JPH0797384A - Silicone-based hydantoin derivative, ultraviolet light absorber and external preparation for skin - Google Patents

Abstract

PURPOSE:To obtain a new derivative suitable for an ultraviolet light absorber and an external preparation for skin, having ultraviolet light absorption characteristics in the UV-A region, soluble in a silicone oil, showing excellent water resistance and oil resistance. CONSTITUTION:This derivative is a silicone compound containing a unit of formula I (R<1> is a 1-4C alkyl, phenyl, etc.; R<2> and R<3> are an alkylene, an oxyalkylene; (m) is 0-3; (a) is 0-5 and another unit of formula II ((n) is 0-3; R<4> is as shown for R<1>) capable of existing in the siloxane, such as a derivative of formula III. The derivative, for example, is obtained by reacting a compound of formula IV such as 3,4-dimethoxybenzaldehyde with hydantoin in the presence of an amino acid such as glycine, reacting the reactional product with a silicone compound which is a siloxane containing a unit of formula V (Y is a halogen) and a unit of the formula II capable of existing in the siloxane.

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]

BACKGROUND OF THE INVENTION Ultraviolet light is known to cause various changes in the skin. When UV rays are dermatologically classified, 400-320 nm long-wavelength UV rays called UV-A,
Mid-wavelength ultraviolet light called UV-B from 320 to 290 nm,
It is divided into short wavelength ultraviolet rays called UV-C having a wavelength of 290 nm or less. Normally, most of the ultraviolet rays that humans are exposed to are the sun's rays, but the ultraviolet rays that reach the ground are UV-A and U.
In V-B, UV-C is absorbed in the ozone layer and hardly reaches the ground. UV- in the ultraviolet that reaches the ground
B has been found to cause erythema and blisters on the skin, and UV-A has been shown to cause blackening of the skin and promote skin aging when acted over a long period of 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, along with increasing consumer demand for white skin throughout the four seasons and preventing skin aging,
VA 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 ultraviolet absorbers have a silicone base such as dimethylsiloxane which is excellent in water resistance and oil resistance and does not easily run off by sweat or a water bath in order to maintain its effect. It has become widely used. This is not only water- and oil-resistant function of silicone base, but also good elongation, refreshing feeling,
It is also largely due to usability such as non-greasiness.

However, the existing UV-A absorbers have extremely low compatibility with silicone bases. Therefore, the external preparation containing the silicone base is
It is difficult to mix the -A absorber together, and the amount used is very small, which is a drawback that the UV-A absorber does not exhibit its full function.

Therefore, it has been strongly desired to develop a UV-A absorber which is soluble in a silicone base, has excellent water resistance, and protects the skin from ultraviolet rays in the UV-A region.

As a result of earnest studies in view of such circumstances, the present inventor has found that a silicone-based hydantoin derivative is a compound which can satisfy the above-mentioned properties, and has completed the present invention.

[0009]

That is, the object of the present invention is to dissolve UV-A in a silicone base and
It is intended to provide a substance that absorbs ultraviolet rays in the 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 represented by To be done.

[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, n-propyl, isopropyl, n-butyl, isobutyl, t-butyl, phenyl group and trimethyl. Examples thereof include siloxy 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 1 to 3. Examples of R ² and R ³ include, for example, —CH
_{2 -, - (CH 2)} 2 -, - (CH 2) 3 -, -CH
_{2 CH (CH 3) CH 2} -, -CH 2 CH 2 CH (C
_{H 3) -, -CH (CH} 3) CH 2 CH 2 -, -C
_{(CH 3) 2 CH 2 CH} 2 -, - (CH 2) 5 --CH
_{2 CH 2 CH 2 CH (CH} 2 CH 3) -, - CH 2 CH
_{2 CH 2 CH 2 CH (CH} 3) -, - (CH 2) 7 -,
_{-CH 2 CH 2 OCH 2 CH 2} -, - CH 2 CH 2 CH
₂ OCH ₂ −, and the like. Examples of X include methoxy, ethoxy, isopropoxy, butoxy, t-butoxy, hexyloxy, octyloxy and the like. a
Represents the number of substitutions of X and is an integer of 0-5.

