JP3229383B2 - Alkyl-aryl 1,3-propanedione silicone derivative and external preparation for skin containing the same - Google Patents

Description

DETAILED DESCRIPTION OF THE INVENTION

[0001]

FIELD OF THE INVENTION The present invention relates to an alkyl-aryl 1,
The present invention relates to a 3-propanedione silicone derivative and an external preparation for skin containing the same, particularly to an improvement in the ability to absorb ultraviolet light in the UV-A region.

[0002]

2. Description of the Related Art Ultraviolet rays contained in sunlight are dermatologically long-wavelength ultraviolet rays (UV-320 nm).
A), medium wavelength ultraviolet light (UV-320 nm to 290 nm)
B) It is classified into a short wavelength ultraviolet ray (UV-C) of 290 nm or less. Among them, ultraviolet light having a wavelength of 290 nm or less is absorbed by the ozone layer and does not reach the surface of the earth. Ultraviolet rays reaching the earth's surface have various effects on human skin. Among the ultraviolet rays reaching the ground, UV-B forms erythema and blisters on the skin and also promotes melanin formation. On the other hand, UV-A induces browning of the skin, promotes a decrease in skin elasticity and generation of wrinkles, and causes rapid aging. It may also promote the onset of the erythema reaction, or enhance this response for certain patients, and even cause phototoxic or photoallergic reactions. Various UV absorbers have been developed to protect the skin from such harmful effects of UV-A.

[0003] As existing UV-A range ultraviolet absorbers,
Benzophenone derivatives, dibenzoylmethane derivatives, benzotriazole derivatives, and the like have been used as UV-A absorbers and have been incorporated into skin external preparations. On the other hand, in recent years, for skin external preparations containing an ultraviolet absorber, silicone bases such as dimethylsiloxane, which have excellent water resistance and do not easily run off due to sweat or a water bath, are widely used in order to maintain their effects. It has become. The use of these silicone bases is largely attributable to the advantages of ease of use, such as good spreadability, refreshing feeling and non-stickiness, as well as water resistance.

[0004]

However, there is a problem that the existing ultraviolet absorber in the UV-A range has a remarkably low compatibility with a silicone base. In addition, since the absorbent is generally a dark-colored crystal and has drawbacks such as crystallization due to low temperature in the product and coloring of clothes, the amount used is limited to a very small amount, and the UV-A absorbent has There was a drawback that the function was not sufficiently exhibited. The present invention has been made in view of the above-mentioned problems of the prior art, and an object of the present invention is to provide a substance which dissolves in a silicone base and shields ultraviolet rays in the UV-A region, and a skin external preparation containing the same. It is in.

[0005]

Means for Solving the Problems As a result of intensive studies by the present inventors to achieve the above object, an alkyl-aryl 1,3-propanedione silicone derivative has an excellent UV
-A It was found that it had absorptivity and usability, and the present invention was completed. That is, alkyl of claim 1, wherein - an aryl 1,3-propanedione silicone derivative is characterized and Turkey represented by the following general formalized 2.

[0006]

Embedded image (However, R ¹ is a hydroxyl group, an alkyl group having 1 to 8 carbon atoms or an alkoxy group having 1 to 8 carbon atoms, R ² is an alkyl group having 1 to 7 carbon atoms, and R ³ is a divalent having 2 to 10 carbon atoms. Alkylene group or oxyalkylene group, R ⁴ is the same or different
And may be an alkyl group having 1 to 4 carbon atoms, a phenyl group or a trimethylsiloxy group, m, n is an integer of from 0 to 3, p is 0
Or 1 is represented. )

Hereinafter, the configuration of the present invention will be described in more detail. Alkyl according to the present invention - an aryl 1,3-propanedione silicone derivative is it express by Formula 2.
Examples of R ¹ include hydroxyl, methyl, ethyl, propyl, isopropyl, butyl, isobutyl, sec-
Butyl group, t-butyl group, n-amyl group, isoamyl group,
n-hexyl group, 2-ethylbutyl group, n-octyl group,
Alkyl group such as 2-ethylhexyl group, methoxy group, ethoxy group, propoxy group, isopropoxy group, butoxy group, isobutoxy group, s-butoxy group, t-butoxy group, n-amyloxy group, isoamyloxy group, n-hexyloxy group And alkoxy groups such as 2-ethylbutoxy group, n-pentyloxy group, n-octyloxy group and 2-ethylhexyloxy group.

