JP2693659B2 - Organosilicon compound and cosmetics containing the same - Google Patents

Description

DETAILED DESCRIPTION OF THE INVENTION

[0001]

BACKGROUND OF THE INVENTION 1. Field of the Invention The present invention relates to a novel organosilicon compound which is soluble in an oil agent for cosmetics and has a high ultraviolet absorption effect, which has not been described in any literature, and a cosmetic composition containing the same.

[0002]

2. Description of the Related Art In recent years, the harmful effect of ultraviolet rays on the skin has become a problem, and ultraviolet rays in the mid-wavelength region (UV-B: 290 to 320 n, which causes conventional sunburn).
m), as well as having high penetrability into the skin, causing ultraviolet rays in the long wavelength region (UV-A: 3) that causes increased spots and freckles.
20-400 nm) blocking has come to be demanded.
As an ultraviolet absorber that efficiently absorbs this long wavelength region, "Persol 1789" (manufactured by Givaudan Co., Ltd., 4-
tert-butyl-4′-methoxydibenzoylmethane) and “Tinuvin P” (Ciba Geigy Co., Ltd., 2-
A benzotriazole compound represented by (2′-hydroxy-5′-methylphenyl) benzotriazole),
Alternatively, benzophenone compounds such as 2,2'-dihydroxy-4,4'-dimethoxybenzophenone are known. These compounds have been put to practical use as a compounding agent for medical use, cosmetics, etc., and as various plastic additives. However, all of them have poor dispersibility and solubility in the substrate, so that there is a problem that the compounding amount is limited or precipitation occurs.

In order to improve such drawbacks, for example, an alkoxysilyl group is introduced into a compound having a benzotriazole skeleton or a benzophenone skeleton and cohydrolyzed with chlorosilane or alkoxysilane to form a polysiloxane molecule. It has been proposed to incorporate them (Japanese Patent Laid-Open Nos. 57-21391 and 57-21).
No. 432, No. 58-10591, No. 58-21307.
No. 5, No. 61-111360, No. 62-187740.
No. each publication). However, the compounds obtained by co-hydrolyzing these do not have solubility in oil agents such as ester oils, hydrocarbon oils and silicone oils. Further, when the compound introduced with an alkoxysilyl group is directly added to the above oil agent, there is a drawback that it is hydrolyzable and lacks stability. In particular, when such a hydrolyzable compound is used for medical or cosmetic purposes, there arises a problem that the substance produced by hydrolysis has irritating properties on the skin, mucous membranes and the like. In particular, the compound having a benzotriazole skeleton has its own stimulating property and photosensitizing property, and is not suitable for medical use, cosmetic use and the like.

As a type of the above-mentioned improved stability, it has been proposed to use a polysiloxane derivative containing no alkoxysilyl group (JP-A-63-230681).
And Japanese Patent Publication No. 52-50074). However, when a compound having a benzotriazole skeleton is used, it is not preferable in terms of safety as described above. On the other hand, it has been proposed to use a polysiloxane derivative having a dibenzoylmethane skeleton as a compound having a high absorptivity in a long wavelength region of ultraviolet rays (Japanese Patent Laid-Open No. 7563/1990).
(See Japanese Patent Publication No. 3).

[0005]

DISCLOSURE OF THE INVENTION Problems to be Solved by the Invention
The compounds shown in No. 633 have very good solubility in oil agents such as ester oils, hydrocarbon oils and silicone oils, and also have excellent absorptivity in the long wavelength region of ultraviolet rays. However, polysiloxane compounds are unstable under acidic conditions, causing siloxane bond degradation. For example, in cosmetics and the like, when mixed in a weakly acidic solution form or in an emulsion composition, etc., there is a problem that when the siloxane bond is decomposed, a hardly soluble compound having a dibenzoylmethane skeleton is deposited. .

