Cross Reference to Related Applications
Technical Field
[0002] This disclosure relates to aqueous emulsions of a gel or gel paste containing a silicone
elastomer or a silicone organic elastomer from the reaction of an organohydrogensiloxane
having at least two SiH containing cyclosiloxane rings in its molecule and a compound
having at least two aliphatic unsaturated groups in its molecule.
Background
[0003] Gels and gel pastes containing a silicone elastomer or a silicone organic elastomer
have recently been described in
PCT/US07/006833,
PCT/US07/006894, and
PCT/US07/006936; which are assigned to the same assignee or the present application. The present
disclosure relates to aqueous emulsion compositions of these gels and gel pastes containing
a silicone elastomer or a silicone organic elastomer.
WO 03/093369 discloses compositions comprising at least one compound with at least one aliphatic
unsaturation, at least one cyclic organohydrogensilicon compound with at least one
Si-H per molecule and a platinum group metal catalyst.
Summary
[0004] This disclosure relates to aqueous emulsions comprising:
- i) a gel or gel paste containing a silicone elastomer or a silicone organic elastomer
from the reaction of;
- A) an organohydrogensiloxane having at least two SiH containing cyclosiloxane rings
in its molecule,
- B) a compound having at least two aliphatic unsaturated groups in its molecule, and
- C) a hydrosilylation catalyst,
- D) an optional carrier fluid, and
- ii) an emulsifier.
The Emulsion may further comprise E) an optional personal or healthcare active.
[0005] The present disclosure further relates to a process for preparing an aqueous emulsion
comprising:
- I) mixing
- i) a gel or gel paste containing a silicone elastomer or a silicone organic elastomer
from the reaction of;
- A) an organohydrogensiloxane having at least two SiH containing cyclosiloxane rings
in its molecule,
- B) a compound having at least two aliphatic unsaturated groups in its molecule, and
- C) a hydrosilylation catalyst,
- D) an optional carrier fluid,
- E) an optional personal or healthcare active, and
- ii) an emulsifier,
- II) admixing incremental amounts of water to the mixture of step 1 to form a water
continuous emulsion,
- III) optionally, shear mixing the water continuous emulsion.
Detailed Description
[0006] The present disclosure relates to aqueous emulsion compositions comprising:
- i) a gel or gel paste containing a silicone elastomer or a silicone organic elastomer
and ii) an emulsifier. The aqueous emulsion compositions may optionally contain E)
a personal or healthcare active.
[0007] The gel or gel pastes containing a silicone elastomer or a silicone organic elastomer
useful as component i) may be selected from those as described in
PCT/US07/006833,
PCT/US07/006894, and
PCT/US07/006936, which are herein incorporated by reference for their teaching of silicone elastomer
gels or gel pastes.
[0008] The gel or gel pastes useful as component i) contain a silicone elastomer from the
reaction of;
- A) an organohydrogensiloxane having at least two SiH containing cyclosiloxane rings
in its molecule,
- B) a compound having at least two aliphatic unsaturated groups in its molecule, and
- C) a hydrosilylation catalyst.
The silicone elastomer may be dispersed in;
- D) an optional carrier fluid, which when used further constitutes the gel or gel paste
composition. The aqueous emulsions may optionally contain;
- E) a personal or healthcare active.
(A) The organohydrogensiloxane having at least two SiH containing cyclosiloxane rings
[0009] Component (A) in the present invention is an organohydrogensiloxane having at least
two SiH containing cyclosiloxane rings in its molecule. Organohydrogensiloxanes suitable
as component A) in the present invention are any organopolysiloxanes having in its
molecule at least two cyclosiloxane rings with at least one silicon bonded hydrogen
(SiH) unit on each siloxane ring. Organopolysiloxanes are well known in the art and
are often designated as comprising any number of (R
3SiO
0.5), (R
2SiO), (RSiO
1.5), or (SiO
2) siloxy units where R is independently any organic group. When R is methyl in the
siloxy unit formulas of an organopolysiloxane, the respective siloxy units are often
designated as M, D, T or Q siloxy units. Cyclosiloxane rings contain at least three
siloxy units (that is the minimum needed in order to form a siloxane ring), and may
be any combination of (R
3SiO
0.5), (R
2SiO), (RSiO
1.5), or (SiO
2) siloxy units that forms a cyclic structure, providing at least one of the cyclic
siloxy units on each siloxane ring contains one SiH unit, that is there is at least
one (R
2HSiO
0.5), (RHSiO), or a (HSiO
1.5) siloxy unit present in the ring. These siloxy units can be represented as M
H, D
H, and T
H siloxy units respectively when R is methyl.
[0010] The cyclosiloxane rings of A) the organohydrogensiloxane are linked together by a
divalent organic or siloxane group, or combination thereof. The divalent linking group
may be designated as Y and the cyclosiloxane as G. Thus, the organohydrogensiloxane
of the present invention may be represented by the general formula G-[Y-G]
a, where G is a cyclosiloxane as described above and Y is a divalent organic, a siloxane,
a polyoxyalkylene group, or combination thereof, and the subscript a is greater than
zero.
[0011] When Y is a divalent organic, it may be a divalent hydrocarbon containing 1 to 30
carbons, either as aliphatic or aromatic structures, and may be branched or un-branched.
Alternatively, Y can be an alkylene group containing 2 to 20 carbons, or alternatively
containing. 4 to 12 carbons.
[0012] When Y is a divalent organic, it may also be selected from an organic polymer, such
as a polyoxyalkylene group.
[0013] When Y is a siloxane group it may be selected from any organopolysiloxane containing
at least two divalent hydrocarbon groups, designated as R
1. Thus, the siloxane linking group can be any organopolysiloxane comprising at least
two siloxane units represented by the average formula R
1 R
mSiO
(4·m)/2
wherein
R is an organic group,
R
1 is a divalent hydrocarbon, and
m is zero to 3
The R
1 group may be present on any mono, di, or tri-siloxy unit in an organopolysiloxane
molecule, for example; (R
1R
2SiO
0.5), (R
1RSiO), or (R
1SiO
1.5), as well as in combination with other siloxy units not containing an R
1 substituent, such as (R
3SiO
0.5). (R
2SiO), (RSiO
1.5), or (SiO
2) siloxy units where R is independently any organic group providing there arc at least
two R
1 substituents in the organopolysiloxane. Representative R
1 groups include; ethylene, propylene, butylene, isobutylene, hexylene, and similar
homologs. Alternatively, R
1 is ethylene.
[0014] Representative, non-limiting, examples of such siloxane based structures suitable
as siloxane linking groups include;
(R
2R
1SiO
0.5)(R
2SiO)
x(R
2R
1SiO
0.5)
(R
3SiO
0.5)(R
2SiO)
x(R
1RSiO)
yR
3SiO
0.5)
(R
3SiO
0.5)(R
2SiO)
x(R
1RSiO)
y(RSiO
1.5)
z(R
3SiO
0.5)
where x ≥ 0, y ≥ 2, and z is ≥ 0
[0015] Organohydrogensiloxane having at least two SiH containing cyclosiloxane rings (component
A) may be prepared via a hydrosilylation reaction of
a) an organohydrogencyclosiloxane having at least two SiH units on the siloxane ring
and,
B) a compound or mixture of compounds having at least two aliphatic unsaturated groups
in its molecule.
The organohydrogencyclosiloxane (a) having at least two SiH units on the siloxane
ring may contain any number of siloxy units (as defined above) provided there are
at least two SiH units on the cyclosiloxane ring. For example, the cyclic siloxane
can comprise any number of M, M
H, D, D
H, or T
H siloxy units. Representative, non-limiting examples of such organohydrogenecyoclosiloxanes
useful to prepare component (A) have the average formula D
HaD
b where a is ≥ 1 und b is ≥ 0, and a + b ≥3. Alternatively, the organohydrogencyclosiloxane
may be selected from those having the formula [(CH
3)HSiO]
g where g is 3 8, such as D
H4, D
H5, D
H6, or mixtures thereof.
[0016] Suitable compounds containing at least two aliphatic unsaturated hydrocarbon groups
in its molecule are described below as component B).
[0017] Hydrosilylation reactions involving organohydrogensiloxanes and unsaturated compound
are well know. Any suitable hydrosilylation catalysts know in the art may be used,
or alternatively may be selected from those described below as component C). Any of
the known hydrosilylation techniques and reactions may be employed to pr-epare component
A) from i) organohydrogencyclosiloxane having at least two SiH units non the siloxane
ring and, B) a compound or mixture of compounds having at least two aliphatic unsaturated
groups in its molecule. However, the reaction is conducted in such a manner to provide
an organohydrogensiloxane having at least two SiH containing cyclosiloxane rings in
its molecule.
[0018] Thus, component A of the present invention contains at least two silicon-bonded hydrogen
atom per molecule, alternatively at least 4 silicon-bonded hydrogen atoms per molecule,
or alternatively at least 6 silicon-bonded hydrogen atoms per molecule. This can be
accomplished by using in the hydrosilylation reaction a molar excess of the a) the
organohydrogencyclosiloxane having at least two SiH units on the siloxane ring vs.
the compound containing at least two aliphatic unsaturated groups in its molecule.
The molar excess may be expressed as the molar ratio of SiH units to unsaturated group,
such ratio may range from 2/1 to 8/1, alternatively from 2/1 to 6/1, or alternatively
from 3/1 to 4/1.