R ² may be any alkyl group having 1 to 7 carbon atoms, but is preferably a secondary or tertiary carbon atom bonded to a carboxyl group. Particularly preferred R
Examples of ² include an isopropyl group, a tert-butyl group, an ethylpropyl group, an ethylpentyl group, and the like. R
³ may be any alkyl group having 2 to 10 carbon atoms.
Ku, examples of R ³ _{include, -CH 2 CH 2 -, -} CH 2 CH 2
CH ₂ —, —CH ₂ CH (CH ₃ ) CH ₂ —, —CH (CH
_{3) CH 2 CH 2 -,} - CH 2 CH 2 CH (CH 3) -, - C
_{H 2 CH 2 CH 2 CH 2} -, - CH 2 CH 2 OCH 2 CH 2 -,
Hexylene, cyclohexylene, decylene group and the like are mentioned, and an alkylene group having 2 to 4 carbon atoms is particularly preferable. Examples of R ⁴ include a methyl group, an ethyl group, a propyl group, an isopropyl group, a butyl group, an isobutyl group, a t-butyl group, a phenyl group, a trimethylsiloxy group, and the like. For this reason, it is preferred that the methyl group or a part thereof is a phenyl group or a trimethylsiloxy group.

M represents the number of substituents and is an integer of 0 to 3. n represents the number of repeating units of siloxane;
-3. p is 0 or 1. R ⁴ is the same,
Or may be different, and include a methyl group, an ethyl group, a propyl group, an isopropyl group, a butyl group, an isobutyl group, a t-butyl group, a phenyl group, a trimethylsiloxy group, and the like. Or a trimethylsiloxy group.
No.

The alkyl-aryl 1,3-propanedione silicone derivative of the present invention may be a liquid or resinous solid at room temperature depending on the molecular weight.
It can be used as an absorbent. The alkyl-aryl 1,3-propanedione silicone derivative of the present invention can be synthesized by a two-step reaction of the following first step Claisen condensation reaction and second step hydrosilylation reaction. First stage

Embedded image Or

Embedded image Repetitive containing one of Si-H groups in the second stage + molecule
A siloxane having 2 to 5 repeating units → Chemical formula 2 In the above reaction formula, R ¹ , R ² , m, n, and p are as defined in Chemical formula ² , and A is a C 1-5 carbon atom. Alkyl group,
B is an alkenyl or oxyalkenyl group having 2 to 10 carbon atoms . The Claisen condensation reaction of the first stage is described in H
Auer et al. “Organic Reactions”
8, p59, John Wiley and Sons
Inc. , New York 1954, and according to the present invention.

That is, methyl alkyl ketone or substituted acetophenone and fatty acid or substituted alkyl phenyl or benzoic acid in the presence of a base, for example, in the presence of an alkali alcoholate, hydroxide or amide compound, sodium hydride, and toluene , Isopropyl ether, tetrahydrofuran, 1,2-dimethoxyethane,
The reaction can be carried out in a solvent such as dimethylsulfoxide or dimethylformamide between room temperature and the boiling point to obtain an alkyl-aryl 1,3-propanedione derivative. The second stage reaction is a hydrosilylation reaction.
It is known that this reaction is usually promoted by a platinum group metal, a compound of the platinum group metal, or a complex compound of the metal (JP-A-60-108431, JP-A-60-2106).
32, JP-A-1-50711, etc.) Alkylphenyl 1,3-propanedione derivative ,
Also reaction of the repeating unit number of 2 to 5 white <br/> hexane containing one SiH groups, conventional catalysts, such as platinum supported on carbon, chloroplatinic acid, acetylacetone platinum complex, and unsaturated compounds The reaction is promoted by a platinum complex, a platinum complex of an unsaturated siloxane, a rhodium compound and a complex of a platinum compound.

The reaction is carried out at atmospheric pressure in a solvent such as toluene, xylene, hexane, tetrahydrofuran or tetrachloroethylene at 50 ° C. or below the boiling point of the solvent.
If the reaction is continued until the i-H group disappears, the desired alkyl-aryl 1,3-propanedione silicone derivative is obtained. The base of the external preparation for skin according to the present invention may be any base as long as the alkyl-aryl 1,3-propanedione silicone derivative can be dissolved. It is excellent in usability such as goodness, refreshing feeling, and non-greasy, and can have functions such as high water resistance and hardly flow into sweat and water.

