JP2601738B2 - Cosmetics - Google Patents

Description

DETAILED DESCRIPTION OF THE INVENTION

[0001]

BACKGROUND OF THE INVENTION 1. Field of the Invention The present invention relates to a cosmetic composition which has no stickiness, gives a refreshing feel and is stable.

[0002]

2. Description of the Related Art Oily gel cosmetics conventionally used are known to form an oil film on the skin surface, prevent water evaporation, have excellent water repellency, and have little makeup loss. Has features. However, the oily gel cosmetic has a problem that the oily component has a strong oily feeling and a sticky feeling when applied. On the other hand, silicone oil is known as an oily base excellent in lubricity and water repellency, gives a refreshing feel and improves oil resistance. However, when silicone oil is used as an oil component, it is difficult to gel uniformly, and furthermore, the formed gel also lacks stability and has a drawback that the silicone oil exudes.

[0003] Accordingly, an object of the present invention is to obtain a gel cosmetic having excellent stability while taking advantage of the characteristics of oil resistance, water resistance and excellent feel possessed by silicone oil.

[0004]

In view of the above circumstances, the present invention has been intensively studied to develop a stable gel cosmetic containing silicone oil. It has been found that a composition containing an organically modified silicone of the formula (1) forms a stable gel and is excellent in water resistance, oil resistance, usability, and stability over time, and has completed the present invention.

That is, the present invention provides the following component (A):
(B) and (C) (A) Oil gelling agent (B) The following general formula (1)

[0006]

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[Wherein, R¹~ R¹²At least one of
Is the following formula (2) -Q-O-CH_TwoCH (OR¹³) CH_TwoOR¹⁴ (2) (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. ), The remainder being 1 to 30 carbon atoms
A linear, branched or cyclic hydrocarbon group of the formula:
(3) -X-R^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. )
And l, m, and n represent numbers from 0 to 2,000,
R when l + m + n = 0¹~ R^Three, R^Ten~ R¹²Of which
At least one represents a group (2). Where R¹~ R¹²
One of which is Q is trimethylene and R¹³And R¹⁴Together
Group (2) which is a hydrogen atom, and all of the rest are methyl
Except when it is a group. Alkyl glyceryl represented by the formula
It is intended to provide a cosmetic composition containing (C) silicone oil.

As the oil gelling agent of the component (A) used in the present invention, any general oil gelling agent can be used. Specifically, 12-hydroxystearic acid; higher fatty acid esters of dextrin with palmitic acid, stearic acid and the like; dialkyl phosphate polyvalent metal salts such as aluminum dicetyl phosphate and calcium dicetyl phosphate (Japanese Patent Publication No. 1-41222); Polyalkylaluminum dialkyl phosphate (JP-A-1-193278); dibutylamide lauroylglutamate (manufactured by Ajinomoto Co., Inc., GP-
1); metal soaps such as aluminum stearate and the like are exemplified. One or more oil gelling agents may be used, and the compounding amount is preferably 0.5 to 20% by weight (hereinafter simply indicated by "%"). Outside this range, a stable gel may not be obtained, which is not preferred.

The alkyl glyceryl ether-modified silicone of the component (B) used in the present invention is represented by the above formula (1).
Examples of the divalent hydrocarbon group of 20 include trimethylene, tetramethylene, pentamethylene, hexamethylene, heptamethylene, octamethylene, nonamethylene, decamethylene, undecamethylene, dodecamethylene, tetradecamethylene, hexadecamethylene, octadecamethylene, and the like. And a branched alkylene group such as propylene, 2-methyltrimethylene, 2-methyltetramethylene, 2-methylpentamethylene, and 3-methylpentamethylene. 1 to ¹³ carbon atoms represented by R ¹³ or R ¹⁴
5 as the hydrocarbon group, methyl, ethyl, propyl,
Butyl, pentyl, isopropyl, sec-butyl, t
Examples thereof include linear, branched or cyclic alkyl groups such as tert-butyl, neopentyl, and cyclopentyl. The divalent hydrocarbon group containing an ether bond and / or an ester bond represented by X includes-(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. Can be 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 Linear alkyl groups such as eicosyl, hexaeicosyl, octaeicosyl, and triacontyl; isopropyl, sec-butyl, tert-
Examples thereof include a branched alkyl group such as butyl, neopentyl, 1-ethylpropyl, and 1-heptyldecyl; and a cyclic alkyl group such as cyclopentyl, cyclohexyl, abiethyl, and cholesteryl. L, m, and n are 0 or more and 200 in view of the availability of the raw material organohydrogenpolysiloxane and the operability at the time of production.
It is preferable to set the range to 0 or less.

