JP3086241B2 - Cosmetics - Google Patents

Description

The present invention relates to a cosmetic containing a sterol derivative of silicone.

[Prior art] Cosmetics are formulated with various oils in order to improve the water resistance and oil resistance of the cosmetic film. In selecting this oil, its viscosity, polarity, solubility, etc. are taken into consideration. Is done.
Generally, highly viscous oil agents such as polybutene and rosin derivatives, polar oil agents having high skin affinity such as lanolin derivatives, lecithin and castor oil, and silicone oils having low solubility in water and oil are used.

Of these oils, the use of high viscosity oils or polar oils with high skin affinity can improve the adhesion to the skin and improve the water resistance and oil resistance of the cosmetic film. There is a drawback that the oil film is easily formed and the oil film feels thick.

In cosmetics containing a large amount of powder such as foundation, eyeshadow, and blusher, the surface of the powder is often hydrophilic, so that surface treatment with an oil agent has been performed to improve water resistance. Was. Furthermore, in recent years, many treatments with silicone oil have been observed, and improvement in oil resistance as well as water resistance has been attempted. However, when the surface of the powder is treated to improve the water resistance and oil resistance of the powder itself, there is a problem that the adhesion to the skin is reduced and the durability of the makeup tends to be insufficient.

Accordingly, there has been a demand for an oil agent for cosmetics which has no stickiness or oiliness, does not feel thickness, has high adhesiveness, and is excellent in water resistance and oil resistance.

On the other hand, sterols are important constituents of biological membranes widely distributed in the living world, and among them, cholesterol is blended in cosmetics as an emulsifier, etc. because it has excellent affinity for skin, excellent permeability, and high safety. I have. But,
Cholesterol has a high melting point of 146 to 150 ° C. and high crystallinity, so that it is difficult to mix and has a problem with stability over time.

Lanolin is an oil agent containing a large amount of sterols in composition, and various derivatives are known which have high adhesion to skin, emollient properties, and film-forming properties, and have improved color tone, odor and the like.

However, examples of application of sterols to cosmetics include surfactants and solid oils, but no examples have been used for the purpose of improving adhesion, water resistance, and oil resistance.

[Problems to be solved by the invention]

Therefore, the present invention makes use of the properties of sterols having high suitability for skin such as safety, and adherence, water resistance,
Gives oil resistance and has no stickiness or oiliness.
An object of the present invention is to obtain a cosmetic oil agent that does not make the user feel the thickness, and to provide a cosmetic using the oil agent.

[Means for solving the problem]

The present inventors have conducted intensive studies to solve the above-mentioned problems, and as a result, esterified the hydroxyl group of sterol with a carboxylic acid containing a terminal double bond, and further hydrosilylated this double bond with a silicone having a Si-H group. The present inventors have found that the sterol derivative of silicone obtained by the above method is an oil agent meeting the above-mentioned object, and completed the present invention.

That is, the present invention provides a compound represented by the general formula (I) Wherein R ¹ is a methyl group or a group —R ² —COOR ³ (R ² is a group —CH _{2
CH 2 -, - CH 2 CH} 2 CH 2 -, -CH 2 CH 2 CH 2 -OCH 2 CH 2 -, - or -CH ₂ CH ₂ -Ph- (Ph is a phenylene group - (CH _{2) 10} R ³ represents a monovalent residue excluding the hydroxyl group of sterol). However, at least one of R ^{1 in} one molecule is a group represented by the formula —R ² —COOR ³ . m and n each represent an integer of 0 or more.] The present invention provides a cosmetic containing a sterol derivative of silicone represented by the following formula:

 Hereinafter, the present invention will be described in detail.

The sterol derivative of silicone used in the present invention can be synthesized by esterifying a hydroxyl group of sterol with a carboxylic acid having a terminal double bond, and further hydrosilylating the double bond with a silicone having a Si-H group.

As the sterol as a raw material, any sterol having a hydroxyl group capable of esterification may be used, and the hydroxyl group is located at the 3-position, 16-position, 17-position, particularly 3-position of the steroid skeleton (cyclopentanophenanthrene ring). Are preferred. Such sterols include, for example, cholesterol, ergosterol, lanosterol, phytosterol, estradiol and the like. Among them, cholesterol is particularly preferable in consideration of the availability and productivity as a cosmetic oil agent.

In addition, as the carboxylic acid containing a terminal double bond of other raw materials, CH ₂ = CHCOOH, CH ₂ = CHCH ₂ COOH, CH ₂ = CHCH ₂ OCH ₂ CH ₂ COOH, CH ₂ = CH (CH ₂ ) ₈ COOH, Is mentioned.