When a silicone base is used in the external preparation for skin according to the present invention, the silicone base is not particularly limited. For example, chain polysiloxanes such as dimethylpolysiloxane, methylpolysiloxane and methylhydrogenpolysiloxane are used. And cyclic polysiloxanes such as decamethylpolysiloxane, dodecamethylpolysiloxane, and tetramethylhydrogenpolysiloxane, polyethers, fatty acid-modified polysiloxanes, higher alcohol-modified polysiloxanes, and amino-modified polysiloxanes. The external preparation for skin of the present invention includes other components usually used in cosmetics and the like, such as oils, lubricating oils, antioxidants, surfactants, preservatives, sequestering agents, fragrances, water, alcohol, A tackifier or the like can be appropriately compounded as needed.

The dosage form of the external preparation for skin of the present invention is arbitrary, and may be any of powder, cream, paste, stick, liquid, spray, foundation, etc., and may be emulsified using an emulsifier. Good. Although the alkyl-aryl 1,3-propanedione silicone derivative of the present invention is sufficiently effective when used alone, other UV-B absorbers such as Escalol 507 may be used if necessary.
A p-aminobenzoic acid derivative such as (manufactured by Bandike), a p-methoxycinnamic acid derivative such as neoheliopan (manufactured by Herman Andrimer), a salicylic acid derivative,
In addition to benzylidene camphor derivatives, urocanic acid or derivatives thereof, or inorganic pigments such as titanium dioxide and zinc oxide, they can be used in combination with other UV-A absorbers. The compounding amount of the compound in the present invention varies depending on the above-mentioned dosage form and the extent to which the UV protective action is required, but is generally 0.1 to 20% by weight, preferably 0.5 to 10% by weight. % By weight.

[0015]

EXAMPLES Hereinafter, the present invention will be described in more detail with reference to examples. Note that the present invention is not limited to these examples. Unless otherwise specified, the compounding amount is shown in% by weight. Alkyl-aryl 1,3-propanedione silicone
Derivative Properties and Solubility Tests Examples of the alkyl-aryl 1,3-propanedione silicone derivatives used in the present invention are Compounds 1 to 6 below, and 2-hydroxy-4-methoxybenzophenone (Comparative Compound 1) as a comparative compound, 4 The solubility of isopropyldibenzoylmethane (Comparative Compound 2) was determined using silicone oils such as silicone KF56 and silicone KF96.
(10cs Shin-Etsu Chemical Co., Ltd.) and squalane. Compound 1

Embedded image Compound 2

Embedded image Compound 3

Embedded image Compound 4

Embedded image Compound 5

Embedded image Compound 6

Embedded image Compound 7

Embedded image Compound 8

Embedded image Compound 9

Embedded image In Chemical Formulas _{5 to} 13, Si ₂ , Si ₃ and Si ₅ are represented by the following chemical formulas. Si ₂

Embedded image Si ₃

Embedded image Si ₅

Embedded image Table 1 shows the solubility (w / w) of each compound at room temperature (25 ° C.). About what completely dissolves at 25 ° C ○
The mark, and even those that were slightly turbid, were indicated by x.

[0016]

[Table 1] Property Solubility Silicon KF56 Silicon KF96 Squalane 30% 50% 30% 50% 30% 50% 化合物 Compound 1 colorless oil ○ ○ ○ ○ ○ ○ Compound 2 colorless oil ○ ○ ○ ○ ○ ○ Compound 3 colorless oil ○ ○ ○ ○ ○ ○ Compound 4 pale yellow oil ○ ○ ○ × ○ ○ Compound 5 colorless oil ○ ○ ○ ○ ○ ○ Compound 6 colorless Oil ○ ○ ○ ○ ○ ○ Compound 7 Light yellow oil ○ ○ ○ ○ ○ ○ Compound 8 Light yellow oil ○ ○ ○ ○ ○ ○ Compound 9 Light yellow solid ○ ○ ○ ○ ○ ○ ────────── ────────────────────────── Comparative compound 1 Light yellow solid × × × × × × Comparative compound 2 Light yellow solid × × × × × ×───────────────────────────────────

