JP2720134B2 - Fluorine-modified silicone, method for producing the same, and cosmetic containing the same - Google Patents

Description

DETAILED DESCRIPTION OF THE INVENTION

[0001]

BACKGROUND OF THE INVENTION 1. Field of the Invention The present invention relates to a fluorine-modified silicone derivative, a method for producing the same, and a cosmetic containing the same, and more particularly, a novel fluorine-modified silicone derivative having excellent water / oil repellency and a method for producing the same. The present invention relates to a method, and a cosmetic containing the same, which has a long lasting feel and a good feeling in use.

[0002]

2. Description of the Related Art
BACKGROUND ART Various water-repellent cosmetics have been used for the purpose of protecting the skin from water and sweat and for preventing makeup loss due to water and sweat. For example, skin protection cosmetics such as skin creams and skin lotions and makeup cosmetics contain a silicone oil or silicone resin as a water repellent component. However, these silicone oils and silicone resins have a certain effect on water repellency, but do not have a sufficient effect on oil repellency. Therefore, there is a problem that cosmetics containing these components cause makeup loss due to sebum.

[0003] For this reason, various attempts have been made to develop compounds having both water repellency and oil repellency.
For example, JP-A-2-295912 discloses that cosmetics containing a specific fluorine-modified silicone compound are excellent in water resistance and sebum resistance.

By the way, the water-repellent and oil-repellent base used in cosmetics has (a) sufficient water and oil repellency against sweat and sebum, (b) excellent emulsion stability, C) It is necessary to satisfy all conditions such as low viscosity and good usability.

[0005] However, the above-mentioned fluorine-modified silicone compound cannot sufficiently satisfy these conditions, especially in terms of oil repellency. On the other hand, various novel fluorine-modified silicone compounds have been developed [for example, J. Am.
Fluorine Chem. , 39 , 61 (198
8); Fluorine Chem. , 45 , 35
5 (1989)], but no specific application of these compounds has been reported yet.

Accordingly, while being excellent in water repellency and oil repellency,
There has been a demand for the development of a compound that is blended with a cosmetic to give a good feeling of use without causing makeup collapse.

[0007]

Means for Solving the Problems The present inventors have conducted intensive studies in view of such circumstances, and as a result, the specific fluorine-modified silicone derivative described below has excellent water and oil repellency and has a favorable effect on cosmetics. The present inventors have found that they show suitability, and have completed the present invention.

That is, the present invention firstly provides the following general formulas (1) and (2)

[0009]

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[In the formula, R _f is a perfluoroalkyl group having 1 to 20 carbon atoms or H (CF ₂ ) _k- (k is 1 to 20)
Represents an ω-H-perfluoroalkyl group represented by R), R represents a hydrocarbon group having 2 to 16 carbon atoms, and R ¹ , R ² and R ³ may be the same or different Good, a linear or branched aliphatic hydrocarbon group having 1 to 20 carbon atoms or an alicyclic or aromatic hydrocarbon group having 5 to 10 carbon atoms, m is an integer of 2 to 16 , N represents an integer of 1 to 6, x represents an integer of 0 to 50, p represents an integer of 1 to 200, q represents an integer of 0 to 200, and p + q ≧ 5]. And a chain-like fluorine-modified silicone derivative (A) having two polysiloxane units.

The present invention secondly provides the following general formula (3):
(4)

[0012]

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(Wherein R ¹ , R ² , R ³ , p and q are as defined above) and a silicone derivative (5) having two polysiloxane units and a compound represented by the following general formula (6):

[0014]

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Wherein R _f , R, m, n and x have the same meanings as defined above, respectively.
Is provided.

The present invention provides, thirdly, the following general formula (7):
(8)

[0017]

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(Wherein p ′ represents an integer of 1 to 200;
q ′ represents an integer of 0 to 200, and R _f , R, R ¹ ,
R ² , R ³ , m, n and x have the same meanings as defined above, respectively.) A cosmetic comprising a fluorine-modified silicone derivative (B) having two polysiloxane units represented by the formula (B): Things.

