JPH07216090A - Fluorine-modified silicone, method for producing the same and cosmetic containing the same - Google Patents

Abstract

PURPOSE:To obtain the subject silicone having specific siloxane units, having an excellent water-repelling and oil-repelling property, well compatible with skin, and suitable for cosmetics. CONSTITUTION:This silicone is a fluorine-modified silicone derivative having silicone units of formula I (R<1> is a 1-20C aliphatic hydrocarbon, a 5-10C alicyclic or an aromatic hydrocarbon; (m) is 0-10) and has a polymerization degree of 1-400, preferably the silicone having 1-200 units of formula I and 0-200 silicone units of formula II (R<2>, R<3> are each a 1-20C aliphatic hydrocarbon, a 5-10C alicyclic or an aromatic hydrocarbon).

Description

Detailed Description of the Invention

[0001]

FIELD OF THE INVENTION The present invention relates to a fluorine-modified silicone, a method for producing the same, and a cosmetic composition containing the same, more specifically, a novel fluorine-modified silicone having excellent water / oil repellency, a method for producing the same and the same. The present invention relates to a cosmetic containing a long-lasting makeup and a good feeling in use.

[0002]

2. Description of the Related Art Conventionally, various water-repellent cosmetics have been used for the purpose of protecting the skin from water and sweat and for preventing makeup from being damaged by water and sweat. For example, a skin protection cosmetic such as a skin cream or a skin lotion or a makeup cosmetic contains a silicone oil or a silicone resin as a water-repellent component. However, although these silicone oils and silicone resins have some effect on water repellency, they do not have sufficient effect on oil repellency. Therefore, there is a problem that cosmetics containing these components may cause makeup deterioration due to sebum.

Therefore, attempts have been made in various fields to develop compounds having both water repellency and oil repellency.
For example, JP-A-2-295912 discloses that cosmetics containing a fluorine-modified silicone compound such as trifluoropropyl silicone have excellent water resistance and sebum resistance.

By the way, the water-repellent / oil-repellent base used in cosmetics has (a) sufficient water-repellency and oil-repellency against sweat and sebum, and (b) excellent emulsion stability, (C) It is necessary to satisfy all the conditions such as strong mechanical contact (for example, when held with a handkerchief, tissue, etc.), difficulty in removing makeup, and (d) low viscosity and good usability.

[0005]

However, the above-mentioned fluorine-modified silicone compound still does not sufficiently satisfy these conditions, and its emulsion stability is poor due to its poor compatibility with general cosmetic bases. Poor, it has a low skin affinity, so it is easy to remove by contact (for example, when it is held by a handkerchief, tissue, etc.), and furthermore, it has a problem that it has a poor spreadability during application because of its high viscosity.

Therefore, in addition to being excellent in water and oil repellency,
It has been desired to develop a compound that is stable even when blended in cosmetics and gives a good feeling of use without causing makeup deterioration when used.

[0007]

Means for Solving the Problems As a result of intensive studies in view of such circumstances, the present inventors have found that a fluorine-modified silicone derivative having a specific branched perfluoroalkyl group described below has excellent water repellency and oil repellency. The inventors have found that they are well adapted to the skin and exhibit good compatibility with cosmetics, and have completed the present invention.

That is, the present invention provides at least one general formula (1)

[0009]

[Chemical 5]

[Wherein R ¹ represents 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, and m is 0 to The invention provides a fluorine-modified silicone derivative (A) having a degree of polymerization of 1 to 400, which has a siloxane unit represented by the formula [10], and a method for producing the same.

The present invention also provides a cosmetic containing the fluorine-modified silicone derivative (A).

The fluorine-modified silicone derivative (A) of the present invention has a degree of polymerization (number of siloxane units) of 1 to 400.
And in which at least one of the above general formula (1)
The compound containing the fluorine-modified siloxane unit is more preferably 1 to 200 of the fluorine-modified siloxane unit and 0 to 200 of the siloxane unit represented by the following general formula (2).

