JPH0948703A - Make-up article consisting of silicone-ester wax - Google Patents

Abstract

PROBLEM TO BE SOLVED: To produce an improved cosmetic and a drug preparation for individual use by using a new silicone-ester wax having at least one specific ester part as a substitute for various natural waxes. SOLUTION: This cosmetic contains a silicone-ester wax expressed by formula I (R is H or an organic group; R<1> is >=12C ester-containing group; (a) is 0-3; (b) is 0-3; the average of a+b is a value to give an essentially liner siloxane chain; R<1> is a group derived from a carboxylic acid having an olefinic unsaturated group on the terminal and an alcohol, etc.) and has a melting point of 40-90 deg.C. The R<1> of the wax is especially preferably the group of formula II ((x) and (y) are each an integer of >=4). Preferably, the carboxylic acid is undecylenic acid and the alcohol is stearyl alcohol. The group R<1> is especially preferably derived from trimethylolpropane monoallyl ether and stearic acid. The wax is used as a stick cosmetic such as lipstick, bronze, rouge and eye shadow.

Description

Detailed Description of the Invention

[0001]

BACKGROUND OF THE INVENTION The present invention relates to new waxes and processes for making such waxes. More specifically, the present invention relates to novel silicones having at least one ester moiety (residue) composed of at least 12 carbon atoms.
The present invention relates to cosmetics composed of ester wax. The cosmetics are cosmetics and personal care products. Cosmetic manufacturers are constantly trying to improve their personal products such as lipsticks, eye shadows, bronze, blushers, lotions, hand creams and the like. For example, a good lipstick must have certain maximum and minimum thixotropy. That is, it must soften sufficiently to provide a smooth, uniform coating with minimal pressure. The coating should withstand some mild rubbing during eating and drinking. In addition, the composition of the lipstick should be such that only the lipstick area of the lip is colored, and the lipstick oozes into the surrounding tissues of the mouth, bleeds into streaks, or becomes thin. It shouldn't spread. As well as good "gloss" and "feel", moisture resistance and ease of application are important properties.

Conventionally, in the cosmetics industry, various natural waxes such as carnauba wax and candelilla wax have been generally used to impart various properties such as hardness, thixotropy, melting point and ease of application. .
Lanolin and various derivatives are commonly used due to their softening properties and some tack and drag. Highly refined grades of castor oil are primarily used to impart viscosity to molded sticks, and then as a solvent for bromo derivatives of fluorescein which give rise to persistent properties in coatings. It has now been found that certain novel silicone-ester waxes having at least one ester moiety having at least 12 carbon atoms can be used in place of many natural waxes to obtain improved cosmetic preparations. Was issued.

[0003]

SUMMARY OF THE INVENTION It is an object of the present invention to provide novel silicone-ester waxes useful in cosmetic and personal preparations. Another object of the present invention is to provide a method of making the novel silicone-ester waxes of the present invention. According to one aspect of the invention, there is provided a novel silicone-ester wax having at least one ester moiety having at least 12 carbon atoms. This silicone-ester wax preferably has the following general formula (Formula 3).

[0004]

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Here, R is hydrogen or an organic group, and R is
¹ is an ester-containing group having at least 12 carbon atoms, a is an integer of 0 to 3, b is an integer of 0 to 3, and the sum of a + b has an average value of about 1.0 to about 3 0.0. However, there is at least one R ¹ group.

In accordance with the method of the present invention, the novel silicone-ester wax is prepared by reacting an ester having an olefinic unsaturation at the end with an organohydrogenpolysiloxane in the presence of an effective amount of a hydrosilation catalyst. .

[0007]

DESCRIPTION OF THE INVENTION In one aspect, the present invention provides a cosmetic composition comprising a novel silicone-ester wax having at least one ester moiety having at least 12 carbon atoms. The silicone-ester wax of the present invention preferably has the following general formula (Formula 4).

[0008]

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Here, R is hydrogen or an organic group, R ¹ is an ester-containing group having at least 12 carbon atoms, a is an integer of 0 to 3, and b is an integer of 0 to 3. And the sum of a + b has an average value of about 1.0 to about 3.0. However, there is at least one R ¹ group. Preferably, the silicone-ester wax of the present invention has a melting point of at least about 30C, more preferably from about 40C to about 90C.

It will be appreciated by those skilled in the art that the siloxane chains may be almost linear or resinous (eg highly branched). It is preferred that the siloxane be substantially linear. Of course, mixtures of linear and resinous polysiloxanes are also within the scope of the present invention. The starting polysiloxane used to prepare the silicone-ester wax of Formula 4 is preferably an organohydrogenpolysiloxane. Preferred organohydrogenpolysiloxanes are linear polymers having the general formula (5).

[0011]

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Where R is an organic group, R ² is hydrogen or an organic group, and x and y vary such that the viscosity of the polymer is from about 5 to about 1000 centipoise at 25 ° C.
However, when x is 0, R ² is hydrogen. Such linear hydride polymers preferably have about 10 to 100 mole% of Si-H containing siloxy units.