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

[0015]

[Chemical 3]

The benzaldehyde derivative (2) and hydantoin (3) are added in the presence of amino acids such as glycine and alanine or salts thereof in water or an aqueous solution at room temperature to 150 ° C.
At room temperature for 1 to 20 hours to obtain (4). Then
(4) in a solvent such as N, N-dimethylformamide or dimethylsulfoxide in the presence of a base such as KOH, NaOH or K ₂ CO _{3 to} give a silicone compound A [Chemical Formula 4 (R ¹ is an alkyl group having 1 to 4 carbon atoms] Group, a phenyl group or a trimethylsiloxy group, R ² and R ³ represent an alkylene group or an oxyalkylene group, Y represents a halogen element such as Br, Cl, I. Further, m represents an integer of 0 to 3). Siloxane having at least one unit represented, and other units which may be present in the siloxane are represented by the general formula O
It is a compound represented by _{(4-n) / 2} SiR ⁴ _n (n is an integer of 0 to 3, R ⁴ represents an alkyl group having 1 to ⁴ carbon atoms, a phenyl group or a trimethylsiloxy group). ] And room temperature ~
By reacting at 200 ° C. for 5 minutes to 50 hours (1)
Can be obtained.

[0017]

[Chemical 4]

Alternatively, (4) is added with KOH, in a solvent such as N, N-dimethylformamide or dimethylsulfoxide.
In the presence of a base such as NaOH or K ₂ CO ₃ , the silicone compound B [Chemical formula 5 (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, Z Represents a hydrogen atom or a methyl group, and m represents an integer of 0 to 3), which is a siloxane having at least one unit represented by the following formula. , General formula O
It is a compound represented by _{(4-n) / 2} SiR ⁴ _n (n is an integer of 0 to 3, R ⁴ represents an alkyl group having 1 to ⁴ carbon atoms, a phenyl group or a trimethylsiloxy group). ] And room temperature ~
(1) can also be obtained by reacting at 150 ° C. for 30 minutes to 50 hours.

[0019]

[Chemical 5]

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 has excellent elongation,
A feeling of freshness, a feeling of non-greasiness and excellent water resistance,
It is preferable because it provides oil resistance and further 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 in its field of application, 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 any dosage form such as powder, cream, paste, stick, liquid, spray, foundation, etc. may be used. You may emulsify to a W / O type or an O / W type using an emulsifier. The blending amount varies depending on the above dosage form, but is generally 0.1 to 30% by weight.
Is preferable, and more preferably 0.2 to 20% by weight.

[0024]

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

Example 1 (1) 3,4-dimethoxybenzaldehyde 83.0
g, hydantoin 50.0 g, glycine 28.1 g, sodium hydroxide 7.5 g, and water 200 ml were stirred at about 75 ° C. for 8 hours. After cooling, the obtained crystals were collected by filtration, washed with water and dried to give 5- (3,4-dimethoxybenzylidene) hydantoin 112.4 g (yield 90.6%).

(2) N, N-dimethylformamide (D
To 100 ml of MF), 12.40 g of the above 5- (3,4-dimethoxybenzylidene) hydantoin, 25.32 g of the silicone compound represented by the following chemical formula 6, and 0.4 g of sodium hydroxide were stirred at about 120 ° C. for 3 hours.

[0027]

[Chemical 6]

(3) After cooling, DMF was distilled off under reduced pressure,
A slightly yellow solid was obtained. This solid was recrystallized from methanol to obtain 20.77 g (yield 62.0%) of the silicone-based hydantoin derivative of the present invention represented by the following Chemical formula 7.

[0029]

[Chemical 7]

Example 2 (1) The reaction was carried out in the same manner as in Example 1 except that 24.48 g of the silicone compound represented by the following chemical formula 8 was changed from the chemical compound 6 shown below.

[0031]

[Chemical 8]

(2) 19.12 g of the silicone-based hydantoin derivative of the present invention represented by the following chemical formula 9 (yield 58.3)
%) Was obtained.

[0033]

[Chemical 9]

Example 3 (1) N, N-dimethylformamide (DMF) 100
12.40 g of 5- (3,4-dimethoxybenzylidene) hydantoin obtained in Example 1 and 19.23 g of a silicone compound represented by the following chemical formula 10 were stirred in ml at about 120 ° C. for 5 hours.

[0035]

[Chemical 10]

(2) After cooling, DMF was distilled off under reduced pressure. The residue was recrystallized from methanol and
The silicone-based hydantoin derivative 1 of the present invention represented by
8.12 g (yield 60.8%) was obtained.