Further, as the silicone, those represented by the following general formula (II) are used.

(In the formula, R ⁴ represents a methyl group or a hydrogen atom. However, at least one of R ^{4 in} one molecule is a hydrogen atom. M and n each represent an integer of 0 or more.) Specific examples of such a silicone For example, Both ends hydrogen siloxane, such as One-end hydrogen siloxane, such as And the like.

These silicones have the formula (II) wherein m is 0 to 500,
n is preferably a degree of polymerization of 0 to 100, by controlling the degree of polymerization, from solid to paste-like
It is possible to obtain a sterol derivative of silicone having various liquid properties and feeling of use.

In order to produce the sterol derivative of silicone used in the present invention, first, an alcoholic hydroxyl group of sterol is esterified with a carboxylic acid having a terminal double bond. This esterification can be carried out by an ordinary esterification recipe using an acid catalyst such as sulfuric acid or p-toluenesulfonic acid.
The esterification can also be carried out by deriving a carboxylic acid into a carboxylic acid chloride and dehydrochlorinating the hydroxyl group of the sterol with the acid chloride.

Next, the terminal double bond of the obtained ester is hydrosilylated with silicone having a Si-H group. This reaction proceeds by a method using a platinum-based catalyst, and the desired product can be obtained with a high yield.

The formed sterol derivative of silicone can be isolated by removing volatiles from the reaction system.

The obtained sterol derivative of silicone can be used as it is or after being processed into a powder to be incorporated into cosmetics.

In order to treat the powder to be incorporated into the cosmetic, the sterol derivative of silicone is used in an amount of 5 to 500 parts by weight per 100 parts by weight of the powder, and the mixture is heated and stirred at a temperature equal to or higher than the melting point of the sterol derivative of silicone. The treated powder may be incorporated into the cosmetic by a known method.

The amount of the sterol derivative of the silicone is preferably 1 to 50% by weight of the total amount of the cosmetic, and the cosmetics blended in this range have excellent adhesion, water resistance, and oil resistance, and therefore have very long lasting cosmetics. Tall, non-greasy and non-greasy.

In the cosmetic of the present invention, in addition to the silicone sterol derivative, components used in ordinary cosmetics, for example, oils other than the silicone sterose derivative, white pigments, extender pigments, coloring pigments, organic powders, pearls, tars Dyes, surfactants, polymer compounds, gelling agents, ultraviolet absorbers, antioxidants, preservatives, polyhydric alcohols, fragrances, cosmetic ingredients, water, and the like can be appropriately selected and blended.

The use and form of the cosmetic of the present invention are not particularly limited, and may be in a wide range such as a basic cosmetic, a makeup cosmetic, a hair cosmetic, and the like.

〔The invention's effect〕

The sterol derivative of the silicone used in the present invention is easy to handle as a cosmetic oil because the sterol properties, such as crystallinity, which is a property of sterols, decrease and the melting point decreases. It can also be blended in a processed form. When this is blended, it is possible to obtain a cosmetic having excellent adhesiveness, water resistance and oil resistance, and having a long lasting makeup and a feeling of use.

〔Example〕

 Next, an example will be described.

Production Example 1 Cholesterol 387 g (1 mol), undecylenic acid 184 g
(1 mol), 0.95 g (0.005 mol) of p-toluenesulfonic acid, and 600 g of toluene were charged into a flask, and the reaction was carried out for 16 hours while refluxing toluene while dehydrating. 5% Na
Wash twice with HCO ₃ water, then with water three times, strip the organic layer and cholesterol undecylenate CH ₂ = CH (CH ₂ ) ₈ COOR ⁵ (where R ⁵ is a cholesterol residue 525 g was obtained. ^{13 of} this one
The C-NMR spectrum was as shown in FIG.

Next, 608 g of the obtained cholesterol undecylenate
(1.1 mol), the following formula 363 g (0.5 mol) of hydrogen siloxane, 500 g of toluene and 2.5 g of a 0.5% octyl alcohol solution of chloroplatinic acid are charged into two flasks, and reacted under reflux of toluene for 5 hours. 893 g of the product were obtained. Its ¹³ C-NMR spectrum is
As shown in the figure, it was found that it had the following structure.

Production Example 2 Cholesterol undecylenate 608 g (1.1 mol), the following formula , 240 g (0.2 mol) of hydrogen siloxane, 500 g of toluene and 2.5% of a 0.5% isopropyl alcohol solution of chloroplatinic acid are charged into two flasks, and reacted under reflux of toluene for 5 hours. Obtained. This was confirmed to have the following structure by ¹³ C-NMR.

Example 1 A lipstick was made as follows.

