CA1306752C - Silicone-ester waxes - Google Patents

Abstract

NOVEL SILICONE ESTER WAXES

Abstract of the Disclosure There are provided novel silicone-eater waxes useful in cosmetic and personal care formulations, having the general unit formula

Description

~6~

60SI 1026 (60SI 1131) . .

.
` NOVEL SILICONE-~STER W~XES--.-~ - _ :: `
Background of the Inventi~n .
The present invention relates to novel waxes and methods for making such waxes. More particularly, the present inven-tion relates to novel silicone-ester waxes having at least one ester moiety comprised of at least about twelve carbon atoms.
.
Cosmetics manufacturers are continually attempting to provide improved personal products such as lipsticks, eye~
- shadows, bronzes, blushes, lotions, handcreams, and the like.
A good lipstick~- for example, must possess a certain maximum and minimum of thixotropy; i.e.9 it must soften enough to yield a smooth, even application with a minimum of pressure.
The applied film should to some extent be impervious to the rnild abrasion encount~red during eating and drinking. Further~
more, the lipstick should be of such composition as to color only that portion of the lip to whioh it is applied, and should not bleed, streak or feather into the surraunding tissue of the mouth. Resistance to moisture and ease Df application are also important properties as are a good "glossl' and "feel".

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.~, .

3~3q~ 60SI lOZ6 ( 60SI 1131) Heretofore it has been the general practice in the cosmetics art to utilize various natural waxes such as carnauba wax, candelilla wax, and the like to impart different characteristics such as hardness, thixotropy, melting point, and ease of application. Lanolin and various derivatives are often used for their emollient properties and for a degree of tackiness and drag. A highly refined grade of castor oil is used primarily to impart viscosity to the molded stick and, secondly, as a solvent for bromo derivatives of fluorescein which produce indelibility in the applied film.

It has now been found that certain novel silicone-ester waxes having at least one ester moiety of at least twelve carbon atoms can be used in place of many natural waxes to provide improved cosmetic formulations.

lS Summary of the Invention It is an object of the present invention to provide nnvel silicone-ester waxes useful in cos~etic and personal care formulations.

It is another object of the present invention to provide a method for making the novel silicone-ester waxes oF the present invention.

In accordance with ane aspect of the present invention there are provided novel silicone-ester waxes having at least one ester moiety of at least twelve carbon atoms. Preferably, the silicone-ester waxes have the general formula . ' 60SI 1026 (60SI 1131) : Ra : I , ( SiO )~

R b where R is hydroyen or an organic radical, Rl j5 an ester-containing radical having at least l2 carbon atoms, a is an integer from O to 3 inclusive, b is an integer from O to 3 inclusive, and the sum of a ~ b has an average value of from about l~O to about 3.0, with the proviso that there is present at least one Rl radical.

~` According to a method of the present invention, the novel silicone-ester waxes are prepared by reacting an ester haYing terminal olefinic unsaturat;on with an organohydrogenpolysilox-: ane in the presence of an effective amount of hydrosilation catalyst.

D~:c~ o~ or the Invention In its broadest aspect, the present invention provides novel silicone-ester waxes having at least one ester moiety of at least twelve carbon atoms. Preferably, the s~licone ester . ~ waxes of the present invention have the general~formula ., . , ,;,, .~ ... ..

- ~ ~3g~

60SI 1026 (60SI 1131) ( SiO ) 4 _ (a ~ b~
R b where R is hydrogen or an organic radical t Rl is an ester-containing radical having at least 12 carbon atoms; a is an integer from 0 to 3 inclusive; b is an integer from 0 to 3 inclusive, and the sum of a ~ b has an average value of from about 1.0 to about 3.0; with the proviso that there is present at least one Rl radical. Preferably, the silicone-ester waxes of the present invention have a melting point of at least about 30C and, more preferably, have a melting point of from about 40C to about 90~C.

Those of ordinary skill in the art will appreciate that the siloxane ch-ain can be substantially linear or resinous (e.g.
highly branched~. It is preferred that the siloxane be sub-stantially linear. Of course, mixtures of linear and resinous lS polysiloxanes are also contemplated by the present invention.

The starting polysiloxanes utilized to make the silicone-ester waxes of formula I are preferably organohydrogenpoly-siloxanes. The preferred organohydrogenpolysiloxanes are linear polymers of the general formula R2 _ SiO ~ SiO ~ x ~ SiO ~ Si - R2 R H R R

,... ,... . _ ._.. _ ;_.. _ .. ,_,.. ; . .... j ...... ........ .......... .... .

.,, ~ .

. . , - .

