JP2844453B2 - New siloxane derivatives - Google Patents

Description

DETAILED DESCRIPTION OF THE INVENTION

[0001]

BACKGROUND OF THE INVENTION 1. Field of the Invention The present invention relates to a novel siloxane derivative having a surfactant activity, which is useful as an emulsifier, a method for producing the same, and a cosmetic containing the same.

[0002]

2. Description of the Related Art Silicone compounds having a surfactant activity are classified into compounds having an anionic hydrophilic group, compounds having a cationic hydrophilic group, and compounds having a betaine hydrophilic group according to the type of modified hydrophilic group. And a compound having a nonionic hydrophilic group.

As the compound having a nonionic hydrophilic group, a polyoxyalkylene-modified silicone surfactant having a polyoxyalkylene group as a hydrophilic group is known, but this compound has poor emulsion stability. When used as an emulsifier for cosmetics or the like, it was necessary to further add a thickener such as silica or a viscous mineral to obtain satisfactory emulsion stability.

On the other hand, as a nonionic hydrophilic group other than polyoxyalkylene, a polyhydric alcoholic hydroxyl group is conceivable, but silicone surfactants having a polyhydric alcoholic hydroxyl group as a hydrophilic group are almost unknown at present. It is 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 only.

Further, silicone compounds modified with a glycerin group, which is a polyhydric alcoholic hydroxyl group, are known, and are disclosed in JP-A-62-195389 and JP-A-64-1.
Although these compounds are described in JP-A-6793 and JP-A-63-101388, these compounds are surface modifiers for synthetic resins utilizing the reactivity of hydroxyl groups, and their surface activity is unknown.

[0006] As described above, nonionic silicone-based surfactants having satisfactory performance are almost none at present.

[0007]

Under these circumstances, the present inventors have conducted intensive studies and 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. Finding something,
The present invention has been completed.

That is, the present invention provides the following general formula (I)

[0009]

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(Wherein Q represents a divalent hydrocarbon group having 3 to 20 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 hydrogen) The remainder being a straight-chain, branched or cyclic hydrocarbon group having 1 to 30 carbon atoms or a group represented by the following formula (III):

[0011]

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(Wherein X is an ether bond and / or
A divalent hydrocarbon group containing a tell bond is represented by R ¹⁵Has 1 to 3 carbon atoms
And 0 represents a linear, branched or cyclic hydrocarbon group. )
Where l, m and n are 0 or more and 2000 or less
And when l + m + n = 0, R¹~ R^Three, R^Ten
~ R¹²At least one of which is group (II). However
Then R¹~ R¹²At least one of them is Q
R with Len¹³And R¹⁴Is a group (II) in which both are hydrogen atoms
When the above, the linear, branched or cyclic having 1 to 30 carbon atoms
At least one of the hydrocarbon groups has 6 to 30 carbon atoms.
It is a chain, branched or cyclic hydrocarbon group. ]
Siloxane derivative, method for producing the same, and containing the same
Provide cosmetics.

[0013]

