JPH04145097A - Sterol derivative of silicone and cosmetic containing said derivative - Google Patents

Abstract

NEW MATERIAL:A compound expressed by the formula [R<1> is methyl or -R<2>-COOR<3> (R<2> is bifunctional organic group; R<3> is monofunctional residue obtained by removing OH from sterol) with a proviso that at least one of R<1> in a molecule is -R<2>-COOR<3>; m>0 and n>0]. USE:Useful as oiling agent for cosmetic giving cosmetic having dampish feeling with high affinity for skin, excellent in water and oil resistances. PREPARATION:Alcoholic hydroxyl group in sterol is esterified with terminal double bond-containing carboxylic acid by using an acid catalyst such as sulfuric acid. Next, the terminal double bond in the resultant ester is hydrosilylated with silicone having Si-H group by using a platinum-based catalyst.

Description

DETAILED DESCRIPTION OF THE INVENTION [Industrial Field of Application] The present invention relates to a novel silicone sterol derivative that has not been published in any literature, and a cosmetic containing the same.

[Conventional technology]

Cosmetics contain various oils to improve the water resistance and oil resistance of the cosmetic film, and when selecting the oil, its viscosity, polarity, solubility, etc. are taken into consideration. In general, the viscosity of polybutene, rosin derivatives, etc.
Polar oils with high skin affinity such as high oil agents, lanolin derivatives, lecithin, and castor oil, or silicone oils with low solubility in water and oil are used.

Among these oils, if a large amount of highly viscous oils or polar oils with high skin affinity are used, the adhesion to the skin will be improved and the water and oil resistance of the cosmetic film will be improved. It has the disadvantage that it tends to cause lumps and the oil film feels thick.

In addition, in cosmetics containing a large amount of powder, such as foundations, eye shadows, and blushers, the surface of the powder is often hydrophilic, so surface treatment with an oil agent is performed to improve water resistance. Ta. Furthermore, in recent years, treatments with silicone oil have become commonplace, and efforts are being made to improve oil resistance as well as water resistance. However, when the powder surface 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 makeup durability tends to be insufficient.

Therefore, there has been a need for an oil agent for cosmetics that is not sticky or oily, does not give a feeling of thickness, has high adhesion, and has excellent water resistance and oil resistance.

On the other hand, sterols are important constituents of biological membranes that are widely distributed throughout the living world, and among them, cholesterol has excellent affinity and permeability to the skin, and is also highly safe.
It is added to cosmetics as an emulsifier. However, since cholesterol has a high melting point of 146 to 150° C. and is highly crystalline, it is difficult to blend and also has problems with stability over time.

In addition, lanolin is an oil containing a large amount of sterols, and has adhesion to the skin, emollient properties,
Various derivatives are known that have high film-forming properties and improved color tone, odor, etc.

However, as an example of the application of sterols to cosmetics,
Although there are examples of it being used as a surfactant or solid oil agent, there is no example of its use for the purpose of improving adhesion, water resistance, or oil resistance.

[Problem to be solved by the invention]

Therefore, the present invention makes use of the properties of sterols that are highly suitable for the skin, such as safety, and provides them with adhesion, water resistance, and oil resistance, and also has no stickiness or oiliness and does not feel thick. The purpose of the present invention is to obtain an oil agent for cosmetics that does not cause oxidation.

[Means to solve the problem]

As a result of intensive research to solve the above problems, the present inventor esterified the hydroxyl group of sterol with a terminal double bond-containing carboxylic acid, and further hydrosilylated this double bond with silicone having a 5i-H group. The present invention was completed based on the discovery that a novel silicone sterol derivative obtained by this method, which has not been described in any literature, is an oil agent that meets the above-mentioned purpose.

That is, the present invention provides the general formula (I) [wherein R1 is a methyl group or a group -R"-COOR3(R
2 represents a divalent organic group, and R3 represents a monovalent residue other than the hydroxyl group of the sterol. However, at least one of R1 in one molecule is a group represented by the formula -R'-COOR3.

1 and n represent integers of 0 or more.] The present invention provides a silicone sterol derivative represented by the following formula and a cosmetic containing the same.

The present invention will be explained in detail below.

The silicone sterol derivative of the present invention is obtained by esterifying the hydroxyl group of the sterol with a terminal double bond-containing carboxylic acid,
Furthermore, it can be synthesized by hydrosilylating this double bond with a silicone having a 5i-H group.

