethylpolysiloxane (100cs) 5.0 Dimethylpolysiloxane (2,500,000cs) 3.0 Liquid paraffin 15.0 Polyether-modified silicone 6.0 p-methoxy cinnamon Acid 2-Ethylhexyl ester 5.0 3- (1-Naphthyl) propenoic acid 2-Ethylhexyl ester 4.0 Perfume 0.2 <Aqueous phase part> Purified water 43.1 L-Glutamic acid sodium 3.0 1,3-butylene Glycol 5.0 Preservative 0.2

Formulation Example 3 (O / W cream) An O / W cream was prepared according to the following formulation. The preparation method is such that the oil phase part and the water phase part are each heated and dissolved at 70 ° C.,
The oil phase part was added to the water phase part and sufficiently emulsified by an emulsifying machine. The emulsion was cooled to 30 ° C. with a heat exchanger and then filled in a container to obtain an O / W cream. <Oil phase part> Decamethylcyclopentasiloxane 3.0 wt% Liquid paraffin 8.0 Isopropyl myristate 2.0 Vaseline 4.0 Cetanol 4.0 Stearic acid 3.0 Glyceryl monoisostearate 3.0 p-Dimethylamino Benzoic acid 2-ethylhexyl ester 3.0 3- (6-Methoxy-2-naphthyl) propenoic acid 2-ethylhexyl ester 1.0 Preservative 0.2 Perfume 0.2 <Water phase part> Glycerin 10.0 Propylene glycol 5 0.0 hyaluronic acid 0.01 potassium hydroxide 0.2 purified water 53.39

Formulation Example 4 (Lotion) A lotion was prepared according to the following formulation in the same manner as in Formulation Example 3 above. <Oil phase part> Dimethylpolysiloxane (5cs) 10.0wt% Methylphenylpolysiloxane (20cs) 7.0 Stearic acid 1.0 p-Methoxycinnamic acid 2-ethylhexyl ester 5.0 3- (4-methoxy- 1-Naphthyl) propenoic acid ethylhexyl ester 10.0 Preservative 0.2 Perfume 0.2 <Water phase part> Glycerin 5.0 Montmorillonite 0.5 Potassium hydroxide 0.2 Purified water 60.9

Formulation Example 5 (dual use foundation) A dual use foundation was prepared according to the following formulation. The preparation method is to mix Part A with a Henschel mixer,
What was heated and melt | dissolved in this part B was added and mixed, it grind | pulverized, and this was shape | molded to the inside plate, and the dual-use foundation was obtained. <Part A> Silicone treated titanium oxide 9.5 wt% Silicone treated mica 40.0 Silicone treated talc 20.45 Silicone treated iron oxide 7.5 Spherical nylon powder 10.0 <Part B> Trimethylolpropane triisostearate 5. 0 Squalane 3.0 Bee wax 2.0 3- (6-Methoxy-2-naphthyl) propenoic acid 2-ethylhexyl ester 0.5 Sorbitan trioleate 1.0 Vitamin E 0.05 Preservative 0.5 Perfume 0.5

Formulation Example 6 (Stick cosmetic) A stick cosmetic was prepared according to the following formulation.
The preparation method is as follows: Part A is mixed with a Henschel mixer, to which part B is heated and dissolved is added and further mixed and ground. Next, after adding the one in which the C part is dissolved, thoroughly mixing,
It was formed into a stick. <Part A> Titanium oxide 10.0 wt% Zinc oxide 7.0 Mica 16.0 Red iron oxide 1.5 Yellow iron oxide 1.5 Black iron oxide 1.0 <Part B> Dimethylpolysiloxane (20cs) 29.4 Trimethylolpropane-tri-2-ethylhexanoate 8.0 Liquid paraffin 7.0 p-Dimethylaminobenzoic acid 2-ethylhexyl ester 5.0 3- (1-Naphthyl) propenoic acid isopropyl ester 3.0 Sorbitan sesquiole ATE 1.0 Antioxidant 0.1 <Part C> Microcrystalline wax 2.0 Ceresin 1.0 Solid paraffin 6.0 Perfume 0.5

Formulation Example 7 (makeup base cream) A makeup base cream was prepared according to the following formulation. The preparation method is such that the oil phase part and the water phase part are each heated and dissolved at 70 ° C., the water phase part is added to the oil phase part to emulsify and disperse, and then cooled,
A makeup base cream was obtained. <Oil phase part> Squalane 19.0 wt% Glyceryl triisostearate 10.0 Isopar G 5.0 Sorbitan sesquioleate 1.0 Polysiloxane Ethylene-modified organopolysiloxane 3.0 p-Methoxycinnamic acid 2-ethylhexyl ester 1.0 3- (6-Methoxy-2-naphthyl) propenoic acid 2-ethylhexyl ester 1.0 Antioxidant Appropriate amount Perfume Appropriate amount <Water phase part> 1,3-Butylene glycol 5.0 Fine particle titanium oxide 10. 0 Preservative Appropriate amount Purified water Residual

[0036]

INDUSTRIAL APPLICABILITY The 3-naphthylpropenoic acid ester derivative according to the present invention has excellent UV-A absorption ability, exhibits high solubility in nonpolar oils, and discolors in the presence of metal ions. There is nothing to do. Therefore, the above-mentioned derivative can be blended as a UV-A absorber into various skin external preparations, particularly non-polar oil-based skin external preparations,
It is possible to obtain an external preparation for skin which is excellent in ultraviolet protection effect, water resistance, feeling in use and product stability.

Claims (3)

[Claims] 1. A 3-naphthylpropenoic acid ester derivative represented by the following general formula 1. [Chemical 1] (In the formula, R ¹ and R ² are each a hydrogen atom, a hydroxyl group or C
_{1 to} C ₈ alkoxyl group, R ³ represents a C _{2 to} C ₁₈ alkyl group or alkenyl group. ) 2. An ultraviolet absorber comprising one or more of the 3-naphthylpropenoic acid ester derivative according to claim 1. 3. A skin external preparation containing one or more of the 3-naphthylpropenoic acid ester derivative according to claim 1.