[0006]

Means for Solving the Problems Accordingly, the present inventors have:
Ester oils, hydrocarbon oils, and silicone oils that are soluble, yet have excellent absorptivity in the long-wavelength region of ultraviolet light, and since there is a need for a UV absorber that does not decompose even under acidic conditions, As a result of earnest research for such an absorbent, the general formula

[0007]

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(Where R ¹ is a general formula And R ² is a hydrogen atom, a hydroxy group, or an alkyl group or an alkoxy group having 1 to 10 carbon atoms, and R ³ is the same or different alkyl group having 1 to 30 carbon atoms, a phenyl group , or 1 halogenated carbon atom
Is an alkyl group or a phenyl group of 30 , a is 0 or 1, b is 0 or 1, and a + b is 1 or 2, c is an integer of 0 to 5, d is 0 or 1, n is 2
The present invention has been accomplished by finding a novel compound represented by the formula (6 is an integer of 6).

The present invention will be described in detail below.
The compound of the present invention is represented by the above general formula, and examples of R ^{2 in} the formula include a hydrogen atom, a hydroxy group, a methyl group, an ethyl group, a propyl group, a butyl group, a pentyl group, a hexyl group, Heptyl group, octyl group, nonyl group,
Examples thereof include alkyl groups such as decyl group, and alkoxy groups such as methoxy group, ethoxy group, propoxy group, butoxy group. Examples of R ³ include methyl group, ethyl group, propyl group, butyl group, pentyl group, hexyl group,
Alkyl group such as heptyl group, octyl group, nonyl group, decyl group; phenyl group; halogenated alkyl group such as trifluoropropyl group, heptadecafluorodecyl group, chloropropyl group, chlorophenyl group and phenyl group Can be done. Preferably, an alkyl having 1 to 10 carbon atoms
Ru and phenyl are preferred.

The novel method for synthesizing an organosilicon compound of the present invention is the acetophenone compound (1) containing an alkenyloxy group having a double bond at the terminal.

[0011]

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And benzoic acid esters (2)

[0013]

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Alternatively, benzoic acid esters containing an alkenyloxy group having a double bond at the terminal (3)

[0015]

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And acetophenone compound (4)

[0017]

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Alternatively, an acetophenone compound (1) containing an alkenyloxy group having a double bond at the terminal and an benzoic acid compound (3) containing an alkenyloxy group having a double bond at the terminal are condensed under a basic condition to give a diamine at the terminal. Alkenyloxy group-containing dibenzoylmethane skeleton having a heavy bond (5
Or 6)

[0019]

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[0020]

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It can be obtained by synthesizing ## STR1 ## and adding the organohydrogen silane (7) R ³ ₃ SiH (7) thereto. Alternatively, an acetophenone compound having an organic silicon group (8)

[0022]

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And benzoic acid esters (2), or
Benzoic acid esters having an organic silicon group (9)

[0024]

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And acetophenone compound (4) or acetophenone compound (8) having an organic silicon group
It can also be obtained by condensing benzoic acid (9) having an organosilicon group with a basic condition. Further, an alkenyloxy group-containing dibenzoylmethane skeleton having a double bond at the end (10 or 11)

[0026]

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[0027]

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The following dibenzoylmethane skeleton (12 or 13) is obtained by carrying out a thermal rearrangement reaction on

[0029]

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[0030]

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The compound can be obtained, and the compound can also be synthesized by subjecting the alkenyloxy group to an addition reaction with an alkylhydrodienesilane (7). Also,
Acetophenone (1) undergoes thermal rearrangement reaction (14)

[0032]

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Alternatively, it can be obtained by condensation with benzoic acid esters (2) and then addition reaction with organohydrogensilane (7). Also,
Benzoic acid esters (3) were subjected to thermal rearrangement reaction (15)

[0034]

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Alternatively, it can be obtained by condensation with acetophenone (4) and then addition reaction with an organohydrogensilane (7). It can also be obtained by condensing acetophenone (14) and benzoic acid esters (15) and then subjecting them to an addition reaction with organohydrogensilane (7). Also,
Addition reaction of acetophenone (14) and organohydrodienesilane (7) (16)

[0036]

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Then, it can also be obtained by condensation with benzoic acid esters (2). In addition, benzoic acid esters (15) and organohydrodienesilane (7) are subjected to an addition reaction (17)

[0038]

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Then, it can also be obtained by condensation with acetophenone (4). Furthermore, after condensing acetophenone (14) and benzoic acid esters (3), an organohydrogen silane (7) may be subjected to an addition reaction, or benzoic acid esters (15) and acetophenone (1) may be condensed. After that, it can also be obtained by subjecting the organohydrogenenesilane (7) to an addition reaction. The compound of the present invention thus obtained can be incorporated into cosmetics in the same manner as a known ultraviolet absorber.

