JP3073885B2 - Cosmetics - Google Patents

Description

DETAILED DESCRIPTION OF THE INVENTION

[0001]

BACKGROUND OF THE INVENTION 1. Field of the Invention The present invention has a refreshing feeling of use, imparts water and oil repellency to a cosmetic film after application, and eliminates cosmetic ingredients such as medicinal ingredients and pigments due to sweat or sebum. The present invention relates to a cosmetic composition which can prevent the makeup from deteriorating due to aging of the face due to aging, can maintain the initial state, and is stable.

[0002]

2. Description of the Related Art In general, the disappearance of cosmetic ingredients such as medicinal ingredients and pigments, and the deterioration of the face due to aging such as shininess, oil floating, and color dullness are caused by the action of human secretions such as sweat, tears, and sebum. And external factors such as skin movement, contact with hands or clothing, and contact with rain (water).

[0003] Among these factors, makeup breakdown caused by sebum is particularly regarded as a problem, and this is considered to be due to accumulation of residual oil and generated sebum after application of the product. Generally, volatile or non-volatile oils are used in cosmetics. However, when non-volatile oils are mainly used, other volatile components are easily removed due to skin temperature, friction during application, etc. Since it is volatilized, the non-volatile oil component will mainly remain later. Further, sebum generated with the lapse of time is added to this, and the cosmetic ingredients are excessively wetted as oil, and as a result, makeup breakage due to sebum occurs.

On the other hand, as the volatile oil, octamethylcyclotetrasiloxane, decamethylcyclopentasiloxane and the like are usually used from the viewpoint of safety and feeling of use, and these are used as the main components of the oil. Thereby, the above-mentioned sebum collapse can be prevented. But,
These have a high volatilization rate and are volatilized in ten minutes or more immediately after application, so that the touch after application becomes powdery, and there is a problem that the finished state of makeup such as a tight face is poor.

Further, cosmetics containing a liquid perfluoropolyether compound have been proposed for the purpose of imparting water resistance, sebum resistance and oil resistance to the cosmetics (Japanese Patent Application Laid-Open (JP-A) 61).
Nos. 234928 and 63-107911). However, perfluoropolyether compounds have poor compatibility with other additives commonly used in cosmetics, and only perfluoro compounds are used as oils, especially when a large amount is incorporated into emulsified cosmetics. Is difficult to obtain. In addition, there is a problem that growth is heavy and lacks a refreshing feeling.

[0006]

SUMMARY OF THE INVENTION Accordingly, the present invention solves the above-mentioned problems, has excellent water resistance and oil resistance, and has a refreshing feeling at the same time as having no dustiness. Further, it is an object of the present invention to provide a cosmetic composition which has good makeup durability and excellent stability by preventing the wetting and disappearance of the cosmetic component.

[0007]

Under such circumstances, the present inventors have conducted intensive studies and as a result, have found that a combination of a fluorine-modified silicone and a sustained-release silicone whose volatilization rate is close to the sebum generation rate provides water resistance and oil resistance. Can impart an appropriate amount of oil to the skin as well as imparting an excellent feeling of use that is refreshing and powdery, and can maintain the initial cosmetic effect for a long time, In addition, they have found that a cosmetic having excellent stability can be obtained, and have completed the present invention.

That is, the present invention provides (a) a fluorine-modified silicone and (b) a volatilization rate at 30 ° C. of 5.0 ×.
An object of the present invention is to provide a cosmetic characterized by containing a chain silicone and / or a cyclic silicone of 10 ^{-5 to} 1.7 × 10 ^-3 g / cm ² · H.

[0009] The present invention also provides a cosmetic composition which further comprises (c) a powder of a fluorine compound-treated powder in addition to the components (a) and (b).

As the fluorine-modified silicone of the component (a) used in the present invention, for example, the following general formulas (1) to (1)
A compound having one or more structural units represented by (4) and a structural unit represented by the following general formula (5) can be given.

[0011]

Embedded image

[In the formula, R _f and R _{f ′} may be the same or different and each is a linear or branched perfluoroalkyl group having 1 to 20 carbon atoms or the following formula: H (CF ₂ ) _t- (T is 1
R ¹ , R ⁴ and R ⁵ may be the same or different, and may have 1 to 20 carbon atoms, such as a straight chain or a branched chain. A chain aliphatic hydrocarbon group or an alicyclic or aromatic hydrocarbon group having 5 to 10 carbon atoms; R ² is a hydrogen atom, a linear or branched aliphatic hydrocarbon group having 1 to 20 carbon atoms ,
An alicyclic or aromatic hydrocarbon group having 5 to 10 carbon atoms, a perfluoroalkyl group having 1 to 20 carbon atoms or the following formula: H
(CF ₂ ) _t represents an ω-H-perfluoroalkyl group represented by _t- (t represents an integer of 1 to 20); R ³ represents a divalent hydrocarbon group having 2 to 6 carbon atoms X and Y each represent a single bond, -CO- or a divalent hydrocarbon group having 1 to 6 carbon atoms; l represents a number of 2 to 16;
16 represents a number, p represents a number of 1 to 200, and r represents 0 to
5 represents a number, and s represents a number from 0 to 200]

In the structural units represented by the general formulas (1) to (5), as the perfluoroalkyl group represented by R _f and R _{f ′} , any of linear and branched chains can be used. , for _{example, 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 -,
(C ₃ F ₇ ) C (CF ₃ ) ₂ — and the like. In addition, _{t in} H (CF ₂ ) _t — is preferably an integer of 6 to 20.

