JPH0717892A - 1,3-butadienyl ketone derivative, ultraviolet ray absorber and skin external preparation containing the same blended therein - Google Patents

Abstract

PURPOSE:To obtain the novel derivative, excellent in UV-A absorptivity, usability, further UV rays protecting effects, water resistance and feeling of use and useful as an UV rays absorber and a skin external preparation. CONSTITUTION:This 1,3-butadienyl ketone derivative is expressed by formula I [R1 is H, 1-8C alkyl or alkoxy; R2 is H or 1-4C alkyl; R3 is 1-8C alkyl or aryl expressed by formula II (R4 is H, OH or 1-8C alkoxy)], e.g. (4-phenyl-1,3- butadienyl t-butyl ketone. The derivative expressed by formula I is obtained by subjecting a substituted cinnamaldehyde and various methyl ketone derivatives to condensation reaction in the presence of an alkaline catalyst or an acidic catalyst (e.g. pyridine, NaOH or hydrochloric acid) in a solvent (e.g. benzene or toluene) at a temperature between 0 deg.C and the boiling point of the solvent.

Description

Detailed Description of the Invention

[0001]

BACKGROUND OF THE INVENTION 1. Field of the Invention The present invention relates to a 1,3-butadienyl ketone 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, the ultraviolet rays that reach the ground are UV-A
And UV-B, UV-C is absorbed by the ozone layer and hardly reaches the ground.

Although UV-A and UV-B have various effects on human skin, the sunburn phenomenon is most prominent. UV-B sunburns are generally 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 absorbent 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.

[0005]

However, the existing UV-A absorber has a remarkably low compatibility with a non-polar base material and its low absorptivity in the UV-A region. There was a problem that the function of the agent was not fully exerted. The present invention has been made in view of the above-mentioned problems of the prior art, and an object thereof is to have an excellent UV-A absorption ability and to have a sufficient function thereof in order to protect the skin from ultraviolet rays in the UV-A region. The object is to provide a substance capable of exerting the above effects and a skin external preparation containing the substance.

[0006]

Means for Solving the Problems As a result of intensive studies to achieve the above object, the present inventors have found that
The inventors have found that the 3-butadienyl ketone derivative has excellent UV-A absorption ability and usability, and completed the present invention. That is, the 1,3-butadienyl ketone derivative according to the present invention is represented by the following general formula 3.

[Chemical 3] (In the formula, R ¹ is a hydrogen atom, a C _{1 to} C ₈ alkyl group or an alkoxy group, R ² is a hydrogen atom or a C _{1 to} C ₄ alkyl group, and R ³ is a C _{1 to} C ₈ alkyl group or the following. Generalization of 4
Represents an aryl group represented by. )

[0007]

[Chemical 4] (In the formula, R ⁴ represents a hydrogen atom, a hydroxyl group or a C _{1 to} C ₈ alkoxy group.) And, the ultraviolet absorber according to the present invention is one or two kinds of the 1,3-butadienyl ketone derivative. In addition, the external preparation for skin of the present invention contains one or more kinds of the 1,3-butadienyl ketone derivative.

The structure of the present invention will be described in detail below. In the 1,3-butadienyl ketone derivative represented by the general formula 3, R ¹ represents a hydrogen atom, an alkyl group or an alkoxy group having 1 to 8 carbon atoms, and examples of the alkyl group include a methyl group, Ethyl group, propyl group, isopropyl group, butyl group, s-butyl group, t-butyl group, n-pentyl group, isopentyl group, neopentyl group, n-hexyl group, 2-ethylbutyl group, n-octyl group, 2- Examples thereof include an ethylhexyl group, and examples of the alkoxy group include methoxy group, ethoxy group, propoxy group, isopropoxy group, butoxy group, s-butoxy group, t-butoxy group, n-pentyloxy group, isopentyloxy group, Examples thereof include n-hexyloxy group, n-heptaloxy group, 2-ethylbutoxy group, 2-ethylhexyloxy group and the like.

