JP2631550B2 - Novel siloxane derivatives, cosmetic oils and cosmetics containing the same - Google Patents

Description

Description: TECHNICAL FIELD The present invention relates to a novel siloxane derivative, and a cosmetic oil agent and cosmetic containing the same.

[Conventional technology]

Oil bases are extremely important as raw materials for cosmetics,
Various functions are required, but from a dermatological point of view, (1) imparting flexibility to the skin, (2) imparting lubricity on the skin surface, (3) emollient effect by forming a hydrophobic film and It is required to provide a barrier function and (4) suppress the evaporation of water from the skin surface by the same film. Silicone oils such as dimethylpolysiloxane are generally used as the cosmetic oil base,
Examples thereof include liquid paraffin, hydrocarbons such as squalane, jojobo oil, natural and synthetic ester oils such as octyldodecyl myristate, and natural triglycerides such as olive oil. In addition, in order for these oil bases to function more effectively and continuously, they must have high affinity for skin.

[Problems to be solved by the invention]

However, what always matters when using these oil bases is the feel during use. Silicone oils and hydrocarbons with a good feel have a problem in terms of skin affinity, and triglycerides, which have excellent skin affinity, have an unpleasant feel, such as oily and sticky during use,
Furthermore, there is a problem that the skin is subject to enzymatic degradation such as lipase.

[Means for solving the problem]

Under such circumstances, the present inventors have conducted intensive studies to obtain an oil base having excellent feel, being chemically stable, and having excellent skin affinity, and as a result, the following general formula (I) [Wherein at least one of R ¹ , R ² and R ³ is the following formula: Or (One of R ⁵ and R ⁶ is a hydrogen atom, the other is a straight-chain, branched-chain or cyclic alkyl group, alkenyl group or hydroxyalkyl group having 6 to 30 carbon atoms),
R ¹ , R ^2, R ³ , and R ⁴ other than the above are alkyl groups having 1 to ⁴ carbon atoms, and m and n are numbers in which m + n is 1 to 200. The present invention was found to be excellent in properties, to have a good feel, and to be chemically stable.

That is, the present invention provides a novel siloxane derivative represented by the above general formula (I), and a cosmetic oil or cosmetic containing the same.

The siloxane derivative (I) of the present invention can be produced by a conventional method. For example, according to the following reaction formula, siloxane (II) and allyl glyceryl ether (II) are used in the presence of a platinum catalyst.
It is produced by a hydrosilylation reaction with (I) or (IV).

(Wherein at least one of R ^7, R ⁸ and R ⁹ is a hydrogen atom, the remainder is an alkyl group having 1 to 4 carbon atoms, R ^4,
R ⁵ , R ⁶ , m and n have the same meanings as described above. Examples of the siloxane used in the above reaction include pentamethyldisiloxane, heptamethyltrisiloxane, nonamethyltetrasiloxane, undecamethylpentasiloxane, and trisiloxane. Decamethylhexasiloxane,
From a relatively short siloxane chain represented by tetramethyldisiloxane, hexamethyltrisiloxane, octamethyltetrasiloxane, decamethylpentasiloxane, dodecamethylhexanesiloxane, etc., a molecular weight of 15,000
M + n is 1 up to polysiloxanes of long chain length up to about
~ 200, and can be used as long as it contains at least one Si-H group in the molecule.

Allyl glyceryl ether (III) or (I
V) can be easily produced, for example, by reacting glycidyl ethers (V) with allyl alcohol in the presence of a Lewis acid catalyst or a base catalyst according to the following reaction formula.

(In the formula, R ¹⁰ represents a linear, branched or cyclic alkyl group, alkenyl group or hydroxyalkyl group having 6 to 30 carbon atoms.) As the glycidyl ether (V), for example, n-hexyl glycidyl ether , N-octyl glycidyl ether, n-decyl glycidyl ether, n-
Dodecyl glycidyl ether, n-tetradecyl glycidyl ether, n-hexadecyl glycidyl ether,
saturated linear aliphatic glycidyl ether such as n-octadecyl glycidyl ether; 2-ethylhexyl glycidyl ether, 2-hexyldecyl glycidyl ether, 2-
Heptylundecylglycidyl ether, 2-octyldodecylglycidylether, 2-decyltetradecylglycidylether, 5,7,7-trimethyl-2- (1,3,3
-Trimethylbutyl) octyl glycidyl ether; (Having a distribution where p + q = 14 and p = q = 7 as a peak) saturated branched aliphatic glycidyl ether such as methyl branched isostearyl glycidyl ether; cyclohexyl glycidyl ether, cycloheptyl glycidyl ether, cyclooctyl glycidyl Cyclic aliphatic glycidyl ethers such as ether, cyclododecyl glycidyl ether, aviethyl glycidyl ether, dihydroabiethyl glycidyl ether, tetrahydroabiethyl glycidyl ether, cholesteryl glycidyl ether, cholestanyl glycidyl ether; 9-octadecenyl glycidyl ether, farnesyl Unsaturated aliphatic glycidyl ethers such as glycidyl ether; hydroxyalkyl glycidyl ethers such as 12-vidroxcystearyl glycidyl ether Le, and the like.

