JP2613124B2 - Novel siloxane derivative, method for producing the same, and cosmetic containing the same - Google Patents

Description

Description: TECHNICAL FIELD The present invention relates to a novel siloxane derivative having a surfactant activity, which is useful as an emulsifier, a method for producing the same, and a cosmetic containing the same.

[Problems to be solved by conventional technology and invention]

Silicone compounds having a surfactant activity, from the type of the modified hydrophilic group, a compound having an anionic hydrophilic group,
Compounds having a cationic hydrophilic group, compounds having a betaine hydrophilic group, and compounds having a nonionic hydrophilic group
They are roughly classified into species.

Among the above, as the compound having a nonionic hydrophilic group, a polyoxyalkylene-modified silicone surfactant having a polyoxyalkylene group as a hydrophilic group is known. When it is used as an emulsifier, it is necessary to further add a thickener such as silica or a viscous mineral in order to obtain satisfactory emulsion stability.

On the other hand, as a nonionic hydrophilic group other than polyoxyalkylene, a polyhydric alcoholic hydroxyl group is considered, but at present, silicone surfactants having a polyhydric alcoholic hydroxyl group as a hydrophilic group are hardly known,
It is only known that the (poly) glycerin-modified silicone described in JP-B-62-34039 and the sorbitan-modified silicone described in JP-A-57-209295 have a surfactant activity. It is.

Further, silicone compounds modified with a glyceryl group, which is a polyhydric alcoholic hydroxyl group, are known and disclosed in
62-195389, JP-A-64-16793 and JP-A-6
Although these compounds are described in Japanese Patent Application Laid-Open No. 3-101388, these compounds are surface modifiers for synthetic resins utilizing the reactivity of hydroxyl groups, and their surface activity is unknown.

As described above, there are almost no nonionic silicone surfactants having satisfactory performance at present.

[Means for solving the problem]

Under these circumstances, the present inventors have conducted intensive studies, and as a result, have found that a novel siloxane derivative having a glyceryl group described below is a nonionic surfactant suitable as an emulsifier for cosmetics and the like, and completed the present invention. did.

That is, the present invention provides the following general formula (I) [Wherein at least one of R ^{1 to} R ¹² is represented by the following formula (II): (Wherein Q represents a divalent hydrocarbon group having 3 to 20 carbon atoms;
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. ) Is a group represented by the remaining straight-chain having 1 to 30 carbon atoms, in branched or cyclic hydrocarbon group or the following formula ^{(III) -X-R 15 (} III) ( wherein, X represents an ether bond and And / or a divalent hydrocarbon group containing an ester bond, wherein R ¹⁵ is a linear, branched or cyclic hydrocarbon group having 1 to 30 carbon atoms), and l, m and n are Indicates a number from 0 to 2000, and l + m
When + n = 0, at least one of R ^{1 to} R ³ and R ^{10 to} R ¹²
One is a group (II). However, when at least one of R ^{1 to} R ¹² is a group (II) in which Q is trimethylene and R ¹³ and R ¹⁴ are both hydrogen atoms, the straight chain having 1 to 30 carbon atoms;
At least one of the branched or cyclic hydrocarbon groups is a straight, branched or cyclic hydrocarbon group having 6 to 30 carbon atoms. ] It is intended to provide a siloxane derivative represented by the formula, a method for producing the siloxane derivative, and a cosmetic containing the same.

In the general formula (I), the number of carbon atoms represented by Q is 3 to
20 divalent hydrocarbon groups include trimethylene, tetramethylene, pentamethylene, hexamethylene, heptamethylene, octamethylene, nonamethylene, decamethylene,
Linear alkylene groups such as undecamethylene, dodecamethylene, tetradecamethylene, hexadecamethylene, and octadecamethylene; propylene, 2-methyltrimethylene,
Examples include branched alkylene groups such as 2-methyltetramethylene, 2-methylpentamethylene, and 3-methylpentamethylene. Examples of the hydrocarbon group having 1 to 5 carbon atoms represented by R ¹³ or R ¹⁴ include straight-chain and branched chains such as methyl, ethyl, propyl, butyl, pentyl, isopropyl, sec-butyl, tert-butyl, neopentyl, and cyclopentyl. Or a cyclic alkyl group. As the divalent hydrocarbon group containing an ether bond and / or an ester bond represented by _{X 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 an integer from 3 to 20), CH _{2 r} O—CO—, CH _{2 r} COO—, and the like. Further, as a 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, tetra Straight-chain alkyl groups such as eicosyl, hexaeicosyl, octa-eicosyl, and triacontyl; branched-chain alkyl groups such as isopropyl, sec-butyl, tert-butyl, neopentyl, 1-ethylpropyl, and 1-heptyldecyl; cyclopentyl, cyclohexyl, And cyclic alkyl groups such as abiethyl and cholesteryl. It is preferable that l, m and n are in the range of 0 or more and 2000 or less from the viewpoint of availability of the raw material organohydrogenpolysiloxane, operability at the time of production, and the like.