R¹, R^FourAnd R^FiveA hydrocarbon group represented by
Are, for example, methyl, ethyl, propyl,
Tyl, pentyl, hexyl, heptyl, octyl
Linear alkyl groups such as phenyl, nonyl, and decyl;
Propyl group, s-butyl group, t-butyl group, neopentyl
Group, 1-ethylpropyl group, 2-ethylhexyl group, etc.
Branched-chain alkyl group; cyclopentyl group, cyclohexyl
Cyclic alkyl group such as group; aromatic such as phenylnaphthyl group
And hydrocarbon groups. Also, R ^ThreeIndicated by
The divalent hydrocarbon group is a straight-chain or straight-chain having 2 to 4 carbon atoms.
Is preferably a branched alkylene group, particularly an ethylene group,
Propylene groups are preferred.

As the fluorine-modified silicone of the component (a) having such a structural unit, for example, the following general formula (6):

[0016]

Embedded image

[In the formula, at least one of Z ¹ and Z ² represents a structural unit selected from the general formulas (1), (2), (3) and (4), and the remainder represents a single bond; , R ⁴ and R ⁵ have the same meanings as described above], or the following general formula (7);

[0018]

Embedded image

[In the formula, Z ³ is a general formula (1), (2),
A structural unit selected from (3) and (4), wherein R ⁶ is a linear or branched aliphatic hydrocarbon group having 1 to 20 carbon atoms or an alicyclic or aromatic carbon group having 5 to 10 carbon atoms; Represents a hydrogen group, u represents a number of 0 to 200, and s, R ⁴ and R ⁵ have the same meanings as described above].

The groups in each of the structural units represented by the general formulas (1) to (5) and the fluorine-modified silicone represented by the general formulas (6) and (7) are used to prevent makeup collapse and improve usability. In consideration of the following, the following are preferable. R _f and R _{f ′ each} represent a linear or branched perfluoroalkyl group having 6 to 20 carbon atoms or the following formula: H (CF ₂ ) _t- (t
Represents an integer of 6 to 20), and is preferably an ω-H-perfluoroalkyl group represented by the following formula: R ¹ , R ⁴ and R ⁵ may be the same or different, and are preferably a linear or branched aliphatic hydrocarbon group having 1 to 4 carbon atoms. R ² is a hydrogen atom, a perfluoroalkyl group having 6 to 20 carbon atoms, or ω-H-perfluoro represented by the following formula: H (CF ₂ ) _t- (t is an integer of 6 to 20) Alkyl groups are preferred. R ³ is preferably a divalent hydrocarbon group having 2 to 4 carbon atoms. X and Y are preferably a single bond, -CO- or a divalent hydrocarbon group having 1 to 4 carbon atoms, and l is 2 to 10,
Particularly, the number of 2 to 5 is preferable, and m and n are 2 to 5, respectively.
10, preferably 1 to 6, p is preferably 1 to 100, particularly preferably 1 to 10, r is 0 to 20, particularly 0 to 5
Is preferable, and s is preferably a number of 0 to 100, particularly preferably 0 to 10. The arrangement of the structural units of the fluorine-modified silicone represented by the general formula (7) may be alternate, block, or random.

Preferred examples of the fluorine-modified silicone as the component (a) include a polymerization degree described in JP-A-5-247214, which has structural units represented by the general formulas (2) and (5). 2 to 200 fluorine-modified silicones, commercially available FSL-300 manufactured by Asahi Glass Co., Ltd., X-22-819, X-22-820, X manufactured by Shin-Etsu Chemical Co., Ltd.
22-821, X-22-822 and FL-100,
FS1265 manufactured by Toray Dow Corning Silicone Co., Ltd. can be mentioned.

The fluorine-modified silicone of the component (a) comprises 1
Species or a combination of two or more species can be used, and it is preferable to mix 0.01 to 99% by weight (hereinafter simply referred to as%) in the total composition, particularly 0.01 to 80%, and more preferably 0.1 to 80% by weight.
When the content is 1 to 70%, it is preferable because the makeup lasts better and the feeling of use is good.

Among the component (b) used in the present invention, the chain silicone may be linear or branched.
For example, the following general formula (8) or (9):

[0024]

Embedded image

(Wherein R ⁷ may be the same or different and each represents an alkyl group or a halogenated alkyl group; v represents an integer of 3 to 6; w represents 0 or 1; 4
Which is an integer).
In formula (8) or (9), the alkyl group represented by R ⁷ preferably has 1 to 3 carbon atoms, and examples thereof include a methyl group, an ethyl group, and a propyl group. Examples thereof include a 3,3,3-trifluoropropyl group.

Examples of such a chain silicone include:
Among the compounds represented by the general formula (8), those having high purity (90% or more) in which v is 4 or less include, for example, KF96L (2cSt) manufactured by Shin-Etsu Silicone, and Dow Corning Silicone manufactured by Toray Dow Corning Silicone. Commercial products such as SH-200C (2cSt) can be mentioned. Those exceeding these can be produced, for example, according to the following reaction formula.

[0027]

Embedded image

(Wherein, R ⁷ has the same meaning as described above;
Represents an integer of 3 to 8), that is, a cyclic silicone (1
0), trialkylchlorosilane (11) and water in the presence of an inorganic solid compound, whereby y is 4
And a chain silicone (8) having a high purity exceeding the above.