A preferred organohydrogenpolysiloxane resin comprises units of the formula (Formula 6) and SiO ₂ units.

[0014]

[Chemical 6]

However, the sum of R and H vs. Si varies from 1.0 to 3.0. Such resins may also contain a limited number of bifunctional units.

These and other suitable organohydrogenpolysiloxanes are described, for example, in US Pat. Nos. 3,344,111 and 3,436,366, both of which are incorporated herein by reference. Well known in the industry. R in the above formula
The group may be any substituted or unsubstituted organic group, for example an alkyl group such as methyl, ethyl, propyl, hexyl, octyl, decyl, cyclohexyl, cycloheptyl, phenyl, tolyl, xylyl, naphthyl and the like. There are aryl groups, aralkyl groups such as phenylethyl, benzyl and the like, or those in which one or more hydrogen atoms of these are substituted with, for example, halogen, cyano, amino and the like. Most preferably, all R groups are methyl or a mixture of methyl and phenyl. The invention is based on the discovery that silicone-ester waxes, which are particularly useful in cosmetic preparations, can be prepared from organohydrogenpolysiloxanes and alcohol esters of fatty acids with terminal olefinic unsaturation. That is, R ¹ in the above formula (Formula 4) can be represented by the following general formula (Formula 7) before the reaction with the organohydrogenpolysiloxane.

[0017]

[Chemical 7]

Here, x and y are independently selected integers of 4 or more, preferably 8 or more. Such compounds can be prepared by reacting alcohols with carboxylic acids having terminal olefinic unsaturation.
For example, the following (Formula 8) is given as an example.

[0019]

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As another method, R ¹ of the formula (Formula 4) before the reaction with the organohydrogenpolysiloxane can be produced by reacting an alcohol having an olefinic unsaturation at the terminal with a carboxylic acid. . For example, there are the following (formula 9 and formula 10).

[0021]

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[0022]

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If only one ester moiety is desired, a monoalcohol such as allyl alcohol or its homolog can be used instead. Other variations will be apparent to those of ordinary skill in the art. However, R ¹ prior to reacting with the organohydrogenpolysiloxane must contain at least 12 carbon atoms to impart a waxy consistency to the composition of formula (Chem. 4) (at least 20 are preferred) and also contain terminal olefinic unsaturation. The terminal olefinic unsaturation allows this organic ester to be added to the organohydrogenpolysiloxane in the presence of a hydrosilation catalyst. Suitable hydrosilation catalysts are well known in the art and are described, for example, in US Pat. No. 3,159,
No. 601, No. 3,159,662, No. 3,220,9
70, No. 3,516,946 and No. 3,814.
There are platinum-containing catalysts as described in US Pat. No. 730, which are all incorporated by reference in the disclosure herein. Other suitable hydrosilation catalysts are those based on rhodium, ruthenium, palladium, osmium, iridium and platinum metals. Generally, the olefinically unsaturated ester can be added to the organohydrogenpolysiloxane in the presence of about 10 to about 500 ppm, based on metal, of the catalyst. For example,
The above-mentioned organic ester can be added to the organohydrogenpolysiloxane to give a novel silicone-ester as shown in the following formulas (Formula 11 and Formula 12).

[0024]

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[0025]

[Chemical 12]

The number of ester moieties required to impart a waxy consistency to the final product is the number of siloxy units, whether the polysiloxane is fluid or resinous,
It will be appreciated by those skilled in the art that they will vary depending on the number of carbon atoms in the ester moiety. Based on the above description, those skilled in the art will be able to select, without undue experimentation, suitable reactants for producing the novel silicone-ester waxes of the present invention. It is also believed that the silicone-ester waxes of this invention may contain long chain alkyl groups to raise the melting point of the wax and improve its consistency. Such long chain alkyl groups are at least about 16 carbon atoms in length, preferably about 24 to about 36 carbon atoms in length. The terminal olefinic unsaturation should be present so that this long chain alkyl can be added to the organohydrogenpolysiloxane by a hydrosilation reaction, ie.

[0027]

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In order that those skilled in the art can more easily carry out the present invention, the following non-limiting examples are given. All parts and percentages are by weight unless otherwise noted.

[0029]

【Example】

[Example 1] 87 g of trimethylolpropane monoallyl ether (TMPMAE) was added to a 1-liter round bottom three-necked flask equipped with a stirrer, a thermometer and a reflux head.
Stearic acid 284 g, p-toluenesulfonic acid catalyst 1
g, and 400 g of toluene as solvent, the mixture was heated to 120 ° C. (reflux) and kept at this temperature for 6 hours. During this time, water was removed by toluene / water azeotropy. Esterification proceeded completely. It was confirmed from the infrared spectrum that the peak of the organic acid disappeared and ester was produced. When the reaction was completed, the p-toluenesulfonic acid catalyst was neutralized with sodium hydrogen carbonate. To the ester thus prepared was added an effective amount of a platinum-containing catalyst prepared according to US Pat. No. 3,814,730, the mixture was warmed to 105 ° C., at which point hydrogen terminated polydiorganosiloxane was added. An exotherm was noted and the addition rate was fairly fast. After adding an equivalent amount of organohydrogenpolysiloxane to the reaction vessel, the solution was heated to reflux until all Si-H was consumed (confirmed by IR analysis). The resulting silicone-ester wax was vacuum stripped to remove toluene and then filtered through Celite # 545 while hot to improve appearance. The melting point of this wax is 30 ° C. and can be represented by the following formula (Formula 14).