In the alkyl glyceryl ether-modified silicone (1), at least one of R ^{1 to} R ¹² is used.
One is preferably a compound in which Q in group (2) is a straight-chain or branched-chain alkyl group having 3 to 20 carbon atoms, and the remainder is a straight-chain or branched-chain alkyl group having 1 to 30 carbon atoms. In the cosmetic of the present invention, as the component (B) when the component (C) having a low silicone oil content is blended, a compound represented by the following formula (4), (5) or (6) is used. Preferably, the compound represented by the formula (5) is particularly preferable in consideration of skin irritation.

[0011]

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[Wherein, R ^1A represents a linear or branched alkyl group having 8 to 24 carbon atoms, s is 0 to 3, and t is 8 to 2;
4, u is 3 to 100, w is 2 to 50, v is 1 / 2w to 6
w and x represent 8 to 18, y represents 8 to 18, and z represents 0 to 1. These alkyl glyceryl ether-modified silicones (1) can be used alone or in combination of two or more.

The alkyl glyceryl ether-modified silicone (1) can be produced, for example, according to the following reaction formula. (A) Method for producing alkyl glyceryl ether-modified silicone (1a) having no group (3)

[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
Indicates a number less than 00. Q 'represents a hydrocarbon group having 3 to 20 carbon atoms and having at least one double bond, R ¹³ and R ¹⁴ are as defined above. At least one of R ¹ ′ to R ¹² ′ is a group (2), and the rest is a group having 1 carbon atom.
Up to 30 linear, branched or cyclic hydrocarbon groups. Provided that ^one of R ¹ ′ to R ¹² ′ is a group (2) in which Q is trimethylene and R ¹³ and R ¹⁴ are both hydrogen atoms;
Except when all the rest are methyl groups. ]

That is, an alkenyl glyceryl ether (2 ') is reacted with an organohydrogen polysiloxane (4) having at least one silicon-hydrogen bond, thereby obtaining an alkyl glyceryl ether modified without an group (3). The silicone (1a) is obtained. (B) Process for producing alkyl glyceryl ether-modified silicone (1b) having group (3)

[0017]

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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; Has the same meaning as described above. 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, and R ¹⁵ has the same meaning as described above. At least one of R ¹ ″ to R ¹² ″ is a group (2), at least one of the remaining is a group (3), and the rest is a linear, branched or cyclic C ^{1 to} C 30 group. Is a hydrocarbon group. ]

That is, by reacting an alkenylglyceryl ether (2 ') and a compound (3') with an organohydrogenpolysiloxane (4 ') having at least two silicon-hydrogen bonds, a group (3) is formed. Alkyl glyceryl ether-modified silicone (1
b) is obtained. Here, either of the compound (2 ') and the compound (3') may be reacted with the compound (4 ') first, or simultaneously with the compound (4').

The raw material organohydrogenpolysiloxane (4) or (4 ') has at least one in its 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.

The compound (2 ') is 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

[0022]

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(R ′ represents an integer of 1 to 18;
And q are the same as described above).

The above-mentioned reactions (a) and (b) are carried out in the presence of a catalyst, and catalysts generally used for hydrosilylation, for example, free radical initiators; photoinitiators;
Metal complex compounds such as ruthenium, rhodium, palladium, osmium, iridium, and platinum; and 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 catalyst may be used in an amount sufficient to promote the reaction between the organohydrogenpolysiloxane (4) or (4 ') and the alkenyl glyceryl ether (2') and / or the compound (3 '). Although not particularly limited, the range is preferably from 10 ^-6 to 10 ^-1 mol per mol of the olefin used.