The cyclic silicone used in this reaction (10)
Examples include: hexamethylcyclotrisiloxane, hexaethylcyclotrisiloxane, trimethyltrivinylcyclotrisiloxane, octamethylcyclotetrasiloxane, octaethylcyclotetrasiloxane, tetramethyltetravinylcyclotetrasiloxane, tetra (trifluoropropyl) tetramethyl Examples thereof include cyclotetrasiloxane, decamethylcyclopentasiloxane, and dodecamethylcyclohexasiloxane; examples of the trialkylchlorosilane (11) include trimethylchlorosilane, triethylchlorosilane, and dimethylethylchlorosilane. As the inorganic solid compound, those which are insoluble in the reaction solvent and are uniformly dispersed in the reaction solution are preferable, and examples thereof include silica gel, titanium dioxide and silica / alumina, and silica gel is particularly preferable. Here, silica gel refers to an amorphous silicic acid polymer, and any type can be used, but the reaction rate is fast at the same weight,
Those having a small particle size are preferred.

The reaction is carried out by adding a trialkylchlorosilane (11) to a mixture of the cyclic silicone (10), the inorganic solid compound and water. The amount of the trialkylchlorosilane (11) used is 2 to 10 moles, particularly 2 to 4 moles, per mole of the cyclic silicone (10).
More preferably, it is 3 times the molar amount. The amount of the inorganic solid compound used can be selected according to the reactivity of the cyclic silicone (10) and the trialkylchlorosilane (11), but is in the range of 1 to 50% based on the cyclic silicone (10). Is preferred. Further, the amount of water used is stoichiometric excess, that is, 1 to 1 with respect to the cyclic silicone (10).
The molar amount is preferably 500 times, especially 5 to 20 times. No reaction solvent is required, but cyclic silicone (10)
When hexamethylcyclotrisiloxane which is a solid at room temperature is used, it is preferable to use a solvent in order to smoothly carry out the reaction. As the solvent in this case, a hydrocarbon solvent that does not mix with water, such as pentane, hexane, heptane, benzene, and toluene, is preferable.

After the addition of chlorosilane, it depends on the reactivity of the cyclic silicone (10) used.
Let react for ~ 20 hours. The linear silicone (8) thus obtained is subjected to distillation under normal pressure or reduced pressure, preferably under reduced pressure, to obtain unreacted cyclic silicone (1).
0) and trialkylchlorosilane (11). The recovered cyclic silicone (10) and trialkylchlorosilane (11) can be used again for the reaction.

The branched silicone represented by the general formula (9) can be produced, for example, according to the following reaction formula.

[0033]

Embedded image

(Wherein, R ⁷ , w and x have the same meaning as described above, and X represents a halogen atom). That is, the reaction of tri- or tetrahalogenosilane (12) with hydroxyorganopolysiloxane (13) Thereby, a branched silicone (9) can be obtained. This reaction is
It is preferable to carry out in the presence of a base.

In the component (b), the cyclic silicone includes, for example, the following general formula (14):

[0036]

Embedded image

(Wherein R ⁸ and R ⁹ may be the same or different and represent an alkyl group, an alkenyl group, an aryl group or a halogenated alkyl group, and a represents a number of 6 to 8). Can be listed.

In the general formula (14), among the groups represented by R ⁸ and R ⁹ , the alkyl group is preferably one having 1 to 10 carbon atoms, for example, methyl group, ethyl group, propyl group, isopropyl group, n -Butyl group, tert-butyl group, pentyl group, hexyl group, heptyl group, octyl group, nonyl group, decyl group, etc .; The alkenyl group is preferably one having 2 to 6 carbon atoms, for example, vinyl Groups, 1-propenyl group, allyl group, 1-butenyl group, 2-pentenyl group and the like; aryl groups such as phenyl group; and halogenated alkyl groups such as 3 , 3,3
-Trifluoropropyl group and the like.

As a specific example of the cyclic silicone represented by the general formula (14), DC246 manufactured by Dow Corning Toray Silicone Co., Ltd. can be mentioned as a commercially available product. Such a cyclic silicone can be obtained as a by-product during the synthesis of a cyclic organopolysiloxane having a small number of siloxane units (e.g., 5 or less) such as octamethylcyclotetrasiloxane. Is difficult to obtain in large quantities as a single product. However, according to, for example, the method represented by the following reaction formula, a large amount of highly pure substances can be obtained.

[0040]

Embedded image

(Wherein, R ⁸ and R ⁹ have the same meanings as described above, X represents a halogen atom, b represents an integer of 3 to 5, c represents an integer of 0 to 2) By reacting the dihalogenosilane derivative (16) with the, ω-dihydroxyorganopolysiloxane (15), a cyclic silicone represented by the general formula (14) can be obtained.

The α, ω- used as a raw material in this reaction
The dihydroxyorganopolysiloxane (15) can be produced, for example, according to the following reaction formula.

[0043]

Embedded image

(Wherein R ⁸ , R ⁹ and b have the same meaning as described above), that is, the cyclic silicone (17) is reacted with chlorosilane (18) and water in the presence of an inorganic solid compound to obtain α, An α, ω-dihydroxyorganopolysiloxane (15) can be obtained by converting it into an ω-dihydrogen organopolysiloxane (19) and then hydroxylating it. In addition, as an inorganic solid compound used here, the same thing as the above can be mentioned.

The α, ω-dihydrogen organopolysiloxane (20) is hydroxylated to form α, ω-dihydrogen organopolysiloxane (20).
Without dihydroxyorganopolysiloxane (21),
By reacting this with chlorosilane (18),
An α, ω-dihydrogen organopolysiloxane (19) in which the number of siloxanes has been extended by 2 units can be obtained.
α, ω-dihydroxyorganopolysiloxane (15)
Can be obtained.