BEST MODE FOR CARRYING OUT THE INVENTION In the above general formula (I), Q is
Examples of the divalent hydrocarbon group having 3 to 20 carbon atoms include:
Limethylene, tetramethylene, pentamethylene, hexa
Methylene, heptamethylene, octamethylene, nonameti
Len, decamethylene, undecamethylene, dodecametyl
, Tetradecamethylene, hexadecamethylene, octa
Linear alkylene groups such as decamethylene; propylene, 2-
Methyltrimethylene, 2-methyltetramethylene, 2-
Methylpentamethylene, 3-methylpentamethylene, etc.
Examples include a branched alkylene group. R¹³Or R¹⁴Indicated by
Examples of the hydrocarbon group having 1 to 5 carbon atoms include methyl,
Chill, propyl, butyl, pentyl, isopropyl, s
ec-butyl, tert-butyl, neopentyl, cycl
Linear, branched or cyclic alkyl groups such as lopentyl
No. And an ether bond represented by X and / or
As the divalent hydrocarbon group containing an ester bond,-(CH_Two)_r-(O
C_TwoH_Four)_p-(OC _ThreeH₆)_q-O- (where p and q are 0 or more and 50 or less
, R is an integer of 3 to 20),-(CH_Two)_r-O-CO-,-
(CH_Two)_r-COO- and the like. In addition, straight carbon
Examples of a chain, branched or cyclic hydrocarbon group include methyl,
Chill, propyl, butyl, pentyl, hexyl, octyl
Le, decyl, dodecyl, tetradecyl, hexadecyl,
Octadecyl, eicosyl, doeicosyl, tetraei
Kosyl, hexaeicosyl, octaeicosyl, thoria
Linear alkyl group such as contyl; isopropyl, sec-
Butyl, tert-butyl, neopentyl, 1-ethyl
Branched alkyl groups such as propyl and 1-heptyldecyl;
Cyclopentyl, cyclohexyl, abiethyl, choles
And a cyclic alkyl group such as teryl. And
l, m and n are organohydrogenpo as raw materials
The availability of siloxane and the operability during production
From the point of view, it is preferable to be in the range of 0 or more and 2000 or less.
No.

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

(1) Method for producing siloxane derivative (Ia) having no group (III)

[0016]

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[In the formula, at least one of R ^{16 to} R ²⁷ is a hydrogen atom, and the rest is a linear, branched or cyclic hydrocarbon group having 1 to 30 carbon atoms. More than 20
00, and when l + m + n = 0, R ^{16 to} R ^16
At least one of ¹⁸ , R ^{25 to} R ²⁷ is a hydrogen atom. Q 'has 3 carbon atoms having at least one double bond.
２０20 to 炭化 20, and R ¹³ and R ¹⁴ have the same meaning as described above. At least one of R ¹ ′ to R ¹² ′ is group (II), and the rest is a linear, branched or cyclic hydrocarbon group having 1 to 30 carbon atoms. When l + m + n = 0, R ¹ 'to R ^3', at least one of R ¹⁰ '~R ^12'
One is a group (II). However, ^one of R ¹ ′ to R ¹² ′
One is a group (II) in which Q is trimethylene, R ¹³ and R ¹⁴ are both hydrogen atoms, and the rest are all methyl groups. ]

That is, an alkenyl glyceryl ether (II ') is reacted with an organohydrogenpolysiloxane (IV) having at least one silicon-hydrogen bond to produce a siloxane derivative (Ia) having no group (III). ) Is obtained.

(2) Method for producing siloxane derivative (Ib) having group (III)

[0020]

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In the formula, at least two of R ¹⁶ ′ to R ²⁷ ′ are hydrogen atoms, and the rest is a linear, branched or cyclic hydrocarbon group having 1 to 30 carbon atoms, and l, m and n Has the same meaning as described above, and when l + m + n = 0, R ¹⁶ ′
At least two of R ¹⁸ ′ and R ²⁵ ′ to R ²⁷ ′ 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;
R ¹⁵ has the same meaning as described above. Of R ¹ ″ to R ¹² ″,
At least one is a group (II), at least one of the remaining groups is a group (III), and the rest is a linear, branched or cyclic hydrocarbon group having 1 to 30 carbon atoms, and l + m + n =
When 0, at least one of R ¹ ″ to R ³ ″ and R ¹⁰ ″ to R ¹² ″ is a group (II), and the other one is a group (III). ]

That is, an alkenyl glyceryl ether (II ') and a compound (III') are reacted with an organohydrogenpolysiloxane (IV ') having at least two silicon-hydrogen bonds to form a group (III)
) Is obtained. Here, either of the compound (II ') and the compound (III') may be reacted with the compound (IV ') first, or simultaneously with the compound (IV').

The raw material organohydrogenpolysiloxane (IV) or (IV ') has at least one compound per molecule.
Having at least two [(IV)] or at least two [(IV ')] silicon-hydrogen bonds,
There is no particular limitation on the molecular structure and the like, and various known materials can be used. However, from the viewpoint of easy availability of raw materials, operability at the time of production, etc., l, m and n are 0 or more and 2000 or less Are preferred.