The raw material sterol may be any sterol as long as it has a hydroxyl group that can be esterified, but the hydroxyl group is at the 3rd, 16th, or 17th positions, especially the 3rd position of the steroid skeleton (cyclopentanophenanthrene ff1). Preferably. Such sterol derivatives include evacholesterol, ergosterol, lanosterol,
Examples include phytosterols and estradiol.

Among these, cholesterol is particularly preferred in consideration of its usability and productivity as a cosmetic oil.

Further, as the terminal double bond-containing carboxylic acid of other raw materials, any carboxylic acid having a double bond at the terminal and a carboxyl group in the molecule may be used, for example, CH2=CHC0,
CH,=CHCH2C0 Kano, [:)12=cHcl(2
0CH2CH, CD Kano, CH2=CH(CH2) ac
Furthermore, silicone has the following general formula (I
I) is used.

(In the formula, R4 represents a methyl group or a hydrogen atom. However, 1
At least one of R4 in the molecule is a hydrogen atom.

(m and n represent integers of 0 or more) Specific examples of such silicones include double-terminated hydrogen siloxanes such as , single-terminated hydrogen siloxanes such as , and side chain hydrogen siloxanes such as .

These silicones have formula (n) in which m is 0 to 500.
, n preferably has a degree of polymerization of D to 1000. By controlling this degree of polymerization, silicone sterol derivatives having various properties and sensations in use, from solid to pasty to liquid, can be obtained.

To produce the silicone sterol derivative of the present invention, first, the alcoholic hydroxyl group of the sterol is esterified with a terminal double bond-containing carboxylic acid.

This esterification can be carried out using a conventional esterification recipe using an acid catalyst such as sulfuric acid or p-toluenesulfonic acid. Esterification can also be carried out by dehydrochlorination of the hydroxyl group of the sterol and the acid chloride by deriving a carboxylic acid into a carboxylic acid chloride.

Next, the terminal double bond of the obtained ester is 5i-1(
Hydrosilylation with silicone containing groups. This reaction proceeds by a method using a platinum-based catalyst, and the desired product can be obtained in good yield.

The produced silicone sterol derivative can be isolated by distilling off volatiles from the reaction system.

The obtained silicone sterol derivative can be used as it is or in the form of processed powder to be incorporated into cosmetics.

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

It is preferable that the amount of silicone sterol derivatives blended is 1 to 50% by weight of the total amount of cosmetics.Cosmetics blended in this range have excellent adhesion, water resistance, and oil resistance, and therefore have extremely long-lasting makeup. It has a high texture and is not sticky or oily.

In addition to silicone sterol derivatives, the cosmetics of the present invention include ingredients used in ordinary cosmetics, such as oils other than silicone sterol derivatives, white pigments, extender pigments,
Coloring pigments, organic powders, pearl agents, tar pigments, surfactants, polymer compounds, gelling agents, ultraviolet absorbers, antioxidants, preservatives, polyhydric alcohols, fragrances, beauty ingredients, water, etc. are selected as appropriate. It can be blended with

The cosmetics of the present invention are not particularly limited in their use or form, and include basic cosmetics, makeup cosmetics,
It can be applied to a wide range of products such as hair cosmetics.

[Effects of the Invention] The silicone sterol derivative of the present invention has a reduced crystallinity, which is a property of sterols, and a lower melting point, so it is easy to handle as an oil for cosmetics, and it can be directly blended into cosmetics as it is, and can also be used in cosmetics. It can also be blended in a processed form into powder for food use. And when you combine this,
It is possible to obtain a cosmetic with excellent adhesion, water resistance, and oil resistance, long lasting makeup, and good feeling of use.

〔Example〕

Next, examples will be given and explained.

Example 1 Cholesterol 387g (1 mol), undicilenic acid 1
84g (1 mol), p-toluenesulfonic acid 0.95g
(0,005 mol) and 600 g of toluene were charged into a flask, and the reaction was carried out for 16 hours while dehydrating under toluene reflux. The reaction solution was washed twice with 5% NaHCOs water and then three times with water, and the organic layer was stripped to give cholesterol undecylenate CL=C)l (CL), C0OR' (where RS represents a cholesterol residue). (the same applies hereinafter) 525 g was obtained. The C-NMR spectrum of this product was as shown in FIG.