R ¹ , R ² and R of the fluorine-modified silicone derivative (A) or (B) having the polysiloxane unit (1) or (7) and (2) or (8) of the present invention.
Examples of the hydrocarbon group represented by ³ include linear alkyl groups such as methyl, ethyl, propyl, butyl, pentyl, hexyl, heptyl, octyl, nonyl, and decyl; isopropyl, sec-butyl, tert-butyl, neopentyl, Branched alkyl groups such as -ethylpropyl and 2-ethylhexyl; cyclic alkyl groups such as cyclopentyl and cyclohexyl; aromatic hydrocarbon groups such as phenyl and naphthyl; and the hydrocarbon groups represented by R include: A linear or branched alkylene group having 2 to 5 carbon atoms is preferable, and an ethylene group, a propylene group and the like are particularly preferable.

The perfluoroalkyl group represented by R _f in the polysiloxane unit (1) or (7) may be a straight-chain or branched-chain perfluoroalkyl group. CF _3- , C ₂ F _5- , C ₄ F _9- , C
_{6 F 13 -, C 8 F} 17 -, C 10 F 21 -, H (CF 2) 2 -, H (CF 2) 4 -, H
(CF ₂ ) ₆ −, H (CF ₂ ) ₈ − and the like.

The fluorine-modified silicone derivative (A) of the present invention comprises a silicone derivative (5) having a polysiloxane unit represented by the general formula (3) or (4) and a perfluoro compound represented by the general formula (6). It can be produced by reacting with an alkyl compound.

The silicone derivative (5) is not particularly limited in molecular structure and the like as long as it contains at least one polysiloxane unit (3) or (4).
In addition, various known materials can be used. Specific examples of the silicone derivative (5) include hydrogen methylpolysiloxane having one terminal such as pentamethyldisiloxane and tridecamethylhexasiloxane, tetramethyldisiloxane, hexamethyltrisiloxane, octamethyltetrasiloxane, and dodecamethylhexasiloxane. Such as “TSF484” and “TSF48” manufactured by Toshiba Silicone Co., Ltd. and commercially available methyl hydrogen polysiloxane.
And "KF99" manufactured by Shin-Etsu Chemical Co., Ltd.

The compound represented by the general formula (6) can be produced, for example, according to the following reaction route.

[0024]

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(Wherein, X represents a halogen atom, R _f ,
R, m, n and x are as defined above), that is, a halogenated alkene (9) and a fluorine-containing alcohol (10)
Is reacted under basic conditions to give compound (6)
Can be obtained. In this reaction, the general formula (9)
The compound represented by the formula (1) is at least 1 molar equivalent, preferably from 1.1 to 1.1, relative to the compound represented by the formula (10).
Use 5 moles. Examples of the base include an alkali metal, an alkali metal hydride, an alkali metal hydroxide, an alkaline earth metal hydride, an alkaline earth metal hydroxide, and a quaternary ammonium salt. The above reaction is carried out using a solvent as necessary, at 30 ° C. to 150 ° C., preferably 4 ° C.
It is carried out by heating and stirring in a temperature range of 0 ° C to 100 ° C.

The reaction between the compound (6) thus obtained and the silicone derivative (5) is carried out in the presence of a catalyst. The catalysts used include those commonly used for hydrosilylation, such as free radical initiators;
Photoinitiators; complex compounds of metals such as ruthenium, rhodium, palladium, osmium, iridium and platinum; and those in which these are supported on silica gel or alumina. Among these, in particular, chloroplatinic acid, Speier
Reagents (chloroplatinic acid in isopropyl alcohol solution) and the like are preferred. The amount of the catalyst used is not particularly limited as long as it is an amount sufficient to promote the reaction between the silicone derivative (5) and the compound (6), and is not particularly limited, but is 10 ⁻⁶ to 10 ^{− with} respect to 1 mol of the compound (6). A range of ¹ mol is preferred.

In this reaction, the use of a reaction solvent is not essential, but the reaction may be carried out in a suitable solvent, if necessary. The reaction solvent is not particularly limited as long as it does not inhibit the reaction. Examples thereof include hydrocarbon solvents such as pentane, hexane, and cyclohexane; benzene solvents such as benzene, toluene, and xylene; diethyl ether;
Preferred are ether solvents such as diisopropyl ether; alcohol solvents such as methanol, ethanol, isopropyl alcohol and butanol.