The reaction of the α, ω-dihydroxyorganopolysiloxane (15) with the dihalogenosilane derivative (16) is carried out, for example, in the presence of a base such as pyridine, in the presence of pentane,
The reaction is performed in a hydrocarbon-based solvent such as hexane, heptane, benzene, and toluene or a halogenated hydrocarbon-based solvent such as chloroform and dichloromethane. Since this reaction is a ring closure reaction by two molecules, the solution is preferably as dilute as possible to improve the yield. Specifically, a low-concentration α, ω-dihydroxyorganopolysiloxane (15) and also a low-concentration solution of a base and a dihalogenosilane derivative (16) are dissolved in a large amount of an organic solvent as much as possible.
It is preferable to drop at the same speed over as long a time as possible. The concentration of the reaction solution is 0.001 to 10 mol /
l, preferably 0.05 to 1 mol / l, and the dropping time is 1 to 100 hours, preferably 5 to 20 hours.

In this reaction, α, and α are selected depending on the number of siloxane units of the intended cyclic silicone (14).
A plurality of combinations of the ω-dihydroxyorganopolysiloxane (15) and the dihalogenosilane derivative (16) (for example, dialkyldihalogenosilane, α, ω-dihalogenoorganopolysiloxane) can be considered. It can be appropriately selected in consideration of the above. For example, in the case of obtaining tetradecamethylcycloheptasiloxane, an α, ω-dihydroxyorganopolysiloxane (15) having an R ⁸ = R ⁹ = methyl group and b = 4 is used, and a dialkyldihalogenosilane (16) is used. Is preferably used as dimethyldichlorosilane. Also,
To obtain hexadecamethylcyclooctasiloxane, α, ω-dihydroxyorganopolysiloxane (1
As 5), those having R ⁸ = R ⁹ = methyl group and b = 4 are used, and α, ω-dihalogenoorganopolysiloxane (1
6) as R ⁸ = R ⁹ = methyl group, c = 1, X = Cl
It is preferable to use

The chain silicone and the cyclic silicone as the component (b) have a volatilization rate at 30 ° C. of 5.0 × 10 ⁻⁵ or more.
1.7 × 10 ⁻³ g / cm ² · H, preferably 6.7 × 10
^{-5 to} 1.7 × 10 ⁻³ g / cm ² · H. If it is less than 5.0 × 10 ⁻⁵ g / cm ² · H, elongation is heavy,
Those lacking a refreshing feeling and exceeding 1.7 × 10 ⁻³ g / cm ² · H are not preferred because the feel becomes powdery. In addition,
This volatilization rate can be determined by precisely weighing about 1 g of a chain silicone or a cyclic silicone in a petri dish (diameter 48 mm), placing it on a hot plate having a surface temperature of 30 ° C., and examining the weight loss over time. . As such a chain silicone and a cyclic silicone, for example, tetradecamethylhexasiloxane (1.6 × 10
^{-4 g / cm 2 · H)} , hexadecanol Methylheptadecanoic siloxane ^{(2.1 × 10 -4 g / cm} 2 · H), tetradecanol methyl cycloheptanone siloxane ^{(1.3 × 10 -4 g / cm} 2 · H)
And the like.

In the present invention, the volatilization rate at 30 ° C. is from 5.0 × 10 ^{−5 to} 1.7 × 10 ⁻³ g / cm ² ···
Silicones other than H can also be used, and any types or combinations of silicones can be used as long as the volatilization rate of the entire silicone compound falls within the above range.

The chain silicone and / or cyclic silicone of the component (b) is preferably contained in the total composition in an amount of 1 to 70%, more preferably 1 to 40%, more preferably 1 to 30%, to further prevent makeup loss. It is preferable because it is possible.

It is preferable that the cosmetic of the present invention further contain a powder treated with a fluorine compound in addition to the components (a) and (b), since the makeup can be further prevented from being lost. As the fluorine compound-treated powder, for example, the following general formula (22);

[0052]

Embedded image

(In the formula, R _{f ″} represents a perfluoroalkyl group or a perfluorooxyalkyl group having 3 to 21 carbon atoms, and may be linear or branched, of a single chain length, or of a mixed chain length. D represents an integer of 1 to 12,
e shows the number of 1-3. M ¹ represents a water-soluble cation such as hydrogen, metal, ammonium, substituted ammonium, etc.) Perfluoroalkyl group-containing phosphate (see US Pat. No. 3,632,744), monoester of fluoroalkyl phosphate diethanolamine salt Isomers and diesters (see JP-A-62-250074), resins having a perfluoroalkyl group (see JP-A-5-25974)
No. 5-167209), ethylene tetrafluoride resin,
Powders treated with a perfluoroalcohol, a perfluoroepoxy compound, a sulfoamide type fluorophosphoric acid, a perfluorosulfate, a perfluorocarboxylate, a perfluoroalkylsilane (see JP-A-2-218603), and the like. Can be. Of these,
In the general formula (11), R _{f ″} represents a perfluoroalkyl group or a perfluorooxyalkyl group having 5 to 18 carbon atoms, d represents an integer of 1 to 4, e represents a number of 1 to 2,
A powder in which M ¹ is treated with a perfluoroalkyl group-containing ester which is a water-soluble cation such as hydrogen, metal, ammonium, or substituted ammonium is preferred.

The base powder to be treated with these fluorine compounds is not particularly limited as long as it is a pigment or a substance which absorbs ultraviolet rays substantially insoluble in water and oil. Iron, ultramarine, zinc oxide, magnesium oxide, zirconium oxide, mica, sericite, talc, silica, kaolin, chromium hydroxide, inorganic pigments such as carbon black, nylon powder, polymethyl methacrylate, styrene-divinylbenzene copolymer, Organic powders such as polyethylene powders and organic dyes can be mentioned. Among these, when the cosmetic is a foundation, titanium oxide, iron oxide, zinc oxide, sericite, mica, talc, nylon powder and the like are preferable. In order to treat these powders with the above-mentioned fluorine compound, a conventional method may be used, for example, a wet treatment method such as a coacervation method or a topping method, or a dry treatment method such as a spray dry method or a CVD method. Method.

