JP2587797B2 - Cosmetics - Google Patents

Description

DETAILED DESCRIPTION OF THE INVENTION

[0001]

The present invention is useful for emulsifiers.
The present invention relates to a novel siloxane derivative having a surfactant activity, 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. Among the above, as the compound having a nonionic hydrophilic group, a polyoxyalkylene-modified silicone-based surfactant having a polyoxyalkylene group as a hydrophilic group is known. When used as an emulsifier, it was 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 conceivable, but silicone surfactants having a polyhydric alcoholic hydroxyl group as a hydrophilic group are currently almost unknown. The (poly) glycerin-modified silicone described in JP-B-62-34039 and JP-A 57-2
It is only known that the sorbitan-modified silicone described in JP 09295 has a surface-active action.

Also, silicone compounds modified with a glyceryl group, which is a polyhydric alcoholic hydroxyl group, are known, and are disclosed in JP-A-62-195389, JP-A-64-16793 and JP-A-63-101388. Although described in the gazette, these compounds are surface modifiers for synthetic resins utilizing the reactivity of hydroxyl groups, and their surface activity is unknown.

As described above, nonionic silicone surfactants having satisfactory performance are almost none at present.

[0006]

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. They found something and completed the present invention.

That is, the present invention provides the following general formula (1)

[0008]

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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) And the remainder is a linear, branched or cyclic hydrocarbon group having 1 to 30 carbon atoms or the following formula (3):

[0010]

Embedded image -XR ¹⁵ (3)

(Wherein X is an ether bond and / or
A divalent hydrocarbon group containing a tell bond is represented by R ^FifteenHas 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 is a group (2). However
Then R¹~ R¹²One of which is Q is trimethylene and R¹³
And R¹⁴Is a group (2), both of which are hydrogen atoms, and
Except when all are methyl groups. ]
Loxane derivative, method for producing the same, and cosmetic containing the same
Offer a fee.

In the general formula (1), Q is
Examples of the divalent hydrocarbon group having 3 to 20 carbon atoms include trimethylene.
, Tetramethylene, pentamethylene, hexamethylene
, Heptamethylene, octamethylene, nonamethylene,
Decamethylene, undecamethylene, dodecamethylene, te
Toradecamethylene, Hexadecamethylene, Octadecame
Linear alkylene group such as styrene; propylene, 2-methyl
Trimethylene, 2-methyltetramethylene, 2-methyl
Branched chains such as pentamethylene and 3-methylpentamethylene
Examples include an alkylene group. R¹³Or R¹⁴Indicated by
Examples of the hydrocarbon group having 1 to 5 carbon atoms include methyl, ethyl,
Propyl, butyl, pentyl, isopropyl, sec-butyl
Tyl, tert-butyl, neopentyl, cyclopentyl, etc.
Linear, branched or cyclic alkyl groups.
An ether bond and / or an ester bond represented by X
As a divalent hydrocarbon group containing-(CH_Two)_r-(OC_TwoH_Four)_p-(OC_ThreeH
₆)_q-O- (where p and q are numbers from 0 to 50, r is 3
Integer of 20 or more),-(CH_Two) _r-O-CO-,-(CH_Two)_r-COO-
And the like. Furthermore, a linear or branched chain having 1 to 30 carbon atoms
Or, as the cyclic hydrocarbon group, methyl, ethyl,
Pill, butyl, pentyl, hexyl, octyl, deci
, Dodecyl, tetradecyl, hexadecyl, octade
Sill, eicosyl, doeicosyl, tetraeicosyl,
Hexaeicosyl, octaeicosyl, triacontyl
Linear alkyl groups such as isopropyl, sec-butyl, ter
t-butyl, neopentyl, 1-ethylpropyl, 1-
Branched-chain alkyl groups such as heptyldecyl; cyclopentene
, Cyclohexyl, abiethyl, cholesteryl, etc.
Alkyl group and the like. And l, m and n
Is the organohydrogenpolysiloxane used as the raw material
From the viewpoint of easy availability and operability during manufacturing,
It is preferable that the upper limit be 2000 or less.

The siloxane derivative (1) of the present invention can be produced, for example, according to the following reaction formula. (1) Siloxane derivative (1a) having no group (3)
Formula:

[0014]

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[Wherein, 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 (2), 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 group (2). However, ^one of R ¹ ′ to R ¹² ′
One is a group (2) 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 (2 ') is reacted with an organohydrogenpolysiloxane (4) having at least one silicon-hydrogen bond to obtain a siloxane derivative (1a) having no group (3). ) Is obtained.