The hydrosilylation proceeds at 0 to 200 ° C., and takes into account the reaction speed and the coloration of the product.
It is preferably performed at 0 ° C. The reaction time is 0.5 to 2
It is preferably about 4 hours.

In order to control various properties such as viscosity, solubility and emulsion stability of the fluorine-modified silicone derivative (A) obtained by the above reaction, the types of the silicone derivative (5) and the compound (6) must be controlled. What is necessary is just to change suitably the combination of quantity etc.

The fluorine-modified silicone derivative (A) of the present invention thus obtained is excellent in water and oil repellency and its properties such as viscosity can be controlled depending on the purpose. When used as an oil agent, it can be made to have a long lasting makeup and an excellent feeling upon use. In this case, the blending amount of the fluorine-modified silicone derivative (A) is not particularly limited, but is usually 0.001 to 90% by weight (hereinafter simply referred to as "%"), preferably 0.1 to 90% by weight.
70% is preferred.

The cosmetic of the present invention may further contain a known fluorine-modified silicone derivative having a p + q of less than 5 in the polysiloxane units (1) and (2) in the same manner as in the above (A). . That is, the cosmetic of the present invention contains the fluorine-modified silicone derivative (B). Among them, the fluorine-modified silicone derivative (A)
Is particularly preferred.

In the cosmetic of the present invention containing the fluorine-modified silicone derivative (B), oils commonly used in cosmetics can be used. Such oils include:
For example, cyclic silicones such as octamethylcyclotetrasiloxane, decamethylcyclopentasiloxane and dodecamethylcyclohexasiloxane; non-volatile silicones such as methylpolysiloxane, dimethylpolysiloxane and methylphenylpolysiloxane; animal and vegetable fats and oils such as squalane and palm oil Other hydrocarbons, higher fatty acid esters, liquid paraffin, iso-liquid paraffin, and the like.

Further, the cosmetics of the present invention may contain, if necessary, components to be added to ordinary cosmetics, such as petrolatum, lanolin, ceresin, microcrystalline wax, carnauba wax, candelilla wax, higher fatty acids, higher alcohols and the like. Water-soluble and oil-soluble polymers; coloring agents such as inorganic and organic pigments, inorganic and organic pigments and organic dyes treated with silicone or fluorine compounds; anionic activators, cationic activators, Ionic activators,
Surfactants such as dimethylpolysiloxane / polyoxyalkylene copolymer and polyether-modified silicone; other water, preservatives, antioxidants, dyes, thickeners, pH adjusters,
A fragrance, an ultraviolet absorber, a humectant, a blood circulation promoter, a cooling agent, an antiperspirant, a bactericide, a skin activator, and the like can be appropriately compounded as long as the effects of the present invention are not impaired. In particular, when a pigment surface-treated with a fluorine compound is used, it is preferable because makeup is not lost due to sebum.

The cosmetic of the present invention is not particularly limited in the form and type of the cosmetic, and can be produced according to a usual method. Examples of the type include oil-based cosmetics, emulsified cosmetics, aqueous cosmetics, lipsticks, blushers, foundations, skin cleansers, hair cleansers, hair tonics, hair styling, hair tonics, hair restorers, and the like.

[0035]

According to the present invention, there are provided: 1. Has high water and oil repellency. 2. Good compatibility with cosmetic base. 3. High emulsion stability. 4. Low viscosity and non-sticky A chain-like fluorine-modified silicone derivative (A) having excellent characteristics such as extremely low skin irritation can be obtained easily and conveniently. Furthermore, cosmetics containing the fluorine-modified silicone derivative (B) have good cosmetic durability and excellent feeling in use.

[0036]

EXAMPLES The present invention will be described below in more detail with reference to examples, but the present invention is not limited to these examples. In the following examples, some of the chemical formulas are abbreviated as follows.

[0037]

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Embodiment 1

[0039]

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100 ml 2 equipped with a cooling tube and a magnetic stirrer
In a one-necked flask, under a nitrogen atmosphere, 45 ml of toluene and 15.0 g of tridecamethylhexasiloxane (MD ₄ ^MH ) (3
_{3.8mmol), C 6 F 13 -} (CH 2) 2 -O-CH 2 CH = CH 2 ( hereinafter, abbreviated as Compound 6a) 16.4g (40.5mmol), 2 % isopropyl alcohol of chloroplatinic acid 26.7 μl of solution
(0.8 × 10 ⁻³ mmol), and the mixture was stirred at 110 ° C. for 4 hours. The reaction mixture was cooled to room temperature, 1.0 g of activated carbon was added, and the mixture was stirred at room temperature for 1 hour. The unreacted compound (6a) was distilled off under reduced pressure to obtain 25.8 g of the target compound (1a) as a colorless and transparent oil (yield: 90%).