Such a fluorine compound-treated powder can be used alone or in combination of two or more kinds. It is preferable that the powder be used in an amount of 0.01 to 99% in the total composition, and particularly 0.1 to 99%.
It is preferable to mix 1 to 99%, more preferably 1 to 95%, because it is excellent in makeup durability and good in use feeling. In the case of a powder type foundation, it is preferable to add 20 to 95%, and in the case of a liquid type foundation, 1 to 95% is used.
It is preferable to mix up to 40%.

In the cosmetic of the present invention, in addition to the above-mentioned components, if necessary, components to be added to ordinary cosmetics can be added. For example, petrolatum, lanolin, ceresin,
Solids such as microcrystalline wax, carnauba wax, candelilla wax, higher fatty acids, higher alcohols, etc.
Semisolid oil, water-soluble and oil-soluble polymers, inorganic and organic pigments, inorganic and organic pigments treated with silicone, coloring agents such as organic dyes, anionic activators, cationic activators,
Nonionic surfactants, dimethylpolysiloxane / polyoxyalkylene copolymers, surfactants such as polyether-modified silicone, water, preservatives, antioxidants, dyes, thickeners, pH adjusters, fragrances, UV absorption Agents, moisturizers, blood circulation enhancers, cooling agents, antiperspirants, bactericides, skin activators, and the like can be blended within a qualitative and quantitative range that does not impair the objects and effects of the present invention.

The cosmetic of the present invention can be produced according to a conventional method, and can be applied as many cosmetics such as blusher, eyeshadow, foundation, whitening, cream, lotion and the like.

[0058]

Industrial Applicability The cosmetic of the present invention has excellent water resistance and oil resistance, and at the same time, allows an appropriate amount of oil to remain on the skin. Therefore, it has a light feeling without stickiness and has no powdery feeling after use and no feeling of tightness of the skin. In addition, it is possible to prevent the medicinal and cosmetic ingredients from wetting or disappearing due to sweat, sebum, and the like, to prevent the makeup from breaking down due to aging of the face over time, and to stably maintain the initial makeup state. Furthermore, it has excellent stability of cosmetics

[0059]

EXAMPLES The present invention will be described in more detail with reference to the following Examples, but it should not be construed that the invention is limited thereto. In the following, some of the chemical formulas are abbreviated as follows.

[0060]

Embedded image

Production Example 1 150 g of a pigment was placed in a round bottom flask (or kneader).
Heat to 60 ° C. with mixing. In addition, (C ₆ F ₁₃
13 g of CH ₂ CH ₂ O) ₂ P (O) OH dissolved and heated (50 ° C.) in 1500 g of isopropyl ether was added and mixed at 60 ° C. for 4 hours. After that, 50-6
At 0 ° C., isopropyl ether was distilled off under reduced pressure and dried to obtain 157 g of a fluorine compound-treated pigment.

Production Example 2 150 g of a pigment was placed in a round bottom flask (or kneader).
Heat to 60 ° C. with mixing. In addition, (C ₈ F ₁₇
13 g of CH ₂ CH ₂ O) ₂ P (O) OH dissolved and heated (50 ° C.) in 1500 g of isopropyl ether was added and mixed at 60 ° C. for 4 hours. After that, 50-6
Isopropyl ether was distilled off under reduced pressure at 0 ° C. and dried to obtain 161 g of a fluorine compound-treated pigment.

Production Example 3

[0064]

Embedded image

[0065] double neck flask 100ml equipped with a condenser and magnetic stirrer, under nitrogen atmosphere, methyl hydrogen polysiloxane _{^{(H MD 4 M H) 11.0g}} (25.5mmol), C 8
_{F 17 -CH 2 CH 2 -O-} CH 2 CH (OH) CH 2 -O-
35.4 g (61.3 mmol) of CH ₂ CH = CH _2, 40 μl of a 2% isopropyl alcohol solution of chloroplatinic acid
(1.2 × 10 ⁻³ mmol) and stirred at 60 ° C. for 6 hours. The reaction mixture was cooled to room temperature, and the unreacted compound was distilled off under reduced pressure to obtain 38.0 g of the target fluorine-modified silicone (A-1) represented by the above formula as a colorless and transparent oil (yield). 94%).

Production Example 4

[0067]

Embedded image

The apparatus used in Production Example 3 has the following formula:

[0069]

Embedded image

The methyl hydrogen polysiloxane represented by
6.0 g (14.0 mmol) of Shiba Silicone Co., Ltd.
₆F₁₃-CH_TwoCH_Two-O-CH_Two)_TwoCH-O-CH_TwoCH
= CH _Two27.6 g (33.5 mmol), 2 of chloroplatinic acid
110.5 μl (4.0%)
× 10^-3mmol), and in the same manner as in Production Example 3,
The desired fluorine-modified silicone represented by the above formula (A
-2) 23.2 g was obtained as a colorless and transparent oil (yield)
80%).

Production Example 5

[0072]

Embedded image

The apparatus used in Production Example 3 was placed under a nitrogen atmosphere.
Xylene 12 ml, methyl hydrogen polysiloxane ^(H MD ₄ M
^{H) 12.0g (27.8mmol), C} 10 F 21 -CH 2 CH
_{2 -O-CH 2 CH = CH} 2 40.4g (66.8mmo
l) 2% chloroplatinic acid solution in isopropyl alcohol 1
In the same manner as in Production Example 3, 41.0 g of the objective fluorine-modified silicone (A-3) represented by the above formula was added in an amount of 01 μl (3.1 × 10 ⁻³ mmol) to give a colorless and transparent wax. (Yield 90%). Its melting point is 3
7.0 ° C.