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

(1) Siloxane derivative (Ia) having no group (III)
Recipe [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 each represent a number of 0 or more and 2000 or less,
When 1 + m + n = 0, at least one of R ^{16 to} R ¹⁸ and R ^{25 to} R ²⁷ is a hydrogen atom.

Q ′ has 3 to 3 carbon atoms having at least one double bond.
It has 20 hydrocarbon groups 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 straight-chain, branched-chain or emotional hydrocarbon group having 1 to 30 carbon atoms. When 1 + m + n = 0, ^{1 'to} R
^At least one of ^{3 ′} and R ^{10 ′ to} R ^{12 ′} is a group (I
I). However, ^one of R ^{1 ′ to} R ^{12 ′} is Q
Is a group (II) in which R ¹³ and R ¹⁴ are both hydrogen atoms, and all the rest are methyl groups. 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) Production method of siloxane derivative (Ib) having group (III) [In the formula, at least two of R ^{16 ′ to} R ^{27 ′} are hydrogen atoms, and the riding is a linear, branched or cyclic hydrocarbon group having 1 to 30 carbon atoms, and l, m and n are as defined above. The same meaning is given, and when l + m + n = 0, R ^{16 ′ to} R ^{18 ′} and R ^{25 ′} to
At least two of R27 ^' are hydrogen atoms.

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

X ′ represents 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), and at least one of the remaining groups is a group (III);
The remainder is a linear, branched or cyclic hydrocarbon group having 1 to 30 carbon atoms, and when 1 + m + n = 0, R ^{1 ″ to} R ^{3 ″} , R
^At least one of ^{10 "to} R12 ^" is a group (II);
At least one of the remaining is a group (III).

That is, to an organohydrogenpolysiloxane (IV ') having at least two silicon-hydrogen engagements,
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
V ′) or simultaneously with compound (IV ′).

The raw material organohydrogenpolysiloxane (IV) or (IV ') contains 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.

Further, 'as represented by the general formula (III Compound (III)') in X 'is _{CH 2 = CHCH 2 OC 2 H} 4 p OC 3 H 6 q O- (p and q are as defined above), (R ′ is an integer of 1 or more and 18 or less).

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 in which these are supported on silica gel or alumina. Among these, chloroplatinic acid, spier reagent (isopropyl alcohol solution of chloroplatinic acid) and the like 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 adjuster 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) has Any other ratio may be used as long as there is a sufficient amount of alkenyl glyceryl ether (II ') to have at least one or more silicon-bonded glyceryl groups (II). When emulsifying the oil solution, the group (I
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 is preferably performed at 0 ° C. to 100 ° C. in consideration of the reaction rate and coloring of the product. Further, the reaction time is preferably about 0.5 to 24 hours.

The siloxane derivative (I) of the present invention thus obtained can be suitably used as a cosmetic component, particularly as an emulsifier. There are no particular limitations on the form and type of cosmetics that can be applied, and examples thereof include skin care cosmetics such as emulsions, lotions, and foundations; and hair care cosmetics such as shampoos, rinses, and treatments. The compounding amount of the siloxane derivative (I) of the present invention in the cosmetic is not particularly limited, but is usually 0.001 to 90% by weight, particularly 1 to 50% by weight.
A range of weight% is preferred.