[0040]

EXAMPLES The present invention will be further described with reference to examples. These do not limit the invention of the present application. Example 1 4-allyloxyacetophenone (56 g) and methyl benzoate (345 g) were charged into a reactor, and the internal temperature was 150 ° C.
Heated. A 28% sodium methoxide methanol solution (74 g) was gradually added dropwise through a dropping funnel. At this time, methanol was distilled off while distilling off. After the dropwise addition was completed, the mixture was stirred for 1 hour and then cooled to room temperature. After adding water (200 ml), 10% sulfuric acid (200 g) was added dropwise while cooling the reactor with ice water.
After separating the aqueous layer, toluene (500 ml) was added and the mixture was washed with water. The mixture was neutralized with a 5% aqueous sodium hydrogen carbonate solution, separated into aqueous layers, and washed again with water. The solvent and unreacted methyl benzoate and the like were removed under reduced pressure. The reddish brown residue was recrystallized from ethanol to give 4-allyloxydibenzoylmethane (50
g) was obtained. It was a white crystal having a melting point of 54 to 57 ° C.

Next, 4-allyloxydibenzoylmethane (42 g) and toluene (100 g) were charged into a reactor, and the internal temperature was set to 80 ° C. A 2-propanol solution containing 2% by weight of chloroplatinic acid (0.1 g) was added, and tributylsilane (36 g) was gradually added through a dropping funnel. After the addition was completed, the internal temperature was maintained at 80 to 100 ° C and the mixture was stirred for 4 hours.
The reaction solution was air-cooled to room temperature, activated carbon (1 g) was added, and the mixture was further stirred at room temperature for 2 hours. After filtering off the activated carbon, it is heated under reduced pressure (5 mmHg) at 150 ° C. for 1 hour to remove the solvent and unreacted tributylsilane.

[0042]

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70 g of was obtained. The appearance was a transparent liquid with a yellow color, and the viscosity at 25 ° C. was 431 cs. The ultraviolet absorption spectrum of the product is as shown in FIG. The solute concentration of the ultraviolet absorption spectrum measurement sample was 1.
It was set to 03 mg / 100 ml of ethanol. The infrared absorption spectrum is as shown in FIG. When 10% by weight was added to various oils used for cosmetics and the solubility at room temperature was investigated, isononyl isononanoate, isocetyl myristate, glyceryl tri-2-ethylhexanoate, triethyl citrate, isooctanoic acid were used as ester oils. It was uniformly dissolved in cetyl, squalane as a hydrocarbon oil, and methylphenyl silicone oil (“KF56” manufactured by Shin-Etsu Chemical Co., Ltd.) as a silicone oil.

Example 2 Next, a formulation example of a cosmetic product obtained by blending the organosilicon compound obtained in the above example will be shown. [Formulation Example 1] Oily foundation (A) component; Kaolin: 20.0 wt% Titanium oxide: 12.0 wt% Sericite: 8.0 wt% Coloring pigment: Appropriate amount (B) component; Carnauba wax: 4 0.0 wt% dimethylpolysiloxane: 5.0 wt% (viscosity at 25 ° C .: 50 cs) Organosilicon compound obtained in Example 1: 8.0 wt% octamethylcyclotetrasiloxane: 42.0 wt% sorbitan sesqui Olate: 1.0% by weight (C) component; Fragrance: appropriate amount The above component (B) was stirred at 70 ° C. to dissolve and homogenize, and then the component (A) was added and dispersed by stirring to cool. The obtained mixture was kneaded with a three-roll mill three times, and then the component (C) was added to obtain an oily foundation. The obtained oily foundation was excellent in ultraviolet absorbency and water resistance, and had a refreshing feeling of use with excellent extensibility.