From the above results, it is understood that all the compounds according to the present invention have excellent solubility in silicone base. Water resistance test After thoroughly washing and drying the entire inner surface of the lower arm of 10 male panels with soap, 0.5 g of a sample solution is applied to the entire inner surface of the lower arm. Then, 3 cm ² of the rubbing part was acetonitrile 2
Extract with 0 ml and measure the absorbance of the solution with a spectrophotometer (this is referred to as absorbance A). After the extraction, the washing machine (NA-400 manufactured by Matsushita Electric Co., Ltd.) is set at a high swirl, and 10 l of water whose water temperature is adjusted to 30 ± 2 ° C. is continuously discharged per minute. After the lower arm is immersed in this washing machine for 2 minutes, it is dried with a dryer and extracted with acetonitrile in the same manner as described above. Let the absorbance of this solution be B. The evaluation of the water resistance was calculated by the following formula and indicated by the residual ratio on the skin. Calculation of Residual Ratio Residual ratio (%) = (absorbance B / absorbance A) × 100 The sample solution is the silicone derivative 1, 2, 5, or 5 of the present invention.
Escalol 507 was selected as a comparative compound, and 3 g of each was dissolved in 97 g of silicone KF56 for adjustment. Table 2 below shows the residual ratio.

[0018]

[Table 2] ──────────────────────────────────── Sample liquid Panel No. 1 No. 2 No. 5 Comparative Example A 97,4 98.9 98.6 82 .3B 95.7 101.3 101.3 80.6 C 97.8 98.6 98.8 84.5 D 97.3 99.3 99.9 79.8 E 96.5 99.3 99. 8 80.3 F 98.9 98.9 99.9 83.8 G 95.9 99.3 102.5 89.2 H 96.8 99.9 101.3 80.4 I 97.5 98.9 97.8 83.9 J 96.7 99.4 99.8 85.1 {Average 97.1 99.4 100.0 83.0}よ り From these results, The alkyl-aryl 1,1 according to the invention
The 3-propanedione silicone derivative has better water resistance than the conventional UV absorber Escalol 507,
It was revealed that it did not easily run off due to sweat, water bath, etc. Example 1 Preparation of Compound 1 (Chemical Formula 5) 1- (3-methoxy-4-allyloxyphenyl) -3-
tert-butyl 1,3-propanedione 2.5 g, 1,
1.7 g of 1,1,3,3-pentamethyldisiloxane,
To a mixture of 20 ml of toluene was added 0.5 mg of hexachloroplatinic acid (IV) hexahydrate, and the mixture was stirred at 100-105 ° C for 6 hours.
Allowed to react for hours. After completion of the reaction, toluene was distilled off under reduced pressure, and the residue was separated and purified by silica gel column chromatography (eluted with a mixture of 2 v / v% ethyl acetate-hexane) to obtain 2.6 g of a colorless oil. The yield was 68.4%. The ultraviolet absorption spectrum of Compound 1 is shown in FIG. λ _max : 335 nm (ε = 24090) Mass spectrum M ⁺ m / e 438

Example 2 Preparation of compound 2 (formula 6) 1- (3-methoxy-4-allyloxyphenyl) -3-
tert-butyl 1,3-propanedione 13.0 g, 1,
To a solution of 1,1,3,5,5,5-heptamethyltrisiloxane 11.0 g and toluene 30 ml was added a tetramethyldivinyldisiloxane platinum complex toluene solution (platinum content 4 w /
0.03 g) was added and refluxed for 5 hours with stirring. After the completion of the reaction, toluene was distilled off under reduced pressure, and the residue was separated and purified by silica gel chromatography (eluted with a mixture of 2 v / v% ethyl acetate-hexane) to obtain 10.2 g of the desired product. The yield was 47.1%. The ultraviolet absorption spectrum of Compound 2 is shown in FIG. λ _max : 334 nm (ε = 23550) Mass spectrum M ⁺ m / e 512

Example 3 Preparation of compound 5 (formula 10) 1- (3-allyl-4,5-dimethoxyphenyl) -3
-(1-ethylpentyl) -1,3-propanedione (3.4 g), 1,1,1,3,5,5,5-heptamethyltrisiloxane (2.4 g) and toluene (20 ml) were added to a solution of tetramethylvinyldithione. 0.01 g of a siloxane platinum complex toluene solution (containing 4 w / w% of platinum) was added and reacted under reflux for 6 hours. After completion of the reaction, toluene was distilled off under reduced pressure, and the residue was applied to a silica gel column. Elution with a 1 v / v mixture of ethyl acetate and hexane gave 4.1 g of the desired product. The yield was 73.2%. Colorless oil λ _max : 334 nm (ε = 23500) Mass spectrum M ⁺ m / e 568