The following ¹ H-NMR [δ ppm, in CDCl ₃ , CHCl
₃ standards (7.24 ppm)]. δ: -0.03 to 0.02 (m, 39H, SiC H ₃ ), 0.41 to 0.51 (m, 2H, Ha),
1.46 ~ 1.61 (m, 2H, Hb), 2.18 ~ 2.47 (m, 2H, He), 3.35 (t, J
= 6.8 Hz, 2H, Hc), 3.61 (t, J = 6.9 Hz, 2H, Hd) The above Ha to He indicate that they are protons at the following positions.

[0042]

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Embodiment 2

[0044]

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In the apparatus used in Example 1, 30 m
l, hydrogen polysiloxane ( ^HMD_FourM^H) 11.
0 g (25.6 mmol), 24.8 g (6
1.4 mmol), 2% isopropyl alcohol of chloroplatinic acid
101 μl (3.1 × 10^-3mmol) and run
24.9 g of the desired compound (1b) was prepared in the same manner as in Example 1.
Was obtained as a colorless transparent oil (yield 79%).

The following ¹ H-NMR [δ ppm, in CDCl ₃ , CHCl
₃ standards (7.24 ppm)]. δ: 0.01 to 0.03 (m, 36H, -SiC H ₃ ), 0.43 to 0.51 (m, 4H, Ha),
1.47 to 1.61 (m, 4H, Hb), 2.20 to 2.47 (m, 4H, He), 3.36 (t, J
= 6.8 Hz, 4H, Hc), 3.64 (t, J = 6.8 Hz, 4H, Hd) The above Ha to He indicate that they are protons at the following positions.

[0047]

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Embodiment 3

[0049]

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In the apparatus used in Example 1, 35 m
l, hydrogen polysiloxane ( ^HMD₆M^H) 11.
2 g (19.3 mmol), 18.8 g of compound (6a) (4
6.5 mmol), 2% isopropyl alcohol of chloroplatinic acid
30.7 μl (0.93 × 10^-3mmol)
The target compound (1c) was obtained in the same manner as in Example 1.
4 g were obtained as a colorless transparent oil (yield 95%).

The following ¹ H-NMR [δppm, in CDCl ₃ , CHCl
₃ standards (7.24 ppm)]. δ: -0.02 to 0.02 (m, 48H, -SiC H ₃ ), 0.43 to 0.51 (m, 4H, H
a), 1.48 to 1.62 (m, 4H, Hb), 2.20 to 2.47 (m, 4H, He), 3.34
(t, J = 6.9Hz, 4H, Hc), 3.64 (t, J = 6.9Hz, 4H, Hd)

[0052]

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Embodiment 4

[0054]

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In the apparatus used in Example 1, 20 m
1, hydrogen polysiloxane (MD ₂ ^DH ₂ M)
8.0 g (18.6 mmo, manufactured by Toshiba Silicone Co., Ltd.)
1), 18.0 g (44.7 mmol) of compound (6a)
l), 2% chloroplatinic acid solution in isopropyl alcohol 2
9 μl (0.89 × 10 ⁻³ mmol) was added, and 20.3 g of the target compound (1d) was obtained as a colorless and transparent oil in the same manner as in Example 1 (87% yield).

The following ¹ H-NMR [δppm, in CDCl ₃ , CHCl
₃ standards (7.24 ppm)]. δ: -0.01 to 0.03 (m, 36H, -SiC H ₃ ), 0.44 to 0.52 (m, 4H, H
a), 1.50-1.64 (m, 4H, Hb), 2.20-2.48 (m, 4H, He), 3.35
(t, J = 6.9 Hz, 4H, Hc), 3.69 (t, J = 6.9 Hz, 4H, Hd) The above Ha to He indicate that they are protons at the following positions.