R ² represents a hydrogen atom or an alkyl group having 1 to 4 carbon atoms, and examples of the alkyl group include methyl group, ethyl group, propyl group, isopropyl group, butyl group, s-butyl group and t-butyl group. Groups and the like. R ³ has 1 carbon atom
To 8 or an aryl group represented by the general formula 4 above, and examples of the alkyl group include a methyl group, an ethyl group, a propyl group, an isopropyl group, a butyl group, a s-butyl group, a t-butyl group, Examples thereof include n-pentyl group, isopentyl group, neopentyl group, n-hexyl group, 2-ethylbutyl group, n-octyl group, 2-ethylhexyl group and the like. R ⁴ in the general formula ⁴ is a hydrogen atom,
It represents a hydroxyl group or an alkoxy group having 1 to 8 carbon atoms, and examples of the alkoxy group include those exemplified for R ¹ .

The 1,3-butadienyl ketone derivative of the present invention is obtained by subjecting a substituted cinnamic aldehyde and various methyl ketone derivatives to a condensation reaction in a solvent between 0 ° C. and the boiling point of the solvent using an alkaline catalyst or an acidic catalyst. Can be obtained by Examples of the solvent used in the reaction include benzene, toluene, diethyl ether, tetrahydrofuran, dioxane, hexane, methyl alcohol, ethyl alcohol, dimethylformamide, dimethyl sulfoxide, pyridine, piperidine, stable against water or other alkali or acid. Any solvent can be used, and a mixed solvent thereof may be used.

Examples of the catalyst used in the reaction include organic bases such as pyridine, piperidine, pyrrolidine and triethylamine, and inorganic bases such as sodium hydroxide, potassium hydroxide, potassium carbonate, sodium hydride and sodium amide. , Hydrochloric acid, sulfuric acid, p-toluenesulfonic acid and the like can also be used. Incidentally, R ^{1 of} the present invention is 1,
A p-xylidene ketone derivative having a 3-butadienyl ketone group is disclosed in JP-A-4-134041, and a styryl ketone derivative having a 1,3-butadienyl group is a styryl group is disclosed in JP-A-4-134042. It is disclosed to be used as. However, they are difficult to synthesize or have a low UV-A absorption ability, so that it is difficult to effectively use them as UV-A absorbers.

On the other hand, the 1,3-butadienyl ketone derivatives according to the present invention are all U of 320 to 370 nm.
It exhibits extremely strong absorption in the VA region and can be used as a UV-A absorber. Further, it has high solubility in non-polar oils and can be blended in various skin external preparations, and in particular, it can be blended at a high concentration in non-polar oil-based skin external preparations, and has an ultraviolet protection effect, water resistance and It is possible to obtain an external preparation for skin that is excellent in usability. The base used in the external preparation for skin of the present invention is not a problem as long as the 1,3-butadienyl ketone derivative can be dissolved therein, but in particular liquid paraffin, squalane, a non-polar oil such as silicone oil By using, it is possible to obtain excellent feeling of use 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 base is not particularly limited, but for example, chain polysiloxanes such as dimethylpolysiloxane, methylpolysiloxane, methylhydrogenpolysiloxane, decamethylcyclopolysiloxane, dodecamethylcyclosiloxane, etc. 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, for example, any of powder, cream, paste, stick, liquid, spray, foundation and the like, and an emulsifier is used. It may be an emulsion. The blending amount of the 1,3-butadienyl ketone 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 0.1 to 20% by weight, preferably 0.5 to 10% by weight.

Further, the 1,3-butadienyl ketone derivative of the present invention exerts its effect sufficiently even if used alone, but if necessary, other UV-A absorber or UV-B absorber is used. It is also possible to use together with. 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.