Production Example 6

[0075]

Embedded image

The apparatus used in Production Example 3 was charged with 19.0 g (44.1 mmol) of methyl hydrogen polysiloxane (MD ₂ ^DH ₂ ^MH ) (manufactured by Toshiba Silicone Co., Ltd.) and C ₈ F ₁₇ —CH ₂ CH ₂ −
_{O-CH 2 CH = CH 2} 53.3g (105.8mmol)
Was charged. Next, after the temperature in the flask was raised to 80 ° C., 174.5 μl of a 2% isopropyl alcohol solution of chloroplatinic acid was added, and the mixture was stirred for 5 hours. After cooling the reaction mixture to room temperature, 50 ml of hexane and activated carbon 2.
2 g was added, and the mixture was stirred at room temperature for 1 hour. Thereafter, the activated carbon was filtered off, and the solvent was distilled off. The unreacted compound was distilled off under reduced pressure to obtain 49.4 g of the objective fluorine-modified silicone (A-4) represented by the above formula as a colorless and transparent oil (yield: 78%).

Production Example 7

[0078]

Embedded image

The apparatus used in Production Example 3 was charged with 25.0 g (58.0 mmol) of methyl hydrogen polysiloxane (MD ₂ ^DH ₂ ^MH ) (manufactured by Toshiba Silicone Co., Ltd.) and CH ₂ ＣＨCH—CH ₂ —C.
50.1 g (139.2 mmol) of (CF ₃ ) ₂ C ₃ F ₇ was charged. Next, after raising the temperature in the flask to 80 ° C., a 2% chloroplatinic acid solution in isopropyl alcohol 23 was added.
0.0 μl (7.0 × 10 ⁻³ mmol) was added, and the mixture was stirred for 5 hours. Hereinafter, in the same manner as in Production Example 6, 58.3 g of the target fluorine-modified silicone (A-5) represented by the above formula is obtained.
Was obtained as a colorless transparent oil (yield 87%).

Production Example 8

[0081]

Embedded image

In the apparatus used in Production Example 3, 20 m
l, methyl hydrogen polysiloxane (MD _TwoD^H _TwoM^H) 6.4
g (14.9 mmol), C₆F₁₃-CH_TwoCH_Two-O-CH_Two
CH (OCOC₇F₁₅) -CH_Two-O-CH_TwoCH = CH
_Two31.2 g (35.6 mmol), 2% isochloroplatinic acid
58.9 μl of propyl alcohol solution (0.89 × 10
^-3mmol), and the target was prepared in the same manner as in Production Example 3.
Fluorine-modified silicone represented by the above formula (A-6)
25.2 g was obtained as a colorless and transparent oil (yield: 78).
%).

Production Example 9 Tetradecamethylcycloheptasiloxane (formula (14)
Where R ⁸ = R ⁹ = methyl group, a = 7): pH =
446.3 g of a 7.3 phosphate buffer solution, 2.2 g of 1,4-dioxane and 22.3 g of 5% palladium on carbon
Was placed in a 5-liter three-necked flask equipped with a stirrer. To this, 270 g of 1,11-dihydrogendecamethylhexasiloxane was added dropwise over 1 hour, and after completion of the addition, stirring was continued for another 1 hour. Next, 5% palladium carbon was filtered, and 2 liters of benzene was added. At this time, since the solution was separated into two layers, the lower aqueous layer was separated, and 0.4 liter of water was added to wash the benzene layer.
After repeating this operation twice more, the obtained 1,11
-A benzene solution of dihydroxydodecamethylhexasiloxane was concentrated under reduced pressure to 1.5 liters. Benzene 3
Liter into a 10 liter three-necked flask equipped with a stirrer, and dimethylchlorosilane 8
1.5 g of a benzene solution of 1.3 g and 99 g of pyridine and 1.5 l of a benzene solution of 1,11-dihydroxydodecamethylhexasiloxane were added at the same speed to 12 l.
It was dropped over time. After completion of the dropwise addition, stirring was further continued for 2 hours, and the precipitated pyridine hydrochloride was filtered. The filtrate was concentrated under reduced pressure to a total volume of 2 liters, the benzene layer was twice with 0.5 liter of water, twice with 0.5 liter of 10% sodium hydrogen carbonate solution and finally with 0.5 liter of water. Washed twice. The benzene was distilled off, and the resulting solution was distilled under reduced pressure to give 150.5 g of the title compound (46.3% yield).
I got The volatilization rate of the obtained tetradecamethylcycloheptasiloxane at 30 ° C. is 1.3 × 10 ⁻⁴ g / cm.
² · H.