As the compound (II '), a compound represented by the general formula (II')
In which Q ′ is an ω-alkenyl group. Compound (III ') is represented by the general formula (III')
X '

[0025]

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And the like are preferred.

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;
Complex compounds of metals such as ruthenium, rhodium, palladium, osmium, iridium, platinum and the like; those in which these are supported on silica gel or alumina. Of these, chloroplatinic acid, spear reagent (isopropyl alcohol solution of chloroplatinic acid) and the like are particularly preferable.
The amount of the catalyst used is the amount of the organohydrogenpolysiloxane (IV) or (IV ') and the alkenyl glyceryl ether (I
Any amount may be used as long as it is sufficient to promote the reaction with I ') and / or compound (III'), and is not particularly limited, but is in the range of 10 ^-6 to 10 ^-1 mol per mol of olefin used. Is preferred.

In this reaction, the use of a reaction solvent is not essential, but the reaction may be carried out in an appropriate 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. Solvents such as alcohol solvents such as methanol, ethanol, isopropyl alcohol, and butanol. When an alcohol-based 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 alkenyl glyceryl ether (II ') and / or the compound (II) for the organohydrogenpolysiloxane (IV) or (IV') used in this reaction
The proportion of I ') can be determined as long as the obtained siloxane derivative (I) has a sufficient amount of alkenyl glyceryl ether (II') to have at least one silicon-bonded glyceryl group (II) in the molecule. The ratio may be arbitrary,
When emulsifying a carbon-based oil agent using the obtained compound (I), the total number of units of the group (II) and the group (III) should be in the same ratio as the number of remaining dimethylsiloxane units or in a range thereof. In the case of emulsifying a silicone oil agent, the total number of units of the group (II) and the group (III) is preferably in the range of 1/5 or less of the number of remaining dimethylsiloxane units.

The hydrosilylation proceeds at 0 ° C. to 200 ° C., but takes into account the reaction speed and the coloration of the product.
It is preferable to carry out at a temperature of ° C. The reaction time is 0.5 to 24.
It is preferable to set it to about an hour.

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 preferably in the range of 0.001 to 90% by weight, particularly preferably 1 to 50% by weight.

[0032]

EXAMPLES 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) 1,1,3,3-tetramethyldisiloxane 9 was placed in a 100 ml two-necked flask equipped with a cooling tube and a magnetic stirrer.
7 g (0.72 mol) and 30 g of 1-hexene (0.3 g)
6 mol), 0.72 g (7.2 mmol) of a 5% solution of chloroplatinic acid in isopropyl alcohol was added, and the mixture was stirred in an ice water bath for 16 hours. Colorless transparent liquid 5 by distillation
2.8 g (bp 55-61 ° C./4 Torr) (yield 67
%). The obtained product was confirmed to be 1-hexyl-1,1,3,3-tetramethyldisiloxane by IR and NMR spectra.

(2) 10 units provided with a cooling pipe and a magnetic stirrer
In a 0 ml two-necked flask, 1-hexyl synthesized in (1) was added.
15 g of 1,1,3,3-tetramethyldisiloxane (6
9 mmol), 12 g of allyl glyceryl ether (91 mmo)
l), 1.8 g of 10% ethanol solution of potassium acetate
(1.8 mmol) and 24 g of isopropyl alcohol, and 0.18 g (0.017 mmol) of a 5% solution of chloroplatinic acid in isopropyl alcohol was added thereto.
Stir for 7 hours. After evaporating the solvent, the reaction product was purified through a silica gel column, and 22 g of a colorless and transparent liquid (yield 93
%). The obtained product was confirmed by IR and NMR spectra to be 3- (3-hexyl-1,1,3,3-tetramethyldisiloxanyl) propyl glyceryl ether (A).