[0013]

[Chemical 6]

[In the formula, R ² and R ³ may be the same or different, and may be a linear or branched aliphatic hydrocarbon group having 1 to 20 carbon atoms or an alicyclic or aromatic group having 5 to 10 carbon atoms. Indicates a group hydrocarbon group]

Examples of the hydrocarbon group represented by R ¹ , R ² and R ³ in the fluorine-modified silicone derivative (A) of the present invention include methyl, ethyl, propyl, butyl, pentyl, hexyl, heptyl, octyl, nonyl, Linear alkyl group such as decyl; isopropyl, sec
Examples include branched-chain alkyl groups such as -butyl, tert-butyl, neopentyl, 1-ethylpropyl, and 2-ethylhexyl; cyclic alkyl groups such as cyclopentyl and cyclohexyl; and aromatic hydrocarbon groups such as phenyl and naphthyl.

The number (p) of fluorine-modified siloxane units (1) of the fluorine-modified silicone derivative (A) of the present invention is preferably 1 to 200, particularly preferably 1 to 50, and the number (q) of siloxane units (2). Is preferably 0 to 200, more preferably 0 to 50, and further preferably 2 to 50. The structural ratio p / q of these structural units is preferably in the range of 4/1 to 1/4. Further, of the fluorine-modified silicone derivative (A), a side chain type modified silicone having a fluorine-modified siloxane unit (1) in the chain is preferable.

Further, preferred fluorine-modified silicones include those of the following formula (A ').

[0018]

[Chemical 7]

[Wherein p ′ represents an integer of 0 to 200,
When p ′ is an integer of 1 to 200, R ^{4 to} R ⁹ may be the same or different, and may be a linear or branched aliphatic hydrocarbon group having 1 to 20 carbon atoms or an aliphatic hydrocarbon group having 5 to 10 carbon atoms. Represents a cyclic or aromatic hydrocarbon group, and when p ′ is 0, R ⁴
At least one of R ⁹ to R ⁹ is a group-(CH ₂ ) _{m + 2} --C (CF ₃ ) ₂ (C ₃ F ₇ ).
And the rest represent 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. R ¹ , R ² , R ³ , m and q
Is the same as above]

Among these, the following formulas (A'-1) to
(A'-3) is preferable, and (A'-3) is particularly preferable.

[0021]

[Chemical 8]

[Wherein, m, p and q are the same as above]

The fluorine-modified silicone derivative (A) of the present invention contains, for example, at least one compound represented by the general formula (3):

[0024]

[Chemical 9]

[Wherein R ¹ is the same as above] and a silicone derivative (B) having a degree of polymerization of 1 to 400 having a siloxane unit and a general formula (4)

[0026]

[Chemical 10]

It can be produced by reacting with a perfluoroalkyl compound represented by the formula [wherein m represents an integer of 0 to 10].

The silicone derivative (B) may be any one containing at least one siloxane unit (3).
The molecular structure and the like are not particularly limited, and various known ones can be used. Specific examples of the silicone derivative (B) include one-terminal type methyl hydrogen polysiloxane such as pentamethyldisiloxane and tridecamethylhexasiloxane, tetramethyldisiloxane, hexamethyltrisiloxane, octamethyltetrasiloxane,
Both-end-type methylhydrogenpolysiloxanes such as dodecamethylhexasiloxane and commercially available methylhydrogenpolysiloxanes such as "TSF484", "TSF483" manufactured by Toshiba Silicone Co., Ltd., "KF99" manufactured by Shin-Etsu Chemical Co., Ltd., etc. Is mentioned.

The compound represented by the general formula (4) can be obtained, for example, from W. Dmowski and Wozniaacki,
J. Fluorine Chem. , 36 (1987)
It can be manufactured by the following method according to the method described in 385.