Production Example 10 Hexadecamethylcyclooctasiloxane (formula (14)
Where R ⁸ = R ⁹ = methyl group, a = 8): pH =
430 g of the 7.3 phosphate buffer solution, 2.1 g of 1,4-dioxane and 10.7 g of 5% palladium on carbon were placed in a 5-liter three-necked flask equipped with a stirrer. To this, 251.7 g of 1,11-dihydrogendecamethylhexasiloxane was added dropwise over 1 hour, and after the addition was completed, stirring was further continued for 1 hour. Next, 5% palladium carbon was filtered, and 2 liters of benzene was added. At this time, the solution was separated into two layers, and the lower aqueous layer was separated.
0.4 L of water was added to wash the benzene layer. After repeating this operation two more times, the obtained benzene solution of 1,11-dihydroxydodecamethylhexasiloxane was concentrated under reduced pressure to 1.5 liter. 3 liters of benzene was placed in a 10 liter three-necked flask equipped with a stirrer, and 1.5 liters of a benzene solution of 122.5 g of 1,3-dichlorotetrasiloxane and 95.4 g of pyridine were added to the mixture under stirring. 1.5 liters of a benzene solution of dihydroxydodecamethylhexasiloxane is
It dripped at the same speed over 12 hours. After dropping, 2 more
Stirring was continued for an hour, and the precipitated hydrochloride of pyridine was filtered. The filtrate was concentrated under reduced pressure to a total volume of 3 l, and the benzene layer was washed twice with 0.5 l of water, twice with 0.5 l of a 10% sodium hydrogen carbonate solution and finally twice with water. The benzene was distilled off, and the obtained solution was distilled under reduced pressure to obtain 127.3 g of the title compound (yield: 35.6%).
I got The volatilization rate of the obtained hexadecamethylcyclooctasiloxane at 30 ° C. is 5.2 × 10 ⁻⁵ g / cm.
² · H.

Production Example 11 Tetradecamethylhexasiloxane (in the formula (8), R ⁷
Are all methyl groups, v = 4): In a 500 ml flask equipped with a dropping funnel, 100 g of octamethylcyclotetrasiloxane, 60.6 g of water, silica gel (Kieselgel 60, manufactured by Merck, 250 to 400 mesh) 1
0.1 g was added, and 109.9 g of trimethylchlorosilane was added dropwise over 1 hour with sufficient stirring. After 10 hours, the stirring was stopped, the silica gel was filtered, and the obtained filtrate was concentrated under reduced pressure to remove excess trimethylchlorosilane. Transfer the resulting solution to a separatory funnel to separate the aqueous layer,
The oil layer was separated twice with 50 ml of water, 50 ml of a saturated aqueous solution of sodium hydrogencarbonate and twice with 50 ml of water. The obtained solution was distilled under reduced pressure to obtain 63.5 g (yield 78%) of the title compound. 30 of the obtained tetradecamethylhexasiloxane
The volatilization rate at 1.6 ° C. was 1.6 × 10 ⁻⁴ g / cm ² · H.

Production Example 12 Hexadecamethylheptasiloxane (in the formula (8), R ⁷
Are all methyl groups, v = 5): In a 500 ml flask equipped with a dropping funnel, 150 g of decamethylcyclopentasiloxane, 73.2 g of water, silica gel (Kieselgel 60, manufactured by Merck, 250 to 400 mesh)
2 g was added, and 132 g of trimethylchlorosilane was added dropwise over 1 hour with sufficient stirring. After 11 hours, the stirring was stopped, the silica gel was filtered, and the obtained filtrate was concentrated under reduced pressure to remove excess trimethylchlorosilane. The resulting solution was transferred to a separatory funnel to separate the aqueous layer, and the oil layer was washed twice with 50 ml of water and 50 ml of a saturated aqueous sodium hydrogen carbonate solution.
l, and liquid separation was performed twice with 50 ml of water. The resulting solution was distilled under reduced pressure to obtain 78.8 g (yield: 67.1%) of the title compound. 30 of the obtained hexadecamethylheptasiloxane
The rate of volatilization at ° C. was 2.1 × 10 ⁻⁴ g / cm ² · H.

Examples 1 to 13 and Comparative Examples 1 to 4 (Two-layer liquid foundation): Two-layer liquid foundations having the compositions shown in Tables 1 to 5 were produced by the following method.
The obtained foundation was evaluated for long-lasting makeup, powderiness and lightness by the following methods. Table 6 shows the results.

(Preparation method) After the oil phase was dissolved at room temperature, a pigment was added and dispersed with a disper. Next, the aqueous phase was added with stirring and emulsified to obtain a two-layer liquid foundation.

(Evaluation Method) Make-up: Sensory evaluation was carried out by 12 specialized panelists, and a five-point evaluation was made according to the following criteria. 5:10 to 12 were judged to be good. 4: 8 to 9 persons are judged to be good. 3: 6 to 7 persons were judged to be good. 2: 4 to 5 persons were judged to be good. 1: It was judged that less than 4 people were good. Powderiness and refreshing feeling: Sensory evaluation was performed by 10 specialized panelists and evaluated according to the following criteria. ：: Eight or more were judged to be good. Δ: 4 to 7 persons were judged to be good. ×: It was judged that less than 4 people were good.

[0090]

[Table 1]

[0091]

[Table 2]

[0092]

[Table 3]

[0093]

[Table 4]

[0094]

[Table 5]

* 1: Evaporation rate at 30 ° C. 9.4 × 10
^-4 g / cm ² · H * 2: Volatility at 30 ° C. 1.7 × 10 ⁻³ g / cm ² · H
H * 3: volatilization rate at 30 ° C. 6.6 × 10 ⁻³ g / cm ² ·
H

[0096]

[Table 6]

As is evident from Table 6, the cosmetics of the present invention were all excellent in the long-lasting, powdery and refreshing feeling. Also, the emulsion stability was excellent.

Examples 14 to 19 and Comparative Example 5 (Emulsion):
Emulsions having the compositions shown in Table 7 were produced by a conventional method, and the emulsion stability was tested by the following method.

(Evaluation Method) The emulsion was stored at 40 ° C., and the condition after one month was visually observed and evaluated according to the following criteria. ：: good without state change. Δ: Slight separation / aggregation. X: Separation / aggregation, poor emulsification.

[0100]

[Table 7]

From the results shown in Table 7, the emulsions of the present invention did not change at all and maintained the initial emulsified state.