[0017]

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 1,3-Butadienyl Ketone Derivative] The production methods of the following compounds 1 to 4 will be described. Compound 1: (4-phenyl-1,3-butadienyl) -t-butyl ketone Compound 2: {4- (4-methoxyphenyl) -1,3-butadienyl} -t-butyl ketone Compound 3: (4-phenyl-1 , 3-Butadienyl) -2-hydroxyphenyl ketone Compound 4: (3-Methyl-4-phenyl-1,3-butadienyl)
-2-hydroxyphenyl ketone

Production Example 1 (Production of Compound 1) 3.2 g of potassium hydroxide was dissolved in a mixed solvent of 50 ml of ion-exchanged water and 40 ml of ethyl alcohol, and 5.0 g (0.038 mol) of cinnamaldehyde and pinacolone were dissolved therein. 3.8 g (0.038 mol), ethyl alcohol 10 m
1 of the mixed solution was added dropwise. After completion of dropping, the mixture was stirred at room temperature for 1 day, the solvent was distilled off under reduced pressure, 100 ml of ion-exchanged water was added to acidify the hydrochloric acid, and the mixture was extracted with diethyl ether. After the extract was dried over anhydrous sodium sulfate, the solvent was distilled off under reduced pressure, and the residue was separated and purified by silica gel chromatography (eluted with ethyl acetate: hexane = 1: 8 mixture) to obtain 4.0 g of the target substance as a pale yellow solid. Got

The nuclear magnetic resonance spectrum (NMR) data, maximum absorption wavelength (λmax), mass spectrum data and melting point of the obtained target substance were as follows. NMR (CDCl ₃ , δ); 7.43-7.49 (m,
3H), 7.31-7.37 (m, 3H), 6.94.
(S, 1H), 6.92 (d, J = 9.2 Hz, 1
H), 6.68 (d, J = 14.8 Hz, 1H), 1.
19 (s ,, 9H) λmax (ethanol) 322 nm (ε = 31.5)
00) Mass spectrum M ⁺ m / e 214 Melting point 50-52 ° C

Production Example 2 (Production of Compound 2) 1.0 g of potassium hydroxide was dissolved in a mixed solvent of 30 ml of ion-exchanged water and 20 ml of ethyl alcohol, and 4-
A mixed solution of 3.0 g (0.0185 mol) of methoxycinnamaldehyde, 1.85 g (0.0185 mol) of pinacolone, and 10 ml of ethyl alcohol was added dropwise. After completion of dropping, the mixture was stirred at room temperature for 1 day, the solvent was distilled off under reduced pressure, 50 ml of ion-exchanged water was added to acidify the hydrochloric acid, and the mixture was extracted with diethyl ether. The extract was dried over anhydrous sodium sulfate, the solvent was evaporated under reduced pressure, and the residue was separated and purified by silica gel chromatography (eluted with ethyl acetate: hexane = 1: 6 mixture) to give 1.84 g of the desired product as a pale yellow solid. Got

The nuclear magnetic resonance spectrum (NMR) data, maximum absorption wavelength (λmax), mass spectrum data and melting point of the obtained target substance were as follows. Also, FIG.
Shows a UV spectrum at a concentration of 10 ppm (solvent; ethyl alcohol). NMR (CDCl ₃ , δ); 7.45 (dd, J = 1)
4.8, 10.8Hz, 1H), 6.89 (t, J = 1
5.2 Hz, 1 H), 6.88 (d, J = 8.8 Hz,
2H), 6.79 (dd, J = 15.2, 10.8H
z, 1H), 6.63 (d, J = 14.8 Hz, 1
H), 3.83 (s, 3H), 1.19 (s, 9H) λmax (ethanol) 348 nm (ε = 39,6)
00) Mass spectrum M ⁺ m / e 244 Melting point 84-86 ° C

Production Example 3 (Production of Compound 3) 1.32 g of cinnamic aldehyde and 1.36 g of orthohydroxyacetophenone were dissolved in 10 ml of ethyl alcohol, and 1.1 g of potassium hydroxide was added to ion-exchanged water while stirring at room temperature. A solution dissolved in 3 ml was added. After stirring at room temperature for 48 hours, pour into 60 ml of ice water and add pH with concentrated hydrochloric acid.
Was adjusted to about 3, a solid was precipitated. This solid was collected by filtration and recrystallized from ethyl alcohol to obtain 1.8 g of the desired product as an orange solid. The structure is the nuclear magnetic resonance spectrum (NM
R). The maximum absorption wavelength (λmax), mass spectrum data, and melting point of the obtained target substance were as follows. λmax (ethanol) 359 nm (ε = 36,7)
00) Mass spectrum M ⁺ m / e 250 Melting point 159-160 ° C