Example 4 Preparation of compound 7 (Chemical formula 11) 25.1 g of 1- {3-methoxy-4- (2-methyl-2-propenoxy) phenyl} -3-tert-butyl-1,3-propanedione 1,1,1,3,5,5,5-heptamethyltrisiloxane 20.2 g, toluene 50 ml
Was added with 0.05 g of the platinum catalyst described in Example 2 and reacted at 100 ° C. to 110 ° C. for 18 hours. After completion of the reaction, toluene was distilled off, and the residue was distilled under reduced pressure to separate and purify the target product. The yield is 28.8 g. The ultraviolet absorption spectrum of Compound 7 is shown in FIG. Pale yellow oil, boiling point bp 182-184 ° C./2 mmHg λ _max : 334 nm (ε = 27350) Mass spectrum M ⁺ m / e 526

Example 5 Preparation of compound 8 (formula 12) 1- {3-methoxy-4- (4-pentenoxy) phenyl} -3-tert-butyl-1,3-propanedione 3
8.7 g, 1,1,1,3,5,5,5-heptamethyltrisiloxane 29.7 g and 0.02 g of the platinum catalyst described in Example 2 were dissolved in 70 ml of toluene.
The reaction was performed at 4 ° C. for 4 hours. After completion of the reaction, toluene was distilled off, and the residue was distilled under reduced pressure to obtain the objective compound 39.7.
g was obtained. The ultraviolet absorption spectrum of Compound 8 is shown in FIG. Pale yellow oil, boiling point bp 215-225 ° C (bath temperature) /
2 mmHg λ _max : 334 nm (ε = 23220) Mass spectrum M ⁺ m / e 540

Example 6 Preparation of Compound 9 (Formula 13) 1- (3-Methoxy-4-allyloxyphenyl) -3-
1- (3-methoxy-4-hydroxy-5-allylphenyl) -3-tert-butyl-1,3- obtained by Claisen rearrangement reaction of tert-butyl-1,3-propanedione
Propanedione (pale yellow crystal, melting point 115-116 ° C)
18.4 g, 1,1,1,3,5,5,5-heptamethyltrisiloxane 15.5 g and the platinum catalyst 0.02 g described in Example 2 were dissolved in 50 ml of toluene.
The reaction was performed at 0 ° C. for 6 hours. After completion of the reaction, toluene was distilled off, and the residue was subjected to silica gel column chromatography (7.
(v / v% eluted with a mixture of ethyl acetate and hexane) to obtain 21.7 g of the desired product. The ultraviolet absorption spectrum of Compound 9 is shown in FIG. Light yellow solid, melting point 38-39 ° C. λ _max : 342 nm (ε = 24000) Mass spectrum M ⁺ m / e 512 Specific examples of the formulation of the external preparation for skin according to the present invention will be described below.

Example 7 Sunscreen cosmetics (oil type) (1) Decamethylcyclopentasiloxane 47.0% (2) Dimethylpolysiloxane (10 cs / 25 ° C.) 12.0 (3) Methylphenyl polysiloxane (20 cs) / 25 ° C) 13.0 (4) Silicone resin 5.0 (5) Escalol 507 3.0 (6) Compound 2 20.0 <Production method> (1) to (6) were mixed and dissolved sufficiently. After filtration, the product is obtained. <Sunscreen effect> The sunscreen effect was tested using the sunscreen cosmetic according to Example 7 and a comparative example in which compound 2 (component (6)) was completely replaced with methylphenylpolysiloxane (component (3)). did. That is, in the actual use test on the beach, the two samples were separately applied to half of the body of 10 panelists, and a questionnaire survey on the degree of sunburn and a skin trouble were conducted. Table 3 shows the results.

