JP3088222B2 - UV absorber and external preparation for skin - Google Patents

Description

DETAILED DESCRIPTION OF THE INVENTION

[0001]

The present invention relates to an ultraviolet absorbent and a skin external preparation. More specifically, an ultraviolet absorbent comprising a silicone-based hydantoin derivative which is dissolved in silicone oil, has excellent water resistance and oil resistance, and has ultraviolet absorption characteristics at a wavelength in the UV-A region, and an external skin containing the same Agent.

[0002]

2. Description of the Related Art Ultraviolet rays are known to cause various changes on the skin. Dermatologically, ultraviolet rays are classified into long-wavelength ultraviolet rays called UV-A of 400-320 nm, medium-wavelength ultraviolet rays called UV-B of 320-290 nm, and short-wavelength ultraviolet rays called UV-C of 290 nm or less. Normally, most of the ultraviolet light to which humans are exposed is sunlight, but the ultraviolet light that reaches the ground is UV-
In A and UV-B, UV-C is absorbed in the ozone layer and hardly reaches the ground. Among the ultraviolet rays reaching the ground, UV-B causes erythema and blisters on the skin, and UV-A
Has been found to promote skin aging when it works over a long period of time, resulting in darkening of the skin.

Heretofore, a number of UV-B absorbers have been developed, but UV-A has received much attention because it has been accepted as an ultraviolet ray that makes the skin healthy brown at the seaside in summer. Did not. However, in recent years, there has been an increase in consumers' demands for white skin throughout the four seasons, and the UV
-A absorbents are gaining attention.

[0004] As existing UV-A absorbers, benzophenone derivatives, dibenzoylmethane derivatives, benzotriazole derivatives and the like are known, and have been used by being blended in external preparations such as cosmetics and quasi-drugs.

On the other hand, in recent years, cosmetics to which an ultraviolet absorber is blended include silicone bases such as dimethylsiloxane, which are excellent in water resistance and oil resistance, which do not easily run off due to sweat or a water bath in order to maintain their effect. It is becoming widely used. This is largely attributable to the water resistance and oil resistance of the silicone base, as well as the ease of use, such as good elongation, freshness and non-stickiness.

However, existing UV-A absorbers have extremely low compatibility with silicone bases. Therefore, an external preparation containing a silicone base is a conventional UV
The compounding of the -A absorber becomes difficult, the amount of the compounding is limited to a very small amount, and the function of the UV-A absorber is not sufficiently exhibited.

[0007] Therefore, U is dissolved in a silicone base, has excellent water resistance, and protects the skin from ultraviolet rays in the UV-A region.
The development of VA absorbers has been strongly desired.

The inventor of the present invention has conducted intensive studies in view of such circumstances, and as a result, has found that silicone-based hydantoin derivatives are:
It was found that the compound could satisfy the above properties,
The present invention has been completed.

[0009]

That is, an object of the present invention is to provide a substance which dissolves in a silicone base and absorbs ultraviolet rays in the UV-A region, and a skin external preparation containing the substance. .

[0010]

An object of the present invention is to provide a siloxane having at least one unit represented by the general formula ₍₂₎ , wherein the other unit which may be present in the siloxane is a compound represented by the general formula O _{(4-n ) / 2} SiR ⁴ _n , which is achieved by an ultraviolet absorbent comprising a silicone-based hydantoin derivative and a skin external preparation characterized by containing the silicone-based hydantoin derivative.

[0011]

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

Examples of R ¹ and R ⁴ defined in the formula of the silicone-based hydantoin derivative of the present invention include methyl, ethyl, n-propyl, isopropyl, n-butyl, isobutyl, t-butyl, phenyl group, trimethyl And a siloxy group. m represents the number of substitution of R ¹ and is an integer of 0 to 3. Further, n represents the number of substitutions of R ⁴ and is an integer of 0 to 3. Examples of R ² include, for example, - (CH _{2) 3} -
_{, -CH 2 CH (CH 3)} CH 2 -, -CH 2 CH
_{2 CH (CH 3) -,} -CH (CH 3) CH 2 CH 2
—, —C (CH ₃ ) ₂ CH ₂ CH ₂ —, and the like. Examples of R ³ include methyl, ethyl, n- propyl, n- butyl, t- butyl, n- hexyl, 2-ethylhexyl, n- decyl, n- tetradecyl, isostearyl, n- octadecyl, and the like. Examples of X include methoxy, ethoxy, isopropoxy, butoxy and the like. a represents the number of substitutions of X and is an integer of 0 to 3.