[0019] Alternatively, the organohydrogensiloxane useful as component A) may be selected
from any of the organohydrogensiloxanes taught in
WO03/093349, which is herein incorporated by reference for its teaching of suitable organohydrogensiloxanes.
[0020] The organohydrogensiloxane useful as component A) in the present invention typically
have a viscosity from 5 to 50,000 mPa·s, alternatively from 10 to 10,000 mPa·s, or
alternatively from 25 to 2,000 mPa·s.
[0021] Additives known as inhibitors or stabilizers may be added to component A). Inhibitors
such as those described in
WO 03/093369 may be added for the purpose of stabilizing component A) during storage, or prior
to the addition of component B) to prepare the silicone elastomer gel. The inhibitor
may be selected from any compound known to have inhibiting effects Of platinum based
hydrosilylation reactions. A particularly preferred inhibitor is vitamin A palmitate,
or VAP. When VAP is used, it is typically added at 0.05 to 2.0 parts per 100 parts
of component A).
(B) The Compound or mixture of compounds having at least two aliphatic unsaturated
hydrocarbon groups in its molecule
[0022] Component (B) is a compound, or any mixture of compounds, containing at least two
aliphatic unsaturated groups in its molecule. The compound may be any diene, diyne
or ene-yne compound. Diene, diyne or ene-yne compounds are those compounds (including
polymeric compounds) wherein there are at least two aliphatic unsaturated groups with
some separation between the groups within the molecule. Typically, the unsaturation
groups are at the termini of the compound, or pendant if part of a polymeric compound.
Compounds containing terminal or pendant unsaturated groups can be represented by
the formula R
2-Y-R
2 where R
2 is a monovalent unsaturated aliphatic hydrocarbon group containing 2 to 12 carbon
atoms, and Y is a divalent organic or siloxane group or a combination of these. Typically
R
2 is CH
2=CH-, CH
2=CHCH
2-, CH
2=C(CH
3)CH
2- or CH≡C-, and similar substituted unsaturated groups such as H
2C=C(CH
3)-, and HC≡C(CH
3)-.
[0023] The compound having the formula R
2-Y-R
2 as component B) may be considered as being a "organic", "hydrocarbon", "organic polymer",
"polyether" or "siloxane", or combinations thereof, depending on the selection of
Y. Y may be a divalent hydrocarbon, a siloxane, a polyoxyalkylene, a polyalkylene,
a polyisoalkylene, a hydrocarbon-silicone copolymer, or mixtures thereof.
[0024] In one embodiment, the component (B) is selected from an organic compound, herein
denoted as (B
1), having the formula R
2-Y
1-R
2 where R
2 is a monovalent unsaturated aliphatic group containing 2 to 12 carbon atoms and Y
1 is a divalent hydrocarbon,. The divalent hydrocarbon Y
1 may contain 1 to 30 carbons, either as aliphatic or aromatic structures, and may
be branched or un-branched. Alternatively, the linking group Y
1 in B
1 may be an alkylene group containing 1 to 12 carbons. Component (B
1) may be selected from α, ω - unsaturated alkenes or alkynes containing I to 30 carbons,
and mixtures thereof. Component (B
1) may be exemplified by, but not limited to 1,4-pentadiene, 1,5-hexadiene; 1,6-heptadiene;
1,7-octadiene, 1,8-nonadiene. 1,9-decadiene, 1,11-dodecadiene, 1,13-tetradecadiene,
and 1,19-eicosadiene, 1,3-butadiyne, 1,5-hexadiyne (dipropargyl), and 1-hexene-5-yne.
[0025] In another embodiment, the component (B) is selected from a R
2-Y
2-R
2 compound where Y
2 is a siloxane, herein denoted as (B
2). The Y
2 siloxane group may be selected from any organopolysiloxane bonded to at least two
organic groups having aliphatic unsaturation, designated as R
2, to form R
2-Y
2-R
2 structures. Thus, component (B
2) can be any organopolysiloxane, and mixtures thereof, comprising at least two siloxane
units represented by the average formula R
2R
mSiO
(4-m)/2
wherein
R is an organic group.
R
2 is a monovalent unsaturated aliphatic group as defined above, and
m is zero to 3
[0026] The R
2 group may be present on any mono, die, or tri siloxy unit in an organopolysiloxane
molecule, for example; (R
2R
2SiO
0.5), (R
2RSiO), or (R
2SiO
1.5), as well as in combination with other siloxy units not containing an R
2 substituent, such as (R
3SiO
0.5), (R
2SiO), (RSiO
1.5), or (SiO
2) siloxy units where R is independently any organic group, alternatively a hydrocarbon
containing 1 to 30 carbons, alternatively an alkyl group containing 1 to 30 carbons,
or alternatively methyl; providing there are at least two R
2 substituents in the organopolysiloxane.
[0027] Representative, non-limiting, examples of such siloxane based R
2-Y
2-R
2 structures suitable as component (B
2) include:
(R
2R
2SiO
0.5)(SiO
2)
w(R
2R
2SiO
0.5)
(R
2R
2SiO
0.5) (SiO
2)
w(R
2SiO)
x(R
2R
2SiO
0.5)
(R
2R
2SiO
0.5)(R
2SiO)
x(R
2R
2SiO
0.5)
(R
3SiO
0.5)(R
2SiO)
x(R
2RSiO)
y(R
3SiO
0.5)
(R
3SiO
0.5)(R
2SiO)
x(R
2RSiO)
y(RSiO
1.5)
z(R
3SiO
0.5)
(R
3SiO
0.5)(R
2SiO)
x(R
2RSiO)
y(SiO
2)
w(R
3SiO
0.5)
where w ≥ 0, x ≥ 0, y ≥ 2, and z is ≥ 0, R is an organic group, and
R
2 is a monovalent unsaturated aliphatic hydrocarbon group.
[0028] B
2 may be selected from vinyl functional polydimethylsiloxanes (vinyl siloxanes), such
as those having the average formula:
CH
2=CH(Me)
2SiO[Me
2SiO]
xSi(Me)
2CH=CH
2
Me
3SiO[(Me)
2SiO]
x[CH
2=CH(Me)SiO]
ySiMe
3
wherein Me is methyl,
x ≥ 0, alternatively x is 0 to 200, alternatively x is 10 to 100,
y ≥ 2, alternatively y is 2 to 200, alternatively y is 10 to 100.
Vinyl functional polydimethylsiloxanes are known, and there are many commercially
available.
[0029] In another embodiment, component (B) is selected from a polyether compound, herein
denoted as (B
3), having the formula R
2-Y
3-R
2 compound where R
2 is as defined above and Y
3 is a polyoxyalkylene group having the formula (C
nH
2nO)
b wherein n is from 2 to 4 inclusive,
b is greater than 2,
alternatively b can range from 2 to 100,
or alternatively b can range from 2 to 50.
The polyoxyalkylene group typically can comprise oxyethylene units (C
2H
4O), oxypropylene units (C
3H
6O), oxytetramethylene or its isomer oxybutylene units (C
4H
8O), or mixtures thereof. Thus, the R
2-Y
3-R
2 compound may be selected from a polyoxyalkylene group having the formula R
2-O[(C
2H
4O)
c(C
3H
6O)
d(C
4H
3O)
c]-R
2 where c, d, and e may each independently range from 0 to 100, providing the sum of
c + d + e is greater than 2, alternatively the sum of c + d + e ranges from 2 to 100,
or alternatively the sum of c + d + e ranges from 2 to 50.
[0030] Alternatively, the polyoxyalkylene group comprises only oxypropylene units (C
3H
6O)
d. Representative, non-limiting examples of polyoxypropylene containing R
2-Y
3-R
2 compounds include;
H
2C=CHCH
2O[C
3H
6O]
dCH
2CH=CH
2
H
2C=CHO[C
3H
6O]
dCH=CH
2
H
2C=C(CH
3)CH
2O[C
3H
6O]
dCH
2C(CH
3)=CH
2
HC≡CCH
2O[C
3H
6O]
dCH
2C≡CH
HC≡CC(CH
3)
2O[C
3H
6O]
dC(CH
3)
2C≡CH
where d is as defined above.
Representative, non-limiting examples of polyoxybutylene containing R
2-Y
3-R
2 compounds include:
H
2C=CHCH
2O[C
4H
8O]
cCH
2CH=CH
2
H
2C=CHO[C
4H
8O]
cCH=CH
2
H
2C=C(CH
3)CH
2O[C
4H
8O]
cCH
2C(CH
3)=CH
2
HC≡CCH
2O[C
4H
8O]
cCH
2C≡CH
HC≡CC(CH
3)
2O[C
4H
8O]
cC(CH
3)
2C≡CH
Component B) may also be a mixture of various polyethers, i.e. a mixture ot B
2 components.
[0031] In another embodiment, component (B) is selected from a R
2-Y
4-R
2 compound, herein denoted as (B
4), where R
2 is as defined above and Y
4 is a polyalkylene group, selected From C2 to C6 alkylene units or their isomers.
One Example is polyisobutylene group which is a polymer containing isobutylene unit.
The molecular weight of the polyisobutylene group may vary, but typically ranges from
100 to 10,000 g/mole. Representative, non-limiting examples of R
2-Y-R
2 compounds containing a polyisobutylene group includes those commercially available
from BASF under the tradename of OPPONOL BV, such as OPPONOL BV 5K, a diallyl terminated
polyisobutylene having an average molecular weight of 5000 g/mole.