The siloxane derivative (I) of the present invention thus produced
Can be made into cosmetic oils or cosmetics by combining with any other known cosmetic oils and / or other cosmetic ingredients.

The amount of the siloxane derivative (I) to be added to the cosmetic of the present invention is not particularly limited, but in the case of an emulsion-type cosmetic, it is preferably 0.001 to 90% by weight, more preferably 1 to 50% by weight of the whole composition. There are no particular restrictions on the type of cosmetics, such as water-in-oil or oil-in-water emulsified cosmetics, oily cosmetics, aqueous cosmetics, packs, foundations, lipsticks, skin cleansers,
It can be used as a shampoo, a rinse, a hair styling agent, a hair restorer, a hair restorer and the like. In addition, oils, surfactants, humectants, ultraviolet protective agents, chelating agents, pH adjusters, preservatives, preservatives, thickeners, pigments, which are generally used as cosmetic ingredients, as long as the effects of the present invention are not impaired. Ingredients such as fragrances can be appropriately added.

[Action and effect of the invention]

Since the novel siloxane derivative (I) of the present invention has a siloxane skeleton and a hydrophilic alkyl skeleton containing a hydroxyl group, ether oxygen and the like in the same molecule, it has a good feeling of the siloxane portion and a good skin affinity by the alkyl portion. It has something.