[0057]

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Embodiment 5

[0059]

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In the apparatus used in Example 1, toluene 20 m
1, hydrogen polysiloxane (MD ₃ ^DH ₃ M)
(Manufactured by Toshiba Silicone Co., Ltd.) 7.0 g (12.4 mmo)
1), 18.1 g (44.7 mmol) of compound (6a)
l), 2% chloroplatinic acid solution in isopropyl alcohol 2
9.5 μl (0.89 × 10 ⁻⁸ mmol) was added, and the target compound (1e) 19.7 was obtained in the same manner as in Example 1.
g was obtained as a colorless and transparent oil (yield 89%).

The following ¹ H-NMR [δ ppm, in CDCl ₃ , CHCl
₃ standards (7.24 ppm)]. δ: -0.05 to 0.00 (m, 45H, -SiC H ₃ ), 0.35 to 0.50 (m, 6H, H
a), 1.44 to 1.59 (m, 6H, Hb), 2.18 to 2.42 (m, 6H, He), 3.31
(t, J = 6.9 Hz, 6H, Hc), 3.60 (t, J = 6.9 Hz, 6H, Hd) The above Ha to He indicate that they are protons at the following positions.

[0062]

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Embodiment 6

[0064]

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In the apparatus used in Example 1, xylene 50 m
l, hydrogen polysiloxane ( ^HMD_FourM^H) 15.
0 g (34.8 mmol), C₈F₁₇-(CH_Two)_Two-O-CH_TwoCH = CH
_Two(6b) 42.1 g (83.5 mmol) of chloroplatinic acid
137 μl of 2% isopropyl alcohol solution (4.2 ×
10^-3mmol) in the same manner as in Example 1.
47.0 g of compound (1f) was obtained as a colorless and transparent oil.
(94% yield).

The following ¹ H-NMR [δppm, in CDCl ₃ , CHCl
₃ standards (7.24 ppm)]. δ: 0.02 to 0.06 (m, 36H, -SiC H ₃ ), 0.47 to 0.56 (m, 4H, Ha),
1.44 to 1.67 (m, 4H, Hb), 2.24 to 2.50 (m, 4H, He), 3.39 (t, J
= 6.86Hz, 4H, Hc), 3.68 (t, J = 6.96Hz, 4H, Hd) The above Ha to He indicate that they are protons at the following positions.

[0067]

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Embodiment 7

[0069]

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In the apparatus used in Example 1, xylene 12 m
l, hydrogen polysiloxane ( ^HMD_FourM^H) 12.
0 g (27.8 mmol), C_TenF_{twenty one}-(CH_Two)_Two-O-CH_TwoCH = CH
_Two(6c) 40.4 g (66.8 mmol) of chloroplatinic acid
101 μl of 2% isopropyl alcohol solution (3.1 ×
10^-3mmol) in the same manner as in Example 1.
41.0 g of the compound (1 g) was converted into a colorless and transparent wax-like substance.
(90% yield). Its melting point is 37.0 ° C
Met.

The following ¹ H-NMR [δppm, in CDCl ₃ , CHCl
₃ standards (7.24 ppm)]. δ: -0.02 to 0.02 (m, 36H, -SiC H ₃ ), 0.43 to 0.51 (m, 4H, H
a), 1.46 to 1.62 (m, 4H, Hb), 2.19 to 2.46 (m, 4H, He), 3.34
(t, J = 6.88 Hz, 4H, Hc), 3.64 (t, J = 6.96 Hz, 4H, Hd) The above Ha to He indicate that they are protons at the following positions.

[0072]

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Test Examples The fluorine-modified silicones (1b), (1d), (1e), (1f) and (1g) synthesized in Examples 2, 4, 5, 6, and 7 were compared with conventional products (Comparative Examples 1 to 3). ) And physical properties were compared. Table 1 shows the evaluation items and the results.