, 7~
60SI- 1026 ~60SI 1131) where R is an organic radical, R2 is hydr~yen or an organic radical. and x and y vary such that the polymer has a viscosity of from about 5 to lO00 centipoise at 25~C, with the proviso that if x equals zero R2 is hydrogen. Such linear hydride polymers preferably have from about lO to lO0 mole percent Si-H
containing siloxy units.

The preferred organohydrogenpolysiloxane resins comprise R

R

and SiO2 units, where the sum of R and H to Si varies from l.0 to 3Ø Such resins may also include a limited number of difunctional units.

These and other suitable organohydrogenpolysiloxanes are ~ well known in the art, for example, as described in Unlted States Patent Numbe~s 3,344,111 - and 1 5 .3,436,366.

The R radicals in the foregoing formulas can be any substituted or unsubstituted organic radicals, for example, alkyl radicals such as methyl, ethyl, propyl~ hexyl, octyl, decyl, cyclohexyl, cycloheptyl, and the like; aryl radicals such as phenyl, tolyl, xylyl, naph~hyl, and the like, aralkyl radicals such as phenylethyl, benzyl~ and the like; or any of the foregoing wherein one or more hydrogen atoms is replaced with, for example, a halogen, cyano, amino, or the like. Most preferably7 all of the R radicals are methyl or a mixture sf methyl and phenyl.

,, _ _ ._ _ _ ,._ . ~_ . . .. . .. . . .. .. . . . . .. ..... . .... . .. . . ... .. .. . ..
.
, :, .

60SI 1026 ( 60SI11131) The present invention is based on the discovery that silicone-ester waxes particularly useful in co~metic formulations can be prepared from organohydrogenpQlysiloxanes and alcohol esters of fatty acids having terminal olefinic unsaturation. Thus, Rl of the above formula I~ prior to reaction with the organohydrogenpolysiloxane, can be represented, for example~by the general formula //o CH2 = CH ~ (CH2)x O (CH2)y CH3 where x and y are independently selected integers equal to or greater than 4; and preferably are equal to or greater than 8. Such compounds can be prepared by reacting an alcohol with a carboxylic acid having terminal olefinic unsaturation. Thus, by way of illustration, O

- CH3(CH2)160H + CH2 = CH(CH2)8C, OH
stearyl alcohol undecylenic acid CH2 = CH(CH2)8C

:~ (CH2)16 CH3 Alternatively, Rl of formula I, prior to reaction with the organohydrogenpolysiloxane, can be prepared by reacting an alcohol having terminal olefinic unsaturation with a carboxylic acid. Thus, by way of illustration, ~ 3~
60SI 1026 (60Sit 1131) CH20H ~J
CH3CH2C - CHzO - CH2CH ~ CH2 + 2 CH3(CH2)l6 trimethylolpropane monoallylether stearic acid C, H 3 2 ) 16 C - D
o CH3CH2C - CH20 - CH2 CH = CH
, C~H2 O
C = O
(CH2)16 . : . , , ,: . . . .

60SI 1026 (60SI~131 ~8-If only one ester moiety is desired, the artisan can substitute a mono-alcohol such as9 for example, allyl alcohol or a homolog thereof.

Other variations will be obvious to those of ordinary skill in the art. HoweYer, it should be understood that Rl, prior to reaction with the organohydrogenpolysiloxane, must contain at least 12 carbon atoms and, preferably, at least 20 carbon atoms, so as to impart a waxy consistency to the composition of formula I~ and must also contain terminal olefinic unsaturation.

The terminal olefinic unsaturation allows the organic ester (e.g. Rl) to be added to the organohydrogenpolysiloxane in the presence of a hydrosilation catalyst. Suitable hydrosila-tion catalysts are well known in the art, for example, platinum containing catalysts as described in United States:Patént Numbers 3,159,60 3,169,662; 3,220,970;----3,516,946 and 3,814,7.30 Other suitabie hydro~ilation catalysts can be ~=
based on the metals rhodium, ruthenium, palladium, osmium, irr;dium and platinum. 6enerally, the olefinically unsaturated 2~ ester can be added to the organohydrogenpolysiloxane in the presence of from about 10 to about 500 ppm of catalyst~ based on the metal.

For purposes of illustration, the foregoing organir esters can be added to an organohydrogenpolysilGxane to obtain the novel silicone-esters of the present invention as follows:

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' ~l36~ 60SI 1026 (60SI--1131) ~
CH2 = CH ~CH2)8C + H SiO ~ Pt o (CH2)l6cH3 R

R
~/ .
~OS i - CH2 CH2 ( CH2 ) 8 ~ ~ ~ and (CH2)1fi CH3 ,CH3 ( C H 2 ) 1 6 C = O
O

CH3CH2C - CH20 - CH~ CH = CH2 -~ H SiO \~ Pt ,CH2 R
o C = O

(CH~)16 ' ' ' ' ' , .