〔Example〕

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

Example 1 1- (4,8-dioxa-6-hydroxytetradecyl)
Synthesis of 1,1,3,3,3-pentamethyldisiloxane: i) To 290 g of 3-allyloxy-1-hexyloxy-2-propanol allyl alcohol, slowly and carefully add 1.15 g of metallic sodium under a nitrogen atmosphere. After dissolving and heating to 60 ° C., 79 g of hexyl glycidyl ether was slowly added dropwise over about 80 minutes. After dropping is complete,
Stirring was continued for 4.5 hours. After unreacted allyl alcohol was distilled off from the reaction mixture, 500 ml of ether was added, and the mixture was washed repeatedly with saturated saline until the aqueous layer became neutral. After the ether layer was dried over anhydrous sodium sulfate, ether was distilled off, followed by distillation under reduced pressure to obtain 99 g of 3-allyloxy-1-hexyloxy-2-propanol (bp 86 to 87 ° C./bp).
0.01 mmHg, yield 88%). ¹ H-NMR [[delta] ppm, TMS standard (0 ppm)]: 0.85 (t, 3H) CH 3 1.26 (br, 6H) CH 2 1.49-1.60 (m, 2H) -OCH 2 CH 2 2.49 (d, 1H) - OH 3.40-3.48 (m, 6H) O -CH 2 3.90-3.98 (m, 1H) O-CH 4.03 (d, 2H) CH 2 = CH-CH 2 5.18-5.32 (m, 2H) CH 2 = CH- _{CH 2 5.85-5.95 (m, 1H)} CH 2 = CH-CH 2 ii) the product of the present invention (I a) obtained in i) 3- allyloxy-1-hexyloxy-2-propanol 28 g (0.13 mol), pentamethyl Disiloxane
14.8g (0.10mol), 10m potassium acetate ethanol solution 2m
while isopropyl alcohol 100ml stirred at room temperature as a l and a solvent were added _{H 2 PtCl 6 · 6H 2 O} 2% isopropyl alcohol solution 1 ml. The reaction mixture was heated to 50 ° C., and stirred for 2 hours. Then, insolubles were removed by filtration, and the filtrate was concentrated to obtain about 40 g of a crude product. Flash column chromatography (800g silica gel,
Purification with a developing solvent of hexane: ethyl acetate = 3: 1) gave 11.8 g of the desired compound (Ia) (yield: 32%). ¹ H-NMR [δppm, CDCl ₃ standard (7.24 ppm)]: 0.03-0.04 (s, 15H) Si-CH ₃ 0.42-0.51 (m, 2H) Si-CH ₂ 0.86 (t, 3H) -CH ₃ 1.27 _{(br, 6H) CH 2 3} CH 3 1.49-1.69 (m, 4H) 0-CH 2 -CH 2 - 2.49 (d, 1H) OH 3.40-3.46 (m, 8H) O-CH 2 3.88-3.96 (m ^{, 1H) 0-CH 13 C} -NMR [[delta] ppm, CDCl ₃ reference (77.1ppm)]: (A) 1.97 (b) 0.28 (c) 14.0 Example 2 1- (4,8-dioxa-6-hydroxytetradecyl)
Synthesis of -1,1,3,3,5,5,7,7,9,9,9-undecamethylpensiloxane: In Example 1, 18.0 g of undecamethylpentasiloxane instead of pentamethyldisiloxane (0.05mol)
Compound (Ib) 10.0 g was obtained in the same manner except that was used (yield 35%). ¹ H-NMR [δppm, CDCl ₃ standard (7.24 ppm)]: 0.02-0.07 (s, 33H) Si-CH ₃ 0.46-0.54 (m, 2H) Si-CH ₂ 0.86 (t, 3H) -CH ₃ 1.26 _{(br, 6H) (CH 2} ) 4 -CH 3 1.51-1.63 (m, 4H) O-CH 2 -CH 2 2.47 (d, 1H) OH 3.37-3.46 (m, 8H) O-CH 2 3.88-3.97 (m, 1H) O-CH 13 C-NMR [[delta] ppm, CDCl ₃ reference (77.1ppm)]: (A) 1.86 (b) 1.22 (c) 1.22 (d) 1.13 (e) 0.17 (f) 14.1 Example 3 Synthesis of 1,9-bis (4,8-dioxa-6-hydroxytetradecyl) -1,1,3,3,5,5,7,7,9,9-decamethylpentasiloxane: In Example 1, , 10.8g (0.025mol) of dodecamethylhexasiloxane instead of pentamethyldisiloxane
In the same manner except that was used, 15.1 g of compound (Ic) was obtained (yield 70%). ¹ H-NMR [δppm, CDCl ₃ standard (7.24 ppm)]: 0.02-0.05 (s, 36H) Si-CH ₃ 0.45-0.54 (m, 4H) Si-CH ₂ 0.86 (t, 6H) CH ₂ -CH ₃ 1.26 (br, 12H) (CH ₂ ) 1.48-1.62 (m, 8H) CH ₂ CH ₂ O 2.62 (d, 2H) OH 3.36-3.46 (m, 16H) OCH ₂ 3.88-3.93 (m, 2H) OCH ¹³ C-NMR [δ ppm, CDCl ₃ standard (77.1 ppm)]: (A) 0.14 (b) 1.10 (c) 1.20 (d) 14.0 Example 4 Synthesis of 1- (4-oxa-6-hydroxy-7-methylheptadecyloxyheptyl) -1,1,3,3,5,5,7,7,9,9,9-undecamethylpentasiloxane: i) 3-allyloxy-1-methylheptadecyloxy-2
-Propanol In Example 1i), 32.7 g (0.10 mol) of methyl-branched isostearyl glycidyl ether and allyl alcohol
Except that 58 g (1.0 mol) was used, 33.4 g (0.087 mol) of 3-allyloxy-1-methylheptadecyloxy-2-propanol was obtained in a similar manner (yield 87%). ¹ H-NMR [δ ppm, TMS standard (0 ppm)]: 0.82, 0.85 (t, 6H) -CH ₃ 1.26 (br, 27H)-(CH ₂ 1.55-1.62 (m, 2H) O-CH ₂ CH ₂ 2.47 (d, 1H) -OH 3.41-3.55 ( m, 6H) O-CH 2 3.93-4.0 (m, 1H) O-CH 4.03 (d, 2H) CH 2 = CHCH 2 O 5.17-5.32 (m, 2H) _{CH 2 = CHCH 2 O 5.84-5.96 (} m, 1H) CH 2 = CHCH 2 O ii) compounds in (I d) example 1ii), obtained in the above i) 3- allyloxy-1-methyl-hept-de siloxy 11.0 g of compound (Id) was obtained in substantially the same manner as above except that 12.5 g of 2-propanol and 9.0 g of undecamethylpentasiloxane were used (yield: 59%). ¹ H-NMR [[delta] ppm, CDCl ₃ reference (7.24 ppm)]: 0.01-0.07 (s, 33H) Si -CH 3 0.45-0.53 (m, 2H) Si-CH 2 - 0.82,0.85 (t, 6H) - _{CH 3 1.22 (br, 29H)} -CH 2 - 1.50-1.62 (m, 4H) -OCH 2 CH 2 - 2.57 (d, 1H) -OH 3.36-3.45 (m, 8H) -OCH 2 - 3.85-3.95 ( m, 1H) -OCH- ¹³ C-NMR [δ ppm, CDCl ₃ standard (77.1 ppm)]: (A) 1.86 (b) 1.23 (c) 1.23 (d) 1.14 (e) 0.19 (f) 14.2 Example 5 1,9-bis (4-oxa-6-hydroxy-7-methylheptadecyloxyheptyl) -1,1,3,3,5,5,7,7,9,9-
Synthesis of Decamethylpentasiloxane: In Example 4ii), decamethylpentasiloxane 1
Except that 3.8 g (0.20 mol) was used, 14.6 g of compound (Ie) was obtained in a similar manner (yield: 68%). ¹ H-NMR [δppm, CDCl ₃ standard (7.24 ppm)]: 0.02-0.05 (s, 30H) Si-CH ₃ 0.45-0.57 (m, 4H) Si-CH ₂ 0.82 (t, 6H) -CH ₃ 0.85 _{(t, 6H) -CH 3 1.23} (br, 58H) -CH 2 - 1.50-1.66 (m, 8H) CH 2 CH 2 O 2.51 (d, 2H) OH 3.36-3.51 (m, 16H) O-CH 2 3.88-3.96 (m, 2H) O-CH ¹³ C-NMR [δ ppm, CDCl ₃ standard (77.1 ppm)]: (A) 0.18 (b) 1.15 (c) 1.24 (d) 14.2 Example 6 Synthesis of 1- (4,7-dioxa-6-hydroxymethylpentacosa) -1,1,3,3-pentamethyldisiloxane: i) 1-allyloxy-3-benzyloxy-2-octadecyloxypropane allyl alcohol 232g (4.0mol) under nitrogen atmosphere
1.9 g (0.08 mol) of sodium metal was slowly and carefully added to dissolve, heated to 60 ° C., and then 65.7 g (0.40 mol) of benzyl glycidyl ether was added dropwise over about 30 minutes.
After completion of the dropwise addition, stirring was continued at 60 ° C. for another 5 hours. After unreacted allyl alcohol was distilled off from the reaction mixture, 500 ml of ether was added, and the mixture was washed repeatedly with saturated saline. After the ether layer was dried over anhydrous sodium sulfate, the ether was distilled off, followed by distillation under reduced pressure to obtain 63.0 g of 1-allyloxy-3-benzyloxy-2-propanol (bp 105-
109 ° C./0.05 Torr, yield 71%).