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 ratio of the alkenyl glyceryl ether (2 ') and / or the compound (3') to the organohydrogenpolysiloxane (4) or (4 ') used in this reaction is determined by the ratio of the obtained alkyl glyceryl ether-modified silicone ( As long as 1) has a sufficient amount of alkenyl glyceryl ether (2 ′) to have at least one silicon-bonded glyceryl group (2) in the molecule, the ratio of the other compounds may be arbitrary, but the resulting compound (1 )), When emulsifying a carbon-based oil, the groups (2) and (3)
In the case where the total number of the units is equal to or more than the number of the remaining dimethylsiloxane units and the silicone oil is emulsified, the total number of the units (2) and (3) remains. It is preferable to set the number of dimethylsiloxane units to 1/5 or less. 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.
The reaction time is preferably about 0.5 to 24 hours.

In the present invention, the component (B) acts as a stabilizer and is contained in the cosmetic of the present invention in an amount of 0.1 to 20.
%, Particularly preferably 0.3 to 6%. If it is less than 0.1%, the cosmetic of the present invention cannot be stabilized, and if it exceeds 20%, the viscosity of the whole system becomes extremely high, and the spread at the time of use is poor, giving an oily feeling and sticky feeling. Is not preferred.

The silicone oil (C) used in the present invention is not particularly limited, and any silicone oil conventionally used in cosmetics can be used. Specific examples include dimethylpolysiloxane, methylphenylpolysiloxane, octamethylcyclotetrasiloxane, and decamethylcyclopentasiloxane. Silicone oil may be used alone or in combination of two or more,
It is preferable that the compounding amount be 50 to 99.2%. If this amount is less than 50%, the feel may be poor, which is not preferred.

In the cosmetic of the present invention, in addition to the above essential components,
Depending on the purpose, a polyether-modified silicone, an oil for general cosmetics,
A humectant, an intercellular lipid (ceramide, etc.), an ultraviolet absorber, a chelate, a pH adjuster, a preservative, a thickener, a pigment, a fragrance, a medicinal ingredient, and the like can be appropriately compounded.

The cosmetic of the present invention is produced by mixing and stirring the above-mentioned components according to a conventional method, and can be made into a gel having a uniform appearance. Further, a stable W / O emulsified cosmetic can be obtained by adding an aqueous phase component thereto. Furthermore, an emulsion or cream-like foundation can be obtained by blending a powder, preferably 10 to 40%, more preferably 15 to 30%, with the gel or emulsion. Examples of the powder include powders generally used in cosmetics, for example, extenders such as talc, mica, kaolin, and sericite; inorganic pigments such as titanium oxide, zinc oxide, iron oxide, and ultramarine blue; titanium mica-based pearl pigments; Blue 4
Organic pigments such as No. 04, Red No. 202 and Yellow No. 401 can be exemplified. In the present invention, one or more of the above powders are arbitrarily selected and used.

[0031]

The cosmetic composition of the present invention, which contains a silicone oil and forms a stable gel, has no oily feeling, gives a refreshing feel, and is excellent in stability over time.

[0032]

EXAMPLES Hereinafter, the present invention will be described in more detail with reference to Production Examples and Examples, but the present invention is not limited thereto. In Production Examples 1 to 10, an alkyl glyceryl ether-modified silicone as the component (B) used in the present invention was produced.

Production Example 1 Nonadecamethylnonasiloxane (20 g, 30 mmol) was placed in a 100 ml two-necked flask equipped with a cooling tube and a magnetic stirrer.
9.5 g of 0-undecenyl glyceryl ether (39 mmo
l), 0.77 g of a 10% ethanol solution of potassium acetate (0.7
8 mmol) and 18.5 g of isopropyl alcohol,
0.20 g of a 2% solution of chloroplatinic acid in isopropyl alcohol
(7.7 × 10 ⁻³ mmol), and the mixture was heated and heated. The temperature of the contents was maintained at 40 ° C. and the mixture was stirred for 3.5 hours. After evaporating the solvent, the obtained reaction product was dissolved in hexane, filtered, and the solvent was distilled off. Then, the obtained reaction product was purified through a silica gel column to give 21.7 g of a colorless and transparent oil (yield: 80%).
%). The obtained product was confirmed to be nonadecamethylnonacyloxanylundecylglyceryl ether (D) by IR and NMR spectra.