Production Example 4 (Production of Compound 4) 3.0 g of α-methylcinnamic acid aldehyde, 2.8 g of orthohydroxyacetophenone, and ethyl alcohol 15
1. Dissolve in ml and stir at room temperature with potassium hydroxide 2.
A solution obtained by dissolving 3 g in 3 ml of ion-exchanged water was added.
After stirring at room temperature for 48 hours, the mixture was poured into 80 ml of ion-exchanged water and the pH was adjusted to about 3 with concentrated hydrochloric acid to precipitate crystals.
The crystals were collected by filtration and recrystallized twice from ethyl alcohol to obtain 3.2 g of the desired product as an orange solid. The structure was confirmed by nuclear magnetic resonance spectrum (NMR). The maximum absorption wavelength (λmax), mass spectrum data and melting point of the obtained target substance were as follows. In addition, 10pp in FIG.
The UV spectrum at m concentration (solvent; ethyl alcohol) is shown. λmax / ethanol 350 nm (ε = 31,9
00) Mass spectrum M ⁺ m / e 264 Melting point 98-100 ° C

[Ultraviolet Absorption Effect] The compounds 1 and 3 as the 1,3-butadienyl ketone derivative of the present invention and a comparative compound (2-hydroxy-4-methoxybenzophenone; UV-A absorber) were used. The ultraviolet absorption effect was measured. As a measuring method, a 10 ppm concentration ethanol solution of each compound was prepared, and the absorbance was measured with a UV IDEC-610 type spectrophotometer manufactured by JASCO Corporation using a quartz cell (1 cm × 1 cm). The ethanol used had a purity of 99.5% (special grade reagent).

As a result, as shown in Table 1, all the test compounds have the maximum absorption wavelength in the UV-A region, but comparing the absorbances at the maximum absorption wavelength, the compounds 1 and 2 are compared even at the same concentration. It was about 3 times or more that of compound a. As described above, the 1,3-butadienyl ketone derivative of the present invention has a markedly higher UV-absorbing effect in the UV-A region than the comparative compound, and by blending the compound, the external preparation for skin having a high sun-blocking effect. It was revealed that

[0026]

[Table 1] ────────────────────────────────── Wavelength Absorbance (nm) Compound 1 Compound 3 Comparative compound ────────────────────────────────── 300 1.04 0.32 0.39 310 1.32 0.46 0.35 320 1.46 0.70 0.40 330 1.42 1.02 0.42 340 1.10 1.28 0.34 350 0.66 1.44 0.20 360 0.32 1.48 0.11 370 0.16 1.38 0.03 380 0.06 1.16 0.00 ───────────────────────── ──────────

[UV Protection Effect Test] Formulation Example 1 (Sunscreen Oil) The UV protection effect of the 1,3-butadienyl ketone derivative of the present invention was actually examined using a human body panel as follows. . <Preparation of Sunscreen Oil> Using the 1,3-butadienyl ketone derivative of Compound 1 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 in place of the compound 1 (total blending amount with respect to the sunscreen oil is 5.0% by weight) was similarly prepared. .

Decamethylcyclopentasiloxane 47.0 wt% Dimethylpolysiloxane (10cs / 25 ° C) 20.0 Methylphenylpolysiloxane (20cs / 25 ° C) 18.0 Silicone resin 10.0 p-Dimethylaminobenzoic acid 2- Ethylhexyl ester 3.0 Compound 1 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 2, when the oil of the blending example 1 was applied, 70% of the panelists showed almost no sunburn, and the remaining 30% 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 30% 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 1,3-butadienyl ketone derivative of the present invention has an excellent UV protection effect and prevents sunburn and skin troubles caused by UV rays. It was

[Table 3] ─────────────────────────────── Panel Sunburn Evaluation Formulation Example 1 Comparative Example ─────── ───────────────────────── A ○ ○ B ○ ○ C ○ × D △ △ E ○ △ F △ × G ○ △ H ○ × I △ △ J ○ △ ──────────────────────────────── No skin trouble 3 cases 3 cases itching 2 cases rash 1 case ────────────────────────────────