To 31 g (0.14 mol) of 1-allyloxy-3-benzyloxy-2-propanol and 500 ml of toluene, 30 g of potassium hydroxide (particulate) and 48.octadecyl chloride.
5 g (0.17 mol) was added, and the mixture was heated and refluxed for 5 hours under azeotropic dehydration conditions. After the organic layer was repeatedly washed with water, toluene was distilled off. Using a silica gel short column, purification was performed to obtain 43.1 g of 1-allyloxy-3-benzyloxy-2-octadecyloxypropane (0.112 mol
l) was obtained (80% yield). ¹ H-NMR [δ ppm, TMS standard (0 ppm)]: 0.88 (t, 3H) -CH ₃ 1.26 (br, 30H) CH ₂ 1.51-1.60 (m, 2H) OCH ₂ CH ₂ 3.52-3.65 (m, 7H _{) OCH 2 3.99 (d, 2H} ) CH 2 = CHCH 2 4.55 (s, 2H) Ph-CH 2 O 5.12-5.31 (m, 2H) CH 2 = CHCH 2 5.79-5.96 (m, 1H) CH 2 _{= CHCH 2 7.24-7.34 (m, 5H} ) Ph-CH 2 ii) compound (I f) obtained in i) 1-allyloxy-3-benzyloxy -
It was added 2-octadecenyl siloxy propane 40 g (0.105 mol) and the mixture H ₂ PtCl ₆ · 4H ₂ O traces directly pentamethyldisiloxane 14 g (0.10 mol), and stirred for about 30 minutes at room temperature. After diluting the reaction mixture with 200 ml of hexane, the origin was removed with a silica gel short column (silica gel 150 g, solvent: hexane / ethyl acetate = 10/1). The solvent was distilled off to obtain 38.7 g of a crude product. Subsequently, this was mixed with 500 ml of methanol and 1.7 g of 10% Pd-C, and hydrogen gas was introduced at room temperature at a rate of 19 ml / min for 14 hours. After removing the catalyst by filtration and distilling off methanol from the filtrate,
Flash column chromatography (silica gel 800
g, solvent: n-hexane / ethyl acetate = 12/1) to obtain 18.7 g of the desired compound (If) (0.
035 mol) was obtained (yield 35%). ¹ H-NMR [δppm, CDCl ₃ standard (7.24 ppm)]: 0.05 (s, 6H) Si-CH ₃ 0.06 (s, 9H) Si-CH ₃ 0.45-0.54 (m, 2H) Si-CH ₂ 0.88 ( _{t, 3H) -CH 3 1.26 (} br, 30H) -CH 2 - 1.51-1.66 (m, 4H) -CH 2 CH 2 O 2.32 (t, 1H) OH 3.38-3.72 (m, 9H) CH 2 O, CHO ¹³ C-NMR [δ ppm, CDCl ₃ standard (77.1 ppm)] (A) 1.99 (b) 0.30 (c) 14.1 Example 7 Synthesis of α, ω-bis (4-oxa-6-hydroxy-7-tetraabiethyloxyheptyl) -dimethylpolysiloxane (Ig): i) 3-allyloxy-1-tetrahydroabiethyloxy-2-propanol In Example 1i), 52.3 g (0.15 mol) of tetrahydroabiethyl glycidyl ether and allyl alcohol 17
In substantially the same manner except that 4 g (3 mol) was used, 48.6 g (0.119 mol) of 3-allyloxy-1-tetrahydroabiethyloxy-2-propanol was obtained (bp 140-155 ° C./0.01 mm).
Hg, 80% yield).