[0032] In yet another embodiment, component (B) is selected from a R
2-Y
5-R
2 compound, herein denoted as (B
5), where R
2 is as defined above and Y
5 is a hydrocarbon-silicone copolymer group. The hydrocarbon-silicone copolymer group
may have the formula
-[R
1a(R
2SiO)
v]
q-
where R
1 and R are as defined above;
u and v are independently ≥ 1, alternatively u ranges from 1 to 20,
alternatively v ranges from 2 to 500, or from 2 to 200,
q is >1, alternatively q ranges from 2 to 500, alternatively q ranges from 2 to 100.
R
2-Y
5-R
2 compounds having a hydrocarbon-silicone copolymer group may be prepared via a hydrosilylation
reaction between an α-ω unsaturated hydrocarbon, such as those described above as
B
1, and an organohydrogensiloxane. A representative, non-limiting example of such a
reaction is shown below.

[0033] Component (B) may also be a mixture of any diene, diyne or ene-yne compound, such
as any combinations of B
1, B
2, B
3, B
4 , and B
5.
[0034] The amounts of component (A) and component (B) used to prepare the present composition
will depend on the individual components and the desired SiH to aliphatic unsaturation
ratio. The ratio of SiH in component (A) to aliphatic unsaturation from component
(B) useful to prepare the compositions of the present invention can be from 10:1 to
1:10, alternatively 5:1 to 1:5, or alternatively 4:1 to 1:4.
[0035] If components (A) and (B) are not the only materials containing aliphatic unsaturated
groups and SiH-containing groups in the present composition, then the above ratios
relate to the total amount of such groups present in the composition rather than only
those components.
(C) The Hydrosilylation Catalyst
[0036] Component (C) comprises any catalyst typically employed for hydrosilylation reactions.
It is preferred to use platinum group metal-containing catalysts. By platinum group
it is meant ruthenium, rhodium, palladium, osmium, indium and platinum and complexes
thereof. Platinum group metal-containing catalysts useful in preparing the compositions
of the present invention are the platinum complexes prepared as described by
Willing. U.S. Pat. No. 3,419,593, and
Brown et al, U. S. Pat. No. 5,175,325, each of which is hereby incorporated by reference to show such complexes and their
preparation. Other examples of useful platinum group metal-containing catalysts can
be found in
Lee et al., U.S. Pat. No. 3,989,668;
Chang et al., U.S. Pat. No. 5,036,117;
Ashby, U.S. Pat. No. 3.159,601;
Lamoreaux, U.S. Pat. No. 3,220.972:
Chalk et al., U.S. Pat. No. 3,296,291;
Modic, U.S. Pat. No. 3,516,946;
Karstedt, U. S. Pat. No. 3,814,730; and
Chandra et al., U.S. Pat. No. 3,928,629 all of which are hereby incorporated by reference to show useful platinum group metal-containing
catalysts and methods for their preparation. The platinum-containing catalyst can
be platinum metal, platinum metal deposited on a carrier such as silica gel or powdered
charcoal, or a compound or complex of a platinum group metal. Preferred platinum-containing
catalysts include chloroplatinic acid, either in hexahydrate form or anhydrous form,
and or a platinum-containing catalyst which is obtained by a method comprising reacting
chloroplatinic acid with an aliphatically unsaturated organosilicon compound such
as divinyltetramethyldisiloxane, or alkene-platinum-silyl complexes as described in
U.S. Patent Application No. 10/017229, filed December 7, 2001, such as (COD)Pt(SiMeCl
2)
2, where COD is 1,5-cyclooctadiene and Me is methyl. These alkene-platinum-silyl complexes
may be prepared, for example by mixing 0.015 mole (COD)PtCl
2 with 0.045 mole COD and 0.0612 moles HMeSiCl
2.
[0037] The appropriate amount of the catalyst will depend upon the particular catalyst used.
The platinum catalyst should be present in an amount sufficient to provide at least
2 parts per million (ppm), preferably 4 to 200 ppm of platinum based on total weight
percent solids (all non-solvent ingredients) in the composition. It is highly preferred
that the platinum is present in an amount sufficient to provide 4 to 150 weight ppm
of platinum on the same basis. The catalyst may be added as a single species or as
a mixture of two or more different species.
(D) The Carrier Fluid
[0038] The silicone elastomers may be contained in an optional carrier fluid (D). Although
it is not required, typically the carrier fluid may be the same as the solvent used
for conducting the hydrosilylation reaction as described above. Suitable carrier fluids
include silicones, both linear and cyclic, organic oils, organic solvents and mixtures
of these. Specific examples of solvents may be found in
U.S. Patent No. 6,200,581, which is hereby incorporated by reference for this purpose.
[0039] Typically, the carrier fluid is a low viscosity silicone or a volatile methyl siloxane
or a volatile ethyl siloxane or a volatile methyl ethyl siloxane having a viscosity
at 25°C in the range of 1 to 1.000 mm
2/sec such as hexamethylcyclotrisiloxane, octamethylcyclotetrasiloxane, decamethylcyclopentasiloxane,
dodecamethylcyclohexasiloxane, octamethyltrisiloxane, decamethyltetrasiloxane, dodecamethylpentasiloxane,
tetradecamethylhexasiloxane, hexadeamethylheptasiloxane, heptamethyl-3-{(trimethylsilyl)oxy)}trisiloxane,
hexamethyl-3,3,bis{(trimethylsilyl)oxy}trisiloxane pentamethyl{(trimethylsilyl)oxy}cyclotrisiloxane
as well as polydimethylsiloxanes, polyethylsiloxanes, polymethylethylsiloxanes, polymethylphenylsiloxanes,
polydiphenylsiloxanes.
[0040] Organic solvents may be exemplified by, but not limited to, aromatic hydrocarbons,
aliphatic hydrocarbons, alcohols, aldehydes, ketones, amines, esters, ethers, glycols,
glycol ethers, alkyl halides and aromatic halides. Hydrocarbons including isododecane,
isohexadecane. Isopar L(C11-C13), Isopar H(C11-C12), hydrogentated polydecen. Ethers
and esters including isodecyl neopentanoate, neopentylglycol heptanoate, glycol distearate,
dicaprylyl carbonate, diethylhexyl carbonate, propylene glycol n butyl ether, ethyl-3
ethoxypropionate, propylene glycol methyl ether acetate, tridecyl neopentanoate, propylene
glycol methylether acetate (PGMEA), propylene glycol methylether (PGME), octyldodecyl
neopentanoate, diisobutyl adipate, diisopropyl adipate, propylene glycol dicaprylate
/ dicaprate, and octyl palmitate. Additional organic carrier fluids suitable as a
stand alone compound or as an ingredient to the carrier fluid include fats, oils,
fatty acids, and fatty alcohols.
[0041] The amount of carrier fluid is such that there is 0 to 98 weight percent, alternatively
0.5 to 80 weight percent, alternatively 5 to 70 weight percent, of carrier fluid in
composition containing (A) and (B) and (D), where the sum of (A), (B), and (D) is
100 weight percent.
E) Personal or Healthcare Active
[0042] Component E) is active selected from any personal or health care active. As used
herein, a "personal care active" means any compound or mixtures of compounds that
are known in the art as additives in the personal care formulations that are typically
added for the purpose of treating hair or skin to provide a cosmetic and/or aesthetic
benefit. A "healthcare active" means any compound or mixtures of compounds that are
known in the art to provide a pharmaceutical or medical benefit. Thus, "healthcare
active" include materials consider as an
active ingredient or
active drug ingredient as generally used and defined by the United States Department of Health & Human Services
Food and Drug Administration, container in Title 21. Chapter I, of the Code of Federal
Regulations, Parts 200-299 and Parts 300 499.
[0043] Useful
active ingredients for use in processes according to the invention include vitamins and its derivatives,
including "pro-vitamins". Vitamins useful herein include, but are not limited to,
Vitamin A
1, retinol, C
2-C
18 esters of retinol, vitamin E, tocopherol, esters of vitamin E, and mixtures thereof.
Retinol includes trans-retinol, 1, 3-cis-retinol, 11-cis-retinol, 9-cis-retinol, and
3,4-didehydro-retinol, Vitamin C and its derivatives, Vitamin B
1, Vitamin B
2, Pro Vitamin B5, panthenol, Vitamin B
6, Vitamin B
12, niacin, folic acid, biotin, and pantothenic acid. Other suitable vitamins and the
INCI names for the vitamins considered included herein are ascorbyl dipalmitate, ascorbyl
methylsilanol pectinate, ascorbyl palmitate, ascorbyl stearate, ascorbyl glucocide,
sodium ascorbyl phosphate, sodium ascorbate, disodium ascorbyl sulfate, potassium
(ascorbyl / tocopheryl) phosphate.
[0044] RETINOL, it should be noted, is an International Nomenclature Cosmetic Ingredient
Name (INCI) designated by The Cosmetic, Toiletry, and Fragrance Association (CTFA),
Washington DC, for vitamin A. Other suitable vitamins and the INCI names for the vitamins
considered included herein are RETINYL ACETATE, RETINYL PALMITATE, RETINYL PROPIONATE,
α-TOCOPHEROL, TOCOPHERSOLAN, TOCOPHERYL ACETATE, TOCOPHERYL LINOLEATE, TOCOPHERYL
NICOTINATE, and TOCOPHERYL SUCCINATE.