[0034]

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[0035] 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)
] 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 - 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 -21.4, -21.7, -21.9, -22.0 , −22.1 b, c, d, e, f, g, h

[0036]

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Production Example 2 In the same manner as in Production Example 1, undecamethylpentasiloxanylundecylglyceryl ether (E) was synthesized (yield: 48%).

[0038]

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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, CDCl ₃ among, 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 (δ ppm, in CDCl _{3 based} on CHCl ₃ (77.2 ppm)
] 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 [[delta] ppm, in CDCl _3, TMS standard (0 ppm)] 7.28, 7.61 a, e -21.4, -21.7, -22.2 b , c, d

[0040]

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Production Example 3 In a 100 ml two-necked flask equipped with a condenser and a magnetic stirrer, 30 g (18.5 mmol) of α, ω-dihydrodimethylpolysiloxane (average chain length: 20) and 11.8 g of 10-undecenyl glyceryl ether ( 48.3 mmol), 1 of potassium acetate
0.95 g (0.97 mmol) of a 0% ethanol solution and 24 g of isopropyl alcohol were charged, and 2% of chloroplatinic acid was added thereto.
0.26 g (0.010 mmol) of an isopropyl alcohol solution was added, and the mixture was heated and heated. Keep the temperature of the contents at 50 ° C.
Stirred for 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 give 35.0 g of a colorless, transparent, highly viscous substance (yield: 89.7 g).
%). The obtained product was confirmed to be α, ω-bis [11- (2,3-dihydroxypropoxy) undecyl] dimethylpolysiloxane (average chain length 20) (F) by IR and NMR spectra.

[0042]

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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 [δ 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 (δppm, in CDCl _{3 based} on CHCl ₃ (77.2 ppm)
] 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 [[delta] ppm, in CDCl _3, TMS standard (0 ppm)]

[0044]

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Production Example 4 In the same manner as in Production Example 3, α, ω-bis [11-
(2,3-Dihydroxypropoxy) undecyl] dimethylpolysiloxane (average chain length 50) (G) was synthesized (yield 95.3%).

[0046]

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IR (liquid film, cm ^-1 ) 3420 (-OH) 2968, 2932 (CH) 1264 (Si-Me) 1094, 1020, 866, 802 (Si-O-Si) ¹ H-NMR [δ 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 (δ ppm, in CDCl _{3 based} on CHCl ₃ (77.2 ppm)
] 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 [[delta] ppm, in CDCl _3, TMS standard (0 ppm)]

[0048]

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Production Example 5 (1) 32.8 g (56.6 mmol) of α, ω-dihydrohexadecamethyloctasiloxane and 4.0 g (28.5 mmol) of 1-decene were charged into a 50 ml two-necked flask equipped with a condenser and a magnetic stirrer. 3.0 mg of chloroplatinic acid (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) 10 g (13.9 mmol) of 1-decyl-15-hydrohexadecamethyloctasiloxane synthesized in (G) was placed in a 50 ml two-necked flask equipped with a condenser and a magnetic stirrer.
4.4 g of 1-undecenyl glyceryl ether (18.0 mmo
l), 0.35 g of a 10% ethanol solution of potassium acetate (0.36m
mol) and 10 g of isopropyl alcohol, and 2% chloroplatinic acid solution in isopropyl alcohol 0.093
g (3.6 × 10 ⁻³ mmol) was added and heated to raise the temperature. 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 on a silica gel column,
11.8 g (88% yield) of a colorless and transparent oil was obtained. The obtained purified product was confirmed to be 15-decylhexadecamethyloctasiloxanylundecylglyceryl ether (H) by IR and NMR spectra.

[0050]

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IR (liquid film, cm ^-1 ) 3400 (-OH) 2964, 2928, 2860 (CH) 1262 (Si-Me) 1096, 1026, 840, 804 (Si-O-Si) ¹ H-NMR [ δ ppm, in CDCl _{3 based} on CHCl ₃ (7.28 ppm)] −0.02 −0.10 (m, 48H) Si-C H ₃ 0.50 (t, 4H) Si-C H ₂ -0.87 (t, 3H) -C H ₃ 1.24 (br, 32H) -C H ₂ -1.47-1.66 (m, 2H) C H ₂ -CH ₂ -O 2.32 (t, 1H) CH ₂ -O H 2.71 (d, 1H) CH-O H 3.36− 3.57 (m, 4H) -C H ₂ -O 3.57-3.73 (m, 2H) -C H ₂ -OH 3.73-3.90 (m, 1H) C H -OH ¹³ C-NMR (δppm, in CDCl ₃ CHCl ₃ standards (77.2 ppm)
] 0.38, 1.25, 1.35 Si- C H 3 1.43 - C H 3 1.85 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

Production Example 6 A 100 ml two-necked flask equipped with a cooling tube and a magnetic stirrer was charged with the compound of the formula (I ').