ii) Compound (Ig) 9.8 g (0.024 mol) of 3-allyloxy-1-tetrahydroabiethyloxy-2-propanol obtained in i), α,
ω-dihydrogendimethylpolysiloxane 36.9 g (0.01 mol), 10% potassium acetate in ethanol solution 0.
While the 47g and isopropyl alcohol 60ml was stirred at room temperature was added _{H 2 PtCl 6 · 6H 2 O2} % isopropyl alcohol solution 0.12g as a solvent. The reaction mixture was heated to 40 ° C., and after stirring for 20 hours, the solvent was distilled off under reduced pressure, and the catalyst was removed by silica gel short column chromatography. Then, under reduced pressure, excess 3-allyloxy-1-
Tetrahydroabiethyloxy-2-propanol was distilled off (230 ° C./0.01 mmHg), and the residue was purified again by silica gel short column chromatography to obtain 35.7 g of the desired compound (Ig) (yield). 79%). ¹ H-NMR [δppm, C ₆ C ₆ reference (7.15 ppm)]: 0.09-0.35 (m, about _{300H) Si-CH 3 0.56-0.68 (} m, 4H) Si-CH 2 0.77-2.05 (m, 70H ) Si-CH ₂ CH ₂ , 2.34 (bs, 2H) OH 2.82-3.57 (m, 16H) O-CH 2 4.00-4.10 (m, 2H) O-CH IR [liquid film, cm ^-1] 3470,2968,2872,1455,1416,1263 , 1098,1023,867,804,70
2 Example 8 Synthesis of α, ω-bis (4-oxa-6-hydroxy-7-tetraabiethyloxyheptyl) -dimethylpolysiloxane (Ih): α, ω-dihydrogendimethylpolysiloxane in Example 7ii) In a similar manner except that was used, 32.5 g of compound (Ih) was obtained (yield: 65%). ¹ H-NMR [δ ppm, C ₆ D ₆ standard (7.15 ppm)]: 0.04-0.39 (m, about 120H) Si-CH ₃ 0.53-0.66 (m, 4H) Si-CH ₂ 0.73-2.02 (m, 70H ) Si-CH ₂ -CH _2, 2.38 (bs, 2H) OH 2.73-3.56 (m, 16H) O-CH 2 3.98-4.09 (m, 2H) O-CH IR [liquid film, cm ^-1] 3496,2968,2938,2872,1455,1416 , 1389,1263,1098,1023,
867,801,699 Example 9 1- (4-oxa-6-hydroxy-7-tetrahydroabiethyloxyheptyl) -1,1,3,3,5,5,7,7,9,9,1
Synthesis of 1,11,13,13,15,15,17,17,17-nonadecamethylnonasiloxane (Ii): 1,1,3,3,5,5,7,7 in Example 7ii) , 9,9,11,11,13,
Substantially in the same manner except that 13,15,15,17,17,17-nonadecamethylnonasiloxane was used, 11.0 g of compound (Ii) was obtained (yield 51%). ¹ H-NMR [δ ppm, C ₆ D ₆ standard (7.15 ppm)]: 0.06-0.28 (m, 57H) Si-CH ₃ 0.52-0.61 (m, 2H) Si-CH ₂ 0.73-2.09 (m, 35H) Si-CH ₂ CH ₂ , 2.43 (bs, 1H) OH 2.78-3.56 (m, 8H) O-CH 2 3.93-4.09 (m, 1H) O-CH IR [liquid film, cm ^-1] 3480,2964,2936,2872,1458,1414 , 1386,1262,1096,1026,
842,802,756,692 Example 10 α, ω-bis {4-oxa-6-hydroxy-7- [5,
Synthesis of 7,7-trimethyl-2- (1,3,3-trimethylbutyl) octyloxy] heptyl} -dimethylpolysiloxane (Ij): i) 3-allyloxy-1- {5,7,7-trimethyl -2-
(1,3,3-trimethylbutyl) octyloxy} -2-
Propanol In Example 1i), 5,7,7-trimethyl-2- (1,3,3
-Trimethylbutyl) octylglycidyl ether 326.
Except that 6 g (1 mol) and 580.8 g (10 mol) of allyl alcohol were used, 3-allyloxy-1- {5,
7,7-trimethyl-2- (1,3,3-trimethylbutyl) octyloxy} -2-propanol 353.4 g (0.92 mol)
(Bp 125-140 ° C./0.01 mmHg, yield 92%).

