JPH0822811B2 - Topical skin - Google Patents

Description

TECHNICAL FIELD The present invention relates to an external preparation for skin which is excellent in moisturizing property, feeling in use and emulsion stability.

[Problems to be Solved by Prior Art and Invention]

Water-in-oil type emulsion external preparations typified by water-in-oil type emulsion cosmetics have excellent properties such as good familiarity to the skin due to the film formed on the skin surface and good makeup lasting. It has been widely used in the past.

On the other hand, however, the water-in-oil type emulsion type external preparation for skin has drawbacks such as badness only at the time of application, oiliness, and stickiness. Therefore, as an oil agent, a silicone oil that has a smooth feeling with a less sticky feel, has a smooth feeling of use, and is excellent in water repellency has been widely used in recent years, but it is difficult to emulsify a silicone oil and it is also excellent in stability. There is a problem that it is extremely difficult to obtain an emulsified system.

On the other hand, polyols such as glycerin, propylene glycol, dipropylene glycol, and 1,3-butylene glycol are widely used as one of the water phase components in order to impart moisturizing properties to cosmetics and the like. However, when polyols are used as the water phase component, there is a problem that emulsification with silicone oil, which is the oil phase component, becomes more difficult.

[Means for solving the problem]

Under such circumstances, as a result of intensive studies by the present inventors, by using a specific siloxane derivative as an emulsifier, an oil phase containing a silicone oil and an aqueous phase containing a polyol can be extremely stably emulsified, Further, by adjusting the concentration of the polyols in the aqueous phase, it was found that a translucent or transparent stable skin external preparation can be obtained,
The present invention has been completed.

That is, the present invention relates to the following components (A), (B) and (C) (A) Oil phase component containing silicone oil 5 to 70% by weight (B) Water phase component containing polyols 20 to 94.5% by weight (C) The following general formula (I) [Wherein at least one of R ^{1 to} R ¹² is represented by the following formula (II): (In the formula, Q represents a divalent hydrocarbon group having 11 carbon atoms, R ¹³ and R ¹⁴ each represent a hydrogen atom or a hydrocarbon group having 1 to 5 carbon atoms, at least one of which is a hydrogen atom.) in a group represented by the linear remaining 1 to 30 carbon atoms, in branched or cyclic hydrocarbon group or the following formula ^{(III) -X-R 15 (} III) ( wherein, X is an ether linkage and / Or a divalent hydrocarbon group containing an ester bond, R ¹⁵ is a linear, branched or cyclic hydrocarbon group having 1 to 30 carbon atoms), and l, m and n are 0. The number is 2000 or more and 2000 or less, and when 1 + m + n = 0, at least one of R ^{1 to} R ³ and R ^{10 to} R ¹² represents a group (II). ] A skin external preparation characterized by containing 0.5 to 30% by weight of an emulsifier consisting of a siloxane derivative represented by the following.

In the present invention, the silicone oil used as the oil phase component (A) may be any one commonly used in cosmetics, and examples thereof include dimethylpolysiloxane, dimethylcyclopolysiloxane, methylphenylpolysiloxane and methylhydrogenpolysiloxane. Siloxane and the like can be mentioned, and in particular, volatile dimethylpolysiloxane, dimethylcyclopolysiloxane and the like can be exemplified as preferable ones in the case of reducing the oily feeling and sticky feeling. These can be used alone or in combination of two or more. Other oily components include hydrocarbons such as squalane, liquid paraffin and vaseline; waxes such as whale wax and carnauba wax; ester oils such as jojoba oil, octyldodecyl myristate and neopentyl glycol dioctanoate; olive oil and macadamia nuts. Natural animal and vegetable oils and fats such as oils; diglyceride and the like can be mentioned. The oil phase component (A) is 5 to 70% by weight, especially 10 to 50% by weight in the total amount of the external preparation for skin.
It is preferable to mix them. Moreover, it is preferable to add 50 to 100% by weight of the silicone oil in the oil phase component.

In the present invention, the polyols used in the aqueous phase component (B) include, for example, propylene glycol, isoprene glycol (manufactured by Kuraray Co., Ltd.), 1,3-butanediol, dipropylene glycol, glycerin, diglycerin, triglycerin and poly. Glycerin, trimethylolpropane, erythritol, pentaerythritol, sorbitan, sorbitol, glucose, maltitol,
Examples thereof include saccharose, trehalose, ethylene oxide or propylene oxide adducts of sugars or sugar derivatives, polyethylene glycol and the like, and particularly preferable are ethylene oxide adducts of sugar derivatives such as glycerin, sorbitol, maltitol and polyoxyethylene methyl glucoside. These are used alone or in combination of two or more. The amount of the polyols to be blended varies depending on the moisturizing properties, the feeling of use, the consistency, etc. of the intended external preparation for the skin, but when 30 to 90% by weight, especially 40 to 65% by weight in the aqueous phase, the refractive index with the oil phase is Since the difference between the two is small, the external appearance of the skin preparation can be semitransparent or transparent. The total amount of the aqueous phase component (B) in the external preparation for skin is 20 to 94.5% by weight, particularly preferably 50 to 90% by weight.