[0030]

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Example 2 Undecylenic acid 116 was placed in a 1-liter three-necked flask equipped with the same equipment as in Example 1.
g, stearyl alcohol 176 g, toluene 300 g as a solvent, and p-toluenesulfonic acid catalyst 0.5.
g. This solution is heated to 120 ° C. and added with toluene /
Water was removed by azeotropic distillation with water. Six hours later, IR scanning confirmed that the organic acid had been converted to an ester. p
-Toluenesulfonic acid catalyst was neutralized with sodium bicarbonate. The effective amount of catalyst used in Example 1 was added to the container and 1
Warmed to 05 ° C. Next, DF1040 fluid [General Electric (General Electric)
(Available from Company). At this point, the addition of the olefin-ester to the organohydrogenpolysiloxane was complete and the resulting wax was vacuum stripped to remove toluene. The hot wax was then filtered through Celite # 545. The wax thus obtained has a melting point of 43 to 45 ° C. and can be represented by the following formula (Formula 15).

[0032]

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Example 3 Using the procedure of Example 1, a mixed mono / diester of trimethylolpropane monoallyl ether (87g) and stearic acid (213g) was prepared. This ester is from Gulf Chemicals
It was produced in the presence of 231 g of C _{30 -34} α-olefin available from Chemicals). When the ester was formed, the p-toluenesulfonic acid catalyst was neutralized and an effective amount of hydrosilation catalyst was added. The mixture was heated to 105 ° C. and the MeHSiO [General Electric Com
1 mol of SS4300c] available from pany) was added to form a methylalkyl / methylester silicone wax. An additional 25 g of α-olefin was needed to quench all Si-H peaks in the IR scan. The melting point of this mixed ester / alkyl wax is 52-55.
° C and can be represented by the following formula.

[0034]

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Example 4 According to the procedure of Example 1, a distearic acid ester of trimethylolpropane monoallyl ether was prepared from 87 g of trimethylolpropane monoallyl ether and 284 g of stearic acid. 30 g of methyl hydrogen silicone fluid (DF1040) was added in the presence of an effective amount of hydrosilation catalyst to obtain a melting point of 3
A silicone-ester wax which can be represented by the following formula (Formula 17) was prepared at 3-34 ° C.

[0036]

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The above-mentioned silicone-ester wax is
Both conventional and completely silicone systems have been used in stick-type cosmetics such as lipsticks, bronze, blushers and eyeshadows.

Claims (12)

[Claims] 1. A general formula (Formula 1): Wherein R is hydrogen or an organic group, R ¹ is an ester-containing group having at least 12 carbon atoms, a is an integer of 0 to 3, b is an integer of 0 to 3, a + b
Is an average value that makes the siloxane chain substantially linear, and there is at least one R ¹ group.]
R ¹ is mainly obtained from a carboxylic acid having olefinic unsaturation at the terminal and an alcohol, or an alcohol having an olefinic unsaturation at the terminal and a carboxylic acid, and has a melting point of Is 40 to 90 ° C. A cosmetic comprising a silicone-ester wax. 2. The cosmetic material according to claim 1, wherein R ¹ has at least 20 carbon atoms. 3. R ¹ is represented by the general formula (Formula 2): (Wherein, x and y are independently selected integers of 4 or more), and the cosmetic according to claim 1. 4. The cosmetic according to claim 3, wherein x and y are independently selected integers of 8 or more. 5. The cosmetic according to claim 4, wherein the carboxylic acid is undecylenic acid and the alcohol is stearyl alcohol. 6. The cosmetic composition according to claim 1, wherein R ¹ has at least 16 carbon atoms. 7. The cosmetic according to claim 6, wherein R ¹ is obtained from trimethylolpropane monoallyl ether and stearic acid. 8. An organic ester having at least 12 carbon atoms, which is a reaction product of a carboxylic acid having terminal olefinic unsaturation and an alcohol, or an alcohol and a carvone having terminal olefinic unsaturation. The reaction product of an acid, an organic ester having at least 12 carbon atoms, is reacted with a linear organohydrogenpolysiloxane in the presence of an effective amount of a hydrosilation catalyst to produce a melting point. Cosmetics composed of silicone-ester wax at 40 to 90 ° C. 9. The cosmetic according to claim 8, wherein the alcohol having olefinic unsaturation at the terminal is allyl alcohol. 10. The cosmetic according to claim 8, wherein the alcohol having olefinic unsaturation at the terminal is trimethylolpropane monoallyl ether. 11. The cosmetic material according to claim 8, wherein the organohydrogenpolysiloxane is a fluid. 12. The cosmetic according to claim 8, which is further reacted with a long-chain alkyl group having olefinic unsaturation at the terminal.