JPH06306085A - Silicon-based hydantoin derivative, ultraviolet absorbing agent and skin external preparation - Google Patents

Abstract

PURPOSE:To obtain the derivative having a specific structure, having maximum absorption in UV-A region and excellent in water resistance and oil resistance and useful as a skin external preparation. CONSTITUTION:The objective derivative consists of siloxanes having at least one unit of formula I [R<1> is 1-4C alkyl, phenyl or trimethylsiloxy; R<2> is (oxy) alkylene having at least two carbons; R<3> is 1-20C alkyl; X is OH, 1-8C alkyl or alkoxy; (m) is 0-3; (a) is 0-3], and other unit which may exist in the siloxanes is expressed by formula II [(n) is 0-3; R is 1-4C alkyl, phenyl or trimethylsiloxy].

Description

Detailed Description of the Invention

[0001]

TECHNICAL FIELD The present invention relates to a novel silicone-based hydantoin derivative, an ultraviolet absorber and a skin external preparation. More specifically, the present invention relates to a novel silicone-based hydantoin derivative which is soluble in silicone oil, has excellent water resistance and oil resistance, and has ultraviolet absorption characteristics in the wavelength range of UV-A.

[0002]

2. Description of the Related Art Ultraviolet rays are known to bring various changes to the skin. If ultraviolet rays are classified dermatologically, 400-320n
m long-wavelength UV-A, called 320-290
nm UV-B, which is a medium wavelength UV, and 290 nm or shorter UV-C, which is a short wavelength UV.
Normally, most of the ultraviolet rays that humans are exposed to are sunlight, but the ultraviolet rays that reach the ground are UV-A and UV-B.
-C is absorbed in the ozone layer and hardly reaches the ground. It is recognized that in the ultraviolet rays reaching the ground, UV-B causes erythema and blisters on the skin, and UV-A causes skin darkening and promotes skin aging when it acts for a long time. .

Although many UV-B absorbers have been developed in the past, UV-A has received much attention because it has been accepted as ultraviolet rays that make the skin a healthy wheat color at the seaside in summer. There wasn't. However, in recent years, consumers' demand for white skin has been increasing throughout the four seasons, and UV protection has been added to prevent skin aging.
-A absorbers are gaining attention.

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

On the other hand, in recent years, cosmetics containing an ultraviolet absorber have a silicone base such as dimethylsiloxane which is excellent in water resistance and oil resistance and does not easily wash off by sweat or a water bath in order to maintain its effect. It has become widely used. This is largely due to the water resistance and oil resistance of the silicone base, as well as the ease of use, the feeling of refreshing, and the non-greasiness of use.

However, the existing UV-A absorbers have extremely low compatibility with silicone bases. Therefore, in the case of an external preparation containing a silicone base, the conventional U
It is difficult to mix the VA absorber, and the amount of the VA absorber used is limited to an extremely small amount, so that there is a drawback that the function of the UV-A absorber cannot be sufficiently exhibited.

Therefore, U which dissolves 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 become highly desirable.

The present inventors have conducted intensive studies in view of such circumstances, and as a result, found that a silicone-based hydantoin derivative is a compound that can satisfy the above-mentioned properties, and completed the present invention.

[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]

This object is siloxanes having at least one unit represented by the general formula 2, and other units which may be present in the siloxane are represented by the general formula O _{(4-n ) / 2} SiR ⁴ n, a silicone-based hydantoin derivative, an ultraviolet absorber comprising the silicone-based hydantoin derivative, and a skin external preparation containing the hysilicone-based hydantoin derivative. To be achieved.

[0011]

[Chemical 2]

The structure of the present invention will be described in detail below.

Examples of R ¹ and R ⁴ defined in the formula of the silicone hydantoin derivative of the present invention are methyl, ethyl, propyl, isopropyl, butyl, isobutyl,
Examples thereof include t-butyl, phenyl group and trimethylsiloxy group. m represents the number of substitutions of R ¹ and is an integer of 0 to 3. In addition, 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 C
_{H (CH 3) -, -CH} (CH 3) CH 2 CH 2 -
_{, -C (CH 3) 2 CH} 2 CH 2 - and the like.
Examples of R ³ are methyl, ethyl, propyl, butyl, t-butyl, hexyl, 2-ethylhexyl, n-
Decyl, n-tetradecyl, isostearyl, n-octadecyl and the like can be mentioned. Examples of X are methoxy,
Examples include 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 of the present invention can be produced, for example, by the following method.