In the general formula (I) showing the siloxane derivative used as the emulsifier (C) in the present invention, the hydrocarbon group having 1 to 5 carbon atoms represented by R ¹³ or R ¹⁴ is methyl, ethyl, propyl, butyl, Pentyl, isopropyl, sec
Examples thereof include linear, branched or cyclic alkyl groups such as -butyl, tert-butyl, neopentyl and cyclopentyl. Further, the divalent hydrocarbon group containing an ether bond and / or an ester bond represented by X is CH _{2 r} OC ₂ H _{4 p} OC ₃ H _{6 q} O- (where p and q are numbers from 0 to 50, r is 3 to 20 _{integer) CH 2 r O-CO-,} CH 2 r COO- , and the like.
Further, as the linear, branched or cyclic hydrocarbon group having 1 to 30 carbon atoms, methyl, ethyl, propyl, butyl, pentyl, hexyl, octyl, decyl, dodecyl, tetradecyl, hexadecyl, octadecyl, eicosyl,
Doeicosyl, Tetraeicosyl, Hexaeicosyl,
Linear alkyl groups such as octaeicosyl and triacontyl; branched chain alkyl groups such as isopropyl, sec-butyl, tert-butyl, neopentyl, 1-ethylpropyl, 1-heptyldecyl; cyclic alkyl groups such as cyclopentyl, cyclohexyl, abiethyl, cholesteryl Groups and the like. Then, l, m and n are preferably in the range of 0 or more and 2000 or less from the viewpoints of easy availability of the organohydrogenpolysiloxane as a raw material and operability during production.

The siloxane derivative (I) can be produced, for example, according to the following reaction formula.

(1) Method for producing siloxane derivative (Ia) having no group (III) [Wherein, at least one of R ^{16 to} R ²⁷ is a hydrogen atom;
The remainder is a linear, branched or cyclic hydrocarbon group having 1 to 30 carbon atoms, and l, m and n represent a number of 0 or more and 2000 or less.

Q'represents a hydrocarbon group having 11 carbon atoms having at least one double bond, and R ¹³ and R ¹⁴ have the same meaning as described above.

At least one of R ¹ ′ to R ¹² ′ is a group (II), and the rest is a linear, branched or cyclic hydrocarbon group having 1 to 30 carbon atoms. That is, by reacting an alkenyl glyceryl ether (II ′) with an organohydrogenpolysiloxane (IV) having at least one silicon-hydrogen bond, a siloxane derivative (Ia) having no group (III).
Is obtained.

(2) Method for producing siloxane derivative (Ib) having group (III) [In the formula, at least two of R ¹⁶ ′ to R ²⁷ ′ are hydrogen atoms, and the rest are linear, branched or cyclic hydrocarbon groups having 1 to 30 carbon atoms, and l, m and n are as described above. Have the same meaning.

Q ', R ¹³ and R ¹⁴ are as defined above.

X ′ is a hydrocarbon group having at least one double bond and containing an ether bond and / or an ester bond,
¹⁵ has the same meaning as described above.

At least one of R ¹ ″ to R ¹² ″ is a group (II), at least one of the rest is a group (III), and the rest is a straight chain, branched chain or cyclic group having 1 to 30 carbon atoms. Is a hydrocarbon group. That is, in the organohydrogenpolysiloxane (IV ′) having at least two silicon-hydrogen bonds,
Alkenyl glyceryl ether (II ') and compound (II
By reacting I '), a siloxane derivative (Ib) having a group (III) is obtained. Here, the compound (I
I ′) and compound (III ′) can be compound (I
It may be reacted with V ′) or simultaneously with compound (IV ′).

The starting material, organohydrogenpolysiloxane (IV) or (IV '), has at least one [(I
V)] or at least two [(IV ′)] silicon-hydrogen bonds are essential, and there are no particular restrictions on the viscosity, molecular structure, etc., and various known materials may be used. Although it is possible, it is preferable that l, m and n are 0 or more and 2000 or less from the viewpoint of availability of raw materials and operability at the time of production.

As the compound (II '), those in which Q' in the general formula (II ') is an ω-alkenyl group are preferable.

As the compound (III ′), in the general formula (III ′), X ′ is CH ₂ ═CHCH ₂ OC ₂ H _{4 p} OC ₃ H _{6 q} O— (p and q are the same as above), (R 'is an integer of 1 or more and 18 or less) and the like are preferable.

The above-mentioned reactions (1) and (2) are carried out in the presence of a catalyst, and catalysts generally used for hydrosilylation, for example, free radical initiators; photoinitiators; ruthenium, rhodium, palladium, osmium, iridium ,
Complex compounds of metals such as platinum; those obtained by supporting these on silica gel or alumina and the like can be mentioned. Among these, chloroplatinic acid and speier reagent (chloroplatinic acid in isopropyl alcohol) are particularly preferable. The amount of the catalyst used is the organohydrogenpolysiloxane (IV) or (I
V ') and alkenyl glyceryl ether (II' may be an amount sufficient to promote the reaction between) and / or compound (III '), it is not particularly limited, 10 with respect to the olefin 1mol used ^- A range of ⁶ to 10 ^-1 mol is preferred.

In this reaction, the use of a reaction solvent is not essential,
The reaction may be carried out in a suitable solvent if necessary. The reaction solvent is not particularly limited as long as it does not inhibit the reaction, and examples thereof include hydrocarbon solvents such as pentane, hexane, and cyclohexane; benzene solvents such as benzene, toluene, and xylene; ethers such as diethyl ether and diisopropyl ether. System solvent: methanol, ethanol,
Examples include alcohol solvents such as isopropyl alcohol and butanol. When an alcohol solvent is used, a pH adjusting agent such as potassium acetate (JP-A-57-149290) is used to prevent or suppress the dehydrogenation reaction between Si-H and -OH. Is preferred.

The ratio of the alkenyl glyceryl ether (II ') and / or the compound (III') to the organohydrogenpolysiloxane (IV) or (IV ') used in this reaction is such that the obtained siloxane derivative (I) is in the molecule. As long as there is a sufficient amount of alkenyl glyceryl ether (II ') having at least one or more silicon-bonded glyceryl groups (II), the other ratios may be arbitrary, but the resulting compound (I) is used for the carbon-based compound. When emulsifying the oil solution of
When the total number of units of I) and group (III) is in the same ratio or more than the number of remaining dimethylsiloxane units, and the silicone oil is emulsified, the groups (II) and (III) are emulsified. It is preferable that the total number of units be in a range of 1/5 or less of the number of remaining dimethylsiloxane units.