7S2 60SI 1026 (60Sg: 1131) : CH3 ( C H2 ) 16 C' D

tH3CH2C - CH2D - CH2 - CH 2 CH2 C = D

( C, H 2 ) I 6 ' ' ' ' , . .

' , :

., , !, . - -~ 60SI 1026. (60SI 1131) The artisan will appreciate that the number of ester moieties required to impart a waxlike consistency to the final product will vary depending upon the number of siloxy units, whether the polysiloxane is fluid or resinous, and the number of carbon atoms in the ester moiety. Based on the foregoing description, the skilled artisan will be able to select suitable reactants for preparing the novel silicone-ester waxes of the present invention without undue experimentation.

It is also contemplated that the silicone-ester waxes of I0 the present invention can contain long chain alkyl radicals to increase the melting point of the wax as well as to improve its consistency Such long chain alkyl radicals are at least about 16 carbon atoms in length and, preferably, are From about 24 to about 36 carbon atoms in length. Terminal olefinic unsatura-tion should be present so that the long chain alkyl can be added to the organohydrogenpolysiloxane via a hydrosilation reaction; i.e. - CH = CH2 ~ HS~ CH2CH2Si _ In order to better enable the artisan to practice the present invention, the following examples are provided by way of illustration and not by way of limitation. All parts and percentages are by weight unless otherwise noted.

EXAMPLES

Example 1 To a one liter round bottom 3-neck flask equipped with stirrer, thermometer, and reflux head, there was added 87 grams ;

_.. .. ..
- ' , . .
-.

60SI 1026(60SI 1131) trimethylolpropane monoallylether (TMPMAE), 284 grams stearic acid, 1 gram p-toluene sulfonic acid catalyst, and 400 grams toluene as sGlvenk.
me mixture was heated to 120C (reflux) and held for 5iX hours, during which time water was removed ~rom the toluene/water azeotrope and-the esterifiaation driven to completion. Infrared spectroscopy indicated deletion of the organic acid peak and the presence of the ester. Once the reaction was complete the p-toluene sulfonic acid catalyst was neutralized with sodium bicarbonate.
To the thus prepared ester there was added an effective amount of platinum-containing catalyst prepared in accordance with US Pat. No.
3,814,730. The mixture was wa~ned to 105C at which time a hydrogen-terminated polydiorganosiloxane was added. An exotherm was noted and the rate of addition was rather rapid. After an e~uivalent amount of organo-hydrogenpolysilo~ane was added to the reaction vessel, the solution was heated at reflux untill all of the Si-H was consumed (based on IR analysis).
The resultant silicone-ester was was stripped under vacuum to remove toluene and thereater filtered while hot through Celitel#545 to improve its appearance. The wax had a melting point o~ 30C and can be represented by the formula _ , 3 ll )2 16 C =O
O
CH2, 3 , 3 3 2 C, CH2O CH2CH2CH2 Si t osi~_ o ; 3 3 O
C=O
(CH2)16 ~3~
60SI 1026 (60SI 1~31) Example 2 TP a one liter 3-neck flask equipped as in Example 1 there was added 116 grams undecylenic acid, 176 grams stearyl alcohol, 300 grams toluene as solvent, and O.S gram p-toluene sulfonic acid catalyst. The solution was heated to 120~C and the water removed from the toluene/water azeotrope. Af~er about 6 hours the IR scan of the reaction mass indicated conversion o~ the organic acid to the ester. The p-toluene sulfonic acid was neutrali~ed with sodium bicarbonate. An effetive amount of the catalyst utilized in Example 1 was added to the vessel and warmed to 105~C. Then 37.7 grams of DF
1040 ~ 1uid (available from 6eneral Electric Company) was added and the vessel heated at 120C for an hour after the methyl-hydrogen silicone fluid (DF 1040) addition. At this time the olefin-ester addition to the organohydrogenpolysiloxane was complete, and the resultant wax was stripped under vacuum to remove toluene. The hot wax was then filtered through Celite #545, The thus obtained wax had a melting poirt of 43 ~-45~C
and can be represented by the formula ( CH2)17 ~' C = O
,CH3 (,CH~)1o CH3 CH3 - SiO ~ $iO ~ Si - CH3 .