[0030]

[Chemical 11]

[Wherein M is an alkali metal, X is Cl,
Represents a halogen atom such as Br or I, and m is the same as above]

That is, hexafluoropropene (5)
The compound (4) can be obtained by reacting the dimer (6) with the halogenated alkene (7). Halogenated alkenes (7) have m of 0 in terms of reactivity and economy.
It is preferable that X is Br or I in the formula (1) to (8). Specific examples thereof include vinyl halide, allyl halide, halogenated butene, halogenated hexene, halogenated octene,
Examples thereof include halogenated decene and halogenated dodecene. In this reaction, the compound represented by the general formula (7) is used in an amount of 1 molar equivalent or more, preferably 1.0 to 1.5 molar equivalents, relative to the compound represented by the general formula (6).
This reaction is carried out by using a solvent as necessary and heating and stirring in the temperature range of 0 to 200 ° C, preferably 10 to 100 ° C.

The reaction of the compound (4) thus obtained with the silicone derivative (B) is carried out in the presence of a catalyst. The catalysts used are those generally used for hydrosilylation, for example free radical initiators;
Examples thereof include complex compounds of metals such as ruthenium, rhodium, palladium, osmium, iridium, and platinum; and those obtained by supporting these on silica gel or alumina. Of these, chloroplatinic acid, Speier's reagent (chloroplatinic acid in isopropyl alcohol) and the like are particularly preferable.
The amount of the catalyst used is the silicone derivative (B) and the compound (4).
The amount is not particularly limited as long as it is sufficient to promote the reaction with, but is not limited to 10 ^-6 to 1 with respect to 1 mol of the compound (4).
A range of 0 ^-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, but for example, hydrocarbon solvents such as pentane, hexane and cyclohexane; benzene solvents such as benzene, toluene and xylene; diethyl ether,
Ether-based solvents such as diisopropyl ether; alcohol-based solvents such as methanol, ethanol, isopropyl alcohol and butanol are preferable.

The hydrosilylation proceeds at 0 to 200 ° C., but 40 to 15 considering the reaction rate and the coloring of the product.
It is preferably carried out 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 (B) and the compound (4), The combination of amounts and the like may be changed appropriately.

The thus obtained fluorine-modified silicone derivative (A) of the present invention is excellent in water repellency and oil repellency, and various properties such as viscosity can be controlled according to the purpose. When used as an oil agent, it can be made to have long-lasting makeup and excellent feeling in use. In this case, the compounding 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 0.01.
-80%, particularly preferably 0.1-70%, and further preferably 3-30%.

In the cosmetic of the present invention containing the fluorine-modified silicone derivative (A), an oil agent used in ordinary cosmetics can be used. As such an oil agent,
Cyclic silicones such as octamethylcyclotetrasiloxane, decamethylcyclopentasiloxane, and dodecamethylcyclohexasiloxane; nonvolatile silicones such as methylpolysiloxane, dimethylpolysiloxane, and methylphenylpolysiloxane; animal and vegetable oils such as squalane and palm oil. Other examples include hydrocarbons, higher fatty acid esters, liquid paraffin, and iso liquid paraffin.

Further, the cosmetics of the present invention may optionally contain other ingredients such as petrolatum, lanolin, ceresin, microcrystalline wax, carnauba wax, candelilla wax, higher fatty acids and higher alcohols. Solid / semi-solid oils; water-soluble and oil-soluble polymers; inorganic and organic pigments, inorganic or organic pigments treated with silicones or fluorine compounds, colorants such as organic dyes; anionic activators, cationic activators, non- Ionic activator,
Surfactants such as dimethylpolysiloxane / polyoxyalkylene copolymer, polyether modified silicone; other water, preservatives, antioxidants, dyes, thickeners, pH adjusters,
A fragrance, an ultraviolet absorber, a moisturizer, a blood circulation promoter, a cooling sensation, an antiperspirant, a bactericide, a skin activator and the like can be appropriately added within a range that does not impair the effects of the present invention. In particular, it is preferable to use a pigment whose surface is treated with a fluorine compound, because it does not damage the makeup caused by sebum.

The cosmetic composition of the present invention is not particularly limited in its dosage form, kind and the like, and can be manufactured by a usual method. Examples of the kind include oily cosmetics, emulsified cosmetics, aqueous cosmetics, lipsticks, blushers, foundations, skin cleansers, hair cleansers, hair tonics, hair styling agents, hair nourishing agents and hair restorers.