Example 20 (Cream Foundation) A cream foundation having the following composition was obtained in the same manner as in Example 1.

(Composition) (%) (1) Fluorine compound-treated pigment (manufactured in the same manner as in Production Example 1) Titanium oxide 6.0 Sericite 8.0 Iron oxide (red, yellow, black) 1.2 ( 2) Decamethylcyclopentasiloxane 15.0 (3) Fluorine-modified silicone (Production Example 14) 20.0 (4) Dimethylpolysiloxane (SH200C, manufactured by Toray Dow Corning Silicone Co., Ltd.) 10.0 (5) Dimethylpolysiloxane poly Oxyalkylene copolymer 5.0 (6) Glycerin 2.0 (7) Water remaining (6) Fragrance trace

This cream-like foundation was excellent in long-lasting makeup and feeling in use.

Example 21 (Powder Foundation): In the following composition, first, a pigment was mixed and pulverized through a pulverizer. This was transferred to a high-speed blender, and a binder and the like were mixed. This was processed with a crusher, and the particle size was adjusted through a sieve, and then compression-molded in a container such as a gold plate to obtain a powder foundation.

[0105]

(Composition) (%) (1) Fluorine compound-treated pigment (manufactured in the same manner as in Production Example 1) Titanium oxide 10.0 Sericite 25.0 Talc 30.0 Kaolin 5.0 Bengala 2.0 Yellow Iron oxide 2.5 Black iron oxide 0.1 Polyethylene powder 4.0 (2) Squalane 2.0 (3) Fluorine-modified silicone (Production Example 6) 7.0 (4) Hexadecamethylheptasiloxane (Production Example 12) 6.0 (5) Preservative appropriate amount (6) Fragrance trace amount

The powder foundation was excellent in keeping makeup and feeling of use.

Example 22 (blusher): A blusher having the following composition was obtained in the same manner as in Example 21.

[0108]

(Composition) (%) (1) Fluorine compound-treated pigment (produced in the same manner as in Production Example 1) Kaolin 40.0 Mica 13.0 Titanium oxide 18.0 Iron oxide (red, yellow, black) 5 2.0 (2) Organic pigment (Red No. 202) 2.4 (3) Fluorine-modified silicone (manufactured by Asahi Glass Co., Ltd., FSL-300) 10.0 (4) Hexadecamethylcyclooctasiloxane (Production Example 10) 10.4 (5) Preservative 0.1 (6) Appropriate amount of fragrance

This blusher was excellent in long-lasting makeup and feeling in use.

Example 23 (Powder Eye Shadow): A pigment other than titanium mica was first mixed and pulverized, and then titanium mica was mixed. Otherwise, in the same manner as in Example 21, a powder eye shadow having the following composition was obtained.

[0111]

(Composition) (%) (1) Fluorine compound-treated pigment (manufactured in the same manner as in Production Example 1) Mica titanium 5.0 sericite 26.0 mica 24.0 Iron oxide (red, yellow, black) 2.0 Ultramarine Blue 10.0 Navy Blue 6.0 (2) Fluorine-modified silicone (manufactured by Toray Dow Corning Silicone Co., Ltd., FS-1265) 7.0 (3) Tetradecamethylcycloheptasiloxane (Production Example 9) 7.0 ( 4) Squalane 3.0 (5) Preservative appropriate amount (6) Fragrance trace amount

The powder eyeshadow was excellent in keeping makeup and feeling of use.

Example 24 (Sunscreen emulsion) A sunscreen emulsion having the following composition was obtained in the same manner as in Example 1.

[0114]

(Composition) (%) (1) Octamethylcyclotetrasiloxane 20.0 (2) Fluorine-modified silicone (Production Example 7) 5.0 (3) Dimethylpolysiloxane polyoxyalkylene copolymer 3.0 (4) Glycerin 2.0 (5) Ethanol 5.0 (6) Remaining water (7) Fluorine compound treated pigment (manufactured in the same manner as in Production Example 1; fine particle titanium oxide) 7.4 (8) Dodecamethylenecyclohexene Sasiloxane (Toray Dow Corning Silicone Co., Ltd., DC-246) 10.0 (9) Octyl methoxycinnamate 2.0 (10) Fragrance trace amount

The sunscreen emulsion was excellent in keeping makeup and feeling of use.

Example 25 (moisturizing cream): A moisturizing cream having the following composition was produced by a conventional method.

[0117]

(Composition) (%) (1) Dimethylpolysiloxane (KF-96L, manufactured by Shin-Etsu Chemical Co., Ltd.) 7.0 (2) Octamethylcyclotetrasiloxane 7.0 (3) Methylphenylpolysiloxane 0 (4) Fluorine-modified silicone (Production Example 6) 7.0 (5) Butylparaben 0.2 (6) Glycerin 5.0 (7) Sodium citrate 1.0 (8) L-ascorbic acid phosphate magnesium Salt 3.0 (9) Methyl paraben 0.2 (10) Purified water

The moisturizing cream was excellent in keeping makeup and feeling of use.

Continuation of front page (56) References JP-A-4-187611 (JP, A) JP-A-4-308520 (JP, A) JP-A-5-247214 (JP, A) JP-A-4-305510 (JP) , A) (58) Field surveyed (Int. Cl. ⁷ , DB name) A61K 7/02 C08L 83/08

Claims (2)

(57) [Claims] (A) a fluorine-modified silicone and (b)
Volatilization rate at 30 ° C. is 5.0 × 10 ^{−5 to} 1.7 × 1
A cosmetic comprising a linear silicone and / or a cyclic silicone of 0 ^-3 g / cm ² · H. 2. The cosmetic according to claim 1, further comprising (c) a fluorine compound-treated powder.