[0015]

[Chemical 3]

After converting the benzaldehyde derivative (2) into an ether form under basic conditions, it is subjected to a thermal rearrangement reaction (3) (Y has at least 2 carbon atoms and has an olefinic unsaturated bond). And a monovalent hydrocarbon group (including those having a plurality of atoms O). Then, (3) and hydantoin are reacted in the presence of an amino acid such as glycine and 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) Acrylic acid such as methyl acrylate, ethyl acrylate, 2-ethylhexyl acrylate in the presence of a base such as KOH, NaOH and K ₂ CO _{3 in} a solvent such as N, N-dimethylformamide and dimethylsulfoxide. The hydantoin derivative (5) is obtained by reacting the ester at room temperature to 150 ° C. for 30 minutes to 20 hours. Then, (1) can be obtained by subjecting (5) and an organohydrogensilane or an organohydrogenpolysiloxane to a hydrosilylation reaction. Usual organic solvents can be used as the reaction solvent, but among them, aromatic organic solvents such as toluene, benzene and xylene are preferable. Moreover, as the 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 as long as the silicone-based hydantoin derivative can be dissolved therein. In particular, the silicone-based base does not easily spread, feels refreshed and is not sticky. It is preferable because it provides a feeling of use, excellent water resistance, oil resistance, and functions such as difficulty in flowing into sweat and water.

The silicone base is not particularly limited,
For example, chain polysiloxanes such as dimethylpolysiloxane, methylpolysiloxane, and methylhydrogenpolysiloxane, cyclic polysiloxanes such as decamethylpolysiloxane, dodecamethylpolysiloxane, tetramethyltetrahydrogenpolysiloxane, and polyether fatty acid-modified polysiloxane. , Higher alcohol-modified polysiloxane, amino acid-modified polysiloxane and the like are used.

The external preparation for skin of the present invention contains other ingredients usually used for 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, perfumes,
Water, alcohol, a thickener and the like can be appropriately blended as necessary. The external preparation for skin of the present invention is not particularly limited to the field of application thereof, and can be used in cosmetics, quasi drugs and the like depending on the characteristics and purpose of the silicone hydantoin derivative used in the present invention.

Here, the dosage form of the external preparation for skin of the present invention is arbitrary, and it may be any dosage form such as powder, cream, paste, stick, liquid, spray and foundation. The emulsifier may be used to emulsify into a W / O type and an O / W type. Further, the compounding amount varies depending on the above-mentioned dosage form, but generally, it is preferably 0.1 to 30% by weight, more preferably 0.2 to 15% by weight.

[0021]

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

Example 1 (1) 60.8 g of vanillin and 53.2 g of allyl bromide were dissolved in 400 ml of acetone, 66.3 g of anhydrous potassium carbonate was added to this solution, and the mixture was stirred at about 50 ° C. for 3 hours. After cooling, the produced salt was filtered off, and acetone was removed under reduced pressure. The residue was heated at 220 ° C. (30 mmHg) for 2 hours and then distilled to yield 68.4 g of 4-hydroxy-3-methoxy-5- (2-propenyl) benzaldehyde (yield 89.1).
%) Was obtained. (Bp 218 to 220 ° C., 18 mmH
g).

(2) Then, 4-hydroxy-3-methoxy-5- (2-propenyl) benzaldehyde 38.
4 g, hydantoin 20.0 g, glycine 10.0 g,
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 to give 5- (4-hydroxy-3-methoxy-5).
-(2-Propenyl) benzylidene) hydantoin 4
3.8 g (yield 79.9%) was obtained.

(3) N, N-dimethylformamide 20
The above 5- (4-hydroxy-3-methoxy-5-
(2-Propenyl) benzylidene) hydantoin 2.7
4 g, methyl acrylate 946 mg, and sodium hydroxide 40 mg were added, and the mixture was stirred at about 50 ° C. for 3 hours. After cooling
Water was added to the reaction solution, and the mixture was extracted with ethyl acetate. The organic layer was washed with water and dried over anhydrous magnesium, and then the solvent was removed under reduced pressure to obtain a slightly yellow solid. This solid was recrystallized from hexane to give 4- (4-hydroxy-3-methoxy-5-
(2-Propenyl) benzylidene) -2,5-dioxo-1-imidazolidine methyl propionate (1.95 g)
(Yield 54.2%) was obtained.