The silicone hydantoin derivative used in the present invention can be produced, for example, by the following method.

[0015]

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The benzaldehyde derivative (2) is converted to an ether form under basic conditions, and then subjected to thermal rearrangement reaction to form (3) (Y has at least two carbon atoms and has an olefinically unsaturated bond. A monovalent hydrocarbon group (including those having a plurality of atoms O). Then, (3) is reacted with hydantoin in the presence of an amino acid such as glycine or alanine or a salt thereof in water or an aqueous solution at room temperature to 150 ° C. for 1 to 20 hours to obtain (4).
(4) a N, N- dimethylformamide, in a solvent such as dimethyl sulfoxide, KOH, NaOH, presence halide of a base such as ^{_{K 2 CO 3 R 3 A (}} A is Br, C
1, I, etc. ) At room temperature to 150 ° C. for 5 minutes to 20 hours to obtain the hydantoin derivative (5). Then, (1) can be obtained by subjecting (5) to a hydrosilylation reaction between organohydrogensilane or organohydrogenpolysiloxane. Normal organic solvents can be used as the reaction solvent,
Among them, aromatic organic solvents such as toluene, benzene and xylene are preferred. As a reaction catalyst, a platinum compound, a palladium compound, a rhodium compound, or the like is used.

The base used in the external preparation for skin of the present invention may be any base as long as the silicone-based hydantoin derivative can be dissolved therein. In particular, the base based on the silicone-based hydantoin derivative has good stretchability, refreshing feeling, non-stickiness, etc. It is preferable because functions such as usability, excellent water resistance and oil resistance, and furthermore, functions such as difficulty in flowing into sweat and water are obtained.

Although there is no particular limitation on the silicone base,
For example, chain polysiloxanes such as dimethylpolysiloxane, methylpolysiloxane and methylhydrogenpolysiloxane, cyclic polysiloxanes such as decamethylpolysiloxane, dodecamethylpolysiloxane, tetramethyltetrahydrogenpolysiloxane, and polyether fatty acid-modified polysiloxane And higher alcohol-modified polysiloxanes and amino acid-modified polysiloxanes.

The external preparation for skin of the present invention includes other components usually used in external preparations for skin such as cosmetics and quasi-drugs,
For example, oil, lubricating oil, ultraviolet absorbers other than the present invention, antioxidants, surfactants, preservatives, sequestering agents, fragrances,
Water, alcohol, a thickener, and the like can be appropriately added as needed. The skin external preparation of the present invention is not particularly limited in its application field, and can be used in cosmetics, quasi-drugs, and the like according to the characteristics and purpose of the silicone-based hydantoin derivative used in the present invention.

Here, the dosage form of the external preparation for skin of the present invention is arbitrary, and may be any dosage form such as powder, cream, paste, stick, liquid, spray, foundation and the like. The emulsion may be emulsified into a W / O type or an O / W type using an emulsifier. The compounding amount varies depending on the above-mentioned dosage form, but is generally 0.1 to 30% by weight.
And more preferably 0.2 to 20% by weight.

[0021]

The present invention will be further described with reference to the following examples. The present invention is not limited by these.

Example 1 (1) 60.8 g of vanillin and 53.2 g of allyl bromide were dissolved in 400 ml of acetone, and 66.3 g of anhydrous potassium carbonate was added to the solution, followed by stirring at about 50 ° C. for 3 hours. After cooling, the generated salt was filtered off, and acetone was distilled off under reduced pressure. The residue was heated at 220 ° C. (30 mmHg) for 2 hours and then distilled to obtain 68.4 g (yield: 89.1%) of 3-methoxy-4- (2-propenyl) oxybenzaldehyde (bp 218 to 220 ° C.). , 18 mmHg).