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~r ._ 60SI -1:026 (60SI 1-131) Example 3 There was prepared a mixed mono/di ester of trimethylolpro-pane monoallyl ether ~87 grams) and stearic acid (213 grams) using the procedure of Example 1. The ester was ~ormed in the presence of 231 yrams C30 34 alpha-olefin available from Gulf Chemicals. Once the ester was formed9 the p-toluene sulfonic acid catalyst was neutralized and an effective amount of hydr~-silation catalyst added. The mixture was heated to 105~C, and 1 mol cf MeHSiO (SS 4300c~ available fro~ General Electric Company) was added to pruduce a methylalkyl/methylester S j1;D
cone wax. An additional 25 grams of alpha-olefin was required to eliminate all of the Si-H peaks on the IR scan. The mixed ester/alkyl wax had a melting point of 52-55C and can be r~pr~sented by the formula CH CH CH
1 3 1 3 1 3 1H3 ~H3 CH3 - SiO ~ SiO ~ SiO ~ SiO ~ Si ~ CH3 .
CH3 CH ,CH2 C~2 C~13 ~H ,C~l2 (CH2)2~-3 CH2 , 2 3 3C~2 - C - CH2 - OC ~ (CH2)16~H3 OH
O
CH CH2 - C - ~CH2 - ~ - (CH2)l6CH3)2 , , ,_ ... ,,,,,, ...... __ ____ _, __ .... , .. , . .. . . ~, . .. ,.. , . , . ........ _ _. _. .. . ... .

, ~ ;

G~S~
`, 60SI 1026 ~60SI 1-`131) Example 4 There was prepared the distearic acid ester of trimethylol-propan~ monoallylether from 87 grams trîmethylolpropane mono-allylether and 284 grams stearic acid following the procedure of Example 1. Thirty grams of methylhydrogen silicone fluid (DF 1040) was added in the presence of an effective amount of hydrosilation catalyst to prepare a silicone-ester wax having a melting point of 33 - 34~C and which can be represented by the fcrmula ~ ~ .
3 , -SiO -)x Si - CH3 -" , ,CH2 ~H2 O
~' ,CH2 o C H 3 C H 2 - .C _( CH 2 - C - ( CH 2 ) ~ 6 C H 3 ) 2 -The foregoing silicone-ester waxes can be used in stick formulation cosmetics, such as lipstickl bronzes, blushes and eyeshadows, in both conventional and fully silic~ne systems.

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Claims (17)

1. A silicone-ester wax comprising moieties of the general unit formula:

where R is hydrogen or an organic radical; R1 is an ester-containing radical having at least 12 carbon atoms; a is an integer from 0 to 3 inclusive, b is an integer from 0 to 3 inclusive; the sum of a + b has an average value to render the siloxane chain substantially linear; there is present at least one R1 radical on said wax; and said wax has a melting point between about 30°C
and 90°C.

2. A composition as in claim 1, wherein R1 has at least 20 carbon atoms.

3. A composition as in claim 1, wherein the silicone-ester wax has a melting point of from about 40°C to about 90°C.

4. A composition as in claim 1, wherein R1 is prepared from a carboxylic acid having terminal olefinic unsaturation and an alcohol.

5. A composition as in claim 4, wherein R1 has the general formula where x and y are independently selected integers equal to or greater than 4.

- 17 - 60SI 1026 (60SI 1131)

6. A composition as in claim 5, wherein x and y are independently selected integers equal to or greater than 8.

7 . A composition as in claim 6, wherein the carboxylic acid is undecylenic acid and the alcohol is stearyl alcohol.

8. A composition as in claim 1, wherein R1 is prepared from an alcohol having terminal olefinic unsaturation and a carboxylic acid.

9. A composition as in claim 8, wherein R1 has at least 16 carbon atoms.

10. A composition as in claim 9, wherein R1 is prepared from trimethylolpropane monoallylether and stearic acid.

11. A silicone-ester wax composition prepared by reacting an organic ester of at least 12 carbon atoms and having terminal olefinic unsaturation with a linear organohydrogenpolysiloxane in the presence of an effective amount of hydrosilation catalyst wherein said silicone ester wax has a melting point between about 30°C and 90°C.

12. A composition as in claim 11, wherein the organic ester is the reaction product of an alcohol and a carboxylic acid having terminal unsaturation.

13. A composition as in claim 11, wherein the organic ester is the reaction product of an alcohol having terminal olefinic unsaturation and a carboxylic acid.

14. A composition as in claim 13, wherein the alcohol having terminal olefinic unsaturation is allyl alcohol.

15. A composition as in claim 13, wherein the alcohol having terminal olefinic unsaturation is trimethylolpropane monoallylether.

- 18 - 60SI 1025 (60SI 1131)

16. A composition as in claim 11, wherein the organohydrogenpolysiloxane is a fluid.

17. A composition as in claim 11, wherein there is further reacted a long chain alkyl radical having terminal olefinic unsaturation.