(4) Methyl 4- (4-hydroxy-3-methoxy-5- (2-propenyl) benzylidene) -2,5-dioxo-1-imidazolidinepropionate obtained in (3) above 3.60 g. 4.44 g of methyl hydrogen polysiloxane shown in Chemical formula 4 (hereinafter abbreviated as MHS)
Is dissolved in 50 ml of toluene,

[0026]

[Chemical 4]

A few drops of chloroplatinic acid (2% 2-propanol solution) 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 4.99 g (yield 69.3%) of a silicone hydantoin derivative. The structure is the NMR spectrum (J
NM FX-270, manufactured by JEOL Ltd.) and MS spectrum (JMS DX-303, manufactured by JEOL Ltd.). NMR data ¹ H-NMR (solvent: CDCl ₃ , CHCl ₃ standard (7.2
6)): 0.03-0.08 (33H), 0.56-0.62 (m, 2H), 1.58-1.70 (m, 2
H), 2.64-2.72 (m, 4H), 3.65 (S, 3H), 3.89 (t, J = 7.3Hz, 2H),
3.95 (s, SH), 6.07 (s, 1H), 6.67 (s, 1H), 6.85-6.89 (m, 2H)
． MS data M / Z 730 (M ⁺ ).

[0028]

[Chemical 5]

Example 2 (1) Methyl acrylate was replaced with 1.10 g of ethyl acrylate.
The reaction was carried out in the same manner as in (1) to (3) of Example 1 except that the reaction time was changed to 4- (4-hydroxy-3-methoxy-5- (2
-Propenyl) benzylidene) -2,5-dioxo-1
-1.40 g (yield 75.0%) of ethyl imidazolidine propionate was obtained.

(2) 3.74 g of ethyl 4- (4-hydroxy-3-methoxy-5- (2-propenyl) benzylidene) -2,5-dioxo-1-imidazolidinepropionate obtained in (1) above. Example 4 with MHS 4.44 g
The reaction was carried out according to (4) of (4) above, and purification was carried out in the same manner.
3%) was obtained. The structure was confirmed by NMR spectrum and MS spectrum. NMR data ¹ NMR (CDCl ₃ , CHCl ₃ ): 0.03-0.08 (33H), 0.6
0 (m, 2H), 1.25 (t, J = 7.1Hz, 2H), 1.58-1.67 (m, 2H), 2.60-2.
73 (m, 4H), 3.89 (t, J = 7.3Hz, 2H), 3.95 (s, 3H), 4.12 (q, J = 7.
1Hz, 2H), 6.06 (s, 1H), 6.68 (s, 1H), 6.86-6.89 (m, 4H), 9.35
(s, 1H) _. MS data M / Z 748 (M ⁺ ).

[0031]

[Chemical 6]

Example 3 (1) 1.54 g of methyl acrylate and butyl acrylate
The reaction was carried out according to (1) to (3) of Example 1 except that the above was changed to 4- (4-hydroxy-3-methoxy-5- (2-
Propenyl) benzylidene) -2,5-dioxo-1-
2.92 g of butyl imidazolidine propionate (yield 7
2.6%) was obtained.

(2) 4- (4-hydroxy-3-methoxy-5- (2-propenyl) benzylidene) -2,5-dioxo-1-imidazolidinepropionate butyl 4.02 g obtained in the above (1). Example 4 with MHS 4.44 g
The reaction was carried out according to (4) of (4) above, and the purification was carried out in the same manner.
6%) was obtained. The structure was confirmed by NMR spectrum and MS spectrum. NMR data ¹ NMR (CDCl ₃ , CHCl ₃ ): 0.03-0.09 (33H), 0.6
0 (m, 2H) 0.90 (t, J = 7.3Hz, 3H), 1.27-1.41 (m, 2H), 1.53-1.7
2 (m, 4H) 2.64-2.72 ((m, 4H), 3.89 (t, J = 7.3Hz, 2H), 3.95 (s,
3H), 4.06 (t, J = 6.6Hz, 2H), 6.04 (s, 1H), 6.68 (s, 1H), 6.85-
6.89 (m, 2H), 9.28 (s, 1H). MS data M / Z 772 (M ⁺ ).

[0034]

[Chemical 7]

Example 4 (1) 4- (4-hydroxy-) was carried out according to (1) to (3) of Example 1 except that methyl acrylate was changed to 2.02 g of 2-ethylhexyl acrylate. 3-Methoxy-5- (2-propenyl) benzylidene) -2,5-dioxo-1-imidazolidine 2-ethylhexyl propionate (3.48 g, yield 76.0%) was obtained.