The hydrosilylation proceeds at 0 ° C to 200 ° C, but it is preferable to carry out at 0 ° C to 100 ° C in consideration of the reaction rate and coloring of the product. The reaction time is preferably about 0.5 to 24 hours.

Further, in the present invention, the emulsifier (C) can sufficiently achieve the purpose by using the siloxane derivative alone.
Further, for example, surfactants such as sorbitan fatty acid ester, glycerin fatty acid ester, polyoxyethylene hydrogenated castor oil, and isostearyl glyceryl ether can be used. The emulsifier (C) is preferably added in an amount of 0.5 to 30% by weight in the total amount of the skin external preparation of the present invention.

The external preparation for skin of the present invention may further contain other components usually used for external preparations for skin in an amount of 0 to 40% by weight, as long as the effects of the present invention are not impaired. Other components include powders, moisturizers, intercellular lipids (ceramide, etc.), ultraviolet absorbers, alcohols, chelates, pH adjusters, preservatives, thickeners, pigments, fragrances, medicinal components, etc. To be

Of these, a liquid or cream-like foundation can be obtained by incorporating 10 to 40% by weight, preferably 15 to 30% by weight, of the powder in the external preparation for skin of the present invention. As the powder, powders generally used in cosmetics, for example, extender pigments such as talc, mica, kaolin, sericite; inorganic pigments such as titanium oxide, zinc oxide, iron oxide, ultramarine blue; titanium mica-based pearl pigment; and Blue No. 404, Red 2
Organic pigments such as No. 02 and yellow 401 can be mentioned.
In the present invention, one or more of the above powders are arbitrarily selected and used.

Skin external preparations to which the present invention is applied include skin care products such as face care creams or emulsions, skin care reams or emulsions, liquid or cream foundations, and the like;
Hair cosmetics; external medicines and the like.

〔Example〕

Hereinafter, the present invention will be described in more detail with reference to examples, but the present invention is not limited thereto.

Production Example 1 (1) In a 100 ml two-necked flask equipped with a cooling tube and a magnetic stirrer, 97 g of 1,1,3,3-tetramethyldisiloxane (0.72 mo
l) and 30 g (0.36 mol) of 1-hexene, and 0.72 g of a 5% solution of chloroplatinic acid in isopropyl alcohol.
(7.2 mmol), and the mixture was stirred for 16 hours in an ice-water bath. 52.8g (bp55-61 ℃ / 4Torr) of colorless transparent liquid by distillation (yield 67
%) Was obtained. The obtained product was confirmed by IR and NMR spectra to be 1-hexyl-1,1,3,3-tetramethyldisiloxane.

(2) In a 100 ml two-necked flask equipped with a cooling tube and a magnetic stirrer, 15 g (69 mmol) of 1-hexyl-1,1,3,3-tetramethyldisiloxane synthesized in (1) and 12 g (91 mmol of allyl glyceryl ether) ), Potassium acetate 10% ethanol solution 1.8 g (1.8 mmol) and isopropyl alcohol 24 g
Was charged, to this was added 0.18 g (0.017 mmol) of a 5% isopropyl alcohol solution of chloroplatinic acid, and the mixture was stirred at 40 ° C. for 17 hours. After the solvent was distilled off, the reaction product was purified by applying it to a silica gel column to obtain 22 g (yield 93%) of a colorless transparent liquid. The obtained product was analyzed by IR and NMR spectra to give 3- (3
-Hexyl-1,1,3,3-tetramethyldisiloxanyl)
It was confirmed to be propyl glyceryl ether (A).

IR (liquid film, cm ^-1 ) 3400 (-OH) 2928 (C-H) 1256 (Si-Me) 1064,842,796 (Si-O-Si) ¹ H-NMR [δppm, in CDCl ₃ , CHCl ₃ standard (7.28ppm)] 0.04,0.06 (s, 12H) Si-C H ₃ 0.08-1.02 (t, 3H) -C H ₃ 1.14-1.46 (br, 8H) -C H ₂ -0.40-0.66 (m, 4H _{) Si-C H 2 - 1.48-1.72} (m, 2H) C H 2 -CH 2 -O 3.32-3.59 (m, 4H) C H 2 -O 3.79-3.98 (m, 1H) C H -OH 3.59- 3.79 (m, 2H) C H 2 -OH 2.83-2.93 (d, 1H) CH-O H 2.46-2.59 (dd, 1H) CH 2 -O H 13 C-NMR [[delta] ppm, in CDCl _3, CHCl ₃ standard (77.2ppm)] _{0.46,0.53 Si- C H 3 14.3,14.4 - C} H 3, C H 2 -CH 2 CH 2 O _{18.5 Si- C H 2 - 64.4 C} H 2 -OH 70.7 C H-OH 72.5 CH 2 C H 2 -O 74.6 CH- C H 2 -O 29 Si-NMR [[delta] ppm, in CDCl _3, TMS standard (0 ppm) 7.22,7.89 Production Example 2 (1) 1-decyl-1,1,3,3-tetramethyldisiloxane was synthesized by the same method as in (1) of Production Example 1 (yield 70%).

(2) According to a method similar to (2) of Production Example 1, 3- (3-
Decyl-1,1,3,3-tetramethyldisiloxanyl) propyl glyceryl ether (B) was synthesized (yield 93
%).