(2) Production method of siloxane derivative (1b) having group (3):

[0018]

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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 ′ is 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 (2), at least one of the remaining groups is a group (3), 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 (2), and at least one of the remaining groups is a group (3). ]

That is, by reacting an alkenyl glyceryl ether (2 ') and a compound (3') with an organohydrogenpolysiloxane (4 ') having at least two silicon-hydrogen bonds, the group (3) is formed. The siloxane derivative (1b) having the above is obtained. here,
Compound (2 ′) and compound (3 ′) can be reacted with compound (4 ′) first, and simultaneously with compound (4 ′)
May be reacted.

The starting material organohydrogenpolysiloxane (4) or (4 ') has at least one compound per molecule.
Having at least two [(4 ')] or at least two [(4')] silicon-hydrogen bonds,
There is no particular limitation on the molecular structure and the like, and various known ones can be used. Are preferred.

As the compound (2 '), a compound represented by the general formula (2')
In which Q ′ is an ω-alkenyl group. Further, as the compound (3 ′), X ′ in the general formula (3 ′) is

[0023]

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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; ruthenium, rhodium, palladium, osmium, iridium And 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 (4) or (4 ') and the alkenyl glyceryl ether (2') and / or the compound (3 ').
Any amount may be used as long as it is a sufficient amount to promote the reaction with olefin.
The range of 0 ^-6 to 10 ^-1 mol 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 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 (2 ') and / or the compound (3') to the organohydrogenpolysiloxane (4) or (4 ') used in this reaction is such that the obtained siloxane derivative (1) is As long as there is a sufficient amount of alkenyl glyceryl ether (2 ') in the molecule to have at least one silicon-bonded glyceryl group (2), other ratios may be arbitrary.
When emulsifying a carbon-based oil agent using the obtained compound (1), the total number of units of the group (2) and the group (3) is set to be equal to or more than the number of remaining dimethylsiloxane units. In the case of emulsifying a silicone-based oil agent, the total number of units of the groups (2) and (3) is preferably within a range of 1/5 or less of the number of remaining dimethylsiloxane units.

Although the hydrosilylation proceeds at 0 to 200 ° C., the hydrosilylation proceeds from 0 to 100
C. is preferably performed at a temperature of. The reaction time is 0.5 to 24.
It is preferable to set it to about an hour.

The siloxane derivative (1) 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 (1) 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.

[0029]

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 97 was placed in a 100 ml two-necked flask equipped with a cooling tube and a magnetic stirrer.
g (0.72 mol) and 30 g of 1-hexene (0.36 mol).
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 52.8 by distillation
g (bp 55-61 ° C./4 Torr) (67% yield).
The obtained product was identified by IR and NMR spectra as 1
-Hexyl-1,1,3,3-tetramethyldisiloxane.

(2) 100 equipped with a cooling pipe and a magnetic stirrer
1-Hexyl-synthesized in (1)
15 g of 1,1,3,3-tetramethyldisiloxane (6
9 mmol), 12 g of allyl glyceryl ether (91 mmo)
l) 1.8 g of a 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).

[0032]

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IR (liquid film, cm ^-1 ) 3400 (-OH) 2928 (CH) 1256 (Si-Me) 1064, 842, 796 (Si-O-Si) ¹ H-NMR [δ ppm, CDCl ₃ among, 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 13 C-NMR [[delta] ppm, in CDCl _3, CHCl ₃ standard (7
7.2 ppm)] _{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, 31.8, 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 [δppm, in CDCl ₃ , TMS standard (0p
pm)] 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) According to a method similar to (2) of Example 1, 3- (3-
Decyl-1,1,3,3-tetramethyldisiloxanyl) propyl glyceryl ether (B) was synthesized (93% yield).

[0035]

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IR (liquid film, cm ^-1 ) 3424 (-OH) 2928 (CH) 1254 (Si-Me) 1066, 840, 796 (Si-O-Si) ¹ H-NMR [δ ppm, CDCl ₃ among, 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 13 C-NMR [[delta] ppm, in CDCl _3, CHCl ₃ standard (7
7.2 ppm)] _{0.42,0.50 Si- C H 3 14.2,14.3 - C} H 3, C H 2 -CH 2 CH 2 O 22.8,23.4,29.48, 29.53, 29.
_{75,29.81,32.1,33.6 - C H 2 - 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, in CDCl _3, TMS standard (0p
pm)] 7.22, 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) 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).