[0037]

[Chemical 11]

Example 4 (1) N, N-Dimethylformamide (DMF) 100
4-96 g of 5- (3,4-dimethoxybenzylidene) hydantoin obtained in Example 1 and 8.82 g of a silicone compound represented by the following Chemical formula 12 were stirred in 120 ml at about 120 ° C. for 3 hours.

[0039]

[Chemical 12]

(2) After cooling, DMF was distilled off under reduced pressure. The residue was purified by silica gel column chromatography (hexane: ethyl acetate = 7: 3) to obtain 6.97 g (yield 53.7%) of the silicone-based hydantoin derivative of the present invention represented by the following chemical formula 13.

[0041]

[Chemical 13]

The structures of Chemical formula 7, Chemical formula 9, Chemical formula 11, and Chemical formula 13 were confirmed by ¹ H-NMR spectrum and infrared absorption spectrum.

The 1H-NMR spectrum is shown by JNM FX.
-270 (manufactured by JEOL Ltd.) using CDCl ₃
Was used as a solvent (internal standard CHCl ₃ ). As a representative example, the ¹ H-NMR spectrum of Chemical formula 7 is shown in FIG.

The infrared absorption spectrum was measured by the potassium bromide tablet method using a 270-30 infrared spectrophotometer (manufactured by Hitachi Ltd.). As a typical example, the infrared absorption spectrum of Chemical formula 7 is shown in FIG.

For the compounds obtained in Examples 1 to 4, UV
-2200 spectrophotometer (manufactured by Shimadzu Corporation) was used to measure the ultraviolet absorption spectrum with an ethanol solvent,
All showed maximum absorption in the UV-A region. From this, it can be said that the silicone hydantoin derivative of the present invention is an excellent UV-A absorber. As a typical example, FIG.
2 shows the ultraviolet absorption spectrum of Chemical formula 7.

Regarding the solubility of the silicone-based hydantoin derivative of the present invention in the silicone-based base, the solubility in dimethylpolysiloxane and methylphenylpolysiloxane was tested under the condition of 25 ° C. In each case, 10% by weight or more was dissolved and excellent solubility was exhibited.

With respect to water resistance and oil resistance, the silicone hydantoin derivative of the present invention was stirred and mixed with oil such as water, 50% etal and liquid paraffin, and the mixture was allowed to stand at 50 ° C. for 60 days. As a result, it was confirmed that hydrolysis and the like did not occur and the water resistance and oil resistance were excellent.

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

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

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

Example 6 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 2) 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 part. (11) to (14) were heated to 70 ° C. to completely dissolve them and then used as an aqueous phase part. The oil phase part was added to the water phase part and emulsified with 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 6 except that (8) was excluded from the formulation of Example 6.

Example 7 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 3) 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) were heated and stirred at 70 ° C. to obtain an oil phase part. (7) to (9) were heated to 70 ° C. to completely dissolve them, and then used as an aqueous phase part. The oil phase part was added to the water phase part and emulsified with 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 7, except that (4) was excluded from the formulation of Example 7.

With respect to Examples 5 to 7 and Comparative Examples 1 to 3 obtained as described above, the ultraviolet protection effect was measured. As the measuring method, 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 after 15 minutes, UV-A irradiation was performed. UV-A irradiation is performed with 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 obtained using the following formula.

[0058]

[Equation 1]

The results are shown in Table 1.

[0060]

[Table 1]

As can be seen from Table 1, the MMD values of the examples are higher than those of the comparative examples. 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.

[0062]

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 can provide a skin external preparation whose base and other components can be freely selected, and at the same time, it is excellent as a sunscreen cosmetic even when exposed to the harsh conditions under hot weather. It is clear that it has an effect.

[Brief description of drawings]

FIG. 1 is a diagram showing a ¹ H-NMR spectrum of a silicone-based hydantoin derivatization 7 obtained in Example 1 of the present invention.

FIG. 2 is a diagram showing an infrared absorption spectrum of silicone-based hydantoin derivatization 7 obtained in Example 1 of the present invention.

FIG. 3 is a diagram showing an ultraviolet absorption spectrum of silicone-based hydantoin derivatization 7 obtained in Example 1 of the present invention.

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 and R ³ are alkylene groups or oxyalkylene groups, X is a hydroxyl group, and 1 to 8 carbon atoms.
Is an alkyl group or 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 5. ) A siloxane having at least one unit represented by the formula (4), and 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 an integer of 0 to 3 and R ⁴ is an alkyl group having 1 to ⁴ carbon atoms, a phenyl group or a trimethylsiloxy group). Silicone 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.