[0041]

The fluorine-modified silicone derivative (A) of the present invention has (1) high water and oil repellency, (2) good compatibility with a cosmetic base, and (3) stable emulsion. Is highly
This fluorine-modified silicone derivative (A) has excellent characteristics such as (4) low viscosity and non-greasiness, (5) high skin affinity and difficulty in removal, and (6) extremely low skin irritation.
The cosmetics containing the composition have an excellent effect that the makeup retention is good and the feeling of use is good.

[0042]

EXAMPLES The present invention will be described in detail below with reference to examples and test examples, but the present invention is not limited thereto. In the following examples, a part of the chemical formula is abbreviated as follows.

[0043]

[Chemical 12]

Example 1

[0045]

[Chemical 13]

100 equipped with stirrer, reflux and thermometer
12.0 g of methyl hydrogen polysiloxane ( ^H MD ₄ ^MH ) (27.
_{8mmol), H 2 C = CHCH} 2 C (CF 3) 2 (C 3 F 7) ( hereinafter, compound (4
24.1 g (66.8 mmol) was charged. Then, after raising the temperature in the flask to 80 ° C., 110.2 μ of a 2% isopropyl alcohol solution of chloroplatinic acid.
1 (3.3 × 10 ⁻³ mmol) was added, and the mixture was stirred for 5 hours. The reaction mixture was cooled to room temperature, 50 ml of hexane and 1.1 g of activated carbon were added, and the mixture was stirred at room temperature for 1 hr. Then, the activated carbon was filtered off and the solvent was distilled off. The unreacted compound (4a) was distilled off under reduced pressure to obtain 30.3 g of the target compound (1a) as a colorless transparent oily substance (yield 95%).

¹ H-NMR [δppm, in CDCl ₃ , CHCl _3
3 standards (7.24 ppm)] data are shown. δ: 0.00 to 0.05 (m, 36H, -SiC H ₃ ), 0.48 to 0.56 (m, 4H, a),
1.53 to 1.61 (m, 4H, b), 2.08 to 2.19 (m, 4H, c) The above Ha to Hc are protons at the following positions.

[0048]

[Chemical 14]

Example 2

[0050]

[Chemical 15]

The apparatus used in Example 1 was charged with 25.0 g (5%) of methyl hydrogen polysiloxane (MD ₂ D ^H ₂ M).
8.0 mmol), 50.1 g of compound (4a) (139.2)
(mmol) was charged. Then, after the temperature inside the flask was raised to 80 ° C., 230.0 μl (7.0 × 10 ⁻³ mmol) of a 2% isopropyl alcohol solution of chloroplatinic acid was added, and the mixture was stirred for 5 hours. By the same method as in Example 1, 58.3 g of the target compound (1b) was obtained as a colorless transparent oily substance (yield 87%).

¹ H-NMR [δppm, in CDCl ₃ , CHCl _3
3 standards (7.24 ppm)] data are shown. δ: -0.01~0.06 (m, 36H, -SiC H 3), 0.45~0.54 (m, 4H, a),
1.50 to 1.73 (m, 4H, b), 2.09 to 2.22 (m, 4H, c) The above Ha to Hc indicate that they are protons at the following positions.

[0053]

[Chemical 16]

Example 3

[0055]

[Chemical 17]

The apparatus used in Example 1 was charged with 20.0 g (2%) of methyl hydrogen polysiloxane (MD ₈ ^DH ₄ M).
0.1 mmol), 34.7 g (96.6 mm) of compound (4a)
ol) was prepared. Next, after the temperature inside the flask was raised to 80 ° C., 470 μl (14.5 × 10 ⁻³ mmol) of a 2% isopropyl alcohol solution of chloroplatinic acid was added, and the mixture was stirred for 5 hours. In the same manner as in Example 1, the target compound (1
c) 45.7 g was obtained as a colorless transparent oil (yield 9
3%).