The following external preparations for skin of Formulation Examples 2 to 7 were prepared and tested for UV protection effect in the same manner as in Formulation Example 1 above. All had excellent effects, and sunburn and skin trouble due to UV light were observed. It was to prevent. 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-Dimethylaminobenzoic acid Acid 2-ethylhexyl ester 5.0 {4- (4-methoxyphenyl) -1,3-butadienyl} -t-butyl ketone 4.0 Perfume 0.2 <Water phase part> Purified water 43.1 L-sodium glutamate 3 0.0 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-Methoxysilicate Cinnamate 2-ethylhexyl ester 3.0 (4-phenyl-1,3-butadienyl) -isopropyl ketone 1.0 Preservative 0.2 Perfume 0.2 <Water phase part> Glycerin 10.0 Propylene glycol 5.0 Hyalurone 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) 3.0wt% Methylphenylpolysiloxane (20cs) 17.0 Stearic acid 1.0p-Dimethylaminobenzoic acid 2-ethylhexyl ester 5.0 {4- (4-ethyl Phenyl) -1,3-butadienyl} -t-butyl ketone 7.0 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 {4- (4-Ethylphenyl) -1,3-butadienyl} -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 (4-phenyl-1,3-butadienyl) -2-hydroxyphenylketone 3.0 Sorbitan sesquioleate 1.0 Antioxidant 0.1 <Part C> Microcrystalline wax 2.0 Ceresin 1.0 Solid paraffin 6.0 Perfume 0.5

Formulation 7 (makeup base cream) A make-up 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-Methyl-4-phenyl-1,3-butadienyl) -2-hydroxyphenylketone 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

As described above, for the external preparation for skin according to the present invention, the base and other compounding ingredients can be freely selected. Also,
It has the characteristics that it spreads well, has a refreshing feeling, has an excellent feeling of use such as being non-greasy, and that it does not easily flow into sweat or water and the UV protection effect continues.

[0039]

The 1,3-butadienyl ketone derivative according to the present invention has an excellent UV-A absorption ability and usability, and by blending it with the UV-A protective effect, water resistance and usability. It is possible to obtain an excellent external preparation for skin.

[Brief description of drawings]

FIG. 1 is an ultraviolet absorption spectrum diagram of {4- (4-methoxyphenyl) -1,3-butadienyl} -t-butyl ketone according to an example of the present invention.

FIG. 2 is an ultraviolet absorption spectrum diagram of 3-methyl-4-phenyl) -1,3-butadienyl-2-hydroxyphenyl ketone according to an example of the present invention.

─────────────────────────────────────────────────── ───

[Procedure amendment]

[Submission date] August 23, 1993

[Procedure Amendment 1]

[Document name to be amended] Statement

[Correction target item name] 0035

[Correction method] Change

[Correction content]

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 Hensiel 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 beeswax 2.0 {4- (4-ethylphenyl) -1,3-butadienyl} preparative isopropyl ketone 0.5 sorbitan trioleate 1.0 vitamin E 0.05 preservative 0.5 perfume 0 .5

Continuation of the front page (51) Int.Cl. ⁶ Identification code Office reference number FI technical display area C07C 49/794 9049-4H

Claims (3)

[Claims] 1. A 1,3-butadienyl ketone derivative represented by the following general formula 1. [Chemical 1] (In the formula, R ¹ is a hydrogen atom, a C _{1 to} C ₈ alkyl group or an alkoxy group, R ² is a hydrogen atom or a C _{1 to} C ₄ alkyl group, and R ³ is a C _{1 to} C ₈ alkyl group or the following. Generalization of 2
Represents an aryl group represented by. ) [Chemical 2] (In the formula, R ⁴ represents a hydrogen atom, a hydroxyl group or a C _{1 to} C ₈ alkoxy group.) 2. An ultraviolet absorber comprising one or more of the 1,3-butadienyl ketone derivative according to claim 1. 3. An external preparation for skin, comprising one or more of the 1,3-butadienyl ketone derivative according to claim 1.