(2) Next, 3-methoxy-4- (2-
38.4 g of propenyl) oxybenzaldehyde, 20.0 g of hydantoin, 10.0 g of glycine, 2.67 g of sodium hydroxide, and 100 ml of water were stirred at 90 ° C. for 24 hours. After cooling, the obtained crystals were collected by filtration, washed with water and dried, and then dried with 5- (4-hydroxy-3-methoxy-5- (2-
43.8 g of propenyl) benzylidene) hydantoin
(79.9% yield).

(3) N, N-dimethylformamide 20
The above 5- (4-hydroxy-3-methoxy-5)
(2-propenyl) benzylidene) hydantoin 2.7
4 g, ethyl bromide 1.09 g, anhydrous potassium carbonate 829
mg was added and stirred at about 100 ° C. for 5 hours. After cooling, water was added to the reaction solution, and the reaction product was extracted with ethyl acetate. After the extract layer was washed with water and dried over anhydrous magnesium sulfate, the solvent was removed under reduced pressure to obtain a pale yellow solid. The solid was recrystallized from hexane to obtain 1.90 g (yield: 63.0%) of 5- (4-hydroxy-3-methoxy-5- (2-propenyl) benzylidene) -3-ethylhydantoin.

(4) 3.02 g of 5- (4-hydroxy-3-methoxy-5- (2-propenyl) benzylidene) -3-ethylhydantoin obtained in the above (3) and methyl hydrogen polyamine shown in Chemical formula 4 Dissolve 4.44 g of siloxane (hereinafter abbreviated as MHS) in 50 ml of toluene,

[0026]

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Chloroplatinic acid (2% 2-propanol solution)
Several drops were added and the mixture was stirred at about 100 ° C. for 8 hours. After cooling, the toluene layer was washed with water and dried, and then the solvent was removed under reduced pressure. The residue was purified by silica gel column chromatography (eluted with hexane: ethyl acetate = 9: 1) to obtain 4.93 g (yield: 73.4%) of the silicone-based hydantoin derivative of the present invention represented by the following chemical formula (5). .

[0028]

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Example 2 (1) The reaction was carried out according to (3) of Example 1 except that ethyl bromide was changed to 1.37 g of butyl bromide, and 5- (4-hydroxy-3-methoxy-5) was obtained. 2.44 g of-(2-propenyl) benzylidene) -3-butylhydantoin (yield 7)
4.0%).

(2) 5.30 g of 5- (4-hydroxy-3-methoxy-5- (2-propenyl) benzylidene) -3-butylhydantoin obtained in the above (1) was subjected to MHS.
By reacting 4.44 g with (4) of Example 1 and purifying in the same manner, 4.94 g (yield: 73.3%) of the silicone hydantoin derivative of the present invention represented by the following formula (6) was obtained.

[0031]

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Example 3 (1) The reaction was carried out according to (3) of Example 1 except that ethyl bromide was changed to 1.93 g of octyl bromide, and 5- (4-hydroxy-3-methoxy-5) was obtained. 2.90 g (yield 75.2%) of (2-propenyl) benzylidene) -3-octylhydantoin was obtained.

(2) 3.86 g of 5- (4-hydroxy-3-methoxy-5- (2-propenyl) benzylidene) -3-octylhydantoin obtained in the above (1) was subjected to MHS.
4.44 g was reacted with Example 1 (4) and purified similarly to obtain 5.34 g (yield: 70.6%) of the silicone-based hydantoin derivative of the present invention represented by the following formula (7).

[0034]

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Example 4 (1) The reaction was carried out according to (3) of Example 1 except that ethyl bromide was changed to 2.49 g of lauryl bromide, and 5- (4-hydroxy-3-methoxy-5) was obtained. 3.36 g (76.0% yield) of (2-propenyl) benzylidene) -3-dodecylhydantoin was obtained.