[0045] Some examples of commercially available products suitable for use herein are Vitamin
A Acetate and Vitamin C, both products of Fluka Chemie AG, Buchs, Switzerland; COVI-OX
T-50, a vitamin E product of Henkel Corporation, La Grange, Illinois; COVI-OX T-70,
another vitamin E product of Henkel Corporation, La Grange, Illinois, and vitamin
E Acetate, a product of Roche Vitamins & Fine Chemicals, Nutley, New Jersey.
[0046] Component E) may also be a sunscreen agent. The sunscreen agent can be selected from
any sunscreen agent know in the art to protect skin from the harmful effects of exposure
to sunlight. The sunscreen compound is typically chosen from an organic compound,
an inorganic compound, or mixtures thereof that absorbs ultraviolet (UV) light. Thus,
representative non limiting example that can be used as the sunscreen agent include;
Aminobenzoic Acid, Cinoxate, Diethanolamine Methoxycinnamate, Digalloyl Trioleate,
Dioxybenzone, Ethyl 4-[bis(Hydroxypropyl)] Aminobenzoate, Glyceryl Aminobenzoate,
Homosalate, Lawsone with Dihydroxyacetone, Menthyl Anthranilate, Octocrylene, Octyl
Methoxycinnamate, Octyl Salicylate, Oxybenzone, Padimate O, Phenyl benzimidazole Sulfonic
Acid, Red Petrolatum, Sulisobenzone, Titanium Dioxide, and Trolamine Salicylate, cetaminosalol,
Allatoin PABA, Benzalphthalide, Benzophenone, Benzophenone 1-12, 3-Benzylidene Camphor,
Benzylidenecamphor Hydrolyzed Collagen Sulfonamide, Benzylidene Camphor, Sulfonic
Acid, Benzyl Salicylate, Bornelone, Bumetriozole, Butyl Methoxydibenzoylmethane, Butyl
PABA. Ceria/Silica, Ceria/Silica Talc, Cinoxate, DEA-Methoxycinnamate, Dibenzoxazol
Naphthalene, Di-t-Butyl Hydroxybenzylidene Camphor, Digalloyl Trioleate, Diisopropyl
Methyl Cinnamate, Dimethyl PABA Ethyl Cetearyldimonium Tosylate, Dioctyl Butamido
Triazone, Diphenyl Carbomethoxy Acetoxy Naphthopyran, Disodium Bisethylphenyl Tiamminotriazine
Stilbenedisutronate, Disodium Distyrylbiphenyl Triaminotriazine Stilbenedisulfonate,
Disodium Distyrylbiphenyl Disulfonate, Drometrizole, Drometrizole Trisiloxane. Ethyl
Dihydroxypropyl PABA, Ethyl Diisopropylcinnamate, Ethyl Methoxycinnamate, Ethyl PABA,
Ethyl Urocanate, Etrocrylene Ferulic Acid, Glyceryl Octanoate Dimethoxycinnamate,
Glyceryl PABA, Glycol Salicylate, Homosalate, Isoamyl p-Methoxycinnamate, Isopropylbenzyl
Salicylate, Isopropyl Dibenzolylmethane, Isopropyl Methoxycinnamate, Menthyl Anthranilate,
Menthyl Salicylate, 4-Methylbenzylidene, Camphor, Octocrylene, Octrizole, Octyl Dimethyl
PABA, Octyl Methoxycinnamate, Octyl Salicylate, Octyl Triazone, PABA, PEG-25 PABA,
Pentyl Dimethyl PABA, Phenylbenzimidazole Sulfonic Acid, Polyacrylamidomethyl Benzylidene
Camphor, Potassium Methoxycinnamate, Potassium Phenyl benzimidazole Sulfonate, Red
Petrolatum, Sodium Phenylbenzimidazole Sulfonate, Sodium Urocanate, TEA-Phenylbenzimidazole
Sulfonate, TEA-Salicylate, Terephthalylidene Dicamphor Sulfonic Acid, Titanium Dioxide,
Zinc Dioxide, Serium Dioxide, TriPABA Panthenol, Urocanic Acid, and VA/Crotonates/Methacryloxybenzophenone-1
Copolymer.
[0047] The sunscreen agent can be a single one or combination of more than one. Alternatively,
the sunscreen agent is a cinnamate based organic compound, or alternatively, the sunscreen
agent is octyl methoxycinnamate, such as Uvinul® MC 80 an ester of para-methoxycinnamic
acid and 2-ethylhexanol.
[0048] The amount of component E) present in the silicone gel composition may vary, but
typically range as follows,
- 05 to 50 wt%, alternatively 1 to 25 wt %, or alternatively 1 to 10 wt%, based on the
amount by weight of silicone elastomer gel present in the composition, that is total
weight of components A), B), C) and D) in the silicone gel composition.
[0049] The active, component E), may be added to the silicone gel or gel paste composition
either during the making of the silicone elastomer (pre-load method), or added after
the formation of the silicone elastomer gel (post load method). Alternatively, component
E) may be post-added to the aqueous emulsion of the gel or gel paste.
The Silicone Elastomer
[0050] The silicone elastomers of the present invention are obtainable as hydrosilylation
reaction products of components A), B), and C). The term "hydrosilylation" means the
addition of an organosilicon compound containing silicon-bonded hydrogen, (such as
component A) to a compound containing aliphatic unsaturation (such as component B),
in the presence of a catalyst (such as component C). Hydrosilylation reactions are
know in the art, and any such known methods or techniques may he used to effect the
hydrosilylation reaction of components A), B), and C) to prepare the silicone elastomers
of the present invention.
[0051] The hydrosilylation reaction may be conducted in the presence of a solvent, and the
solvent subsequently removed by known techniques. Alternatively, the hydrosilylation
may be conducted in a solvent, where the solvent is the same as the carrier fluid
described as optional component D).
[0052] Alternatively, the silicone elastomers may he prepared by a process comprising:
- I) reacting;
a) an organohydrogencyclosiloxane having at least two SiH units on a siloxane ring.
B) a compound or mixture of compounds having at least two aliphatic unsaturated hydrocarbon
groups in its molecules,
C) a hydrosilylation catalyst
with the proviso that at least 10 weight % of B) is an organic compound, to form
A ) an organohydrogensiloxane having at least two SiH containing cyclosiloxane rings
in its molecule.
wherein the molar ratio of the SiH units of component a) to the aliphatic unsaturated
groups of component B) ranges from 2/1 to 8/1,
alternatively from 2/1 to 6/1.
or alternatively from 3/1 to 4/1,
- II) further reacting;
- A) the organohydrogensiloxane having at least two SiH containing cyclosiloxane rings
in its molecule, with additional quantities of
- B) the compound containing at least two aliphatic unsaturated groups in its molecules,
- C) the hydrosilylation catalyst,
to form a silicons elastomer.
[0053] Components a, A), B), C) are the same as those described above. Also, the reaction
may be conduced under similar conditions as described above.
In aforementioned step II) the molar ratio of the SiH units of component A) to the
aliphatic unsaturated groups of component B) ranges from 10/1 to 1/10,
alternatively from 5/1 to 1/5.
or alternatively from 4/1 to 1/4.
Gelled compositions containing the Silicone Elastomer
[0054] The silicone elastomers can be added to a carrier fluid (as described above as component
D) to form gelled compositions, or alternatively be prepared first in a separate reaction
and then added to the carrier fluid to obtain a gel. The gelled compositions of the
present invention may be characterized by their hardness or firmness. Useful tests
to characterize the gels are those recommended by the
Gelatin Manufacturers Institute of America such as the use of a "Texture Analyzer" (model TA.XT2, Stable Micro Systems, Inc.,
Godalming, England). The gel sample is subject to a compression test with the Texture
Analyzer having a probe with a 5.0 kg load cell. The probe approaches the surface
of the gel at a speed of 0.5 mm/sec and continues compression into the gel to a distance
of 5.0 mm, then holds for I second before retreating. The Texture Analyzer detects
the resistance force the probe experiences during the compression test. The force
exhibited by the load cell is plotted as a function of time.
[0055] The hardness of the silicon customers, gels and elastomer blends (SEBs) for purposes
of this invention is defined as the resistance force detected by the probe oil the
"Texture Analyzer" during the compression test. Two data may used to characterize
hardness: Force 1, the force at the maximum compression point (i.e. the 5.0 mm compression
point into the gel surface), and Area F-T: the area-force integration during the 1
second hold at the maximum compression point. The average of a total of 5 tests are
typically performed for each gel.
[0056] The value obtained for Force 1 is converted into Newton (N), by dividing the gram
force value by 101.97. (i.e. 1 Newton equals 101.97 g force based on the size of the
probe used in this instrument). The second property reported by Texture Analyzer measurement
is Area F-T 1:2, in g force-sec. This is the area integration of the force vs. test
time cure. This property is indicative of a gel network since it indicates ability
to sustain resistance to the compression force, which is relevant to elastomers and
gels. The value is reported in g force-sec, and is converted to Newton sec in SI unit
by dividing the value in g force-sec by 101.97.
[0057] The silicone gels of the present invention has a compression hardness of at least
200 Newton /m
2, alternatively 400 Newton / m
2_, or alternatively 600 Newton / m
2.
Gel Paste compositions containing the Silicone Elastomer
[0058] The gelled compositions of the present invention can be used to prepare gel paste
or gel blend compositions containing actives by;
- I) shearing the silicone elastomer gel, as described above,
- II) combining the sheared silicone elastomer gel with additional quantities of
D) the Carrier fluid, as described above, and optionally
E) a personal or health care active
to form a gel paste or bend composition.
