Note: Descriptions are shown in the official language in which they were submitted.
~6~
60SI 1026 (60SI 1131)
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- 1 -
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` 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)
--2--
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
CH 20H OH
trimethylolpropane monoallylether stearic acid
C, H 3
2 ) 16
C - D
o
CH2
CH3CH2C - CH20 - CH2 CH = CH
, C~H2
O
C = O
(CH2)16
CH3
. : . , ,
,: . . . .
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:
.
. , .
'
~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
C H 2 R
CH3CH2C - CH20 - CH~ CH = CH2 -~ H SiO \~ Pt
,CH2 R
o
C = O
(CH~)16
CH3
' ' ' ' ' , .
7S2 60SI 1026 (60Sg: 1131)
: CH3
( C H2 ) 16
C'
D
CH2 R
tH3CH2C - CH2D - CH2 - CH 2 CH2
CH2 R
C = D
( C, H 2 ) I 6
CH3
' ' ' ' , . .
'
, :
., ,
!,
. - -
~ 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)
- 12 -
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
CH3 2
~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
CH3
( CH2)17 ~'
0
C = O
,CH3 (,CH~)1o CH3
CH3 - SiO ~ $iO ~ Si - CH3
CH3 CH3 CH3
.
.
~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
1 2 CH CH
CH2 , 2 3
0 1
3C~2 - C - CH2 - OC ~ (CH2)16~H3
OH
O
CH CH2 - C - ~CH2 - ~ - (CH2)l6CH3)2
, , ,_ ... ,,,,,, ...... __ ____ _, __ .... , .. , . .. . . ~, . .. ,.. , . , . ........ _ _. _. .. . ... .
, ~ ;
G~S~
`, 60SI 1026 ~60SI 1-`131)
-15-
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
CH3 CH3 CH3
~ ~ .
3 , -SiO -)x Si - CH3
CH3 CH2 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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