IR (liquid film, cm ^-1 ) 3424 (-OH) 2928 (C-H) 1254 (Si-Me) 1066,840,796 (Si-O-Si) ¹ H-NMR [δppm, in CDCl ₃ , CHCl ₃ standard (7.28ppm)] 0.04,0.06 (s, 12H) Si-C H ₃ 0.80-0.95 (t, 3H) -C H ₃ 1.15-1.42 (br, 16H) -C H ₂ -1.48-1.68 (m, 2H _{) C H 2 -CH 2 -O 3.38-3.53} (m, 4H) C H 2 -O 0.38-0.57 (m, 4H) Si-C H 2 - 3.77-3.94 (m, 1H) C H -OH 3.53- 3.77 (m, 2H) C H 2 -OH 3.25-3.32 (d, 1H) CH-O H 2.98-3.08 (t, 1H) CH 2 -O H 13 C-NMR [[delta] ppm, in CDCl _3, CHCl ₃ standard (77.2ppm)] _{0.42,0.50 Si- C H 3 14.2,14.3 - C} H 3, C H 2 -CH 2 CH 2 O _{18.5 Si- C H 2 - 23.5 C} H 2 CH 2 -O 72.4 CH 2 C H 2 -O 74.6 CH- C H 2 -O 70.9 C H-OH 64.3 C H 2 -OH 29 Si-NMR [[delta] ppm, CDCl ₃ in ₃ , TMS standard (0 ppm)] 7.22,7.89 Production Example 3 (1) 1-hexadecyl-1,1,3,3-tetramethyldisiloxane was synthesized by the same method as in (1) of Production Example 1. (Yield 70%).

(2) In the same manner as in (2) of Production Example 1, 3- (3
-Hexadecyl-1,1,3,3-tetramethyldisiloxanyl) propyl glyceryl ether (C) was synthesized (93% yield).

IR (liquid film, cm ^-1 ) 3404 (-OH) 2956 (C-H) 1254 (Si-Me) 1064,840,796 (Si-O-Si) ¹ H-NMR [δppm, in CDCl ₃ , CHCl ₃ standard (7.28ppm)] 0.04,0.06 (s, 12H) Si−C H ₃ 0.81−0.96 (t, 3H) −C H ₃ 1.16−1.41 (br, 28H) −C H ₂ −0.41−0.59 (m, 4H _{) Si-C H 2 - 1.53-1.70} (m, 2H) C H 2 -CH 2 -O 3.36-3.59 (m, 4H) C H 2 -O 3.59-3.80 (m, 2H) C H 2 -OH 2.83 -2.93 (d, 1H) CH- O H 2.46-2.59 (dd, 1H) CH 2 -O H 13 C-NMR [[delta] ppm, in CDCl _3, CHCl ₃ standard (77.2ppm)] 0.47,0.54 Si- C H ₃ 14.3,14.4 − C H ₃ , C H _{2 −} CH ₂ CH ₂ O 18.6 Si- C H ₂ 23.6 C H ₂ CH ₂ -O 64.4 C H ₂ -OH 70.7 C H-OH 72.6 CH ₂ -C H ₂ -O 74.6 CH- C H ₂ -O ²⁹ Si-NMR [δppm, CDCl _{In 3} , the TMS standard (0 ppm)] 7.22,7.93 Production Example 4 20 g (30 mmol) of nonadecamethylnonasiloxane and 9.5 g (30 mmol) of 10-undecenyl glyceryl ether were placed in a 100 ml two-necked flask equipped with a cooling tube and a magnetic stirring bar. , 10% ethanol solution of potassium acetate 0.77g (0.78mmol) and isopropyl alcohol 18.5g were charged, and chloroplatinic acid 2%
0.20 g (7.7 × 10 ⁻³ mmol) of isopropyl alcohol solution was added and heated to raise the temperature. Keep the temperature of the contents at 40 ℃, 3.
Stir for 5 hours. After evaporating the solvent, the obtained reaction product was dissolved in hexane, and the solvent was distilled off by filtration. The obtained reaction product was purified by applying to a silica gel column, and 21.7 g of a colorless and transparent oil (80% yield) was obtained. ) Got. The obtained product was confirmed to be nonadecamethylnonacyloxanyl undecyl glyceryl ether (D) by IR and NMR spectra.

¹ H-NMR [[delta] ppm, in CDCl _3, CHCl ₃ standard (7.28 ppm)] 0.00-0.18 (m, 57H) Si- C H 3 0.48-0.64 (m, 2H) Si-C H 2 1.20-1.42 (br , 16H) −C H ₂ −1.50−1.68 (m, 2H) C H ₂ −CH ₂ −O 3.40−3.58 (m, 4H) C H ₂ −O 3.78−3.96 (m, 1H) C H −OH 3.58 -3.78 (m, 2H) C H 2 -OH 2.67-2.72 (d, 1H) CH-O H 2.21-2.35 (dd, 1H) CH 2 -O H 13 C-NMR [[delta] ppm, in CDCl _3, CHCl ₃ Standard (77.2ppm)] ²⁹ Si-NMR [δppm, in CDCl ₃ , TMS standard (0ppm)] Production Example 5 Pentamethyldisiloxanylundecylglyceryl ether (E) was synthesized in the same manner as in Production Example 4 (yield 56%).