[0035]

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IR (liquid film, cm ^-1 ) 3400 (-OH), 2928 (C-
H), 1256 (Si-Me), 1064, 842, 796 (Si-O-Si)

[0037] ¹ H-NMR [[delta] ppm, in CDCl _3, CHCl ₃ standard (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

The 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 22.8, 23.4 , 23.6, 3.18, 33.2 - C H 2 - 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 [δ 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 (1) of Example 1 (yield 70%).

(2) 3- (3-decyl-1,1,3,3-tetramethyldisiloxanyl) propyl glyceryl ether (B) was synthesized by the same method as in (2) of Example 1. 93%).

[0042]

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IR (liquid film, cm ^-1 ) 3424 (-OH), 2928 (C-
H), 1254 (Si-Me), 1066, 840, 796 (Si-O-Si)

[0044] ¹ H-NMR [[delta] ppm, in CDCl _3, CHCl ₃ standard (7.28 ppm)] 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

[0045]

²⁹ Si-NMR [δ ppm, in CDCl ₃ , TMS standard (0 ppm)] 2.22, 7.89

Example 3 (1) 1-hexadecyl-1,1,3,3-tetramethyldisiloxane was synthesized in the same manner as in (1) of Example 1 (yield 70%).

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

[0049]

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IR (liquid film, cm ^-1 ) 3404 (-OH), 2956 (C-
H), 1254 (Si-Me), 1064, 840, 796 (Si-O-Si)

[0051] ¹ H-NMR [[delta] ppm, in CDCl _3, CHCl ₃ standard (7.28 ppm)] 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

[0052]

²⁹ Si-NMR [δ ppm, in CDCl ₃ , TMS standard (0 ppm)] 7.22, 7.93

Example 4 20 g (30 mmol) of nonadecamethylnonasiloxane was placed in a 100 ml two-necked flask equipped with a condenser and a magnetic stirrer.
9.5 g of 0-undecenyl glyceryl ether (39 mm
ol), 0.77 g of a 10% ethanol solution of potassium acetate
(0.78 mmol) and isopropyl alcohol 18.5
g, and 0.20 g (7.7 × 10 ⁻³ mmol) of a 2% solution of chloroplatinic acid in isopropyl alcohol was added, followed by heating and heating. The contents were kept at 40 ° C. and stirred for 3.5 hours. After distilling off the solvent, the obtained reaction product was dissolved in hexane, filtered and the solvent was distilled off. The obtained reaction product was purified by applying to a silica gel column to obtain 21.7 g of a colorless and transparent oil (yield: 80). %). According to IR and NMR spectra, the obtained product was nonadecamethylnonacyloxanylundecylglyceryl ether (D)
Was confirmed.

[0055]

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¹ H-NMR [δppm, 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 [δ ppm, in CDCl ₃ , based on CHCl ₃ (77.2 ppm)] 0.39, 1.26, 1.34, 1.37, 1.98 Si- C H ₃ 18.5 Si- C H ₂ -23.4, 26.3, 29.6, 29.7 , 29.8, 29.9, 33.7 - 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

[0058] ²⁹ Si-NMR [[delta] ppm, in CDCl _3, TMS standard (0 ppm)] 7.28, 7.60 a, i -21.4, -21.7, -21.9, -22.0, -22.1 b, c, d, e, f, g, h

[0059]

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Example 5 In the same manner as in Example 4, pentamethyldisiloxanylundecylglyceryl ether (E) was synthesized (yield: 56%).

[0061]

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IR (liquid film, cm ^-1 ) 3394 (-OH), 2926, 28
60 (CH), 1254 (Si-Me), 1062, 843 (Si-O-Si)

[0063] ¹ H-NMR [[delta] ppm, in CDCl _3, CHCl ₃ standard (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

[0064] 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 23.4, 26.3, 29.6, 33.6 - 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 [δ ppm, in CDCl ₃ , TMS standard (0 ppm)] 6.97, 7.61

Example 6 In the same manner as in Example 4, undecamethylpentasiloxanylundecylglyceryl ether (F) was synthesized (yield: 48%). At this time, since 1,5-dihydrodecamethylpentasiloxane was contained in the raw material undecamethylpentasiloxane, the 1,5-bis [1
1- (2,3-dihydroxypropoxy) undecyl]
Decamethylpentasiloxane (G) was obtained. The obtained 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 NMR spectra.