[0025]

Table 3 Sample application area of Comparative Example of Example 4--------------------------- Sample application area ------------------------------------------- Panel A ○ × B ○ △ C ○ × D ○ △ E ○ × F ○ × G △ ○ H △ △ I ○ × J ○ △ −−−−−−−−−−−−−−−−−−−−−−−−−−−−−−− −−−−−− Number of skin troubles None None 2 itches 3 Itching 1 rash ---- −−−−−− Evaluation criteria for degree of sunburn Strong sunburn symptoms were observed. × × Sunburn symptoms were observed. △ △ Sunburn symptoms were hardly observed. ○ From these results, alkyl-aryl 1,3- Propanedionesilico It has been clarified that a skin external preparation containing a corn derivative has a higher ultraviolet protection effect and a higher safety without skin troubles than the conventional skin external preparation containing a UV absorber (Escalol 507). Was.

Example 8 Sunscreen cosmetics (W / O cream) (1) Octamethylcyclotetrasiloxane 20.5% (2) Dimethylpolysiloxane (100 cs) 5.0 (3) Dimethylpolysiloxane (2,500,000 cs) 3.0 (4) Liquid paraffin 5.0 (5) Polyether-modified silicone 6.0 (6) Escalol 507 5.0 (7) Compound 5 4.0 (8) Purified water 43.1 (9) L -Sodium glutamate 3.0 (10) 1,3-butylene glycol 5.0 (11) Preservative 0.2 (12) Fragrance 0.2 <Production method> Mix (1) to (7) and (12) Then, the mixture is heated and melted and kept at 70 ° C. to obtain an oil phase. Separately, (8) to (11) are dissolved by heating and maintained at 70 ° C. to obtain an aqueous phase. The aqueous phase is added to the oil phase and sufficiently emulsified by an emulsifier. After the emulsification, the mixture is cooled while being stirred, and when the temperature is reduced to 35 ° C. or less, the mixture is poured into a container and allowed to cool and solidify.

Example 9 Sunscreen cosmetic (O / W cream) (1) Decamethylcyclopentasiloxane 8.0% (2) Liquid paraffin 3.0 (3) Isopropyl myristate 2.0 (4) Vaseline 4 3.0 (5) Cetanol 4.0 (6) Stearic acid 3.0 (7) Glyceryl monoisostearate 3.0 (8) Neoheliopan AV 3.0 (9) Compound 1 1.0 (10) Preservative 0 0.2 (11) Fragrance 0.2 (12) Glycerin 10.0 (13) Propylene glycol 5.0 (14) Hyaluronic acid 0.01 (15) Potassium hydroxide 0.2 (16) Purified water 53.39 < Production Method> (1) to (11) are heated and stirred at 70 ° C. to obtain an oil phase. (12)
After heating (16) to 70 ° C. and completely dissolving the mixture, the mixture is made an aqueous phase.
The oil phase is added to the water phase and emulsified by an emulsifier. The emulsion is cooled to 30 ° C. in a heat exchanger and then filled to obtain a product.

Example 10 Sunscreen lotion (1) Dimethylpolysiloxane (5cs) 10.0% (2) Methylphenylpolysiloxane (20cs) 7.0 (3) Stearic acid 1.0 (4) Escalol 507 5 0.0 (5) Compound 2 10.0 (6) Preservative 0.2 (7) Fragrance 0.2 (8) Glycerin 5.0 (9) Montmorillonite 0.5 (10) Potassium hydroxide 0.2 (11 ) Purified water 60.9 <Production method> (1) to (7) were heated and stirred at 70 ° C to obtain an oil phase. (8) 〜
(11) is heated and dissolved at 70 ° C. to obtain an aqueous phase. The oil phase is added to the aqueous phase and emulsified by an emulsifier. The emulsion is cooled to 30 ° C. in a heat exchanger and filled in a container to obtain a sunscreen lotion.

Example 11 Sunscreen foundation (1) Siliconized titanium oxide 9.5% (2) Siliconized mica 40.0 (3) Siliconized talc 20.45 (4) Siliconized iron oxide 7.5 ( 5) Spherical nylon powder 10.0 (6) Trimethylolpropane triisostearate 5.0 (7) Squalane 3.0 (8) Beeswax 2.0 (9) Compound 6 0.5 (10) Sorbitan triolate 1.0 (11) Preservative 0.5 (12) Vitamin E 0.05 (13) Fragrance 0.5 <Production method> (1) to (5) are mixed with a Henschel mixer, and the mixture is added to (6) to
(13) was heated and dissolved and mixed, and then pulverized after mixing.
This was molded into an inner plate to obtain a sunscreen foundation.