〔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) 97 g (0.72 mol) of 1,1,3,3-tetramethyldisiloxane was placed in a 100 ml two-necked flask equipped with a cooling tube and a magnetic stirrer.
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. 52.8 g of a colorless transparent liquid (bp 55-61 ° C./4 Torr) by distillation (yield 67
%). The obtained product was confirmed to be 1-hexyl-1,1,3,3-tetramethyldisiloxane by IR and NMR spectra.

(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 ), 1.8 g (1.8 mmol) of a 10% ethanol solution of potassium acetate and isopropyl alcohol 2
4 g was charged, and 0.18 g (0.017 mmol) of a 5% solution of chloroplatinic acid in isopropyl alcohol was added thereto, followed by stirring at 40 ° C. for 17 hours. After evaporating the solvent, the reaction product was purified through a silica gel column to obtain 22 g (93% yield) of a colorless transparent liquid.
The obtained product was analyzed by IR and NMR spectra to give 3-
It was confirmed to be (3-hexyl-1,1,3,3-tetramethyldisiloxanyl) 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 [δ ppm, CDCl _{3 based} on CHCl ₃ (7.28 ppm)] 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 Example 2 (1) 1-decyl-1,1,3,3-tetramethyldisiloxane was synthesized in the same manner as in Example 1, (1) (70% yield).

(2) According to a method similar to (2) of 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 (CH) 1254 (Si-Me) 1066,840,796 (Si-O-Si) ¹ H-NMR [δ ppm, in CDCl _{3 based} on CHCl ₃ (7.28 ppm)] 0.04,0.06 (s, 12H) Si- C H 3 0.08-0.95 (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 Medium, TMS standard (0 ppm)] 7.22,7.89 Example 3 (1) 1-hexadecyl-1,1,3,3-tetramethyldisiloxane was synthesized by the same method as (1) in Example 1 ( Yield 70%).

(2) According to a method similar to (2) of 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 [δ ppm, in CDCl _{3 based} on CHCl ₃ (7.28 ppm)] 0.04,0.06 (s, 12H) Si- C H 3 0.81-0.96 (t, 3H) -C H 3 1.16-0.96 (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 -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 [[delta] ppm, CDCl ₃ , TMS standard (0 ppm)] 7.22,7.93 Example 4 20 g (30 mmol) of nonadecamethyl nanosiloxane and 9.5 g (39 mmol) of 10-undecenylglyceryl ether in a 100 ml two-necked flask equipped with a cooling tube and a magnetic stirrer. , 0.77 g (0.78 mmol) of a 10% ethanol solution of potassium acetate and 18.5 g of isopropyl alcohol, and 2% of chloroplatinic acid
0.20 g (7.7 × 10 ⁻³ mmol) of an isopropyl alcohol solution was added, and the mixture was heated and heated. Keep the temperature of the contents at 40 ° C and 3.5
Stirred for 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 (77.2 ppm)] 18.5 Si- C H ₂ - _{64.5 C H 2 -OH 70.7 C H} -OH 72.1 CH 2 - C H 2 -O 72.7 CH- C H 2 -O 29 Si-NMR [[delta] ppm, in CDCl _3, TMS standard (0 ppm)] 7.28,7.60 a, i Example 5 In the same manner as in Example 4, pentamethyldisiloxanylundecylglyceryl ether (E) was synthesized (yield: 56%).

IR (liquid film, cm ^-1 ) 3394 (-OH) 2926,2860 (C-H) 1254 (Si-Me) 1062,843 (Si-O-Si) ¹ H-NMR [δ ppm, 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- C H 2 -O 29 Si-NMR [[delta] ppm, in CDCl _3, TMS standard (0 ppm)] 6.97,7.61 Example 6 Undecamethylpentasiloxanylundecylglyceryl ether (F) was synthesized in the same manner as in Example 4 (yield: 48%). At this time, since 1,5-dihydrodecamethylpentasiloxane was contained in the raw material undecamethylpentanesiloxane, 1,5-bis [11
-(2,3-Dihydroxypropoxy) undecyl] decamethylpentasiloxane (G) was obtained. Got 1,
5-Bis [11- (2,3-dihydroxypropoxy) undecyl] decamethylpentasiloxane (G) was isolated and purified using a silica gel column. Its structure was confirmed by IR and MMR spectra.