IR (liquid film, cm ^-1 ) 3394 (-OH) 2926,2860 (C-H) 1254 (Si-Me) 1064,843 (Si-O-Si) ¹ H-NMR [δppm, CHCl in CDCl _{3 3} reference (7.28 ppm)] 0.05,0.07 (s, 15H) Si- C H 3 0.43-0.62 (m, 2H) Si-C H 2 1.14-1.40 (br, 16H) -C H 2 - 1.50-1.68 ( m, 2H) C H ₂ --CH ₂ --O 3.38-3.58 (m, 4H) C H ₂ --O 3.80-3.95 (m, 1H) C H --OH 3.58-3.80 (m, 2H) C H ₂ --OH 2.72-2.81 (d, 1H) CH- O H 2.31-2.47 (br, 1H) CH 2 -O H 13 C-NMR [[delta] ppm, in CDCl _3, CHCl ₃ standard (77.2ppm)] 0.51,2.14 Si- C H ₃ 18.6 Si− C H ₂ 64.4 C H ₂ -OH 70.7 C H-OH 72.0 CH- C H ₂ -O 72.6 CH ₂ -C H ₂ -O ²⁹ Si-NMR [δppm, in CDCl ₃ , TMS standard (0 ppm)] 6.97, 7.61 Production example 6 Undecamethylpentasiloxanyl undecyl glyceryl ether (F) was synthesized by the same method as in Production Example 4 (yield 48%). At this time, since 1,5-dihydrodecamethylpentasiloxane was contained in the raw material undecamethylpentasiloxane, 1,5-bis [11-
(2,3-Dihydroxypropoxy) undecyl] decamethylpentasiloxane (G) was obtained. Obtained 1,5
-Bis [11- (2,3-dihydroxypropoxy) undecyl] decamethylpentasiloxane (G) was isolated and purified by a silica gel column. Its structure was confirmed by IR and MMR spectra.

IR (liquid film, cm ^-1 ) 3406 (-OH) 2962,2926,2860 (C-H) 1260 (Si-Me) 1035,801 (Si-O-Si) ¹ H-NMR [δppm, in CDCl ₃ , CHCl ₃ standard (7.28 ppm)] −0.02 −0.18 (m, 33H) Si−C H ₃ 0.46 −0.63 (m, 2H) Si−C H ₂ −1.17−1.42 (br, 16H) −C H ₂ − 1.48-1.70 (m, 2H) C H 2 -CH 2 -O 3.38-3.59 (m, 4H) C H 2 -O 3.77-3.97 (m, 1H) C H -OH 3.59-3.77 (m, 2H) C _{H 2 -OH 2.83-2.98 (br, 1H} ) CH-O H 2.46-2.64 (br, 1H) CH 2 -O H 13 C-NMR [[delta] ppm, in CDCl _3, CHCl ₃ standard (77.2ppm)] ²⁹ Si-NMR (δppm, in CDCl ₃ , TMS standard (0 ppm)) 7.28,7.61 a, e −21.4, −21.7, −22.2 b, c, d IR (liquid film, cm ^-1 ) 3404 (-OH) 2924,2856 (C-H) 1260 (Si-Me) 1080,1034,802 (Si-O-Si) ¹ H-NMR [δppm, in CDCl ₃ , CHCl ₃ standard (7.28 ppm)] 0.03,0.05 (s, 30H) Si- C H 3 0.54 (t, 4H) Si-C H 2 1.28 (br, 32H) -C H 2 - 1.48-1.69 (m, _{4H) C H 2 -CH 2 -O} 2.92 (t, 2H) C H 2 -O H 3.20 (d, 2H) CH-O H 3.36-3.57 (m, 8H) C H 2 -O 3.57-3.78 (m , 4H) C H ₂ -OH 3.78-3.96 (m, 2H) C H -OH ¹³ C-NMR [δppm, in CDCl ₃ , CHCl ₃ standard (77.2ppm)] 0.35,1.34 a, b 1.24 c 18.4 Si− C H ₂ − _{64.4 - C H 2 -OH 70.8 -} C H-OH 72.0 -CH 2 - C H 2 -O 72.5 -CH- C H 2 -O 29 Si-NMR [[delta] ppm, in CDCl _3, TMS standard (0 ppm)] - 22.3 C-21.7 B 7.62 A Production Example 7 In a 100 ml two-necked flask equipped with a cooling tube and a magnetic stirrer,
α, ω-dihydrodimethylpolysiloxane (average chain length 2
0) 30 g (18.5 mmol), 10-undecenyl glyceryl ether 11.8 g (48.3 mmol), 0.95 g (0.97 mmol) of 10% potassium acetate in ethanol and isopropyl alcohol 2
4 g was charged, to this was added 0.26 g (0.010 mmol) of a 2% isopropyl alcohol solution of chloroplatinic acid, and the temperature was raised by heating. The temperature of the contents was kept at 50 ° C., and the mixture was stirred for 2 hours. After the solvent was distilled off, the unreacted 10-undecenyl glyceryl ether was distilled off under reduced pressure to obtain a brown highly viscous substance. This brown highly viscous substance was treated with activated carbon to obtain 35.0 g (89.7% yield) of a colorless and transparent highly viscous substance.

The obtained product was identified by IR and NMR spectra.
α, ω-bis [11- (2,3-dihydroxypropoxy)
Undecyl] dimethylpolysiloxane (average chain length 20)
(H) was confirmed.

IR (liquid film, cm ^-1 ) 3420 (-OH) 2964,2928,2860 (C-H) 1262 (Si-Me) 1100,1026,802 (Si-O-Si) ¹ H-NMR [δppm, CDCl ₃ in, CHCl ₃ standard (7.28 ppm)] 0.00 (br, about _{132H) Si-C H 3 0.57} (t, 4H) Si-C H 2 - 1.39 (br, 32H) -C H 2 - 1.47-1.70 ( _{m, 4H) C H 2 -CH} 2 -O 2.22 (br, 2H) -CH 2 -O H 2.62 (br, 2H) -CH-O H 3.30-3.59 (m, 8H) C H 2 -O 3.59- 3.80 (m, 4H) C H ₂ -OH 3.80-3.96 (m, 2H) C H -OH ¹³ C-NMR [δppm, in CDCl ₃ , CHCl ₃ standard (77.2ppm)] 0.39,1.23,1.36 Si- C H ₃ 18.5 Si− C H ₂ − 64.7- C H ₂ OH 70.6- C H-OH 72.0-CH ₂ -C H ₂ -O 72.7-CH- C H ₂ -O ²⁹ Si-NMR (δppm, in CDCl ₃ , TMS standard (0 ppm)) Production Example 8 In the same manner as in Production Example 7, α, ω-bis [11- (2,
3-dihydroxypropoxy) undecyl] dimethylpolysiloxane (average chain length 50) (I) was synthesized (yield 9
5.3%).