(2) 4- (4-Hydroxy-3-methoxy-5- (2-propenyl) benzylidene) -2,5-dioxo-1-imidazolidine propionate 2-ethylhexyl 4 obtained in the above (1). 0.58 g to MHS 4.44
g in the same manner as in Example 1 (4) and purified in the same manner to give 7.27 g of the hydantoin derivative of the present invention (yield 8
7.7%). Structure is NMR spectrum and MS
Confirmed by spectrum. NMR data ¹ NMR (CDCl ₃ , CHCl ₃ ): 0.03-0.08 (33H), 0.6
4 (m, 2H), 0.84-0.90 (m, 6H), 1.26-1.40 (m, 8H), 1.54-1.67
(m, 3H), 2.67 (t, J = 7.7Hz, 2H), 2.73 (t, J = 7.4Hz, 2H), 3.92
(t, J = 7.4Hz, 2H), 3.94 (s, 3H), 4.00 (m, 2H), 5.93 (s, 1H), 6.
68 (s, 1H), 6.77-6.82 (m, 2H), 8.10 (m, 1H). MS data M / Z 828 (M ⁺ ).

[0037]

[Chemical 8]

Example 5 (1) Methyl acrylate was replaced with octadecyl acrylate 3.
The reaction was performed according to (1) to (3) of Example 1 except that the amount was changed to 56 g. 4- (4-hydroxy-3-methoxy-5-
(2-Propenyl) benzylidene) -2,5-dioxo-1-imidazolidine octadecyl propionate 4.8
7 g (yield 80.9%) was obtained.

(2) 4- (4-hydroxy-3-methoxy-5- (2-propenyl) benzylidene) -2,5-dioxo-1-imidazolidine octadecyl propionate (6.02 g) obtained in the above (1) Was reacted with 4.44 g of MHSP according to (4) of Example 1 and purified in the same manner to obtain 7.47 g (yield: 76.9%) of the silicone hydantoin derivative of the present invention. The structure was confirmed by NMR spectrum and MS spectrum. NMR data ¹ NMR (CDCl ₃ , CHCl ₃ ): 0.03-0.08 (33H), 0.6
1 (m, 2H), 0.87 (t, J = 6.6Hz, 3H), 1.25 (br.S, 30H), 1.58-1.6
7 (m, 4H), 2.66 (t, J = 7.7Hz, 2H), 2.72 (t, J = 7.3Hz, 2H), 3.92
(t, J = 7.7Hz, 2H), 3.94 (s, 3H), 4.07 (t, J = 6.7Hz, 2H), 5.93
(s, 1H), 6.68 (s, 1H), 6.78-6.83 (m, 2H) 8.12 (s, 1H) .MS data M / Z 968 (M ⁺ ).

[0040]

[Chemical 9]

The characteristic values of the compounds of the present invention obtained in Examples 1 to 5 are shown in Table 1.

[0042]

[Table 1]

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

The solubility of the silicone hydantoin derivative of the present invention in a silicone base is 25 ° C.
In, the solubility test for dimethylpolysiloxane and methylphenylpolysiloxane was conducted. In all cases, 10% by weight or more was dissolved and excellent solubility was exhibited.

As for water resistance and oil resistance, water, 5
An oil such as 0% by weight etal and liquid paraffin is stirred and mixed with the silicone-based hydantoin derivative of the present invention.
After being left at 60 ° C. for 60 days, it was confirmed that the water resistance and the oil resistance were excellent because hydrolysis and the like did not occur.

Example 6 Sunscreen Cosmetic (Oil Type) (1) Decamethylcyclopentasiloxane 48.0 parts by weight (2) Dimethylpolysiloxane (10CS / 25 ° C.) 20.0 (3) Methylphenylpolysiloxane ( 20CS / 25 ° C.) 20.0 (4) Silicone resin 10.0 (5) Silicone hydantoin derivative (compound of Example 2) 2.0

(Production method) (1) to (5) are mixed, sufficiently dissolved, and then filtered to obtain a product.

Comparative Example 1 A product was obtained in the same manner as in Example 6 except that (5) was excluded from the formulation of Example 6.