IR (liquid film, cm ^-1 ) 3406 (-OH) 2962, 2926, 2860 (CH) 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)] 18.5 Si- C H ₂ - _{64.4 C H 2 -OH 70.7 C H} -OH 72.0 CH 2 - C H 2 -O 72.7 CH- C H 2 -O 29 Si-NMR [[delta] ppm, 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 (CH) 1260 (Si-Me) 1080,103,802 (Si-O-Si) ¹ H-NMR [δppm, in CDCl ₃ CHCl ₃ reference (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) CH 2 -O H 3.20 (d, 2H) CH-O H 3.36-3.57 (m, 8H) C H -O 3.57-3.78 (m, 4H) C _{H 2 -OH 3.78-3.96 (m, 2H} ) C H -OH 13 C-NMR [[delta] ppm, 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- 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 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), 11.8 g (48.3 mmol) of 10-undecenyl glyceryl ether, 0.95 g (0.97 mmol) of potassium acetate 10% ethanol solution and isopropyl alcohol 2
4 g was charged, and 0.26 g (0.010 mmol) of a 2% solution of chloroplatinic acid in isopropyl alcohol was added, and the mixture was heated and heated. The temperature of the contents was kept at 50 ° C., and the mixture was stirred for 2 hours. After distilling off the solvent, 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 (CH) 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-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 [[delta] ppm, 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 [in δppm, CDCl _3, TMS standard (0 ppm)] Example 8 In the same manner as in Example 7, α, ω-bis [11- (2,
3-dihydroxypropoxy) undecyl] dimethylpolychiroxane (containing an average chain length of 50 (I) (yield 95.3
%).

IR (liquid film, cm ^-1 ) 3420 (-OH) 2968,2932 (CH) 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-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 [[delta] ppm, 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 [[delta] ppm, in CDCl _3, TMS standard (0 ppm)] Example 9 (1) 32.8 g (56.6 mmol) of α, ω-dihydrohexadecamethyloctasiloxane and 4.0 g (28.5 mmol) of 1-decene were placed in a 50 ml two-necked flask equipped with a condenser and a magnetic stirrer.
Was added, and 3.0 mg (5.8 × 10 ⁻³ mmol) of chloroplatinic acid was added thereto, followed by stirring 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) 10 g (13.9 mmol) of 1-decyl-15-hydrohexadecamethyloctasiloxane synthesized in (1) and 4.4 g of 10-undecenyl glyceryl ether were placed in a 50 ml two-necked flask equipped with a condenser and a magnetic stirrer. (18.0 mmol), 0.35 g (0.36 mmol) of a 10% ethanol solution of potassium acetate and 10 g of isopropyl alcohol, and 0.093 g (3.6 × 10 3
^-3 mmol), and the mixture was heated and heated. The temperature of the contents was maintained at 40 ° C, and the mixture was stirred at 40 ° C for 3 hours. After evaporating the solvent, the reaction product was purified by applying to a silica gel column.
1.8 g (88% yield) were obtained. The obtained purified product is IR and NMR
The spectrum confirmed that the product was 15-decylhexadecamethyloctasiloxanylundecylglyceryl ether (J).

IR (liquid film, cm ^-1 ) 3400 (-OH) 2964, 2928, 2860 (CH) 1262 (Si-Me) ¹ H-NMR [[delta] ppm, in CDCl _3, CHCl ₃ standard (7.28 ppm)] -0.02-0.10 (m, 48) 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 [[delta] ppm, 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 Example 10 condenser and wherein the 100ml2-necked flask equipped with a magnetic stir bar (K ') 15g of organohydrogensiloxane represented by
mmol), 8.1 g of 10-undecenyl glyceryl ether (33
mmol), 0.65 g (0.6%) of a 10% ethanol solution of potassium acetate.
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 maintained at 40 ° C., and the mixture was stirred for 2.5 hours. After distilling off the solvent and treating with activated carbon, unreacted 10-undecenyl glyceryl ether was distilled off under reduced pressure to obtain a brown viscous product. The IR of the obtained product was confirmed by NMR spectrum to be a compound (K) represented by the following formula.

IR (liquid film, cm ^-1 ) 3400 (-OH) 2968,2932,2860 (CH) 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 Example 11 A compound (L) represented by the following formula was synthesized in the same manner as in Example 10 (97% yield).