[0067]

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IR (liquid film, cm ^-1 ) 3406 (-OH), 2962, 29
26, 2860 (CH), 1260 (Si-Me), 1035, 801 (Si-O-Si)

¹ H-NMR [δ ppm, based on CHCl _{3 in} CDCl ₃ (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

[0070] ¹³ C-NMR [[delta] ppm, in CDCl _3, CHCl ₃ standard (77.2ppm)] 0.37, 1.94, 1.24, 1.32, 1.35 Si- C H 3 18.5 Si- C H 2 - 23.4, 26.3, 29.58, 29.66 , 29.77, 29.84, 33.6 - 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 [δ ppm, in CDCl ₃ , TMS standard (0 ppm)] 7.28, 7.61 a, e -21.4, -21.7, -22.2 b, c, d

[0072]

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IR (liquid film, cm ^-1 ) 3404 (-OH), 2924, 28
56 (CH), 1260 (Si-Me), 1080, 1034, 802 (Si-O-Si)

[0074] ¹ H-NMR [[delta] ppm, 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) CH 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 [δ ppm in CDCl ₃ , based on CHCl ₃
(77.2ppm)]

[0076]

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[0077] 0.35, 1.34 a, b 1.24 c 18.4 Si- C H 2 - 23.4, 26.2, 29.56, 29.64, 29.73, 29.76, 29.8 - 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 [δ ppm, in CDCl ₃ , TMS standard (0 ppm)] -22.3 C -21.7 B 7.62 A

Example 7 30 g (18.5 mmol) of α, ω-dihydrodimethylpolysiloxane (average chain length: 20) was placed in a 100 ml two-necked flask equipped with a condenser and a magnetic stirrer, and 10-undecenyl glyceryl ether. 8 g (48.3 mmol), 0.95 g (0.97 g) of a 10% ethanol solution of potassium acetate.
mmol) and 24 g of isopropyl alcohol, and 0.2% of a 2% solution of chloroplatinic acid in isopropyl alcohol was added.
26 g (0.010 mmol) was added, and the mixture was heated and heated. The content was kept at 50 ° C. and stirred for 2 hours. After distilling off the solvent, unreacted 10-undecenylglyceryl 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.

From the IR and NMR spectra, it was confirmed that the obtained product was α, ω-bis [11- (2,3-dihydroxypropoxy) undecyl] dimethylpolysiloxane (average chain length 20) (H). did.

[0081]

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IR (liquid film, cm ^-1 ) 3420 (-OH), 2964, 29
28, 2860 (CH), 1262 (Si-Me), 1100, 1026, 802 (Si-OS
i)

[0083] ¹ H-NMR [[delta] ppm, in CDCl _3, 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

[0084] 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 - 23.4, 26.3, 29.6, 29.8, 33.7 - 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 [δ ppm, in CDCl ₃ , TMS
Standard (0 ppm))

[0086]

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Example 8 In the same manner as in Example 7, α, ω-bis [11-
(2,3-dihydroxypropoxy) undecyl] dimethylpolysiloxane (average chain length 50) (I) was synthesized (yield 95.3%).

[0088]

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IR (liquid film, cm ^-1 ) 3420 (-OH), 2968, 29
32 (CH), 1264 (Si-Me), 1094, 1020, 866, 802 (Si-O-Si)

¹ H-NMR [δppm, based on CHCl _{3 in} CDCl ₃ (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-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

[0091] 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 23.4, 26.3, 29.6, 29.8, 33.7 - _{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))

[0093]

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Example 9 (1) 32.8 g (56.6 mmol) of α, ω-dihydrohexadecamethyloctasiloxane and 4.0 g of 1-decene were placed in a 50 ml two-necked flask equipped with a condenser and a magnetic stirrer.
(28.5 mmol), and 3.0 mg of chloroplatinic acid was added thereto.
(5.8 × 10 ⁻³ mmol) was added, and the mixture was stirred in a water bath for 6 hours. By distillation, 11.0 g of a colorless transparent liquid (bp 160
° C / 0.005 Torr) (yield 54%). The obtained product was confirmed to be 1-decyl-15-hydrohexadecamethyloctasiloxane by IR and NMR spectra.