ii) Compound (I j) In Example 7ii), 3-allyloxy-1- {5,7,7-trimethyl-2- (1,1) is used instead of 3-allyloxy-1-tetrahydroabiethyloxy-2-propanol.
35.3 g of compound (Ij) was obtained in substantially the same manner as above except that 9.2 g (0.024 mol) of 3,3-trimethylbutyl) octyloxy} -2-propanol was used (87% yield). ¹ H-NMR [δ ppm, C ₆ D ₆ standard (7.15 ppm)]: 0.10-0.41 (m, about 300H) Si-CH ₃ 0.57-0.68 (m, 4H) Si-CH ₂ 0.79-1.95 (m, 74H ) Si-CH ₂ -CH _2, 2.38 (bs, 2H) OH 3.25-3.60 (m, 16H) O-CH 2 4.02-4.13 (m, 2H) O-CH IR [liquid film, cm ^-1] 3450,2964,2908,2872,1472,1416 , 1368,1344,1264,1098,
1026,864,802,702,664 Example 11 α, ω-bis {4-oxa-6-hydroxy-7- [5,
Synthesis of 7,7-trimethyl-2- (1,3,3-trimethylbutyl) octyloxy] heptyl} -dimethylpolysiloxane (Ik): In Example 8, 3-allyloxy-1-tetrahydroabiethyl-2 The compound was prepared in substantially the same manner except that 3-allyloxy-1- {5,7,7-trimethyl-2- (1,3,3-trimethylbutyl) octyloxy} -2-propanol was used instead of propanol. (Ik) 33.38 g was obtained (83% yield). ¹ H-NMR [δppm, C ₆ D ₆ standard (7.15 ppm)]: 0.11-0.36 (m, about _{120H) Si-CH 3 0.55-0.64 (} m, 4H) Si-CH 2 0.79-1.94 (m, 74H ) Si-CH ₂ -CH ₂ 2.40 (bs, 2H) OH 3.24-3.59 (m, 16H) O-CH 2 3.99-4.11 (m, 2H) O-CH IR [liquid film, cm ^-1] 3480,2964,2876,1470,1416,1368 , 1264,1100,1026,864,8
06,700 Example 12 A cream having the composition shown in Table 1 below was produced, and its practical test and the effects of improving and preventing skin roughness were evaluated.

(Manufacturing method) The above oil phase components 1) to 8) are mixed, dissolved by heating, and heated to 70 ° C.
Kept. The aqueous phase parts 9) to 13) were gradually added thereto and emulsified by an emulsifier. After the emulsion was cooled to a final temperature of 30 ° C. in a heat exchanger, filling was performed to prepare a cream (Product 1 of the present invention and Comparative Products 1 to 3).

(Test method) (1) Practical test (panel test) Practical evaluation was carried out by actually using the prepared sample by 10 expert panelists. The evaluation items were four items of familiarity with skin, low stickiness, moist feeling, and overall evaluation.
The following criteria are provided:

◎ Eight or more of the ten respondents answered that they were good. ○: Six to seven of the ten respondents answered that they were good. Δ: 4 to 5 of the respondents answered that they were good. (2) Rough skin score 20- to 50-year-old woman who has rough skin on her cheeks in winter 10
A different cream was applied to the left and right cheeks for two weeks. The next day after the completion of the two-week application, the rough skin was observed with the naked eye, and judged based on the criteria shown in Table 2 below. The results are shown in Table 3 as average scores.