IR (liquid film, cm ^-1 ) 3420 (-OH) 2968,2932 (C-H) 1264 (Si-Me) ¹ H-NMR [[delta] ppm, in CDCl _3, CHCl ₃ standard (7.28 ppm)] 0.08 (br, about _{312H) Si-C H 3 0.57} (t, 4H) Si-C H 2 1.30 (br, 32H) -C _{H 2 - 1.48-1.80 (m, 4H} ) C H 2 -CH 2 -O 2.20 (br, 2H) CH 2 -O H 2.63 (br, 2H) CH-O H 3.38-3.60 (m, 8H) C H _2- O 3.60-3.81 (m, 4H) C H ₂ -OH 3.81-3.97 (m, 2H) C H -OH ¹³ C-NMR [δppm, in CDCl ₃ , CHCl ₃ standard (77.2ppm)] 0.38, 1.22 , 1.36,1.96 Si− C H ₃ 18.5 Si− C H ₂ 64.7 C H ₂ OH 70.8 C H-OH 72.1 CH ₂ C H ₂ -O 72.7 CH C H ₂ -O ²⁹ Si-NMR [δppm, in CDCl ₃ , TMS standard (0 ppm)] Production Example 9 (1) α, ω-dihydrohexadecamethyloctasiloxane was placed in a 50 ml two-necked flask equipped with a cooling tube and a magnetic stirrer.
32.8 g (56.6 mmol) and 1-decene 4.0 g (28.5 mmol) were charged, 3.0 mg (5.8 × 10 ⁻³ mmol) of chloroplatinic acid was added, and the mixture was stirred in a water bath for 6 hours. Colorless transparent liquid 1 by distillation
1.0 g (bp 160 ° C./0.005 Torr) (54% yield) was obtained. The obtained product was identified as 1-decyl-1 by IR and NMR spectra.
It was confirmed to be 5-hydrohexadecamethyloctasiloxane.

(2) In a 50 ml two-necked flask equipped with a condenser and a magnetic stirrer, 10 g (13.9 mmol) of 1-decyl-15-hydrohexadecamethyloctasiloxane synthesized in (1) and 4.4 g of 10-undecenyl glyceryl ether. (18.0 mmol), potassium acetate 10% ethanol solution 0.35 g (0.36 mmol) and isopropyl alcohol 10 g were charged, and chloroplatinic acid 2% isopropyl alcohol solution 0.093 g (3.6 × 10 ^-3 m
mol) was added and heated to raise the temperature. The temperature of the contents was kept at 40 ° C, and the mixture was stirred at 40 ° C for 3 hours. After the solvent was distilled off, the reaction product was purified by applying it to a silica gel column, and a colorless transparent oil 11.8
g (yield 88%) was obtained. The obtained purified product was confirmed to be 15-decylhexadecamethyloctasiloxanil undecyl glyceryl ether (J) by IR and NMR spectra.

IR (liquid film, cm ^-1 ) 3400 (-OH) 2964, 2928, 2860 (C-H) 1262 (Si-Me) ¹ H-NMR [[delta] ppm, in CDCl _3, CHCl ₃ standard (7.28 ppm)] -0.02-0.10 (m, 48H) Si- C H 3 0.50 (t, 4H) Si-C H 2 - 0.87 (t, 3H ) −C H ₃ − 1.24 (br, 32H) −C H ₂ − 1.47−1.66 (m, 2H) C H ₂ −CH ₂ −O 2.32 (t, 1H) CH ₂ −O H 2.71 (d, 1H) CH-O H 3.36-3.57 (m, 4H) -C H 2 -O 3.57-3.73 (m, 2H) -C H 2 -OH 3.73-3.90 (m, 1H) C H -OH 13 C-NMR [δppm , in CDCl _3, CHCl ₃ standard (77.2ppm)] _{0.38,1.25,1.35 Si- C H 3 14.3 - C} H 3 18.5 Si- C H 2 64.5 C H ₂ OH 70.7 C HOH 72.1 CH ₂ C H ₂ O 72.7 CH C H ₂ O Production Example 10 In a 100 ml two-necked flask equipped with a cooling tube and a magnetic stirrer, the formula (K ′) was used. 15g of organohydrogensiloxane represented by
mmol), 8.1 g of 10-undecenyl glyceryl ether (33
mmol), 0.65 g of a 10% ethanol solution of potassium acetate (0.6
6 mmol) and 50 g of isopropyl alcohol, and 0.17 g of a 2% solution of chloroplatinic acid in isopropyl alcohol.
(6.6 × 10 ⁻³ mmol) was added, and the temperature was raised by heating. The temperature of the contents was kept at 40 ° C and stirred for 2.5 hours. After distilling off the solvent and treating with activated carbon, unreacted 10-undecenyl glyceryl ether was distilled off by vacuum distillation to obtain a brown viscous substance. It was confirmed from the NMR spectrum that the obtained product was a compound (K) represented by the formula below.