(2) A 50 equipped with a cooling pipe and a magnetic stirrer
1-decyl-15 synthesized in (1) was placed in a ml two-necked flask.
-10 g of hydrohexadecamethyloctasiloxane (1
(3.9 mmol), 4.4 g (18.0 mmol) of 10-undecenyl glyceryl ether, 0.35 g (0.36 mmol) of a 10% ethanol solution of potassium acetate and 10 g of isopropyl alcohol were charged, and 2 g of chloroplatinic acid was added thereto. %
0.093 g of isopropyl alcohol solution (3.6 × 1
0 ^-3 mmol), and the mixture was heated and heated. The temperature of the contents is 40
C. and stirred at 40.degree. C. for 3 hours. After evaporating the solvent,
The reaction product was purified through a silica gel column to obtain 11.8 g (88% yield) of a colorless and transparent oil. The obtained purified product was confirmed to be 15-decylhexadecamethyloctasiloxanylundecylglyceryl ether (J) by IR and NMR spectra.

[0096]

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IR (liquid film, cm ^-1 ) 3400 (-OH), 2964, 29
28, 2860 (CH), 1262 (Si-Me), 1096, 1026, 840, 804 (Si
-O-Si)

[0098] 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 [δ ppm, in CDCl _{3 based} on CHCl ₃ (77.2 ppm)] 0.38, 1.25, 1.35 Si- C H ₃ 14.3- C H ₃ 18.5 Si- C H ₂ 22.9, 23.4, 26.3, 29.5 , 29.6, 29.7, 29.8, 29.9 , 32.1, 33.6 - C H 2 - 64.5 C H 2 OH 70.7 C HOH 72.1 CH 2 CH 2 O 72.7 CH C H 2 O

Example 10 A 100 ml two-necked flask equipped with a cooling tube and a magnetic stirrer was charged with the compound of the formula (K ').

[0101]

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15 g (4.4 mmol) of an organohydrogensiloxane represented by the following formula: 8.1 g (33 mmol) of 10-undecenylglyceryl ether, 1 g of potassium acetate
0.65 g (0.66 mmol) of a 0% ethanol solution and 50 g of isopropyl alcohol were charged, and 0.17 g of a 2% chloroplatinic acid solution in isopropyl alcohol (6.
6 × 10 ⁻³ mmol), and the mixture was heated and heated. The contents were kept at 40 ° C. and stirred for 2.5 hours. After the solvent was distilled off and activated carbon treatment was performed, unreacted 10
-Undecenyl glyceryl ether was distilled off to obtain a brown viscous substance. The obtained product was confirmed to be a compound (K) represented by the following formula by IR and NMR spectra.

[0103]

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IR (liquid film, cm ^-1 ) 3400 (-OH), 2968, 29
32, 2860 (CH), 1262 (Si-Me), 1096, 1022, 844 (Si-OS
i)

[0105] ¹ H-NMR [[delta] ppm, in CDCl _3, 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 (yield 97%).

[0107]

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IR (liquid film, cm ^-1 ) 3420 (-OH), 2968, 29
32, 2860 (CH), 1264 (Si-Me), 1096, 1026, 802 (Si-OS
i)

¹ H-NMR [δ ppm, in CDCl _{3 based} on CHCl ₃ (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 3.38-3.50 (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

Example 12 A compound (M) represented by the following formula was synthesized in the same manner as in Example 10 (yield: 99%).

[0111]

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IR (liquid film, cm ^-1 ) 3424 (-OH), 2964, 29
28, 2860 (CH), 1262 (Si-Me), 1090, 1034, 864, 798 (Si
-O-Si)

[0113] ¹ H-NMR [[delta] ppm, in CDCl _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 A 100 ml flask equipped with a cooling tube and a magnetic stirrer was charged with a compound of the formula (N ').