IR (liquid film, cm ^-1 ) 3420 (-OH) 2968,2932,2860 (CH) 1264 (Si-Me) 1096,1026,802 (Si-O-Si) ¹ H-NMR [δppm, CDCl ₃ in, 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) CH 2 -O H 2.43-2.68 (br, 4H) CH-O H 3.88-3.50 (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 example 12 example 10 with the compound represented by the following formula by the same method (M) Was synthesized (99% yield).

IR (liquid film, cm ^-1 ) 3424 (-OH) 2964,2928,2860 (CH) 1262 (Si-Me) 1090,1034,864,798 (Si-O-Si) ¹ H-NMR [δ ppm, 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 example 13 formula in 100ml flask equipped with a condenser and magnetic stirrer (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 a 10% solution of potassium acetate in ethanol and 0.12 ml of a 2% solution of chloroplatinic acid in isopropyl alcohol and add 40%.
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 to be a compound represented by the following formula (N) by IR and ¹ H-NMR spectra.

IR (liquid film, cm ^-1 ) 3400 (-OH) 2965, 2925, 2860 (CH) 805,850, 1260 (Si-Me) 1090, 1030 (Si-O-Si) ¹ H-NMR [δppm, CDCl among _3, 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 Example 14 11.7 g (83 mmol) of decene, allyl glyceryl ether
The reaction was carried out in the same manner as in 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 (CH) 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 Test Example 1 The Compound (A) of the Present Invention Produced in Examples 1 to 14
(O) was examined for emulsion stability in a silicone / water system.

Evaluation method Compounds (A) to (O) were added in an amount of 2% by weight to silicone / water = 1/1, and the mixture was thoroughly shaken at room temperature to emulsify.
The mixture was allowed to stand for a day, and the emulsion stability was examined. As the silicone, KF-96 (5cs) and KF-96 (50cs) manufactured by Shin-Etsu Chemical Co., Ltd. were used. Table 1 shows the results.

As shown in Table 1, the product of the present invention showed good emulsifying performance in the silicone / water system.

Example 15 A liquid foundation having the composition shown in Table 2 below was produced, and its emulsion stability was examined. Table 3 shows the results. The manufacturing method is as follows.

(Preparation method) The powder and the fat were mixed, and the powder uniformly dispersed by stirring was heated to 40 ° C., and an aqueous phase adjusted to 40 ° C. was added thereto with stirring to emulsify. Thereafter, the mixture was filled in a glass container and allowed to cool at room temperature.

As is clear from Table 3, the emulsified cosmetic of the present invention showed good stability. In addition, the feeling of use was not sticky, and the spreadability was good.

〔The invention's effect〕

As described above, the novel siloxane derivative (I) of the present invention
Is a nonionic surfactant suitable as an emulsifier,
The cosmetic of the present invention containing this is excellent in emulsion stability.

──────────────────────────────────────────────────の Continuation of the front page (51) Int.Cl. ⁶ Identification code Agency reference number FI Technical indication location C08G77 / 38 NUG C08G77 / 38 NUG (72) Inventor Akira Kawamata 3-1-1 Hanabusa, Utsunomiya City, Tochigi Prefecture References JP-A-61-293226 (JP, A) JP-A-64-16793 (JP, A) JP-A-62-195389 (JP, A) JP-A-1-193276 (JP, A) JP-A-3-6230 (JP, A) JP-A-57-149290 (JP, A) Chem. Phys. Chem. An wendungtech. Grenz flachenactiuen Stoffe, Ber. Int. Kong r. , 6th, Meeting Date 11 Sep 1972-15 Sep 1972, Volume Band 3, 623-30 Chemical Abstracts, 83 [2] (1975), 13046b

Claims (1)

(57) [Claims] 1. The following general formula (I) [Wherein at least one of R ^{1 to} R ¹² is represented by the following formula: And the rest are all methyl groups, or at least one is a straight-chain or branched-chain hydrocarbon group having 6 to 30 carbon atoms, and all others are methyl groups.
l, m and n each represent a number from 0 to 2000, and l + m + n
When = 0, at least one of R ^{1 to} R ³ and R ^{10 to} R ¹² is a group (IIc). ] The siloxane derivative represented by these.