[0059] The silicone elastomer gel compositions of the present invention blends may be considered
as discrete crosslinked silicone elastomer gel particles dispersed in carrier fluids.
Thus, the silicone elastomer compositions are effective rheological thickeners for
lower molecular weight silicone fluids. As such they can be used to prepare useful
gel blend compositions, such as "paste" compositions.
[0060] To make such silicone elastomer blends, the aforementioned silicone elastomer gels
of know initial elastomer content (IEC) are sheared to obtain small particle size
and further diluted to a final elastomer content (FEC). "Shearing", as used herein
refers to any shear mixing process, such as obtained from homogenizing, sonalating,
or any other mixing processes known in the art as shear mixing. The shear mixing of
the silicone elastomer gel composition results in a composition having reduced particles
size. The subsequent composition having reduced particle size is then further combined
with D) the carrier fluid. The carrier fluid may be any carrier fluid as described
above, but typically is a volatile methyl siloxane, such as D5. The technique for
combining the D) the carrier fluid with the silicone elastomer composition having
reduced particle size is not critical, and typically involves simple stirring or mixing.
The resulting compositions may be considered as a paste, having a viscosity greater
than 100,000 cP (mPa·s).
[0061] The emulsions of the present disclosure contain ii) an emulsifier. As used herein,
"emulsifier" refers to any compound or substance that enables the formation of an
emulsion. The Emulsion may be an oil/water emulsion, a watei-/oll emulsion, a multiple
phase or triple Emulsion. Thus the emulsifier may be selected from any ionic, nonionic,
or zwitterionic surfactant capable of stabilizing emulsions. The surfactant may be
an anionic surfactant, cationic surfactant, nonionic surfactant, amphoteric surfactant,
or a mixture of surfactants..
[0062] Representative examples of suitable anionic surfactants include alkali metal soaps
of higher fatty acids, alkylaryl sulphonates such as sodium dodecyl benzene sulphonate,
long chain fatty alcohol sulphates, olefin sulphates and olefin sulphonates, sulphated
monoglycerides, sulphated esters, sulphonated ethoxylated alcohols, sulphosuccinates,
alkane sulphonate, phosphate esters, alkyl isethionates, alkyl taurates, and alkyl
sarcosinates. One example of a preferred anionic surfactant is sold commercially under
the name Bio-Soft N-300. It is a triethanolamine linear alkylate sulphonate composition
marketed by the Stephan Company, Northfield, Illinois.
[0063] Representative examples of suitable cationic surfactants include alkylamine salts,
quaternary ammonium salts, sulphonium salts, and phosphonium salts. Representative
examples of suitable nonionic surfactants include condensates of ethylene oxide with
long chain fatty alcohols or fatty acids such as a C
12-16 alcohol, condensates of ethylene oxide with an amine or an amide, condensation products
of ethylene and propylene oxide, esters of glycerol, sucrose, sorbitol, fatty acid
alkylol amides, sucrose esters, fluoro-surfactants, and fatty amine oxides. Representative
examples of suitable amphoteric surfactants include imidazoline compounds, alkylaminoacid
salts, and betaines.
[0064] Representative examples of suitable commercially available nonionic surfactants include
polyoxyethylene fatty alcohols sold under the tradename BRIJ by Uniqema (ICI Surfactants),
Wilmington, Delaware. Some examples are BRIJ 35 Liquid, an ethoxylated alcohol known
as polyoxyethylene (23) lauryl ether, and BRIJ 30, another ethoxylated alcohol known
as polyoxyethylene (4) lauryl ether. Some additional nonionic surfactants include
ethoxylated alcohols sold under the trademark TERGITOL® by The Dow Chemical Company,
Midland, Michigan. Some example are TERGITOL® TMN-6, an ethoxylated alcohol known
as ethoxylated trimethylnonanol; and various of the ethoxylated alcohols, i.e., C
12-C
14 secondary alcohol ethoxylates, sold under the trademarks TERGITOL® 15-S-5, TERGITOL®
15-S-12, TERGITOL® 15-S-15, and TERGITOL® 15-S-40.
When mixtures containing nonionic surfactants are used, one nonionic surfactant should
have a low Hydrophile-Lipophile Balance (HLB) and the other nonionic surfactant should
have a high HLB, such that the two nonionic surfactants have a combined HLB of 11
-15, alternatively a combined HLB of 12.5-14.5.
[0065] The emulsifier may also be chosen to form a water/oil or a water/silicone emulsifier,
such as silicone polyether emulsifiers. Silicons polyethers (SPEs) generally refer
to silicones containing polyether or polyoxyalkylene groups, which could take in many
different structural forms. Typically such forms are either rake-type or ABA type
SPEs which are derived most commonly from hydrosilylation of SiH functional organosiloxanes
with allyloxy-functional polyethers in the presence of a Pt catalyst
[0066] The silicone polyethers disclosed in
US 4,122,029 may be selected as component ii) and is herein incorporated by reference in its entirety
for its teaching of polydiorganosiloxanepolyoxyalkylene block copolymers containing
at least one polydiorganosiloxane block and at least one polyoxyalkylene block.
[0067] An illustrative, non-limiting silicone polyether useful as an emulsifier is
[Me
3SiO][Me
2SiO]
396[MeR'SiO]
4[OSiMe
3]
where Me is -CH
3 and R' is -(CH
2)
3(EO)
18(PO)
18OH.
[0068] In addition, silicone polyethers useful herein may have the formula [Me
3SiO][Me
2SiO]
10-1000[MeR'SiO]
0-100[MeR"SiO]
1-100[OSiMe
3]
where Me is -CH
3 and R' is -(CH
2)
3(EO)
18(PO)
18OH, R" is an alkyl group containing 1-40 carbon atoms.
[0069] The silicone polyethers disclosed in
US 4,853,474 may be selected as component ii) and is herein incorporated by reference in its entirety
for its teaching of organopolysiloxane-polyoxyalkylene emulsifiers for polar in nonpolar
liquid emulsions wherein the organopolysiloxane-polyoxyalkylene polymer molecule are
intentionally cross linked through a cross linking agent joined thereto by non-hydrolyzable
bonds and being free of internal hydrolyzable bonds.
[0070] Silicone polyether elastomers such as those disclosed in
US 5811487 may be selected as component ii) and is herein incorporated by reference in its entirety
for its teaching of elastomeric silicone polyethers useful as component ii).
[0071] The emulsifier may also be a combination or mixture of various emulsifiers, for examples
any of those described above. The emulsifier may also include the addition of auxiliary
surfactants. Furthermore, the emulsifier or mixture of emulsifiers may be used neat,
or the emulsifier may be dissolved in a hydrophobic solvent, such as a volatile silicone.
[0072] Illustrative, non-limiting commercial products suitable as component ii) include;
DC5225C, DC3225C, DC5200, DC9011, DC9040, DC9050 DC8822A, (Dow Corning Corp., Midland,
MI 48686)
[0073] Other additives can also be incorporated in the emulsion, such as fillers, foam control
agents; anti-freeze agents and biocides.
[0074] The emulsions of the present disclosure may be prepared by any known techniques,
or alternatively made by the following process;
- I) mixing
- i) a gel or gel paste containing a silicone elastomer from the reaction of;
- A) an organohydrogensiloxane having at least two SiH containing cyclosiloxane rings
in its molecule,
- B) a compound having at least two aliphatic unsaturated groups in its molecule, and
- C) a hydrosilylation catalyst,
- D) an optional carrier fluid,
- E) an optional personal or healthcare active, and
- ii) an emulsifier,
- II) admixing incremental amounts of water to the mixture of step 1 to form a water
continuous emulsion,
- III) optionally, shear mixing the water continuous emulsion.
[0075] The components in step I of the above process are the same as those described in
the receding sections. Mixing in step (I) can be accomplished by any method known
in the art to affect mixing of high viscosity materials. The mixing may occur either
as a batch, semi-continuous, or continuous process. Mixing may occur, for example
using, batch mixing equipments with medium / low shear include change-can mixers,
double-planetary mixers, conical-screw mixers, ribbon blenders, double-arm or sigma-blade
mixers; batch equipments with high-shear and high-speed disperses include those made
by Charles Ross & Sons (NY), Hockmeyer Equipment Corp. (NJ); batch equipments with
high shear actions include Banbury-type (CW Brabender Instruments Inc., NJ) and Henschel
type (Henschel mixers America, TX). Illustrative examples of continuous mixers / compounders
include extruders single-screw, twin-screw, and multi-screw extruders, corotating
extruders, such as those manufactured by Krupp Werner & Pfleiderer Corp (Ramsey, NJ),
and Leistritz (NJ); twin-screw counter-rotating extruders, two-stage, extruders, twin-rotor
continuous mixers, dynamic or static mixers or combinations of these equipments.
[0076] The temperature and pressure at which the mixing of step I occurs is not critical,
but generally is conducted at ambient temperature and pressures. Typically, the temperature
of the mixture will increase during the mixing process due to the mechanical energy
associated with shearing such high viscosity materials.
[0077] Step II of the process involves admixing incremental amounts of water to the mixture
of step I to form a water continuous emulsion. Typically 5 to 45 parts water are mixed
for every 100 parts of the step I mixture to form a water-continuous emulsion of the
elastomeric polymer gel or gel paste having an average particle size less than 5 µm
and having sufficient stability to produce a stable lower solids emulsion upon dilution
with water.