IR (liquid film, cm ^-1 ) 3400 (-OH) 2968,2932,2860 (C-H) 1262 (Si-Me) 1096,1022,844 (Si-O-Si) ¹ H-NMR [δppm, CDCl ₃ in, CHCl ₃ standard (7.28 ppm)] 0.01 (s, about _{273H) Si-C H 3 0.38-0.58} (m, 10H) Si-C H 2 - 1.10-1.41 (br, 80H) -C H 2 - 1.44-1.86 (m, 10H) C H 2 -CH 2 -O 3.30-3.55 (m, 20H) C H 2 -O 3.55-3.77 (m, 10H) C H 2 -OH 3.77-3.90 (m, 5H) C H —OH Production Example 11 A compound (L) represented by the following formula was synthesized in the same manner as in Production Example 10 (yield 97%).

IR (liquid film, cm ^-1 ) 3420 (-OH) 2968,2932,2860 (C-H) 1264 (Si-Me) 1096,1026,802 (Si-O-Si) ¹ H-NMR [δppm, CDCl among _3, CHCl ₃ standard (7.28 ppm)] 0.00 (s, about _{390H) Si-C H 3 0.35-0.50} (m, 8H) Si-C H 2 1.08-1.39 (br, 64H) -C H 2 - 1.39 -1.62 (br, 8H) C H 2 -CH 2 -O 1.96-2.29 (br, 4H) C H 2 -O H 2.43-2.68 (br, 4H) CH-O H 3.38-3.50 (m, 16H) C H ₂ —O 3.50-3.70 (m, 8H) C H ₂ —OH 3.70-3.86 (m, 4H) C H —OH Production Example 12 Compound (M) represented by the following formula in the same manner as in Production Example 10 Was synthesized (yield 99%).

IR (liquid film, cm ^-1 ) 3424 (-OH) 2964,2928,2860 (C-H) 1262 (Si-Me) 1090,1034,864,798 (Si-O-Si) ¹ H-NMR [δppm, CDCl among _3, CHCl ₃ standard (7.28 ppm)] 0.00 (s, about _{510H) Si-C H 3 0.34-0.55} (m, 8H) Si-C H 2 1.02-1.38 (br, 64H) -C H 2 - 1.38 -1.66 (br, 8H) C H 2 -CH 2 -O 1.98-2.40 (br, 4H) CH 2 O H 2.40-2.78 (br, 4H) CH-O H 3.26-3.53 (m, 16H) C H 2 -O 3.53-3.70 (m, 8H) C H ₂ -OH 3.70-3.88 (m, 4H) C H -OH Production Example 13 A 100 ml flask equipped with a cooling tube and a magnetic stirrer was of the formula (N '). 10 g of an organohydrogensiloxane represented by the formula (7.5
mmol) and 8.4 g (60.2 mmol) of decene, and 8.3 × 10 ^-3 ml of a 2% solution of chloroplatinic acid in isopropyl alcohol.
Was added and heated to 40 ° C. After 2 hours, 20 g of isopropyl alcohol, 4.6 g (35 mmol) of allyl glyceryl ether,
Add 0.44 g of 10% ethanol solution of potassium acetate and 0.12 ml of 2% isopropyl alcohol solution of chloroplatinic acid.
Heated to ° C. After 2 hours, isopropyl alcohol was distilled off, activated carbon treatment was performed, and unreacted allyl glyceryl ether was distilled off under reduced pressure to obtain 22 g of a colorless viscous substance.
The obtained product was confirmed by IR and ¹ H-NMR spectrum to be a compound represented by the following formula (N).

IR (liquid film, cm ^-1 ) 3400 (-OH) 2965,2925,2860 (C-H) 805,850,1260 (Si-Me) 1090,1030 (Si-O-Si) ¹ H-NMR [δppm, CDCl ₃ in, CHCl ₃ standard (7.28 ppm)] 0.06-0.11 (bs, 90H) Si- C H 3 0.51 (m, 24H) Si-C H 2 -CH 2 - 0.90 (t, 24H) -CH 2 C H _{3 1.28 (br, 136H) -C} H 2 - 1.64-1.68 (br, 8H) -O H Production Example 14 Decene 11.7 g (83 mmol), allyl glyceryl ether
The reaction was performed in the same manner as in Production Example 13 except that 1.1 g (8.3 mmol) was used to obtain 23 g of a compound represented by the following formula (O).

IR (liquid film, cm ^-1 ) 3425 (-OH) 2970,2930,2865 (C-H) 805,845,1260 (Si-Me) 1095,1025 (Si-O-Si) ¹ H-NMR [δppm, CDCl among _3, CHCl ₃ standard (7.28 ppm)] 0.06-0.12 (bs, 90H) Si- C H 3 0.50 (m, 24H) Si-C H 2 -CH 2 - 0.90 (t, 33.2H) -CH 2 C _{H 3 1.28 (br, 179.1H)} -C H 2 - 1.62-1.67 (br, 1.8H) -O H Example 1 Creamy transparent or translucent emulsion composition: An emulsion composition having the composition shown in Table 1 was produced, and the appearance and emulsion stability of each emulsion composition immediately after production were evaluated, and the results are also shown in Table 1. It was

(Manufacturing Method) Components (1) to (3) were mixed, and the components (4) to (8), which had been mixed in advance, were gradually added to the mixture while stirring with an emulsifying machine to emulsify, to obtain an emulsified composition.

(Emulsification stability evaluation method) Each emulsion composition was stored at 25 ° C, and the appearance after one month was visually observed to evaluate the emulsion stability according to the following criteria.

◯: Good with no change in state Δ: Slight separation / aggregation present X: Separation / aggregation present, poor emulsification (Result) As is clear from Table 1, the product of the present invention had an extremely good emulsified state after production, whereas the comparative product was inferior in stability due to separation of the oil agent into the upper layer over time.