[0074]

[Table 1]

* 1 Trifluoropropyl silicone ("X-22-820" manufactured by Shin-Etsu Chemical Co., Ltd.) * 2 "FSL-300" manufactured by Asahi Glass Co., Ltd. It has the following chemical formula:

[0076]

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* 3 Polydimethylsiloxane (“KF-96” manufactured by Shin-Etsu Chemical Co., Ltd.) * 4 The contact angle with water (the angle between the oil film of each oil and the water droplet) is 1
At least 00 ° was rated ◎, and at least 70 ° to less than 100 ° was rated ○. * 5 The contact angle with squalane (the angle between the oil film of each oil and the water droplet) is 30 ° or more ◎, and 20 ° to less than 30 ° is 、, 20
Less than ° was evaluated as x. * 6 Less than 35 cst: ◎, 35 to 80 cst: ○, 80 cst
Those that exceeded were evaluated as ×. * 7 The solubility in octamethylcyclotetrasiloxane was examined.

As is evident from the results shown in Table 1, the fluorine-modified silicone derivative of the present invention has better water and oil repellency, lower viscosity in general, and lower compatibility with the cosmetic base than the conventional product. It turns out that it is favorable.

Production Example 1 Production of Sericite Treated with Fluorine Compound Sericite 1 was placed in a 1-liter round bottom flask (or kneader).
After adding 500 g of ion-exchanged water, 500 ml of ion-exchanged water was added thereto, and a perfluoroalkyl phosphate dioxyethylamine salt [(C _m F _{2m + 1} C ₂ H ₄ O) _y PO (ONH ₂ (CH ₂ CH ₂ OH) ) ₂ ) _3-y ]
[M = 6 to 18 (average chain length; 9), about 1 of 1 <y <2]
33 g of a 7.5% aqueous solution was added, and the mixture was stirred at 40 ° C. Next, 40 ml of 1N hydrochloric acid was added to lower the pH of the aqueous solution to 3 or less, and perfluoroalkylphosphoric acid was precipitated on the powder surface. This was filtered, washed with water and dried to obtain 105 g of the target fluorine compound-treated sericite. I got

Example 8 and Comparative Examples 4 and 5 Two-layer liquid foundations: Two-layer liquid foundations having the compositions shown in Table 2 were produced according to the following production methods, and the foundations were evaluated for their makeup durability, usability, and the like. The method was evaluated. Table 3 shows the results. (Preparation method) After the oil phase is dissolved at room temperature, the pigment is dispersed with a disper. The aqueous phase is added to this with stirring and emulsified to obtain the desired two-phase liquid foundation.

[0081]

[Table 2]

(Evaluation Methods) Makeup and feeling of use: Sensory evaluation was conducted by 10 expert panelists, and the results were shown according to the following criteria. Table 3 shows the results. ○: “Good” is 8 or more. Δ: “Good” is 4 to 7 people. ×: “Good” is less than 4 people.

[0083]

[Table 3]

As is evident from Table 3, the liquid foundation of the present invention was superior in terms of long-lasting makeup and feeling in use as compared with the conventional one containing silicone.

Example 9 Powder foundation: A powder foundation having the composition shown in Table 4 was produced by the following method. (Preparation method) The pigment is mixed and pulverized through a pulverizer. This is transferred to a high-speed blender, and a binder and the like are mixed by heating, and the resulting mixture is added to the pigment and further mixed to make the mixture uniform. This is treated with a crusher, passed through a sieve, and after adjusting the particle size,
After leaving it for several days, it is compression molded in a container such as a gold plate to obtain a powder foundation.

[0086]

(Composition) (% by weight) (1) Fluorine compound-treated pigment (the following pigment is treated in the same manner as in Production Example 1) Titanium oxide 10.0 Sericite 30.0 Mica Balance Kaolin 5.0 Bengala 8 Yellow iron oxide 2.5 Black iron oxide 0.1 (2) Fluorine-modified silicone of Example 6 8.0 (3) Beeswax 2.0 (4) Preservative 0.2 (5) Fragrance trace amount

Example 10 Slight red: Slight red having the composition shown in Table 5 was obtained in the same manner as in Example 9.

[0088]

(Composition) (% by weight) (1) Silicone-treated pigment (commercially available pigment treated with methyl hydrogen polysiloxane) Kaolin Balance Mica 13.0 Titanium oxide 12.0 Red No. 202 2.5 Iron oxide (Red, (Yellow, black) 5.0 (2) Fluorine-modified silicone of Example 5 7.0 (3) Dimethylpolysiloxane ("KF96A", 6cs, manufactured by Shin-Etsu Chemical Co., Ltd.) 5.0 (4) Preservative 1 (5) Fragrance trace

Example 11 Powder Eye Shadow: Table 6
Was obtained by the following production method. (Production method) A pigment other than mica titanium is first mixed and pulverized, and then the mica titanium is mixed. Otherwise, the procedure of Example 9 is repeated to obtain the desired powder eye shadow.