[0078] The amount of water added can vary from 5 to 45 parts per 100 parts by weight of
the premix. The water is added to the premix at such a rate so as to form a water
continuous emulsion of the elastomeric polymer gel or gel paste. While this amount
of water can vary depending on the selection of the gel or gel paste containing a
silicone elastomer and emulsifier, generally the amount of water is from 5 to 45 parts
per 100 parts by weight of the step I mixture, alternatively from 5 to 30 parts per
100 parts by weight of the step I mixture, or alternatively from 5 to 20 parts per
100 parts by weight of the step I mixture.
[0079] Typically the water is added to the premix in incremental portions, whereby each
incremental portion comprises less than 8 weight % of the premix and each incremental
portion of water is added successively to the previous after the dispersion of the
previous incremental portion of water, wherein sufficient incremental portions of
water are added to form the water-continuous emulsion of the gel or gel paste containing
a silicone customer.
[0080] Mixing in step (II) can be accomplished by any method known in the art to affect
mixing of high viscosity materials. The mixing may occur either as a batch, semi-continuous,
or continuous process. Any of the mixing methods as described for step (I), may be
used to affect mixing in step (II).
[0081] While not to be limited by any theory, the present inventors believe step (II) affects
an "inversion" of an oil phase continuous emulsion, formed in step (I), to a water
continuous Emulsion.
[0082] Optionally, the water continuous emulsion formed in step (II) may be further sheared
according to step (III) to reduce particle size and/or improve long term storage stability.
The shearing may occur by any of the mixing techniques discussed above.
Examples
[0083] These examples are intended to illustrate the invention to one of ordinary skill
in the art and should not be interpreted as limiting the scope of the invention set
forth in the claims. All measurement and experiments were conducted at 23°C, unless
indicated otherwise.
Materials description
[0084] The following materials were used in these examples.
Organohydrogensiloxanes
[0085] MeH CYCLICS = methylhydrogen cyclosiloxanes (MeH cyclics) having the formula [(CH
3)HSiO]
x where the average value of x is 4.4.
Siloxane polymers containing unsaturated groups
[0086] VINYL SILOXANE #1 = a dimethylhexenylsiloxy-terminated dimethylpolysiloxane of the
general formula (CH
2=CH(CH
2)
4)(CH
3)
2SiO[(CH
3)
2SiO]
dpSi(CH
3)
2((CH
2)
4(CH
2=CH)), where the average degree of polymerization (dp) was 100 and a viscosity of
170 mm
2/s at 25°C.
[0087] VINYL SILOXANE #2 = a dimethylvinylsiloxy-terminated
dimethylpolysiloxane of the general formula
(CH
2=CH)(CH
3)
2SiO[(CH
3)
2SiO]
dpSi(CH
3)
2(CH=CH
2), where the average degree of polymerization (dp) was 130 and having a viscosity
of 325 mm
2/s at 25°C.
[0088] VINYL SILOXANE #3 = a dimethylvinylsiloxy-terminated dimethylpolysiloxane of the
general formula (CH
2=CH)(CH
3)
2SiO[(CH
3)
2SiO]
dpSi(CH
3)
2(CH=CH
2), where the average degree of polymerization (dp) was 8 and having a viscosity of
4 mm
2/s at 25°C.
α,ω-unsatured polypropylene oxide
[0089] PO20 - Polycerin DUS-80 = α,ω-diallyl polypropylene oxide having 20 propylene oxide
(PO) units from NOF Corporation (Japan).
[0090] MPO20 - Polycerin DMUS-80 = α,ω-dimethallyl polypropylene oxide having 20 propylene
oxide (PO) units from NOF Corporation (Japan).
[0091] PO50 - Unisafe PKA-5018 = α,ω-diallyl polypropylene oxide having 50 propylene oxide
(PO) units from NOF Corporation (Japan).
[0092] Bisallyl PBO = α,ω-diallyl poly(butylene oxide) having the general formula Allyl-(BO)n-PO-(BO)n-Allyl
units with a total of about 20 BO units and a molcular weight of about 1600 g/mole,
from NOF Corporation (Japan).
[0093] Bisallyl PTMG = α,ω-diallyl poly(tetramethylene glycol) having the general formula
Allyl-(TMO)n-Allyl units with a total of about 19 TMO units and a molecular weight
of about 1500 g/mole, from NOF Corporation (Japan).
Hydrosilylation catalyst
[0094] PT CATALYST = SLY-OFF 4000 (Dow Corning Corporation, Midland MI) Pt catalyst used
as provided containing 0.52 weight % Pt.
Carrier Fluids
[0095] D5 FLUID OR 245 FLUID= decamethylcyclopentasiloxane or D5 cyclics, DC 245 Fluid (Dow
Corning Corporation, Midland MI) used as provided.
[0096] IDNP = isodecyl neopentanoate obtained from ISP (International Specialty Products
Co) under the trade name of CERAPHYL SLK.
IDD = isododecane, obtained from Presperse Incorporation (Sumerset, NJ) under the
tradename of Permethyl 99A.
[0097] Stabilizer = Vitamin A palmitate (VAP) and butylated hydroxytoluene (BHT)
Example 1 (reference)
Preparation of an organohydrogensiloxane having at least two SiH containing cyclosiloxane
rings
[0098] These organohydrogensiloxane were made by charging MeH CYCLICS, VINYL SILOXANE #1
(also denoted as M
hexD
100M
hex), and the corresponding carrier fluid into a reaction flask, mixed to homogeneous.
Then catalyzed with about 3-5 ppm of Pt using Sly-Off 4000 Pt catalyst solution (containing
about 0.52% Pt). The mixture was heated to about 50 °C to cause the exothermic hydrosilylation
reaction to occur, and maintained the reaction at a temperature between 50 and 70°C
for about 3 hours. About 0.5 % of VAP / BHT (vitamin A palmitate and butylated hydroxytoluene)
stabilizer was incorporated once the reaction mixture cooled to below 40 °C. The formulations
for these compositions and resulting characterizations are summarized in Table 1.

Example 2 (reference)
Preparation of a hydrocarbon/silicone copolymer as a component B) and a component A) based on it
[0099] A silicone hydrocarbon with diallyl functionality at ends (α,ω-dihexenyl hydrocarbon
oligomers) was prepared by reacting 1,5-hexandiene and tetramethylsiloxane (TMDS)
according to the composition in Table 2. Example # 2A and Example 2B are made in D5
Fluid, as illustrated in the table. Example #2A1 and Example #2B1 are made also to
similar compositions except that they are made in IDD fluid.

Example 3 (reference)
Preparation of silicone elastomer gels
[0100] Representative silicone elastomer gels were prepared using hydrosilyation reactions
with the formulations summarized in the following Table 3. The total of components
(A) and (B) constitutes the gel network, and is called initial elastomer content (IEC)
in the gels in this disclosure. The type and the amount of cosmetic fluid, which is
the component D are shown below.

[0101] Elastomer gels are prepared according to these steps: 1) charge all the components
except catalyst to a glass container (or a reactor) and stir to homogeneous; 2) Charge
the catalyst to the mixture, place the catalyzed mixture in a 70 °C water bath with
stirring until the mixture gelled; and 3) keep the reaction mixture in the 70 °C for
a total of 4 hrs.
[0102] A Texture Analyzer was used to characterize the property of elastomer gels. A detailed
description of the test method can be found in previous ID submission or obtained
from the inventor. Gel hardness, which is determined is a measure of gel compression
stress strength, is calculated using the formula: the value of force 1 from TA is
firstly divided by 101.97 to convert from gram force to Newton unit, then divided
by 1.267 x 10
-4 m
2 area of the TA probe, the result is in Newton / m
2. Another term "Viscosity of Gel" also introduced, which is derived by dividing the
value of Force-time 1-2 by 101.97. then by 1.267 x 10
-4 m
2; the result in Newton.second/m
2 or poise (dyne.s/cm
2) The gel hardness and the viscosity of these silicone polyether gels are found in
the table attached.
Example 4 (reference)
Preparation of silicone polyether elastomer gels
[0103] In the cause of silicone polyether elastomers, a diallyl or dimethallyl functional
polyether is used to form a elastomer gel network with selected % organic content.
The organic polyether content may vary depending on the choice of SiH organohydrocyclosiloxane
and the polyether component. Shown in the following table are three silicone polyether
gels made in D5 fluid.

Example 5 (reference)
Preparation of silicone organic elastomer gels
[0104] A representative silicone organic elastomer gel was prepared from a hexenyl terminated
SiH siloxane to form a elastomer gel network with selected % organic content. The
details of silicone organic elastomer gel preparation Can be found in
PCT/US07/006936.
Table 5. Silicone elastomer gel from Si-organic compound
| Example # |
5A |
5B |
| Batch description |
20% IEC silicone gel in D5 Fluid |
25% IEC silicone gel in IDD |
| SiH Int. |
Example 2B |
Example 2B1 |
| Vinyl extender type |
Example 2A |
Example 2A1 |
| Wt.% Organics in gel |
39.1 |
38.0 |
| Carrier fluid type |
245 Fluid |
IDD |
| SiH:Vi ratio |
0.92 |
0.90 |
| Actual amount |
|
|
| Example 2B (for 5A) or Example 2B1 (for 5B) (50)% conc.), g |
31.66 |
12.78 |
| Example 2A (for 5A) or Example 2A1 (for 5B) (50% conc.), g |
68.35 |
27.22 |
| D5 Fluid or IDD, g |
150.00 |
40.07 |
| Syl-Off 4000, g |
0.15 |
0.05 |
| Total Batch, g |
250.16 |
80.12 |
| Gel appearance |
Soft clear gel |
Clear, hard gel |
Example 6 (reference)
Preparation of silicone elastomer pastes
[0105] Silicone elastomer pastes were made according to the following steps: 1) subject
silicone gels from previous examples to mechanical shearing or grinding to reduce
gels into finite particle size; 2) dilute with additional cosmetic fluid to desired
final elastomer content (FEC); 3) incorporate an optional an vinyl-functional quencher,
VINYL SILOXANE #3, and subject the mixture to 70 °C for 2 hrs to effectively scavenging
any residual SiH in the mixture. The wt % FEC is the total of components (A) and (B)
in elastomer blend, where the total of components (A), (B), and (C) being 100 parts.