[Formulation Example 2] Solid foundation (A) component; Titanium oxide: 20.0% by weight Mica: 36.0% by weight Sericite: 10.0% by weight Talc: 10.0% by weight Colored pigment: Appropriate amount Component (B): Dimethylpolysiloxane: 12.5 wt% (viscosity at 25 ° C .: 50 cs) Organosilicon compound obtained in Example 1: 10.0 wt% Lipophilic glyceryl monooleate: 1.5 wt% % Methyl paraoxybenzoate: Appropriate amount Fragrance: Appropriate amount The above component (A) was pulverized with a two-roll mill, and then the component (B) uniformly dissolved was added and mixed with stirring. Kneading the resulting mixture three times using a three-roll mill,
A solid foundation was obtained. The obtained solid foundation was excellent in ultraviolet absorption and water resistance, and had a refreshing feeling of use.

[Formulation Example 3] Sunblock cream (A) component: Octamethylcyclotetrasiloxane: 40.0% by weight Organosilicon compound obtained in Example 1: 20.0% by weight Trimethylsiloxypolysilicate: 25. 0% by weight Liquid paraffin: 10.0% by weight Carnauba wax: 5.0% by weight Component (B); Fragrance: appropriate amount The above component (A) is stirred at 80 ° C., uniformly dissolved and allowed to cool. , (B) component was added to obtain a sunscreen cream. The obtained sunscreen cream was excellent in ultraviolet absorption and water resistance and had a refreshing feeling of use.

[Formulation Example 4] Sunscreen milky lotion (A) component; Decamethylcyclopentasiloxane: 7.0 wt% Organosilicon compound obtained in Example 1: 3.0 wt% Dimethylpolysiloxane: 2.0 % By weight (viscosity at 25 ° C .: 350 cs) Stearic acid: 2.0% by weight Self-emulsifying glyceryl monostearate: 1.0% by weight Cetanol: 1.0% by weight Component (B); Purified water: 72.5% by weight % Triethanolamine: 1.0 wt% Propylene glycol: 3.0 wt% Titanium oxide: 5.0 wt% Bentonite: 0.5 wt% Methyl paraoxybenzoate: Appropriate amount (C) component; Fragrance: Appropriate amount Above After stirring and dissolving the component (A) at 80 ° C.,
The homogeneous dispersion liquid obtained by stirring the component (B) at 80 ° C. was gradually added with stirring and allowed to cool, and then the component (C) was added and mixed to obtain a sunscreen emulsion. The resulting sunscreen emulsion had a refreshing feel.

[Formulation Example 5] Hair cream (A) component: Methylphenylpolysiloxane: 17.0 wt% (viscosity at 25 ° C .: 20 cs) Organosilicon compound obtained in Example 1: 3.0 wt% Camellia oil 10.0% by weight Salix beeswax: 5.0% by weight Self-emulsifying glycerin monostearate: 3.0% by weight Polyoxyethylene sorbitan monostearate (20EO): 3.0% by weight Reduced lanolin: 1.5% by weight % Microcrystalline wax: 2.0% by weight Methyl paraoxybenzoate: Appropriate amount of component (B); Purified water: 51.0% by weight Borax: 0.5% by weight Glycerin: 3.0% by weight Carboxyvinyl polymer: 0 0.2% by weight (C) component; fragrance: 0.8% by weight The above (A) component is dissolved by stirring at 80 ° C., and then further stirred. Meanwhile, the component (B) heated and dissolved at 80 ° C. was added and mixed, and cooled to 60 ° C. The component (C) was further added to and mixed with the obtained solution and then cooled to 30 ° C. to obtain a hair cream. The obtained hair cream was excellent in ultraviolet absorption and had a refreshing feeling of use.

[Formulation Example 6] Stick-type lipstick (A) component; Methylphenylpolysiloxane: 46.5% by weight (viscosity at 25 ° C: 20 cs) Organosilicon compound obtained in Example 1: 10.0% by weight Reduced lanolin: 20.0% by weight Carnauba wax: 4.5% by weight Candelilla wax: 9.0% by weight Ceresin wax: 2.5% by weight Salix beeswax: 1.5% by weight Cocoa butter: 4.0% by weight Sucrose fatty acid ester: 2.0% by weight Antioxidant: Appropriate amount (B) component; Allantoin: Appropriate amount Red No. 3 aluminum lake: Appropriate amount (C) component; Perfume: Appropriate amount The above (A) component is 85 ° C After stirring and dissolving in (1), a part was sampled, the component (B) was added and mixed, and the mixture was kneaded three times with a three-roll mill to obtain a color paste. The above color paste was added to and mixed with the rest of the component (A), and then uniformly dispersed by a disper mixer. Then, the component (C) was added thereto, the mixture was put into a mold, and then rapidly cooled to obtain a stick-type lipstick.
The stick-type lipstick obtained was excellent in ultraviolet absorption and water resistance, and had a glossy and refreshing feeling during use.