[0090]

(Table 6) (Composition) (% by weight) (1) Water- and oil-repellent powder (the powder treated in the same manner as in Production Example 1 is later mixed) Titanium mica 4.9 Sericite Balance Mica 25.0 Oxidation Iron (red, yellow, black) 2.0 Ultramarine 9.0 Navy blue 12.0 (2) Fluorine-modified silicone of Example 6 8.0 (3) Squalane 2.0 (4) Vaseline 1.5 (5) Sorbitan Trioleate 1.0 (6) Preservative 0.1 (7) Fragrance trace

Example 12 Dual-Use Powder Foundation: A dual-use powder foundation having the composition shown in Table 7 was obtained in the same manner as in Example 11.

[0092]

(Composition) (% by weight) (1) Silicone-treated pigment (commercially available pigment treated with methyl hydrogen polysiloxane) Mica Balance Talc 4.8 Titanium oxide 14.0 Titanium mica 3.5 Iron oxide (red, yellow) 8.2 Black zinc oxide 4.5 Aluminum oxide 10.0 Barium sulfate 5.0 (2) Fluorine-modified silicone of Example 4 6.0 (3) Lanolin 3.0 (4) Vaseline 1.0 (5 ) Isopropyl myristate 1.0 (6) Preservative 1.5 (7) Fragrance trace

Example 13 Two-layer sunscreen emulsion:
Example 8 A two-layer sunscreen emulsion having the composition shown in Table 8 was prepared.
Was obtained in the same manner as described above.

[0094]

(Composition) (% by weight) (1) Octamethylcyclotetrasiloxane 25.0 (2) Fluorine-modified silicone of Example 3 15.0 (3) Dimethylpolysiloxane / polyoxyalkylene copolymer 0 (4) Glycerin 2.0 (5) Ethanol 12.0 (6) Purified water balance (7) Octyl methoxycinnamate 2.0 (8) Silicone-treated pigment (commercially available pigment treated with methyl hydrogen polysiloxane) Zinc oxide 5.5 Titanium oxide 2.0 Talc 5.0 (9) Fragrance trace

Example 14 Nutritional cream: A nutritional cream having the composition shown in Table 9 was obtained by the following method. (Production method) (1) to (5) were mixed and heated to 75 ° C.
(6), (7) and (10) are mixed into this mixture,
The mixture heated to 70 ° C. is added with stirring to emulsify. After the emulsification, the mixture is cooled to 60 ° C., (8) and (9) are added thereto, and further cooled to room temperature to obtain a nutritional cream.

[0096]

(Composition) (% by weight) (1) Polyoxyethylene (50) hydrogenated castor oil 2.0 (2) Potassium sulfate 0.5 (3) Fluorine-modified silicone of Example 7 6.0 (4) Liquid paraffin 5.0 (5) hexadecyl-2-ethylhexanoate 2.0 (6) sodium benzoate 0.3 (7) propylene glycol 2.0 (8) acetic acid-d1-α-tocopherol 0.1 ( 9) Fragrance 0.1 (10) Purified water balance

Example 15 Hand cream: A hand cream having the composition shown in Table 10 was obtained by the following method. (Preparation method) (1) to (5) are mixed and heated to 75 ° C.
The mixture of (6) to (8) heated to 75 ° C. is gradually added thereto under stirring to emulsify. Cool to room temperature to obtain a hand cream.

[0098]

(Table 10) (Composition) (% by weight) (1) Polyoxyethylene (20) Sorbitan palmitate 1.5 (2) Aluminum chloride 0.8 (3) Isopropyl myristate 4.5 (4) Dimethylpolysiloxane ( (KF-96A, 6cs, Shin-Etsu Chemical Co., Ltd.) 4.0 (5) Fluorine-modified silicone of Example 7 6.0 (6) Methyl parahydroxybenzoate 0.2 (7) Sorbitol 10.0 (8) ) Purified water balance

Example 16 Cream foundation (water-in-oil type) A cream foundation having the composition shown in Table 11 was obtained by the following method. (Preparation method) (1) to (6) are mixed and heated to 75 ° C.
(7) is dispersed by a disper. The mixture of (9) to (14) is heated to 75 ° C. and gradually added under stirring to emulsify. Then cooled to 30 ° C (8)
And (15), and further cooled to room temperature to obtain the desired creamy foundation (W / O type).