[0053]

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15 g (4.4 mmol) of the organohydrogensiloxane represented by the formula (1), 8.1 g (33 mmol) of 10-undecenylglyceryl ether, 0.65 g (0.66 mmol) of a 10% ethanol solution of potassium acetate and 50 g of isopropyl alcohol were charged. 0.17 g (6.6 × 10 ⁻³ mmol) of a 2% solution of chloroplatinic acid in isopropyl alcohol was added to the mixture.
Heated and heated. The content was kept at 40 ° C. and stirred for 2.5 hours. After distilling off the solvent and treating with activated carbon, unreacted 10-undecenylglyceryl ether was distilled off under reduced pressure to obtain a brown viscous substance. The product obtained is I
The compound was confirmed to be the compound (I) represented by the following formula by R and NMR spectra.

[0055]

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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 [δ 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

Production Example 7 A compound (J) represented by the following formula was synthesized in the same manner as in Production Example 6 (yield: 97%).

[0058]

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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 [δ 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

Production Example 8 A compound (K) represented by the following formula was synthesized in the same manner as in Production Example 6 (yield: 99%).

[0061]

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IR (liquid film, cm ^-1 ) 3424 (-OH) 2964, 2928, 2860 (CH) 1262 (Si-Me) 1090, 1034, 864, 798 (Si-O-Si) 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

Production Example 9 In a 100 ml flask equipped with a cooling tube and a magnetic stirrer, the formula (L ') was added.

[0064]

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10 g (7.5 mmol) of organohydrogensiloxane and 8.4 g (60.2 mmol) of decene were added, and 8.3 × 10 ^-3 mmol of a 2% chloroplatinic acid solution in isopropyl alcohol was added, followed by heating to 40 ° C. did. Two hours later, 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 the mixture was heated to 40 ° 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 product obtained is I
The compound was represented by the following formula (L) by R and ¹ H-NMR spectra.

[0066]

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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) ¹ H-NMR [ [delta] ppm, in CDCl _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 - 1.90 (t, 24H) -CH _{2 C H 3 1.28 (br,} 136H) -C H 2 - 1.64-1.68 (br, 8H) -O H 3.44-3.87 (m, 28H) -C H 2 -O -, - C H -O-

Production Example 10 11.7 g (83 mmol) of decene, allyl glyceryl ether
The reaction was carried out in the same manner as in Production Example 9 except that 1.1 g (8.3 mmol) was used to obtain 23 g of a compound represented by the following formula (M).

[0069]

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IR (liquid film, cm ^-1 ) 3425 (-OH) 2970, 2930, 2865 (OH) 805, 845, 1260 (Si-Me) 1095, 1025 (Si-O-Si) ¹ H-NMR [ [delta] ppm, in CDCl _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 3.45-3.88 (m, 6.5H) -C H 2 -O -, - C H - O-

Example 1 Each of the components (B) produced in Production Examples 1 to 10 (E, F,
(G, I, J, K, M)
Dissolve, pour into sample bottle, cool it,
A gel cosmetic was obtained. This was determined according to the following evaluation criteria. Table 1 shows the results. Evaluation criteria ○: solidified uniformly △: thickened but unstable ×: complete separation

[0072]

[Table 1]

From Table 1, it was found that when gelling was performed using only the gelling agent for general oil, the product could not be solidified uniformly, whereas the product of the present invention solidified uniformly.

Example 2 A cosmetic was obtained in the same manner as in Example 1 except that the components shown in Table 2 were used. The separation of the silicone oil of each of these cosmetics was examined one month after production. Table 2 shows the results.