[0038]

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IR (liquid film, cm ^-1 ) 3404 (-OH) 2956 (CH) 1254 (Si-Me) 1064, 840, 796 (Si-O-Si) ¹ H-NMR [δ ppm, CDCl ₃ among, 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 13 C-NMR [[delta] ppm, in CDCl _3, CHCl ₃ standard (7
7.2 ppm)] _{0.47,0.54 Si- C H 3 14.3,14.4 - C} H 3, C H 2 -CH 2 CH 2 O 22.9,23.5,29.5, 29.6, 29.8
0, 29.84, 29.9, 32.1, 33.6- C
_{H 2 - 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, in CDCl _3, TMS standard (0p
pm)] 7.22, 7.93

EXAMPLE 4 Nonadecamethylnonasiloxane (20 g, 30 mmol) 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 evaporating 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). %). The resulting product is
It was confirmed by IR and NMR spectra that it was nonadecamethylnonacyloxanylundecylglyceryl ether (D).

[0041]

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¹ H-NMR [δ ppm, in CDCl ₃ , CHC
l 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 (7
7.2 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

[0043]

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

[0045]

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IR (liquid film, cm ^-1 ) 3394 (-OH) 2926, 2860 (CH) 1254 (Si-Me) 1062, 843 (Si-O-Si) ¹ H-NMR [δ ppm, CDCl ₃ among, 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 13 C-NMR [[delta] ppm, in CDCl _3, CHCl ₃ standard (7
7.2 ppm)] _{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 [[delta] ppm, in CDCl _3, TMS standard (0p
pm)] 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.

[0048]

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IR (liquid film, cm ^-1 ) 3406 (-OH) 2962, 2926, 2860 (CH) 1260 (Si-Me) 1035, 801 (Si-O-Si) ¹ H-NMR [δ ppm, 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 (7
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

[0050]

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[0051]

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IR (liquid film, cm ^-1 ) 3404 (-OH) 2924, 2856 (CH) 1260 (Si-Me) 1080, 1034, 802 (Si-O-Si) ¹ H-NMR [δ 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 (7
7.2 ppm)]

[0053]

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[0054] 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 (0p
pm)]-22.3 C-21.7 B 7.62 A

Example 7 30 g (18.5 mmol) of α, ω-dihydrodimethylpolysiloxane (average chain length: 20) in a 100 ml two-necked flask equipped with a condenser and a magnetic stirrer, 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 thereto.
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 the solvent was distilled off, 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 analyzed by IR and NMR spectra to find α, ω
-Bis [11- (2,3-dihydroxypropoxy) undecyl] dimethylpolysiloxane (average chain length 20)
(H) was confirmed.

[0056]

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IR (liquid film, cm ^-1 ) 3420 (-OH) 2964, 2928, 2860 (CH) 1262 (Si-Me) 1100, 1026, 802 (Si-O-Si) 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 ¹³ C-NMR [[delta] ppm, in CDCl _3, CHCl ₃ standard (77.2ppm)] 0.39,1.23,1. _{6 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

[0058]

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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%).

[0060]

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IR (liquid film, cm ^-1 ) 3420 (-OH) 2968, 2932 (CH) 1264 (Si-Me) 1094, 1020, 866, 802 (Si-OS)
i) 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-O 2.20 (br, 2H) CH 2 -O H 2.63 (br, 2H) CH-O H 3.38-3.60 ( m, 8H) C H 2 -O 3.60-3.81 (m, 4H) C H 2 -OH 3.81-3.97 (m, ^{2H) C H -OH 13 C-} NMR [[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

[0062]

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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) (54% yield). The obtained product was analyzed by IR and NMR spectra for 1-decyl-
It was confirmed to be 15-hydrohexadecamethyloctasiloxane.

(2) 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 distilling off the solvent, the reaction product was purified through a silica gel column to obtain 11.8 g of a colorless and transparent oil (88% yield). The obtained purified product was confirmed to be 15-decylhexadecamethyloctasiloxanylundecylglyceryl ether (J) by IR and NMR spectra.

[0065]

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IR (liquid film, cm ^-1 ) 3400 (-OH) 2964, 2928, 2860 (CH) 1262 (Si-Me) 1096, 1026, 840, 804 (Si-OS)
i) 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 [[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 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 C H 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 ').

[0068]

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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 distilling off the solvent and performing an activated carbon treatment, 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.

[0070]

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IR (liquid film, cm ^-1 ) 3400 (-OH) 2968, 2932, 2860 (CH) 1262 (Si-Me) 1096, 1022, 844 (Si-O-Si) 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%).

[0073]

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IR (liquid film, cm ^-1 ) 3420 (-OH) 2968, 2932, 2860 (CH) 1264 (Si-Me) 1096, 1026, 802 (Si-O-Si) ¹ H-NMR [ [delta] ppm, in CDCl _3, CHCl ₃ standard (7.28 ppm)] 0.00 (s, about _{390H) Si-C H 3 0.35-0.50} (m, 8H) Si-C H 2 1.08- 1.39 (br, 64H) -C H 2 - 1.39-1.62 (br, 8H) C H 2 -CH 2 O 1.96-2.29 (br, 4H) 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%).