Example 12 Sunscreen stick cosmetic (1) Titanium oxide 10.0% (2) Zinc oxide 7.0 (3) Mica 16.0 (4) Red iron oxide 1.5 (5) Yellow iron oxide 1.5 (6) black iron oxide 1.0 (7) dimethylpolysiloxane (20 cs) 29.4 (8) trimethylolpropane-tri-2-ethylhexanoate 8.0 (9) liquid paraffin 7.0 (10) Microcrystalline wax 2.0 (11) Celesin 1.0 (12) Solid paraffin 6.0 (13) Escalol 507 5.0 (14) Compound 4 3.0 (15) Fragrance 0.5 (16 ) Antioxidant 0.1 (17) Sorbitan sesquiolate 1.0 <Production method> (1) to (6) were mixed with a Henschel mixer, and (7) to (9), (1)
3), (14), (16), and (17) are added to and mixed with heating and stirring and mixed. Next, a solution obtained by dissolving (10) to (12) and (15) is added to the above mixture, mixed well, and then molded into a stick.

Example 13 Sunscreen Makeup Base (1) Dimethylpolysiloxane (2cs) 19.0% (2) Glyceryl triisostearate 10.0 (3) Isopar G 5.0 (4) Sorbitan sesquiolate 0 (5) Polysiloxane ether-modified organopolysiloxane 3.0 (6) Purified water 45.0 (7) 1,3-butylene glycol 5.0 (8) Fine particle titanium oxide 10.0 (9) Parsol MCX (GIVAUDAN) 1.0) (10) Compound 3 1.0 (11) Suitable amount of preservative (12) Suitable amount of antioxidant (13) Suitable amount of fragrance <Production method> (1) to (5), (9), (10), (12), and (13) were stirred and dissolved at 70 ° C., and were previously heated and dissolved at 70 ° C. (6) to (8),
(11) was added, emulsified and dispersed, and then cooled to obtain a desired sunscreen cosmetic base.

As described above, the external preparation for skin according to the present invention absorbs ultraviolet rays in the UV-A region, is excellent in water resistance, and can freely select a base and other components. Also, it has an advantage that it is excellent in stability even when left as a sunscreen cosmetic under severe conditions such as under the scorching sun. In addition, it has an excellent usability such as good spreadability and a non-greasy feeling with a refreshing feeling, and has an advantage that it hardly flows into sweat or water and the effect of UV-A absorption is maintained for a long time.

[0033]

As described above, the alkyl-aryl 1,3-propanedione silicone derivative according to the present invention has excellent UV-A absorption ability and compatibility with silicone-based materials. Further, the external preparation for skin containing the same can be compounded with a silicone base and can exhibit excellent usability.

[Brief description of the drawings]

FIG. 1 is an ultraviolet absorption spectrum of Compound 1 according to one example of the present invention.

FIG. 2 is an ultraviolet absorption spectrum of Compound 2 according to one example of the present invention.

FIG. 3 shows a compound (Compound 7) according to one example of the present invention.
FIG. 3 is an ultraviolet absorption spectrum diagram of the sample.

FIG. 4 shows a compound (Compound 8) according to one example of the present invention.
FIG. 3 is an ultraviolet absorption spectrum diagram of the sample.

FIG. 5 is a compound (Compound 9) according to one example of the present invention.
FIG. 3 is an ultraviolet absorption spectrum diagram of the sample.

Claims (2)

(57) [Claims] 1. A represented by the following general formalized 1 luer Rukiruariru 1,3-propane dione silicone derivative. Embedded image (However, R ¹ is a hydroxyl group, an alkyl group having 1 to 8 carbon atoms or an alkoxy group having 1 to 8 carbon atoms, R ² is an alkyl group having 1 to 7 carbon atoms, and R ³ is a divalent having 2 to 10 carbon atoms. Alkylene group or oxyalkylene group, R ⁴ is the same or different
And may be an alkyl group having 1 to 4 carbon atoms, a phenyl group or a trimethylsiloxy group, m, n is an integer of from 0 to 3, p is 0
Or 1 is represented. ) 2. The alkyl-aryl 1, according to claim 1,
An external preparation for skin, comprising one or more 3-propanedione silicone derivatives.