Example 7 Sunscreen Cosmetic (Cream) (1) Decamethylpentasiloxane 9.0 parts by weight (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) are heated and stirred at 70 ° C. to form an oil phase part. (11) to (14) are heated to 70 ° C. to completely dissolve them, and then used as an aqueous phase part. The oil phase part is added to the water phase part and emulsified by an emulsifying machine. The emulsion is cooled to 30 ° C. to obtain a product.

Comparative Example 2 A product was obtained in the same manner as in Example 7 except that (8) was excluded from the formulation of Example 7.

Example 8 Sunblock Lotion (1) Dimethylpolysiloxane (5CS / 25 ° C) 10.0 parts by weight (2) Methylphenylpolysiloxane (20CS / 25 ° C) 7.0 (3) Stearic acid 1.0 (4) Silicone-based hydantoin derivative (compound of Example 4) 10.0 (5) Preservative 0.2 (6) Perfume 0.2 (7) Glycerin 5.0 (8) Potassium hydroxide 0.2 (9) ) Purified water 66.4

(Production Method) (1) to (6) are heated and stirred at 70 ° C. to form an oil phase part. After heating (7) to (9) to 70 ° C. to completely dissolve them, a water phase portion is formed. The oil phase part is added to the water phase part and emulsified by an emulsifying machine. The emulsion is cooled to 30 ° C. to obtain a product.

Comparative Example 3 A product was obtained in the same manner as in Example 8 except that (4) was excluded from the formulation of Example 8.

With respect to Examples 6 to 8 and Comparative Examples 1 to 3 obtained as described above, the ultraviolet ray preventing effect was measured. The measuring method is as follows: The above cosmetic containing the product of the present invention is applied to the back of a person in an amount of ² mg / cm ² , and after 15 minutes, UV-A is applied.
Irradiation was performed. UV-A irradiation is a BLB lamp and 36
Ultraviolet rays having an energy amount of 5 nm and 9 J / cm ² were irradiated, and the minimum blackening amount (MMD) was obtained using the following formula.

[0056]

[Equation 1]

The results are shown in Table 2.

[0058]

[Table 2]

As can be seen from Table 2, the MMD value of each of the examples is higher than that of the comparative example. That is, it can be seen that an excellent UV protection effect can be obtained by adding the silicone-based hydantoin derivative of the present invention.

[0060]

The silicone hydantoin derivative of the present invention is an excellent ultraviolet absorber having a maximum absorption in the UV-A region. Further, the ultraviolet absorbent of the present invention is water resistant,
Since it has excellent oil resistance, it is possible to provide a skin external preparation whose base and other ingredients can be freely selected, and at the same time, even when it is left as a sunscreen cosmetic under the harsh conditions such as under hot weather. It has the advantage of excellent stability.

[Procedure amendment]

[Submission date] May 23, 1994

[Procedure Amendment 1]

[Document name to be amended] Statement

[Name of item to be corrected] 0002

[Correction method] Change

[Correction content]

[0002]

BACKGROUND ART UV, are known to provide various changes in the skin. Dermatological classification of ultraviolet rays is divided into long-wavelength ultraviolet rays of 400 to 320 nm called UV-A, medium wavelength ultraviolet rays of 320 to 290 nm called UV-B, and short wavelength ultraviolet rays of 290 nm or shorter called UV-C. Usually, most of the ultraviolet rays humans are exposures are sunlight, ultraviolet radiation reaching the earth UV-
In A and UV-B, UV-C is absorbed in the ozone layer and hardly reaches the ground. Among the ultraviolet rays that reach the ground, UV-B causes erythema and blisters on the skin, and UV-A
Has been found to promote skin aging when it results in blackening of the skin and over time.

[Procedure Amendment 2]

[Document name to be amended] Statement

[Correction target item name] 0010

[Correction method] Change

[Correction content]

[0010]

This object is siloxanes having at least one unit represented by the general formula 2, and other units which may be present in the siloxane are represented by the general formula O _{(4-n ) / 2} SiR silicone hydantoin derivatives characterized by being represented by ⁴ n, an ultraviolet absorber consisting of the silicone-based hydantoin derivatives,及beauty skin external agent characterized by containing the silicon cone type hydantoin derivatives Achieved by

[Procedure 3]

[Document name to be amended] Statement

[Name of item to be corrected] 0024

[Correction method] Change

[Correction content]