[Formulation Example 7] Eye shadow (A) component; Pearl agent: 10.0 wt% Blue ultramarine: 5.0 wt% (B) component; Dimethylpolysiloxane: 28.0 wt% (viscosity at 25 ° C) : 20cs) Octamethylcyclotetrasiloxane: 42.0% by weight Organosilicon compound obtained in Example 1: 5.0% by weight Reduced lanolin: 5.0% by weight Microcrystalline wax: 5.0% by weight (C) Ingredient; Fragrance: Appropriate amount The above component (B) was dissolved by stirring at 80 ° C., and then the component (A) was added and dispersed while stirring. After allowing to cool, the mixture obtained by adding the component (C) was kneaded three times with a three-roll mill to obtain a creamy eye shadow. The obtained eye shadow was excellent in ultraviolet absorption and water resistance, and had a refreshing feeling of use.

[Formulation Example 8] Component of mascara (A); Isoparaffin: 20.0% by weight Octamethylcyclotetrasiloxane: 20.0% by weight Organosilicon compound obtained in Example 1: 7.0% by weight Stearic acid Aluminum: 1.0% by weight (B) component; Bentonite: 15.0% by weight Methylphenylpolysiloxane: 7.0% by weight (viscosity at 25 ° C .: 20 cs) Candelilla wax: 10.0% by weight Hydrogenated polybutene: 5.0 wt% Methyl paraoxybenzoate: Appropriate amount (C) component; Kaolin: 5.0 wt% Iron oxide black: 5.0 wt% The above (A) component was stirred at 80 ° C. to form a gel solution. After that, while further stirring, the mixture was stirred and uniformly dispersed at 80 ° C. (B).
The components were added and uniformly dispersed, and after cooling, the component (C) was added and mixed. Further, kneading was performed three times with a three-roll mill to obtain a mascara. The obtained mascara was excellent in ultraviolet absorption and water resistance and had a refreshing feeling of use. As described above, it has been revealed that the organosilicon compound of the present invention is incorporated into a wide range of cosmetics and is extremely excellent as a compounding agent for cosmetics.

[0052]

The present invention provides a novel organosilicon compound. This compound is a material that has absorptivity in the long-wavelength region of ultraviolet rays and has excellent solubility in an oil agent for cosmetics. Moreover, since it does not contain a hydrolyzable group such as an alkoxy group, it has good stability and high safety, and is particularly useful for cosmetics.

[Brief description of the drawings]

FIG. 1 is a diagram showing an ultraviolet absorption spectrum of an organosilicon compound which is a product obtained in Example 1 of the present invention.

FIG. 2 is a diagram showing an infrared absorption spectrum of an organosilicon compound which is a product obtained in Example 1 of the present invention.

─────────────────────────────────────────────────── ─── Continuation of the front page (51) Int.Cl. ⁶ Identification code Internal reference number FI Technical display location A61K 7/035 A61K 7/035 7/06 7/06 C09K 3/00 104 C09K 3/00 104Z

Claims (2)

(57) [Claims] 1. A compound of the general formula An organosilicon compound represented by. (Where R ¹ is a general formula And R ² is a hydrogen atom, a hydroxy group, or an alkyl group or an alkoxy group having 1 to 10 carbon atoms, and R ³ is the same or different alkyl group having 1 to 30 carbon atoms, a phenyl group , or 1 halogenated carbon atom
Is an alkyl group or a phenyl group of 30 , a is 0 or 1, b is 0 or 1, and a + b is 1 or 2, c is an integer of 0 to 5, d is 0 or 1, n is 2
Is an integer of 6). 2. A cosmetic comprising the organosilicon compound according to claim 1.