[0106] Two silicone elastomer blends in D5 Fluid were made according to the above method.
Both elastomer blends have 10 or lower % elastomer gel content in D5 Fluid: one from
an elastomer gel having 10% elastomer content, the other from an elastomer gel having
17 % elastomer content. The composition and property of these elastomer blends are
found in the following table.
Table 6. Silicone elastomer blend compositions
| Example # |
6A |
6B |
| SEB description |
Si elastomer blend made to 10% FEC in D5 Fluid |
Si elastomer blend made to 8.2% FEC in D5 Fluid |
| SEB composition: |
|
|
| Gel example ID |
Example 3A |
Example 3A |
| %IEC in gel |
10% |
17% |
| Elastomer gel, g |
50.03 |
140.0 |
| D5 Fluid, g |
0 |
150.0 |
| Total (g) |
50.03 |
290.0 |
| %FEC in final elastomer blend |
10.0 |
8.21% |
| Appearance: |
Clear paste |
Clear paste |
| Viscosity, cps |
976,150 |
|
| Particle size: |
|
|
| D (v,0.5), um |
8.11 |
|
| D (v,0.9), um |
57.03 |
|
| Span |
6.88 |
|
Example 7 (reference)
Preparation of silicone polyether elastomer pastes
[0107] Silicone polyether elastomer blend in cosmetic fluids can be prepared from silicone
polyether gels, according to this invention. To make silicone polyether elastomer
bind, a silicone polyether gel of known initial elastomer content (IEC) is first prepared
following the procedure shown above. The silicone polyether gel is then mechanically
sheared or ground into small particle sizes, followed by further dilution with a cosmetic
fluid to desired final elastomer content (FEC). The finished elastomer blend is an
anhydrous dispersion of SPE gel particles of finite size swollen and suspended in
cosmetic fluid. The SPE elastomer blend is clear and has a paste-like consistency.
[0108] Silicone polyether elastomer blends are made according to the following steps: 1)
subject silicone polyether gets from previous examples to mechanical shearing or grinding
to reduce gels into finite particle size, 2) dilute with additional cosmetic fluid
to desired final elastomer content (FEC); 3) incorporate an optional an vinyl-functional
quencher. VINYL SILOXANE #3. and subject the mixture to 70 °C for 2 hrs to effectively
scavenging any residual SiH in the mixture. The wt % FEC is the total of crosslinked,
non-volatile components in elastomer blend.
Table 7. Silicone polyethers Elastomer blend compositions
| Example # |
7A |
7B |
7C |
| SEB description |
Si-Polyether elastomer blend from diallyl PO. made to 10.5% FEC in D5 Fluid |
Si-Polyether elastomer blend from dimethallyl MPO, made to 9.28% FEC in D5 Fluid |
Si-Polyether elastomer blend from diallyl PBO, made to 10.5% FEC in D5 Fluid |
| % Organics in gel |
31% |
30% |
20% |
| SEB composition: |
|
|
|
| Elastomer gel ID |
Example 4A |
Example 4B |
Example 4C |
| % IEC: |
17 % |
17% |
17% |
| Elastomer gel, g |
185.00 |
164.00 |
185.00 |
| D5 Fluid, g |
114.00 |
136.00 |
114.00 |
| Total, g |
299.00 |
300.00 |
299.00 |
| % FEC |
10.52% |
9.29% |
10.52% |
| Appearance: |
Clear paste |
Slightly hazy paste |
Clear paste |
Example 8 (reference)
Preparation of silicone organic elastomer blend
[0109] Silicone organic elastomer blend in cosmetic fluids can be prepared from silicone
organic gels, according to this invention. To make silicone organic elastomer blend,
a silicone organic gel of known initial elastomer content (IEC) is first prepared
following the procedure shown above. The silicone polyether gel is then mechanically
sheared or ground into small particle sizes, followed by further dilution with a cosmetic
fluid to desired final elastomer content (FEC). The finished elastomer blend is an
anhydrous dispersion of Si-Organic gel particles of finite size swollen and suspended
in cosmetic fluid. The Si-Organic elastomer blend is clear and has a paste-like consistency.
Table 8. Silicone organic elastomer blend compositions
| Example # |
8A |
8B |
| SEB description |
Si-Organic elastomer blend from hexenyl-terminated dienes, made to 13.9% FEC in 245
Fluid |
Si-Organic elastomer blend from hexenyl-terminated dienes, made to 11% FEC in IDD |
| % Organic in gel |
39% |
38% |
| SEB composition: |
|
|
| Elastomer gel ID |
Example 5A |
Example 5B |
| % IEC |
20% |
25% |
| Elastomer gel, g |
210.0 |
44.0 |
| 245 Fluid, g |
90.0 |
|
| IDD, g |
|
56.0 |
| Total, g |
300.0 |
100.0 |
| % FEC |
14.0% |
11.0% |
| Appearance: |
Clear paste |
Clear paste |
Example 9
Preparation of nomonic emulsions of silicone elastomer blends
[0110] Water-continuous emulsions of silicone elastomer blend were prepared according to
the following steps:
- 1. Incorporate the surfactants of choice into the SEB, mix under high shear to homogeneous.
When more than one surfactant is used. The surfactant of lower HLB value (Brij 30
in this case) is incorporated first and mix to homogeneous using a high shear device
such as Hauschild Mixer. The surfactant of higher HLB value (Renex 30 in this case)
is incorporated. A high-shear mixer like Hauschild Mixer is preferred, as the starting
SEB is typically has a paste-like consistency.
- 2. De-ionized water is incorporated into the above SEB/surfactants mixture. Water
in small amount installments are added, followed by high shear mixture till the mixture
inverts into a water-continuous mixture. The amount of water required to effect inversion
is typically called inversion water. Additional water is added to the inverted mixture
till a desired wt. % solids is obtained.
- 3. The as-prepared emulsions are subject to additional high-shear process to reduce
the size of emulsions or to improve the consistency of the emulsion. A Microfluidizer
from Microfluidics is used to process these emulsions. The property before and after
Microfluidizer processing are shown below.
Table 9. Emulsion of silicone elastomer blend using non-ionic surfactants
| Example # |
9 |
| Component A: SEB description |
Silicone elastomer blend, made to 8.2% FEC in 245 Fluid |
| Emulsion composition: |
|
| Component A SEB type |
Example 3B |
| Component A: SEB amount, g |
48.47 |
| Component B: Brij 30, g |
0.45 |
| Component B: Renex 30, g |
1.32 |
| Component C: D.I water, g |
49.88 |
| Batch total, g |
100.12 |
| Emulsion property: As emulsified in Hauschild Mixer |
| D(v. 0.5), um |
11.67 |
| D(v, 0.9), um |
49.83 |
| span |
4.25 |
| After additional high-shear process via Microfluidizer |
| Emulsion appearance |
Homogeneous milky |
| % SEB content (component A) |
50.0 |
| D(v, 0.5), µm |
1.71 |
| D(v, 0.9), µm |
4.70 |
Example 10
Preparation of nonionic emulsions of silicone elastomer blends
[0111] Water-continuous emulsions of silicone polyether and silicone organic elastomer blends
were prepared, according to the procedure described above. Illustrated in the following
table are the example of these emulsions and their properties.
Table 10. Emulsion of silicone elastomer blend using non-ionic surfactants
| Example # |
10A |
10B |
10C |
| Component A: SEB description |
Silicone polyether elastomer blend derived from dimethallyl MPO, made to 9.28% FEC
in D5 Fluid |
Silicone polyether elastomer blend derived from diallyl PBO, made to 10.5% FEC in
D5 Fluid |
Silicone organic elastomer blend derived from hexenyl-terminated diene, made to 13.9%
FEC in D5 Fluid |
| Emulsion composition |
|
|
| Component A: SEB type |
Example 7B |
Example 7C |
Example 8A |
| Component A: SEB amount, g |
48.87 |
48.57 |
48.66 |
| Component B: Brij 30, g |
0.44 |
0.45 |
0.44 |
| Component B: Renex 30, g |
1.33 |
1.32 |
1.32 |
| Component C: D.I. water, g |
49.87 |
49.88 |
49.84 |
| Batch total, g |
100.51 |
100.22 |
100.26 |
| Emulsion property: As emulsified in Hauschild Mixer |
|
| D(v, 0.5), um |
5.48 |
1.60 |
3.00 |
| D(v, 0.9), um |
30.69 |
8.05 |
10.08 |
| span |
5.58 |
4.66 |
3.18 |
| After additional high-shear process via Microfluidizer |
|
| Emulsion appearance |
Homogeneous milky |
Homogeneous milky |
Homogeneous milky |
| % SEB content (component A) |
50.0 |
50.0 |
50.0 |
| pH of the emulsion |
6.11 |
5.38 |
4.4 |
| D(v, 0.5), µm |
1.67 |
0.71 |
1.19 |
| D(v, 0.9), µm |
4.19 |
2.31 |
2.07 |
| span |
2.36 |
3.04 |
1.21 |
Example 11
Preparation of cationic emulsions of silicone elastomer blends
[0112]
- 1. Water-continuous cationic emulsions of silicone elastomer blend, silicone polyether
elastomer blend, and silicone organic elastomer blend were prepared according to the
following steps:Incorporate the surfactants of choice into the SEB, mix under high
shear to homogeneous. When more than one surfactant is used. The surfactant of lower
HLB value or non-ionic surfactant (Brij 30 in this case) is incorporated first and
mix to homogeneous using a high shear device such as Hauschild Mixer. The surfactant
of higher HLB value or ionic surfactant (Arquad 16-29 in this case) is incorporated.