Example 13 Emulsion Oil phase component: (% by weight) Compound of the present invention (Id) 5.0 Olive oil 2.0 Cetanol 1.0 Sorbitan sesquioate 1.0 POE (40) Sorbitan monooleate 1.0 Ethyl paraben 0.1 Water phase component: Methyl paraben 0.1 Ethanol 3.0 Glycerin 2.0 Perfume 0.1 Purified water Balance 100.0 According to the above formula, mix and dissolve oil phase components and heat to 70 ° C
Kept. The aqueous phase component was similarly heated and mixed at 70 ° C., and the oil phase was added to the aqueous phase and emulsified by an emulsifier. The emulsion was gradually cooled to prepare an emulsion.

Example 14 Cream Oil phase component: (% by weight) Compound of the present invention (Ie) 20.0 Squalane 5.0 Methanol 2.0 POE (20) Sorbitan monostearate 1.5 Sorbitan monostearate 0.5 Microcrystalline wax 2.0 Butyl paraben 0.1 Water phase component: Glycerin 3.0 Methylparaben 0.2 Perfume 0.1 Purified water Balance 100.0 According to the above formula, mix the oil phase components, heat and dissolve, then 80 ℃
Kept. The aqueous phase component was similarly heated and dissolved at 80 ° C., and the aqueous phase was added to the oil phase to form an emulsion. The cream was slowly cooled.

Example 15 Two-layer liquid foundation (% by weight) Compound of the present invention (Ie) 10.0 Volatile silicone 15.0 POE (10) hydrogenated castor oil 0.2 Dimethyl polysiloxane polyoxyalkylene copolymer 0.3 Powder component: Silicone treatment Titanium oxide 4.0 Silicone-treated talc 8.0 Silicone-treated iron oxide 1.0 Aqueous phase component: Glycerin 5.0 Ethanol 10.0 Perfume 0.1 Purified water Balance 100.0 According to the above formulation, the oil phase component was mixed and the powder component was sufficiently dispersed. The aqueous phase, which was completely homogeneously mixed, was added thereto and emulsified by an emulsifier to obtain a two-layer liquid foundation. Example 16 Emulsion type foundation Oil phase component: (% by weight) Compound of the present invention (Ic) 10.0 Cetanol 1.0 Stearic acid 2.0 Glycerin monostearate 2.0 Propylene glycol monolaurate 1.0 Powder component: Silicone-treated titanium oxide 5.0 Silicone-treated sericite 8.0 Silicone-treated iron oxide 2.0 Aqueous phase component: Glycerin 5.0 Triethanolamine 0.5 Methylparaben 0.2 Fragrance 0.1 Purified water Balance 100.0 An emulsified foundation was prepared according to the above formulation. The oil phase components were mixed, dissolved by heating and kept at 80 ° C. After the powder component was added and dispersed therein, an aqueous phase uniformly mixed at 80 ° C. was added and emulsified and dispersed by an emulsifier. The obtained emulsion was gradually cooled to obtain an emulsion type foundation.

Example 17 Lipstick Base: (% by weight) Compound of the present invention (Ie) 30.0 Castor oil 20.0 Cetanol 25.0 Lanolin 5.0 Candelilla wax 6.0 Carnauba wax 6.0 Tocopherol 0.2 Propyl paraben 0.2 Colorant: Titanium oxide 2.5 Organic dye 5.0 Perfume 0.1 100.0 Lipstick was prepared according to the prescription. The base was dissolved by heating and mixed uniformly. The coloring material was added thereto, kneaded with a roll mill, and uniformly dispersed. This was redissolved, flavor was added, defoamed, poured into a mold and quenched to solidify. The solid was removed from the mold and loaded into a container. Further, after the appearance of the stick was adjusted, it was passed through a flame to make the surface uniform and a lipstick was obtained.

Example 18 Pack (peel-off type) Oil phase component: (% by weight) Compound of the present invention (If) 2.0 Squalane 1.0 POE (10) hydrogenated castor oil 1.0 Powder component: Titanium oxide 10.0 Kaolin 2.0 Water phase component: Glycerin 5.0 Vegum 1.0 Ethanol 6.0 Perfume 0.2 Purified water Balance Film agent: Polyvinyl alcohol 10.0 100.0 According to the above formula, mix the aqueous phase components, heat and dissolve to 70 ° C
Kept. Similarly, the oil phase component was heated and mixed at 70 ° C., added to the aqueous phase, and emulsified by an emulsifier. A powder component and a film agent were added to this emulsion and mixed. The emulsion was gradually cooled to prepare a pack.