[0115]

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10 g (7.5 mmol) of the organohydrogensiloxane and 8.4 g of decene (60.2
mmol), and 8.3 × 10 ⁻³ ml of a 2% chloroplatinic acid solution in isopropyl alcohol was added thereto, followed by heating to 40 ° C. After 2 hours, 20 g of isopropyl alcohol, 4.6 g (35 mmol) of allyl glyceryl ether, 0.44 g of a 10% ethanol solution of potassium acetate and 0.12 ml of a 2% isopropyl alcohol solution of chloroplatinic acid were added, and 40 g of the mixture was added.
Heated to ° C. After 2 hours, isopropyl alcohol was distilled off, and after treatment with activated carbon, 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.

[0117]

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IR (liquid film, cm ^-1 ) 3400 (-OH), 2965, 29
25, 2860 (CH), 805, 850, 1260 (Si-Me), 1090, 1030 (Si
-O-Si)

¹ H-NMR [δ ppm, in CDCl ₃ , based on CHCl ₃
(7.28 ppm)]

[0120]

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Example 14 Example 13 was repeated except that 11.7 g (83 mmol) of decene and 1.1 g (8.3 mmol) of allyl glyceryl ether were used.
The reaction was carried out in the same manner as in the above to obtain 23 g of a compound represented by the following (O).

[0122]

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IR (liquid film, cm ^-1 ) 3425 (-OH), 2970, 29
30, 2865 (OH) 805, 845, 1260 (Si-Me), 1095, 1025 (Si-O-Si)

¹ H-NMR [δ ppm, in CDCl ₃ , based on CHCl ₃
(7.28 ppm)]

[0125]

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Test Example 1 The compounds of the present invention (A) 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, emulsified by shaking well at room temperature, and then 1
The mixture was allowed to stand for a day, and the emulsion stability was examined. Silicone is KF-96 (5cs) and KF-96 (50cs) manufactured by Shin-Etsu Chemical Co., Ltd.
It was used. Table 1 shows the results.

[0127]

[Table 1]

◎ No separation ○ Slightly separated △ Almost separated × Completely separated

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

Example 15 A liquid foundation having the composition shown in Table 2 below was prepared, and its emulsion stability was examined. Table 3 shows the results.
The manufacturing method is as follows. (Preparation method) Powder and fats and oils were mixed, and the powder was uniformly dispersed by stirring and heated to 40 ° C.
The adjusted aqueous phase was added to emulsify. Thereafter, the mixture was filled in a glass container and allowed to cool at room temperature.

[0131]

[Table 2]

* Cosmetic powder having the following composition was used as a raw material powder, and 2% methyl hydrogen polysiloxane (KF99 manufactured by Shin-Etsu Chemical Co., Ltd.) was added to the powder, followed by heat treatment. Was used.

Titanium oxide 8 (parts by weight) Talc 4 Bengala 1.2 Yellow iron oxide 2.6 Black iron oxide 0.2 (Result)

[0134]

[Table 3]

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

[0136]

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

──────────────────────────────────────────────────続 き Continued on the front page (51) Int.Cl. ⁶ Identification symbol FI A61K 7/00 A61K 7/00 J (56) References JP-A-57-149290 (JP, A) JP-A-63-113022 ( JP, A) (58) Field surveyed (Int. Cl. ⁶ , DB name) C08G 77/14 C08G 77/38

Claims (2)

(57) [Claims] 1. The following general formula (I): Wherein at least one of the remaining groups is a linear or branched hydrocarbon group having 6 to 30 carbon atoms, and all others are methyl groups. l, m and n are numbers from 0 to 2000, and when l + m + n = 0, R ^{1 to} R ³ , R
At least one of ¹⁰ to R ¹² is a group (IIb). ]
A siloxane derivative represented by the formula: 2. A method according to claim 1, wherein at least one of R ^{1 to} R ¹² other than the group represented by the formula (IIb) is a hexyl group, a decyl group or a hexadecyl group, and all others are methyl groups. The siloxane derivative according to the above.