[0076]

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IR (liquid film, cm ^-1 ) 3424 (-OH) 2964, 2928, 2860 (CH) 1262 (Si-Me) 1090, 1034, 864, 798 (Si-OS)
i) ¹ H-NMR [δ ppm, based on CHCl _{3 in} CDCl ₃ (7.28 ppm)] 0.00 (s, about 510 H ) Si—CH ₃ 0.34-0.55 (m, 8 H) 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 ').

[0079]

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10 g (7.5 mmol) of the organohydrogensiloxane represented by the following formula, 8.4 g of decene (60.2 g)
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, activated carbon treatment was performed, and unreacted allyl glyceryl luter 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.

[0081]

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IR (liquid film, cm ^-1 ) 3400 (-OH) 2965, 2925, 2860 (CH) 805, 850, 1260 (Si-Me) 1090, 1030 (Si-O-Si)

[0083]

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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 conducted in the same manner as in the above, to obtain 23 g of a compound represented by the following formula (O).

[0085]

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IR (liquid film, cm ^-1 ) 3425 (-OH) 2970, 2930, 2865 (O-H) 805, 845, 1260 (Si-Me) 1095, 1025 (Si-O-Si)

[0087]

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

[0090]

[Table 1]

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

[0094]

[Table 2]

* Cosmetic powder having the following composition was used as a raw material powder, and 2% methyl hydrogen polysiloxane (KF-99 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)

[0096]

[Table 3]

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.

[0098]

As described above, the novel siloxane derivative (1) of the present invention is a suitable nonionic surfactant 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 number Agency reference number FI Technical display location C08G77 / 38 NUF C08G77 / 38 NUF C08L 83/04 LRR C08L 83/04 LRR

Claims (3)

(57) [Claims] 1. The following general formula (1):(Wherein Q represents a divalent hydrocarbon group having 3 to 20 carbon atoms,
R¹³And R¹⁴Represents a hydrogen atom or a carbon atom having 1 to 5 carbon atoms, respectively.
Represents a hydride group, at least one of which is a hydrogen atom
is there. ), And the remainder is a group having 1 to 30 carbon atoms.
A linear or branched hydrocarbon group of the formula or the following formula (3):^Fifteen (3) (wherein X contains an ether bond and / or an ester bond)
A divalent hydrocarbon group represented by R ^FifteenIs a linear chain having 1 to 30 carbon atoms or
Shows a branched-chain hydrocarbon group. ).
l, m and n each represent a number from 0 to 2,000, and l + m
When + n = 0, R¹~ R^Three, R^Ten~ R¹²Less of
One of them is group (2). Where R¹~ R¹²Out of
At least one of Q is trimethylene and R¹³And R¹⁴But
When the groups (2) are both hydrogen atoms,
At least 30 straight-chain or branched-chain hydrocarbon groups
One is a straight-chain or branched-chain hydrocarbon having 6 to 30 carbon atoms.
Elementary group. ] The siloxane derivative represented by
Cosmetics characterized by that. 2. The following general formula (1b):Wherein at least one has 6 to 3 carbon atoms.
0 linear or branched hydrocarbon group or the following formula (3):^Fifteen (3) (wherein X contains an ether bond and / or an ester bond)
A divalent hydrocarbon group represented by R ^FifteenIs a straight chain having 1 to 30 carbon atoms,
Shows a branched or cyclic hydrocarbon group. )
Yes, all the rest are methyl groups. l, m and n are 0
A number not less than 2000 and not more than 2000, and when l + m + n = 0,
R¹~ R^Three, R^Ten~ R¹²At least one of the groups (2
b). ] The siloxane derivative represented by
Cosmetics characterized by that. 3. The following general formula (1c):And the rest are all methyl groups
Or at least one of C 6-30 straight chain or
Is a branched-chain hydrocarbon group, and is represented by the following formula (3):^Fifteen (3) (wherein X contains an ether bond and / or an ester bond)
A divalent hydrocarbon group represented by R ^FifteenIs a straight chain having 1 to 30 carbon atoms,
Shows a branched or cyclic hydrocarbon group. Group represented by)
And all others are methyl groups. l, m and n are 0 or more
It indicates a number of 2000 or less, and when l + m + n = 0, R¹
~ R^Three, R^Ten~ R¹²At least one of the groups (2c)
It is. ] The siloxane derivative represented by
And a cosmetic.