In place of the siloxane derivative (L) of the products 1 to 6 of the invention, siloxane derivatives (D), (F), (H),
The emulsion composition produced using (I), (J), (K) or (M) also showed superior stability to the comparative product.

Example 2 Creamy Emulsion Composition: Emulsion compositions having the compositions shown in Table 2 were produced, and the emulsion stability of each emulsion composition was evaluated. The results are also shown in Table 2.

(Manufacturing method) Components (1) to (3) were mixed, and the components (4) to (6), which had been mixed in advance, were gradually added to the mixture while stirring with an emulsifying machine to emulsify, thereby obtaining an emulsified composition.

(Emulsification stability evaluation method) Evaluation was carried out by the same method and criteria as in Example 1.

(result) As is clear from Table 2, the product of the present invention had an extremely good emulsified state after production, whereas the comparative product was inferior in stability due to separation of the oil agent into the upper layer over time.

In place of the siloxane derivative (M) of the product 7 or 8 of the present invention, siloxane derivatives (D), (F), (H),
The emulsion composition produced using (I), (J), (K) or (L) also showed superior stability to the comparative product.

Example 3 Hand cream: (Component) (% by weight) (1) Siloxane derivative (L) 2.0 (2) Methylphenylpolysiloxane 5.0 (3) Decamethylcyclopentasiloxane 5.0 (4) Dimethylpolysiloxane (50cs) 10.0 ( 5) Fragrance 0.2 (6) Glycerin 20.0 (7) 1.3-Butylene glycol 15.0 (8) Magnesium sulfate 1.0 (9) Purified water 41.8 (Production method) Components (1) to (5) are mixed and stirred with an emulsifier. Then, the premixed components (6) to (9) were gradually added and emulsified to obtain a hand cream.

Example 4 Moisturizing cream: (ingredient) (% by weight) (1) dimethylpolysiloxane (50cs) 10.0 (2) decamethylcyclopentasiloxane 5.0 (3) squalane 8.0 (4) siloxane derivative (I) 2.0 (5) iso Stearyl glyceryl ether 1.0 (6) Glycerin 20.0 (7) 1.3-Butylene glycol 5.0 (8) Sorbitol 5.0 (9) Magnesium sulfate 1.0 (10) Perfume 0.2 (11) Purified water 41.8 (Production method) Components (1) to (5) And (10) were mixed, and the components (6) to (9) and (11), which had been mixed in advance, were gradually added to the mixture while stirring with an emulsifying machine to emulsify the mixture to obtain a moisturizing cream.

Example 5 Creamy foundation: (Component) (% by weight) (1) Siloxane derivative (L) 2.0 (2) Dimethylpolysiloxane (50cs) 10.0 (3) Octamethylcyclotetrasiloxane 8.0 (4) Perfume 0.2 (5) Silicone-treated cosmetic powder ^* 15.0 (6) Glycerin 30.0 (7) Magnesium sulfate 1.0 (8) Purified water 33.8 * For cosmetic powder, use the following composition as raw material powder. 2% by weight of methyl hydrogen polysiloxane (KF99 manufactured by Shin-Etsu Silicone Co., Ltd.)
Was added and then heat-treated.

(Production method) After mixing the components (1) to (4), adding and dispersing the component (5) therein, the components (6) to (8) that have been mixed in advance are gradually added while stirring with an emulsifier. Then emulsify,
A creamy foundation was obtained.

Example 6 Suntan Cream: (Component) (wt%) (1) Siloxane derivative (J) 5.0 (2) Dimethylpolysiloxane (50cs) 15.0 (3) Methylphenylpolysiloxane 5.0 (4) Paradimethylaminobenzoic acid ^* 5.0 (5) Oxybenzone 0.5 (6) Perfume 0.2 (7) Glycerin 8.0 (8) 1,3-Butylene glycol 15.0 (9) Glucose 2.0 (10) Sodium chloride 1.0 (11) Purified water Remainder *: Van Dyke , Escalol 507 (manufacturing method) Components (1) to (6) are mixed, and the components (7) to (11) that have been mixed in advance are gradually added while stirring with an emulsifying machine to emulsify and obtain a suntan cream. It was

The emulsified cosmetics of Examples 3 to 6 were all excellent in stability, moisturizing property, usability and the like.

〔The invention's effect〕

As described above, in the external preparation for skin of the present invention, the oil phase containing silicone oil and the water phase containing polyols are extremely stably emulsified.

Further, by adjusting the concentration of the polyols in the aqueous phase, a semitransparent or transparent stable skin external preparation can be obtained.

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Claims (1)

[Claims] 1. The following components (A), (B) and (C) (A) Oil phase component containing silicone oil 5 to 70% by weight (B) Water phase component containing polyols 20 to 94.5% by weight ( C) The following general formula (I) [Wherein at least one of R ^{1 to} R ¹² is represented by the following formula (II): (In the formula, Q represents a divalent hydrocarbon group having 11 carbon atoms, R ¹³ and R ¹⁴ each represent a hydrogen atom or a hydrocarbon group having 1 to 5 carbon atoms, at least one of which is a hydrogen atom.) in a group represented by the linear remaining 1 to 30 carbon atoms, in branched or cyclic hydrocarbon group or the following formula ^{(III) -X-R 15 (} III) ( wherein, X is an ether linkage and / Or a divalent hydrocarbon group containing an ester bond, R ¹⁵ is a linear, branched or cyclic hydrocarbon group having 1 to 30 carbon atoms), and l, m and n are 0. The number is 2000 or more and 2000 or less, and when 1 + m + n = 0, at least one of R ^{1 to} R ³ and R ^{10 to} R ¹² represents a group (II). ] An emulsifier consisting of a siloxane derivative represented by
An external preparation for skin, characterized by containing 10% by weight.