[0075]

[Table 2]

Table 2 shows that the product of the present invention was stable without exudation of silicone oil, and that the comparative product without using alkyl glyceryl ether-modified silicone had separated and exuded silicone oil. I understood.

Example 3 Sunscreen gel (%) (1) Alkyl glyceryl ether-modified silicone (J) 4 (2) 12-hydroxystearic acid 3 (3) Decamethylcyclopentasiloxane 86 (4) Methylphenylpolysiloxane 5 (5) Isooctyl p-dimethylaminobenzoate 2 (6) Appropriate amount of fragrance Production method: The components (1) to (5) are heated, dissolved uniformly, and then gradually cooled. Perfume (6) was uniformly mixed therein with a disper to obtain a sunscreen gel. This was stable and excellent in usability. Compounds D to I and K prepared in Production Examples were replaced with compound (J) of (1).
When a sunscreen gel was prepared in the same manner as described above, except that each of Nos. To M was used, a gel which was similarly stable and excellent in usability was obtained.

Example 4 Sunscreen cream (%) (1) Alkyl glyceryl ether-modified silicone (L) 4 (2) 12-hydroxystearic acid 3 (3) Decamethylcyclopentasiloxane 65 (4) Dimethylpolysiloxane (6cs) 20) (5) Octyl methoxycinnamate 3 (6) Titanium oxide 5 (7) Appropriate amount of fragrance Production method: Heat the components (1) to (5), dissolve them uniformly, and slowly cool. (6) and (7) were uniformly mixed therein with a disper to obtain a sunscreen cream. This was stable and excellent in usability. In addition,
A sunscreen cream was prepared in the same manner as described above, except that each of the compounds DK and M prepared in Production Examples was used in place of the compound (L) of (1). An excellent one was obtained.

Example 5 Ointment (%) (1) Alkyl glyceryl ether-modified silicone (K) 4 (2) Ca salt of dicetyl phosphate 4 (3) Octamethylcyclotetrasiloxane 60 (4) Dimethylpolysiloxane (6cs) 27 ( 5) Squalane 5 (6) Drug (zinc white) suitable amount Production method: The components (1) to (5) are heated, dissolved uniformly, and then gradually cooled. In this, (6) was uniformly mixed with a disper to obtain an ointment. This was stable and excellent in usability. An ointment was prepared in the same manner as described above except that each of the compounds D to J and L to M prepared in Production Examples was used instead of the compound (K) of (1), and the ointment was similarly stable and used. An excellent feeling was obtained.

Example 6 Polish Cream (%) (1) Alkyl glyceryl ether-modified silicone (M) 4 (2) 12-hydroxystearic acid 4 (3) Octamethylcyclotetrasiloxane 47 (4) Dimethylpolysiloxane (6cs) 10 (5) Amino-modified silicone oil 35 Production method: The components (1) to (5) were heated, uniformly dissolved, and then gradually cooled to obtain a polish cream. This was stable and excellent in usability. A polished cream was prepared in the same manner as described above except that each of the compounds D to L prepared in Production Examples was used instead of the compound (M) of (1), and was similarly stable and excellent in usability. Things were obtained.

 ────────────────────────────────────────────────── ─── Continuation of the front page (72) Koji Yoshino, inventor 557, Imaizumicho, Utsunomiya, Tochigi Prefecture (56) References JP-A-3-44309 (JP, A) JP-A-3-162442 (JP, A)

Claims (1)

(57) [Claims] 1. The following components (A), (B) and (C): (A) an oil gelling agent; (B) the following general formula (1):[Wherein, R¹~ R¹²At least one of the following expressions
(2) -Q-O-CH_TwoCH (OR¹³) CH_TwoOR¹⁴ (2) (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. ), The remainder being 1 to 30 carbon atoms
A linear, branched or cyclic hydrocarbon group of the formula:
(3) -X-R^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. )
And l, m, and n represent numbers from 0 to 2,000,
R when l + m + n = 0¹~ R^Three, R^Ten~ R¹²Of which
At least one represents a group (2). Where R¹~ R¹²
One of which is Q is trimethylene and R¹³And R¹⁴Together
Group (2) which is a hydrogen atom, and all of the rest are methyl
Except when it is a group. Alkyl glyceryl represented by the formula
Ruether-modified silicone (C) Cosmetics containing silicone oil.