(Formulation) (% by weight) (1) Candelilla wax 13.0 (2) Celesin wax 3.0 (3) Carnauba wax 2.0 (4) 10.0 sterol derivative of silicone obtained in Production Example 1 (5) Glyceryl trioctanoate 15.0 (6) ) Safflower oil 10.0 (7) Castor oil balance (8) Titanium mica suitable amount (9) Cosmetics suitable amount (Production method) A. Mix and dissolve (1) to (7) at 80 ° C.

B. Disperse (8) and (9) in A.

C. B was heated to 80 ° C., filled and molded to obtain a lipstick.

Comparative Example 1 A lipstick was obtained in the same manner as in Example 1 except that lanolin was used instead of the sterol derivative of silicone (4) in the formulation of Example 1.

The lipstick obtained above was subjected to a relative evaluation in a use test by a panel of 20 women. Table 1 shows the evaluation items and the results.

Evaluation point Very good ... 4 points Good ... 3 points Normal ... 2 points Bad ... 1 point Very bad ... 0 points Judgment Average score is 3.0 More than 4.0 or less ◎ Average point is 2.0 or more and less than 3.0 ・ ・ ・ ・ ○ Average point is 1.0 or more and less than 2.0 ・ ・ ・ ・ △ Average point is 0 or more and less than 1.0 ・ ・ ・ ・ ・ ・ × Example 2 A liquid foundation was made as follows.

(Formulation) (% by weight) (1) Stearic acid 2.0 (2) Cetyl alcohol 1.5 (3) Glyceryl monostearate 10.0 (4) Octamethylcyclotetra 7.0 siloxane (5) Sorbitan sesquioleate 1.5 (6) Monooleic acid Polyoxy 2.0 ethylene sorbitan (20E.O.) (7) Triethanolamine 0.6 (8) 1,3-butylene glycol 7.0 (9) Carboxyvinyl polymer 0.5 (10) Remaining purified water (11) Treated powder (Note 1) 15.0 (Production method) A. Mix and dissolve (1) to (6) at 80 ° C.

B. Mix and disperse (11) in A.

C. Dissolve (9) in a part of (10).

D. Add (7) and (8) to the remainder of (10) and heat.

E. Add D to B and emulsify.

C was added to FE, and the mixture was cooled and filled to obtain a liquid foundation.

(Note 1) Method for preparing treated powder (Formulation) (Parts by weight) (1) 3.0 sterol derivative of silicone obtained in Production Example 1 (2) Coating material 97.0 (3) Isopropyl alcohol 100.0 (Production method) A. (1) Is added to (3) and dissolved by heating.

B. Mix and disperse (2) in A.

C. Isopropyl alcohol was distilled off to obtain a treated powder.

The liquid foundation obtained as described above had good adhesion, excellent water resistance and oil resistance, and had high cosmetic durability.

Example 3 A cream was made as follows.

(Formulation) (% by weight) (1) Glycerin monostearate 4.0 (2) Polyethylene monostearate 2.0 glycol (40E.O.) (3) Behenyl alcohol 2.0 (4) Cetanol 2.0 (5) Dimethyl polysiloxane (20cs) 0.5 (6) Squalane 3.0 (7) Glyceryl trioctanoate 8.0 (8) 5.0 sterol derivative of silicone obtained in Production Example 2 (9) 1,3-butylene glycol 10.0 (10) Remaining purified water (Preparation method) A. (1) ) To (8) are mixed and dissolved at 70 ° C.

B. Mix and dissolve (9) and (10) at 70 ° C.

A was added to C.B and emulsified to obtain a cream.

The cream obtained as described above had a high affinity for the skin, was excellent in water resistance and oil resistance, and had a moist feeling.

BRIEF DESCRIPTION OF THE DRAWINGS FIG. 1 is a diagram showing the ¹³ C-NMR spectrum of cholesterol undecylenate obtained in Production Example 1 in CCl ₄ , and FIG. it is a chart showing ¹³ C-NMR spectrum in CCl ₄ sterol derivatives.

Claims (1)

(57) [Claims] (1) General formula Wherein R ¹ is a methyl group or a group —R ² —COOR ³ (R ² is a group —CH ₂
CH _2- , -CH ₂ CH ₂ CH _2- , -CH ₂ CH ₂ CH ₂ -OCH ₂ CH ₂ -,-
(CH _{2) 10} - or -CH ₂ CH ₂ -Ph- (Ph represents a phenylene group) and, R ³ represents a shown) monovalent residue obtained by removing the hydroxyl group of sterol. However, at least one of R ^{1 in} one molecule is represented by the formula —R ² —CO
A group represented by OR ^3. m and n each represent an integer of 0 or more].