(3) N, N-dimethylformamide 20
The above 5- (4-hydroxy-3-methoxy-5-
(2-Propenyl) benzylidene) hydantoin 2.7
4 g, methyl acrylate 946 mg, and sodium hydroxide 40 mg were added, and the mixture was stirred at about 50 ° C. for 3 hours. After cooling
Water was added to the reaction solution, and the mixture was extracted with ethyl acetate. The organic layer was washed with water and dried over anhydrous magnesium sulfate , and then the solvent was removed under reduced pressure to obtain a slightly yellow solid. This solid was recrystallized from hexane to give 4- (4-hydroxy-3-methoxy-
Methyl 5- (2-propenyl) benzylidene) -2,5-dioxo-1-imidazolidinepropionate 1.95
g (yield 54.2%) was obtained.

[Procedure amendment 4]

[Document name to be amended] Statement

[Name of item to be corrected] 0027

[Correction method] Change

[Correction content]

A few drops of chloroplatinic acid (2% 2-propanol solution) were added and the mixture was stirred at about 100 ° C. for 8 hours. After cooling
The toluene layer was washed with water , dried over anhydrous magnesium sulfate , and then the solvent was removed under reduced pressure. Silica gel column chromatography of the residue (hexane: ethyl acetate =
The product was purified by elution with 9: 1) to obtain 4.99 g (yield 69.3%) of a silicone hydantoin derivative. The structure is NMR spectrum (JNM FX-270, manufactured by JEOL Ltd.) and MS spectrum (JMS DX-3).
03, manufactured by JEOL Ltd.). NMR data ¹ H-NMR (solvent: CDCl ₃ , CHCl ₃ standard (7.2
6)): 0.03-0.08 (33H), 0.56-0.62 (m, 2H), 1.58-1.70 (m, 2
H), 2.64-2.72 (m, 4H), 3.65 (S, 3H), 3.89 (t, J = 7.3Hz, 2H),
3.95 (s, SH), 6.07 (s, 1H), 6.67 (s, 1H), 6.85-6.89 (m, 2H)
． MS data M / Z 730 (M ⁺ ).

[Procedure Amendment 5]

[Document name to be amended] Statement

[Name of item to be corrected] 0029

[Correction method] Change

[Correction content]

Example 2 (1) Methyl acrylate was replaced with 1.10 g of ethyl acrylate.
The reaction was carried out in the same manner as in (1) to (3) of Example 1 except that the reaction time was changed to 4- (4-hydroxy-3-methoxy-5- (2
-Propenyl) benzylidene) -2,5-dioxo-1
-Ethyl imidazolidine propionate ( 2.80 g, yield 75.0%) was obtained.

[Procedure correction 6]

[Document name to be amended] Statement

[Name of item to be corrected] 0030

[Correction method] Change

[Correction content]

(2) 3.74 g of ethyl 4- (4-hydroxy-3-methoxy-5- (2-propenyl) benzylidene) -2,5-dioxo-1-imidazolidinepropionate obtained in (1) above. Example 4 with MHS 4.44 g
The reaction was carried out according to (4) of (4) above, and purification was carried out in the same manner.
3%) was obtained. The structure was confirmed by NMR spectrum and MS spectrum. NMR data ¹ H-NMR (CDCl ₃ , CHCl ₃ ): 0.03-0.08 (33H),
0.60 (m, 2H), 1.25 (t, J = 7.1Hz, 2H), 1.58-1.67 (m, 2H), 2.60
-2.73 (m, 4H), 3.89 (t, J = 7.3Hz, 2H), 3.95 (s, 3H), 4.12 (q, J
= 7.1Hz, 2H), 6.06 (s, 1H), 6.68 (s, 1H), 6.86-6.89 (m, 4H),
9.35 (s, 1H) _. MS data M / Z 748 (M ⁺ ).

[Procedure Amendment 7]

[Document name to be amended] Statement

[Correction target item name] 0033

[Correction method] Change

[Correction content]

(2) 4- (4-hydroxy-3-methoxy-5- (2-propenyl) benzylidene) -2,5-dioxo-1-imidazolidinepropionate butyl 4.02 g obtained in the above (1). Example 4 with MHS 4.44 g
The reaction was carried out according to (4) of (4) above, and the purification was conducted in the same manner. 5.22 g of the silicone-based hydantoin derivative of the present invention (yield 67.
6%) was obtained. The structure was confirmed by NMR spectrum and MS spectrum. NMR data ¹ H-NMR (CDCl ₃ , CHCl ₃ ): 0.03-0.09 (33H),
0.60 (m, 2H ), 0.90 (t, J = 7.3Hz, 3H), 1.27-1.41 (m, 2H), 1.53
-1.72 (m, 4H) 2.64-2 .72 (m, 4H), 3.89 (t, J = 7.3Hz, 2H), 3.95
(s, 3H), 4.06 (t, J = 6.6Hz, 2H), 6.04 (s, 1H), 6.68 (s, 1H), 6.
85-6.89 (m, 2H), 9.28 (s, 1H). MS data M / Z 772 (M ⁺ ).