Example 19 Lotion Water phase component: (% by weight) Glycerin 5.0 Dye Appropriate amount Purified water Balance Ethanol phase component: Ethanol 10.0 Compound of the present invention (Ia) 0.2 POE (20) stearyl ether 1.5 POE (20) sorbitan monopalmitate 0.5 Ethylparaben 0.1 perfume Appropriate amount 100.0 Glycerin and a dye were added to purified water and dissolved at room temperature. On the other hand, the compound of the present invention (Ia), a surfactant, a paraben and a fragrance were added to ethanol, dissolved at room temperature, and added to the above aqueous phase to solubilize. Filtration gave a lotion.

Example 20 Hair tonic (% by weight) Compound of the present invention (Ib) 0.2 Menthol 0.2 Antibacterial agent: pyrocton auramine 0.1 Methyl nicotinate 0.1 Ethanol 45.0 Purified water Balance 100.0 The above components were heated and dissolved at 70 ° C., and cooled. Got a hair tonic.

Example 21 Hair rinse (% by weight) Stearyltrimethylammonium chloride 2.0 Polyoxyethylene cetyl ether 2.0 Cetanol 1.0 Compound of the present invention (Ic) 3.0 Glycerin 2.0 Methylparaben 0.1 Ethylparaben 0.1 Perfume 0.1 Purified water Balance 100.0 Purified water heated to 70 ° C. Then, methylparaben and a flavor were added and dissolved. The remaining components heated and mixed at 70 ° C. were added to the aqueous phase and emulsified. A slowly cooled hair rinse was obtained.

Example 22 Moisturizing cream (% by weight) Oil phase component: Compound of the present invention (Ig) 8.0 Compound of the present invention (Ij) 2.0 Solid paraffin 2.0 Cetyl 2-ethylhexanoate 5.0 Lanolin 5.0 Beeswax 2.0 Stearyl alcohol 4.0 Self-emulsifying type Glycerol monostearate 1.5 Polyoxyethylene sorbitan monooleate (20.EO) 1.0 Aqueous phase component: Glycerin 5.0 70% sorbite solution 10.0 Ethyl paraben 0.1 Methyl paraben 0.1 Perfume 0.1 Purified water Balance 100.0 Heat the oil phase component according to the above formula Dissolved and kept at 70 ° C. The aqueous phase component was similarly heated and dissolved at 70 ° C., and this aqueous phase was added to the oil phase, and an emulsified product was obtained using an emulsifier. The obtained emulsion was cooled with stirring to obtain a moisturizing cream.

This moisturizing cream had good adhesion to the skin, was less sticky, and gave a moist feel.

Example 23 Creamy foundation (% by weight) Oil phase component: Compound of the present invention (Ih) 10.0 Liquid paraffin 8.0 Squalane 8.0 Neopentyl glycol dioctanoate 3.0 Sorbitan sesquiisostearate 7.0 Aluminum distearate 0.2 Powder component: Titanium oxide 8.0 Talc 5.0 Sericite 2.0 Bengala 0.4 Iron oxide yellow 0.7 Black iron oxide 0.1 Aqueous phase component: Magnesium sulfate 0.7 Maltitol 2.0 Glycerin 3.0 Methyl paraben 0.1 Perfume 0.1 Purified water Balance 100.0 According to the above formula, heat the oil phase component to 70 ° C and homogenize After mixing, the powder components were sufficiently dispersed. The aqueous phase component uniformly mixed at 70 ° C. was gradually added thereto with stirring to emulsify, and cooled with stirring to obtain a creamy foundation.

This cream-like foundation had a good fit to the skin, gave less stickiness and gave a moist feel.

Claims (3)

(57) [Claims] 1. The compound of the general formula (I) [Wherein at least one of R ¹ , R ² and R ³ is the following formula: Or (One of R ⁵ and R ⁶ is a hydrogen atom, the other is a straight-chain, branched-chain or cyclic alkyl group, alkenyl group or hydroxyalkyl group having 6 to 30 carbon atoms),
R ¹ , R ^2, R ³ , and R ⁴ other than the above are alkyl groups having 1 to ⁴ carbon atoms, and m and n each represent a number in which m + n is 1 to 200]. 2. A cosmetic oil containing the siloxane derivative (I) according to claim 1. 3. A cosmetic comprising the siloxane derivative (I) according to claim 1.