¹ H-NMR [δ ppm, in CDCl ₃ , CHCl _3
3 standards (7.24 ppm)] data are shown. δ: 0.00~0.03 (m, 78H, -SiC H 3), 0.44~0.53 (m, 8H, a),
1.50 to 1.66 (m, 8H, b), 2.08 to 2.14 (m, 8H, c) The above Ha to Hc indicate that they are protons at the following positions.

[0058]

[Chemical 18]

Example 4

[0060]

[Chemical 19]

29.5 g (2) of methylhydrogenpolysiloxane (MD ₁₂ ^DH ₄ M) was added to the apparatus used in Example 1.
2.8 mmol), 39.4 g (109.5) of compound (4a).
(mmol) was charged. Then, the temperature inside the flask was raised to 80 ° C., 181 μl (5.5 × 10 ⁻³ mmol) of a 2% isopropyl alcohol solution of chloroplatinic acid was added, and the mixture was stirred for 5 hours. In the same manner as in Example 1, the target compound (1
d) 56.0 g was obtained as a colorless transparent oil (yield 9
0%).

¹ H-NMR [δ ppm, in CDCl ₃ , CHCl _3
3 standards (7.24 ppm)] data are shown. δ: -0.01 ~ 0.02 (m, 102H, -SiC H ₃ ), 0.44 ~ 0.54 (m, 8H,
a), 1.51 to 1.68 (m, 8H, b), 2.08 to 2.15 (m, 8H, c) The above Ha to Hc are protons at the following positions.

[0063]

[Chemical 20]

Test Example 1 The water resistance, oil resistance, compatibility with silicone and the difficulty of removing from the skin when used as cosmetics were measured for the compounds of Examples 1 to 3 and Comparative Examples 1 to 3 shown below. The results are shown in Table 1. [Water resistance] The contact angle with water (the angle between the oil film of each oil agent and the water droplet) was 100 ° or more, and ◯ was 70 to less than 100 °. [Oil resistance] The contact angle with squalane (the angle formed by the oil film of each oil agent and the squalane drop) was 50 ° or more, ⊚, 40 to less than 50 ° was ◯, and less than 40 ° was x. [Silicone Compatibility] The solubility in octamethylcyclotetrasiloxane was examined, and the dissolved one was marked with ◯, and the separated one was marked with x. [Difficult to remove from the skin when used as cosmetics] Black iron oxide 1
g and 1 g of sample were evenly kneaded to make a paste, and this paste was applied thinly and evenly to the center of the male forehead, and after 4 hours, the portion applied with tissue paper was 200 g weight / cm ² Hold down with pressure. The dullness of the cosmetics was evaluated by the degree to which the tissue paper was colored by the black iron oxide transferred to the tissue paper. The evaluation criteria were ⊚ for little coloration, ◯ for slightly coloration, Δ for coloration, and X for considerably coloration.

[0065]

[Table 1]

As is clear from the results shown in Table 1, the fluorine-modified silicone derivative of the present invention is superior in water repellency and oil repellency, has a generally low viscosity, and has compatibility with a cosmetic base as compared with conventional products. It is good, and it is found that when it is used as a cosmetic, it is excellent in being hard to be removed from the skin.

Production Example 1 Production of Fluorine Compound Treated Sericite Sericite 1 was placed in a 1-liter round bottom flask (or kneader).
00 g and ion-exchanged water (500 ml) were added thereto, and then 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 in 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 deposited on the powder surface, which was then filtered, washed with water and dried to obtain 105 g of the target fluorine compound-treated sericite. Got

Examples 5 to 7 and Comparative Examples 4 to 6 Two-layer type liquid foundation: Two-layer type liquid foundations having the compositions shown in Table 2 were produced according to the following production method. It evaluated by the following evaluation method. The results are shown in Table 3. (Production method) After dissolving the oil phase at room temperature, the pigment is dispersed with a disper. The aqueous phase is added to this with stirring and emulsified to obtain the intended two-phase liquid foundation.