Next, 608 g of the obtained cholesterol undecylenate
(1,1 mol), 363 g of hydrogen siloxane represented by the following formula (0,
5 mol), 500 g of toluene and 0.5% of chloroplatinic acid
After reacting for 5 hours under refluxing octoluene, toluene was distilled off under reduced pressure to obtain 893 g of the target product. “C-” of this
The NMR spectrum was as shown in Figure 2, and it was found that it had the following structure.

Example 2 608 g (1.1 mol) of cholesterol undecylenate, 240 g (0,1 mol) of hydrogen siloxane represented by the following formula:
2 mol), 500 g of toluene and 0.5% of chloroplatinic acid
2.5 g of isopropyl alcohol solution was charged into a 21 flask, and reacted for 5 hours under refluxing toluene, and the toluene was distilled off under reduced pressure to obtain 823 g of the target product. This is "['-NM
It was confirmed that R has the following structure.

Example 3 0 Beni was made as follows.

(prescription) (1) Candelilla wax (2) Ceresin wax (3) Carnauba wax (weight%) 13.0 3.0 2.0 (5) Glyceryl trioctanoate (6) Safflower oil (7) Castor oil (8) Mica titanium (9) Pigment (Manufacturing method) All) to (7) are mixed and dissolved at 80°C.

Distribute (8) and (9) to B and A.

15.0 10.0 Appropriate amount of remaining amount Appropriate amount C and B were 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 3 except that lanolin was used instead of the silicone sterol derivative (4) in the formulation of Example 3.

The lipstick obtained above was evaluated in a usage test by a panel of 20 women. The evaluation items and results are shown in Table 1.

Evaluation points Very good...4 points Good...3 points Fair...2 points Bad...1 point Very poor...0 points Judgment average score is 3 .0 or more and 4.0 or less... ◎Average score is 2
．． 0 or more and less than 3.0... O average score is 1.0 or more and 2
．． Less than 0... Δ average score is 0 or more and less than 1.0...
...×Table 1 Example 4 A liquid foundation was made.

(Formulation) (1) Stearic acid (2) Heptyl alcohol (3) Glyceryl monostearate (4) Octamethylcyclotetrasiloxane as follows (5) Sorbitan sesquioleate (6) Polymonooleate Oxyethylene sorbitan (20B, 0.) (wt%) 2.0 1.5 1O30 7,0 1,5 2,0 (7) Triethanolamine 0.6 (8) 1.3-butylene glycol 7.0 (9
) Carboxyvinyl polymer 〇, 5αQ
Purified water Remaining amount Co., Ltd. Processed powder (Note 1) '15.0 (Production method) A. Mix and dissolve (1) to (6) at 80°C.

B and A are mixed and dispersed.

Dissolve (9) in a part of the C0α mouth.

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

Add D to E and B and emulsify.

C was added to F and E, and after cooling, the mixture was filled to obtain a liquid foundation.

(Note 1) Manufacturing method (formulation) of treated powder (parts by weight) (1)
3.0 Steryl derivative of silicone obtained in Example 1 (2) Pigment 97.0 (3) Isopropyl alcohol 100.0
(Manufacturing method) A. Add (1) to (3) and heat and dissolve.

Mix and disperse (2) in B and 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 long lasting makeup.

Example 5 The cream was made as follows.

(Formulation) (wt%) (1
) Glyceryl monostearate 4.0 behenyl alcohol cetanol dimethyl polysiloxane (20 cs) Glyceryl squalane trioctanoate 2.0 2.0 0.5 3.0 8.0 (9) 1.3-butylene glycol αO purified water (manufacturing method ) 10.0 Mix and dissolve remaining amount A, (1) to (8) at 70°C.

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

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

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

[Brief explanation of drawings]

Figure 1 shows the C-NMR spectrum of the cholesterol undecylenate obtained in Example 1 in CCf, and Figure 2 shows the C-NMR spectrum of the silicone sterol derivative obtained in Example 1 in CCZ. I″C-N in
It is a figure showing an MR spectrum. that's all

Claims (1)

[Claims] 1. General formula ▲ Numerical formula, chemical formula, table, etc. ▼ [In the formula, R^1 is a methyl group or a group -R^2-COOR^
3 (R^2 is a divalent organic group, R^3 is a monovalent residue of styrene excluding the hydroxyl group). However, R in one molecule
At least one of 1 is a group represented by the formula -R^2-COOR^3. m and n represent integers of 0 or more] A styrene derivative of silicone. 2. A cosmetic containing the styrene derivative of silicone according to claim 1.