A high-shear mixer like Hauschild Mixer is typical, as the starting SEB is typically
has a paste-like consistency.
- 2. De-ionized watter is incorporated into the above SEB/surfactants mixture. Water
in small amount installments are added, followed by high shear mixture till the mixture
inverts into a water-continuous mixture. The amount of water required to effect inversion
is typically called inversion water. Additional water is added to the inverted mixture
till a desired wt. % solids is obtained.
- 3. The as-prepared emulsion are subject to additional high-shear process to reduce
the size of emulsions or to improve the consistency of the emulsion. A Microfluidizer
from Microfluidics is used to process these emulsions. The property before and after
Microfluidizer processing are shown below.
Table 11. Emulsion of silicone elastomer blend using cationic surfactants
| Example # |
11A |
11B |
11C |
| Component A: SEB type and composition |
Example 6A: silicone elastomre blend made to 8% FEC in 245 Fluid |
Example 7A: silicone polyether elastomer blend made to 9.2% FEC in 245 Fluid |
Example 8B: silicone organic elastomer blend made to 11% FEC in IDD |
| SEB example ID |
Example 6A |
Example 7A |
Example 8B |
| SEB amount, g |
38.03 |
38.00 |
38.08 |
| Brij 30, g |
4.08 |
3.08 |
3.06 |
| Arquad 16-29, g |
12.03 |
9.07 |
9 |
| D.I. water, g |
46.35 |
50.14 |
49.98 |
| Total, g |
100.49 |
100.29 |
100.12 |
| Emulsion Property: As emulsified in Hauschild Mixer |
|
| D(v,0.5), um |
1.26 |
18.96 |
0.27 |
| D(v,0.9), um |
6.80 |
53.42 |
6.42 |
| Span |
5.27 |
2.80 |
23.57 |
| After additional high shear process through Microfluidizer |
|
| appearance |
Homogeneous |
Homogeneous |
Homogeneous |
| pH of emulsion |
7.50 |
4.74 |
7.04 |
| D(v,0.5), µm |
0.22 |
0.42 |
0.21 |
| D(v,0.9), µm |
0.33 |
1.12 |
1.56 |
Example 12
Preparation of anionic emulsions of silicone elastomer blends
[0113] Water-continuous anionic emulsions of silicone elastomer blend, silicone polyether
elastomer blend, and silicone organic elastomer blend are prepared according to the
following steps:
- 1. Incorporate the surfactant of choice into the SEB, mix under high shear to homogeneous.
A high-shear mixer like Hauschild Mixer is preferred, as the starting SEB is typically
has a paste-like consistency.
- 2. De-ionized water is incorporated into the above SEB/surfactants mixture. Water
in small amount installments are added, followed by high shear mixture till the mixture
inverts into a water-continuous mixture. The amount of water required to effect inversion
is typically called inversion water. Additional water is added to the inverted mixture
till a desired wt. % solids is obtained.
- 3. The as-prepared emulsions are subject to additional high-shear process to reduce
the size of emulsions or to improve the consistency of the emulsion. A Microfluidizer
from Microfluidics is used to process these emulsions. The property before and after
Microfliuidizer processing are shown below.
Table 12. Emulsion of silicone elastomer blend using anionic surfactants
| Example # |
12A |
12B |
12C |
| Component A: SEB type and composition |
Example 6A: silicone elastomer blend made to 8% FEC in 245 Fluid |
Example 7A: silicone polyether elastomer blend made to 9.2% FEC in 245 Fluid |
Example 8B: silicone organic elastomer blend made to 11% FEC in IDD |
| Emulsion Composition: |
|
|
| SEB example ID |
Example 6A |
Example 7A |
Example 8B |
| SEB amount, g |
44.1 |
44.3 |
44.0 |
| SLES surfactant, g |
6.0 |
6.1 |
6.0 |
| D.I. water, g |
50.1 |
49.8 |
50.1 |
| Total, g |
100.2 |
100.1 |
100.1 |
| Emulsion Property: As emulsified in Hauschild Mixer |
|
| D(v,0.5), um |
7.95 |
5.90 |
1.42 |
| D(v,0.9), um |
17.49 |
20.18 |
16.8 |
| Span |
2.06 |
3.36 |
11.68 |
| After additional high shear process through Microfluidizer |
|
| Appearance of emulsion |
Homogeneous |
Cream layer atop overtime, but easily remixed to homogeneous |
Cream layer atop overtime, but easily remixed to homogeneous |
| D(v,0.5), µm |
0.78 |
0.74 |
0.69 |
| D(v,0.9), µm |
1.44 |
1.30 |
1.97 |
| Span |
1.53 |
1.43 |
2.66 |
Example 13
Preparation of OMC sunscreen loaded silicone polyether elastomer blends
[0114] Personal care and healthcare actives, particularly hydrophobic actives, may be incorporated
into the silicone or silicone organic elastomer blends. The active containing elastomer
blends are further emulsified into a water-continuous emulsion, according to the current
invention.
[0115] Illustrated in the following table are examples of 2-ethylhexyl methoxycinnamate
(OMC) sunscreen containing elastomer blends that were derived by incorporating OMC
into elastomer blends derived from gels of the hydrosilylation reaction of SiH intermediate
polymer and diallyl poly(oxybutylene), poly(oxytetramethylene) polyethers in either
245 Fluid or IDD. The elastomer bends contain about 20 wt.% OMC and about 10 wt.%
EC.
[0116] Four elastomer polyether elastomer gels, of about 30-32 to organic content, are prepared
using two hydrophobic polyethers to react with 100dp SiH siloxane of Example 1 in
two different carrier fluids.

[0117] OMC is incorporated into these silicone polyether gels to give silicone organic elastomer
blends with about 20% OMC content and a 9.5 - 10% FEC. The composition of these customer
blends are shown below.

Example 14:
Preparation of emulsion of OMC sunscreen loaded silicone polyether elastomer blends
[0118] The following SOEBs are made for this series of examples:

[0119] Emulsions of OMC sunscreen containing silicone polyether elastmer blends were prepared
according to the following steps:
- 1. Incorporate the surfactant(s) into the SEB, mix under high shear to homogeneous.
A high-shear mixer like Hauschild Mixer is preferred, as the starting SEB is typically
has a paste-like consistency. When two surfactants are used, the surfactant with lower
HLB value is usually incorporated first into SEB, mix to homogeneous; then the higher
HLB surfactant is dispersed under shear to the mixture.
- 2. De-ionized water is incorporated into the above SEB/surfactants mixture. Water
in small amount installments are added, followed by high shear mixture till the mixture
inverts into a water-continuous mixture. The amount of water required to effect inversion
is typically called inversion water. Additional water is added to the inverted mixture
till a desired wt. % solids is obtained.
- 3. The as-prepared emulsions are subject to additional high-shear process to reduce
the size of emulsions or to improve the consistency of the emulsion. A Microfluidizer
from Microfiuidics is used to process these emulsions. The property before and after
Microfluidizer processing are shown below.
Table 14. Emulsions of OMC sunscreen loaded silicone elastomer blends
| Example # |
14D |
14E |
14F |
| Component A: SEB description |
OMC loaded silicone polyether elastomer blend derived from Bisally PBO. made to 9.9%
FEC in IDD fluid |
01\1C loaded silicone polyether elastomer blend derived front Bisallyl PTMG, made
to 10.0% FEC in 245 Fluid |
OMC loaded silicone polyether elastomer blend derived from Bisallyl PBO, made to 9.9%
FEC in 245 Fluid |
| Emulsion composition actual |
|
|
| Component A: S EB batch |
14A |
14B |
14C |
| SEB amount, g |
49.98 |
50.02 |
50.08 |
| Component B: Brij 30, g |
0.90 |
0.93 |
0.95 |
| Component B: Renex 30, g |
2.70 |
2.70 |
2.76 |
| D.I. water, g |
49.10 |
46.39 |
46.60 |
| Batch total, g |
102.67 |
100.04 |
100.39 |
| Emulsion property: As emulsified in Hauschild Mixer |
|
| D(v, 0.5), um |
0.28 |
0.28 |
0.27 |
| D(v,0.9), um |
2.08 |
0.61 |
2.69 |
| Span |
6.94 |
1.58 |
9.36 |
| After additional high shear process through Microfluidizer |
|
| Emulsion appearance |
Homogeneous |
Homogeneous |
Homogeneous |
| D(v,0.5), µm |
0.58 |
0.29 |
0.67 |
| D( v,0.9), µm |
2.01 |
2.84 |
3.53 |