(2) MHS was used to obtain 4.42 g of 5- (4-hydroxy-3-methoxy-5- (2-propenyl) benzylidene) -3-dodecylhydantoin obtained in the above (1).
The reaction was carried out according to 4.44 g according to (4) of Example 1, and purification was carried out in the same manner to obtain 6.91 g (yield 85.1%) of the hydantoin derivative of the present invention represented by the following formula (8).

[0037]

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Example 5 (1) The reaction was carried out according to (3) of Example 1 except that ethyl bromide was changed to 3.33 g of stearyl bromide, and 5- (4-hydroxy-3-methoxy-5) was obtained. 4.28 g of (2-propenyl) benzylidene) -3-octadecylhydantoin
(81.3% yield).

(2) 5.26 g of 5- (4-hydroxy-3-methoxy-5- (2-propenyl) benzylidene) -3-octadecylhydantoin obtained in the above (1) was added to M
By reacting with 4.44 g of HS according to (4) of Example 1,
Purification was carried out in the same manner to obtain 7.00 g (yield: 78.1%) of the silicone-based hydantoin derivative of the present invention represented by the following chemical formula (9).

[0040]

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Example 6 (1) The reaction was carried out according to (3) of Example 1 except that ethyl bromide was changed to 3.05 g of cetyl bromide, and 5- (4-hydroxy-3-methoxy-5) was obtained. 4.07 g (81.7% yield) of (2-propenyl) benzylidene) -3-hexadecylhydantoin was obtained.

(2) 4.98 g of 5- (4-hydroxy-3-methoxy-5- (2-propenyl) benzylidene) -3-hexadecylhydantoin obtained in the above (1) is methyl hydrogen Polysiloxane 2.8
3 g was reacted according to (4) of Example 1,

[0043]

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Purification was performed in the same manner to obtain 5.88 g (yield: 80.1%) of the silicone-based hydantoin derivative of the present invention represented by the following formula (11).

[0045]

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The characteristic values of the compounds of the present invention obtained in Examples 1 to 6 are shown in Table 1.

[0047]

[Table 1]

As can be seen from Table 1, the silicone-based hydantoin derivative used in the present invention has a maximum absorption (λmax) in the UV-A region and can be said to be an excellent UV-A ultraviolet absorber.

The solubility of the silicone hydantoin derivative used in the present invention in a silicone base is 25%.
The solubility in dimethylpolysiloxane and methylphenylpolysiloxane was tested under the condition of ° C. In each case,
It dissolved at least 10% by weight and exhibited excellent solubility.

The water resistance and oil resistance are as follows. The silicone hydantoin derivative of the present invention is stirred and mixed with oil such as water, 50% ethanol, liquid paraffin, etc., and left at 50 ° C. for 60 days to prevent hydrolysis. Thus, it was confirmed that water resistance and oil resistance were excellent.

Example 7 Sunscreen cosmetics (oil type) (1) 48.0 parts by weight of decamethylcyclopentasiloxane (2) dimethylpolysiloxane (10 cs / 25 ° C.) 20.0 (3) methylphenylpolysiloxane ( (20 cs / 25 ° C.) 20.0 (4) Silicone resin 10.0 (5) Silicone hydantoin derivative (compound of Example 2) 2.0

(Preparation method) (1) to (5) were mixed and dissolved sufficiently, followed by filtration to obtain a product.

Comparative Example 1 A product was obtained in the same manner as in Example 7 except that (5) was omitted from the formulation of Example 7.

Example 8 Sunscreen Cosmetic (Cream) (1) 9.0 parts by weight of decamethylpentasiloxane (2) Liquid paraffin 3.0 (3) Isopropyl myristate 2.0 (4) Vaseline 5.0 ( 5) Cetanol 5.0 (6) Stearic acid 3.0 (7) Glyceryl monoisostearate 3.0 (8) Silicone hydantoin derivative (compound of Example 4) 2.0 (9) Preservative 0.2 (10) Fragrance 0.2 (11) Glycerin 10.0 (12) Propylene glycol 5.0 (13) Potassium hydroxide 0.2 (14) Purified water 52.4

(Production method) (1) to (10) were heated and stirred at 70 ° C. to obtain an oil phase. After heating (11) to (14) to 70 ° C. and completely dissolving them, they were made into an aqueous phase. The oil phase was added to the aqueous phase and emulsified by an emulsifier. The emulsion was cooled to 30 ° C. to obtain a product.