[Procedure Amendment 8]

[Document name to be amended] Statement

[Correction target item name] 0036

[Correction method] Change

[Correction content]

(2) 4- (4-Hydroxy-3-methoxy-5- (2-propenyl) benzylidene) -2,5-dioxo-1-imidazolidine propionate 2-ethylhexyl 4 obtained in the above (1). 0.58 g to MHS 4.44
g in the same manner as in Example 1 (4) and purified in the same manner to give 7.27 g of the hydantoin derivative of the present invention (yield 8
7.7%). Structure is NMR spectrum and MS
Confirmed by spectrum. NMR data ¹ H-NMR (CDCl ₃ , CHCl ₃ ): 0.03-0.08 (33H),
0.64 (m, 2H), 0.84-0.90 (m, 6H), 1.26-1.40 (m, 8H), 1.54-1.
67 (m, 3H), 2.67 (t, J = 7.7Hz, 2H), 2.73 (t, J = 7.4Hz, 2H), 3.9
2 (t, J = 7.4Hz, 2H), 3.94 (s, 3H), 4.00 (m, 2H), 5.93 (s, 1H),
6.68 (s, 1H), 6.77-6.82 (m, 2H), 8.1 0 (s, 1H). MS data M / Z 828 (M ⁺ ).

[Procedure Amendment 9]

[Document name to be amended] Statement

[Correction target item name] 0039

[Correction method] Change

[Correction content]

(2) 4- (4-hydroxy-3-methoxy-5- (2-propenyl) benzylidene) -2,5-dioxo-1-imidazolidine octadecyl propionate (6.02 g) obtained in the above (1) To MHS4. 44 g was reacted according to (4) of Example 1 and purified in the same manner to obtain 7.47 g (yield: 76.9%) of the silicone hydantoin derivative of the present invention. The structure is NMR spectrum and M
Confirmed by S spectrum. NMR data ¹ H-NMR (CDCl ₃ , CHCl ₃ ): 0.03-0.08 (33H),
0.61 (m, 2H), 0.87 (t, J = 6.6Hz, 3H), 1.25 (br.S, 30H), 1.58-
1.67 (m, 4H), 2.66 (t, J = 7.7Hz, 2H), 2.72 (t, J = 7.3Hz, 2H),
3.92 (t, J = 7.7Hz, 2H), 3.94 (s, 3H), 4.07 (t, J = 6.7Hz, 2H),
5.93 (s, 1H), 6.68 (s, 1H), 6.78-6.83 (m, 2 H), 8.12 (s, 1H). MS data M / Z 968 (M ⁺ ).

[Procedure Amendment 10]

[Document name to be amended] Statement

[Correction target item name] 0042

[Correction method] Change

[Correction content]

[0042]

[Table 1]

Claims (3)

[Claims] 1. A compound represented by the general formula (1): (R ¹ is an alkyl group having 1 to 4 carbon atoms, a phenyl group or a trimethylsiloxy group, R ² is an alkylene group or an oxyalkylene group having at least 2 carbon atoms, R ³ is an alkyl group having 1 to 20 carbon atoms, X is a hydroxyl group,
An alkyl group having 1 to 8 carbon atoms, an alkoxy group having 1 to 8 carbon atoms, m is an integer of 0 to 3, and a is an integer of 0 to 3. ) Having at least one unit represented by the formula ₍₁₎ , the other units that may be present in the siloxane are represented by the general formula O _{(4-n) / 2} SiR ⁴ n (n is 0 to 3). An integer, R ⁴ represents an alkyl group having 1 to ⁴ carbon atoms, a phenyl group, or a trimethylsiloxy group.), A silicone-based hydantoin derivative. 2. An ultraviolet absorber comprising the silicone hydantoin derivative according to claim 1. 3. An external preparation for skin comprising the silicone hydantoin derivative according to claim 1.