[0069]

[Table 2]

(Evaluation method) Makeup retention, residue of foundation and feeling of use: Sensory evaluation was performed by 10 professional panelists, and evaluation was made according to the following criteria. The results are shown in Table 3. ○: 8 or more are “good”. Δ: 4 to 7 are “good”. X: “Good” is less than 4 people.

[0071]

[Table 3]

As is clear from Table 3, the liquid foundation of the present invention had a longer lasting make-up and a better feeling of use than those containing conventional silicone.

Example 8 Powder Foundation: A powder foundation having the composition shown in Table 4 was produced by the following production method. (Production method) The pigments are mixed and passed through a crusher to be crushed. This is transferred to a high-speed blender, a binder and the like are heated and mixed, and the homogenized product is added to the pigment and further mixed to homogenize. After processing this with a crusher and passing it through a sieve to make the particle size uniform,
After leaving it for several days, it is compression molded into a container such as a gold plate to obtain a powder foundation.

[0074]

(Table 4) (Composition) (wt%) (1) Fluorine compound-treated pigment (the following pigment was treated in the same manner as in Production Example 1) Titanium oxide 10.0 Sericite 30.0 Mica balance Kaolin 5.0 Bengal 0.1. 8 Yellow iron oxide 2.5 Black iron oxide 0.1 (2) Fluorine-modified silicone of Example 1 8.0 (3) Beeswax 2.0 (4) Preservative 0.2 (5) Perfume Trace amount

Example 9 Cheeks: Cheeks whose composition is shown in Table 5 were obtained in the same manner as in Example 8.

[0076]

(Table 5) (Composition) (wt%) (1) Silicone-treated pigment (commercial product of methylhydrogenpolysiloxane-treated pigment) 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 2 7.0 (3) Dimethylpolysiloxane ("KF96A" manufactured by Shin-Etsu Chemical Co., Ltd., 6cs) 5.0 (4) Preservatives 0. 1 (5) Fragrance, trace amount

Example 10 Powder eyeshadow: Table 6
A powder eye shadow having the composition of was obtained by the following production method. (Production method) Pigments other than titanium mica are first mixed and pulverized, and then titanium mica is mixed. Others are the same as that of Example 8, and the target powder eye shadow is obtained.

[0078]

[Table 6] (Composition) (% by weight) (1) Water-repellent / oil-repellent powder (those treated in the same manner as in Production Example 1 are mixed later) Mica titanium 4.9 Sericite balance mica 25.0 Oxidation Iron (red, yellow, black) 2.0 Ultramarine 9.0 Dark blue 12.0 (2) Fluorine-modified silicone of Example 3 8.0 (3) Squalane 2.0 (4) Vaseline 1.5 (5) Sorbitan Trioleate 1.0 (6) Preservative 0.1 (7) Fragrance Trace

Example 11 Amphoteric powder foundation: An amphoteric powder foundation whose composition is shown in Table 7 was obtained in the same manner as in Example 10.

[0080]

[Table 7] (Composition) (wt%) (1) Silicone treated pigment (commercial product of methylhydrogenpolysiloxane treated pigment) Mica balance talc 4.8 Titanium oxide 14.0 Mica titanium 3.5 Iron oxide (red, yellow) , Black) 8.2 Zinc oxide 4.5 Aluminum oxide 10.0 Barium sulfate 5.0 (2) Fluorine-modified silicone of Example 1 6.0 (3) Lanolin 3.0 (4) Vaseline 1.0 (5) ) Isopropyl myristate 1.0 (6) Preservative 1.5 (7) Fragrance

Example 12 Two-layer sunscreen emulsion:
Example 5 A two-layer sunscreen emulsion having the composition shown in Table 8 was prepared.
It was obtained by the same production method as in .about.7.