Comparative Example 2 A product was obtained in the same manner as in Example 8 except that (8) was omitted from the formulation of Example 8.

Example 9 Sunscreen lotion (1) 10.0 parts by weight of dimethylpolysiloxane (5 cs / 25 ° C.) (2) methylphenylpolysiloxane (20 cs / 25 ° C.) 7.0 (3) Stearic acid 1.0 (4) Silicone hydantoin derivative (compound of Example 4) 10.0 (5) Preservative 0.2 (6) Fragrance 0.2 (7) Glycerin 5.0 (8) Potassium hydroxide 0.2 (9) ) Purified water 66.4

(Production method) (1) to (6) were heated and stirred at 70 ° C. to obtain an oil phase. After heating (7) to (9) to 70 ° C. and completely dissolving the mixture, the mixture was treated as an aqueous phase. The oil phase was added to the aqueous phase and emulsified by an emulsifier. The emulsion was cooled to 30 ° C. to obtain a product.

Comparative Example 3 A product was obtained in the same manner as in Example 9 except that (4) was omitted from the formulation of Example 9.

With respect to Examples 7 to 9 and Comparative Examples 1 to 3 obtained as described above, the effect of preventing ultraviolet rays was measured. The measuring method was as follows. The above-mentioned cosmetic containing the product of the present invention was applied to the back of a person in an amount of ² mg / cm ² , and 15 minutes later, UV-A irradiation was performed. UV-A irradiation is performed using a BLB lamp at 365 nm,
Ultraviolet rays having an energy amount of 9 J / cm ² were irradiated, and the minimum blackening amount (MMD) was determined using the following equation.

[0061]

(Equation 1)

Table 2 shows the results.

[0063]

[Table 2]

As can be seen from Table 2, the MMD values of the examples are higher than those of the comparative examples. That is, it is understood that an excellent ultraviolet ray preventing effect can be obtained by blending the silicone-based hydantoin derivative.

[0065]

The silicone hydantoin derivative used in the present invention is an excellent ultraviolet absorber having a maximum absorption in the UV-A region. Further, since the ultraviolet absorber of the present invention is excellent in water resistance and oil resistance, it can provide a skin external preparation from which a base and other compounding components can be freely selected, and at the same time, as a sunscreen cosmetic and the like. It is evident that it shows excellent effects even when exposed to the harsh conditions under the scorching sun.

──────────────────────────────────────────────────続 き Continued on the front page (58) Field surveyed (Int. Cl. ⁷ , DB name) C09K 3/00 104 A61K 7/00 A61K 7/42 C07F 7/10-7/18 CA (STN) REGISTRY ( STN)

Claims (2)

(57) [Claims] 1. A compound of the general formula (1) (R ¹ is an alkyl group having 1 to 4 carbon atoms, phenyl group or trimethylsiloxy group, R ² is an alkylene group or oxyalkylene group having at least 2 carbon atoms, R
³ is a linear or branched alkyl group having 1 to 20 carbon atoms,
X is a hydroxyl group, an alkyl group having 1 to 8 carbon atoms or 1 carbon atom;
And m represents an integer of 0 to 3, and a represents an integer of 0 to 3. A) a siloxane having at least one unit represented by the general formula O _{(4-n) / 2} SiR ⁴ _n , wherein n is 0 to
An integer 3 and R ⁴ represent an alkyl group having 1 to ⁴ carbon atoms, a phenyl group or a trimethylsiloxy group. An ultraviolet absorber comprising a silicone-based hydantoin derivative represented by the formula: 2. An external preparation for skin, comprising the silicone-based hydantoin derivative according to claim 1.