[0100]

(Composition) (% by weight) (1) Dimethylpolysiloxane / polyoxyalkylene copolymer 2.0 (2) Fluorine-modified silicone of Example 2 10.0 (3) Dimethylpolysiloxane (Shin-Etsu Chemical Co., Ltd.) ("KF-96A", 6 cs) 5.0 (4) Aluminum stearate 0.2 (5) 1-isostearoyl-3-myristoyl-glycerol 2.0 (6) Octyl methoxycinnamate 2.0 (7) Fluorine compound-treated pigment (the following pigment is treated in the same manner as in Production Example 1) Talc 5.0 Titanium oxide 9.0 Iron oxide (red, yellow, black) 1.2 (8) Decamethylcyclopentasiloxane 15 0.0 (9) Butyl paraoxybenzoate 0.1 (10) Sodium benzoate 0.2 (11) Magnesium sulfate 0.5 (12) Glycerin 5.5 (13) 1,3-Bu Glycol 2.5 (14) Purified water Balance (15) Perfume 0.1

Example 17 Disinfecting cream: A disinfecting cream having the composition shown in Table 12 was obtained by the following method. (Production method) (6) to (11) are mixed so as to be uniform. This is added to the aqueous components (1) to (5) under stirring and emulsified to obtain a desired antiseptic cream.

[0102]

(Composition) (% by weight) (1) Polyoxyethylene (50) hydrogenated castor oil 0.5 (2) Polyoxyethylene (20) sorbitan palmitate 1.0 (3) Glycerin 6.0 (4) ) 1,3-butylene glycol 6.0 (5) Purified water balance (6) Squalane 5.0 (7) Jojoba oil 5.0 (8) Octamethylcyclotetrasiloxane 18.0 (9) Octyl methoxycinnamate 2 0.0 (10) Fluorine-modified silicone of Example 2 30.0 (11) Disinfectant ("Irgasan DP-300") 0.2

The various cosmetics obtained in the above Examples 8 to 17 all had good cosmetic durability and excellent feeling in use.

 ──────────────────────────────────────────────────続 き Continuation of the front page (72) Inventor Masahiko Asahi 4-34-2 Otsuka, Bunkyo-ku, Tokyo (56) References Japanese Patent Publication No. Sho 41-9434 (JP, B1)

Claims (3)

(57) [Claims] 1. The following general formulas (1) and (2): [Wherein, R _f is a perfluoroalkyl group having 6 to 20 carbon atoms or ω-H-perfluoro represented by the formula H (CF ₂ ) _k- (where k is an integer of 6 to 20). Represents an alkyl group, R represents a hydrocarbon group having 2 to 16 carbon atoms,
R ¹ , R ² and R ³ may be the same or different,
A linear or branched aliphatic hydrocarbon group having 1 to 20 carbon atoms or an alicyclic or aromatic hydrocarbon group having 5 to 10 carbon atoms, m represents an integer of 2 to 16, Is 1
X represents an integer of 0 to 50;
And q represents an integer of 0 to 200, and p + q ≧ 5.] A chain fluorine-modified silicone derivative (A) having two polysiloxane units. 2. The following general formulas (3) and (4): Wherein R ¹ , R ² , R ³ , p and q have the same meanings as defined above, respectively, and a silicone derivative (5) having two polysiloxane units, and the following general formula (6): 3] 2. The process for producing a fluorine-modified silicone derivative (A) according to claim 1, wherein the compound is reacted with a compound represented by the formula: wherein R _f , R, m, n and x are as defined above. . 3. The following general formulas (7) and (8): (In the formula, p ′ represents an integer of 1 to 200, and q ′ represents 0 to 2
Represents an integer of 00, and R _f , R, R ¹ , R ² , R ³ , m,
n and x are as defined above, respectively.
A cosmetic comprising a fluorine-modified silicone derivative (B) having one polysiloxane unit.