[0082]

[Table 8] (Composition) (wt%) (1) Octamethylcyclotetrasiloxane 25.0 (2) Fluorine-modified silicone of Example 2 15.0 (3) Dimethylpolysiloxane / polyoxyalkylene copolymer 1. 0 (4) Glycerin 2.0 (5) Ethanol 12.0 (6) Purified water balance (7) Octyl methoxycinnamate 2.0 (8) Silicone-treated pigment (commercial product of methylhydrogenpolysiloxane-treated pigment) Zinc oxide 5.5 Titanium oxide 2.0 Talc 5.0 (9) Fragrance

Example 13 Nutrition cream: A nutrition cream having the composition shown in Table 9 was obtained by the following production method. (Production Method) (1) to (5) were mixed and heated to 75 ° C.
(6), (7) and (10) are mixed in this mixture,
The mixture heated to 70 ° C. is added with stirring to emulsify. After emulsification, the mixture is cooled to 60 ° C., (8) and (9) are added thereto, and the mixture is further cooled to room temperature to obtain a nutrition cream.

[0084]

Table 9 (Composition) (wt%) (1) Polyoxyethylene (50) hydrogenated castor oil 2.0 (2) potassium sulfate 0.5 (3) fluorine-modified silicone of Example 3 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) Perfume 0.1 (10) Purified water balance

Example 14 Hand cream: A hand cream having the composition shown in Table 10 was obtained by the following method. (Production method) (1) to (5) are mixed and heated to 75 ° C.
The mixture of (6) to (8) heated to 75 ° C. is gradually added to this under stirring to emulsify. Cool to room temperature and get hand cream.

[0086]

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

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

[0088]

[Table 11] (Composition) (wt%) (1) Dimethylpolysiloxane / polyoxyalkylene copolymer 2.0 (2) Fluorine-modified silicone of Example 2 10.0 (3) Dimethylpolysiloxane (Shin-Etsu Chemical Co., Ltd.) (KF-96A, 6cs) 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 was 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 16 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 under stirring (1) to (5) and emulsified to obtain the intended disinfecting cream.

[0090]

(Table 12) (Composition) (wt%) (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 3 30.0 (11) Bactericide (“Irgassan DP-300”) 0.2

Each of the various cosmetics obtained in Examples 5 to 16 had good makeup retention and excellent feeling in use.

[Procedure amendment]

[Submission date] September 8, 1994

[Procedure Amendment 1]

[Document name to be amended] Statement

[Name of item to be corrected] 0045

[Correction method] Change

[Correction content]

[0045]

[Chemical 13]

[Procedure Amendment 2]

[Document name to be amended] Statement

[Correction target item name] 0048

[Correction method] Change

[Correction content]

[0048]

[Chemical 14]

[Procedure 3]

[Document name to be amended] Statement

[Name of item to be corrected] 0058

[Correction method] Change

[Correction content]

[0058]

[Chemical 18]

─────────────────────────────────────────────────── ─── Continuation of the front page (51) Int.Cl. ⁶ Identification number Internal reference number FI Technical indication location C08L 83/08 LRR (72) Inventor Masahiko Asahi 4-34-2 Otsuka, Bunkyo-ku, Tokyo

Claims (4)

[Claims] 1. At least one general formula (1): [Wherein, R ¹ represents a linear or branched aliphatic hydrocarbon group or an alicyclic or aromatic hydrocarbon group having 5 to 10 carbon atoms having 1 to 20 carbon atoms, m is 0 to an integer of Indicates]
Having a siloxane unit represented by
The fluorine-modified silicone derivative (A). 2. A polymer having 1 to 200 siloxane units represented by the general formula (1) and 0 to 200 siloxane units represented by the following general formula (2).
The fluorine-modified silicone derivative described. [Chemical 2] [In the formula, R ² and R ³ may be the same or different,
A straight-chain or branched-chain aliphatic hydrocarbon group having 1 to 20 carbon atoms or an alicyclic or aromatic hydrocarbon group having 5 to 10 carbon atoms is shown] 3. At least one general formula (3): [Wherein R ¹ represents 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]. A silicone derivative (B) having a polymerization degree of 1 to 400 and a general formula (4): The method for producing the fluorine-modified silicone derivative (A) according to claim 1, wherein a compound represented by the formula: wherein m represents an integer of 0 to 10 is reacted. 4. A cosmetic comprising the fluorine-modified silicone derivative (A) according to claim 1.