U.S. patent application number 15/174117 was filed with the patent office on 2016-09-29 for alkoxysilane derivatives of n-acyl amino acids, n-acyl dipeptides, and n-acyl tripeptides, and particles and stable oil-in-water formulations using the same.
The applicant listed for this patent is Gelest Technologies, Inc.. Invention is credited to Barry C. ARKLES, Jane C. HOLLENBERG, Youlin PAN.
Application Number | 20160280737 15/174117 |
Document ID | / |
Family ID | 45870899 |
Filed Date | 2016-09-29 |
United States Patent
Application |
20160280737 |
Kind Code |
A1 |
ARKLES; Barry C. ; et
al. |
September 29, 2016 |
ALKOXYSILANE DERIVATIVES OF N-ACYL AMINO ACIDS, N-ACYL DIPEPTIDES,
AND N-ACYL TRIPEPTIDES, AND PARTICLES AND STABLE OIL-IN-WATER
FORMULATIONS USING THE SAME
Abstract
Hydrophilic N-acylamino acid, N-acyl dipeptide, and N-acyl
tripeptide substituted silanes are prepared which can be utilized
as reactive surface treatments for particles of pigments, minerals,
and fillers. These treated particles form stable dispersions in the
aqueous phase of oil-in-water mixtures that are suitable for
cosmetic applications. The treated particles may also be used in
pressed powder and color cosmetic formulations.
Inventors: |
ARKLES; Barry C.;
(Pipersville, PA) ; HOLLENBERG; Jane C.; (Red
Hook, NY) ; PAN; Youlin; (Langhorne, PA) |
|
Applicant: |
Name |
City |
State |
Country |
Type |
Gelest Technologies, Inc. |
Morrisville |
PA |
US |
|
|
Family ID: |
45870899 |
Appl. No.: |
15/174117 |
Filed: |
June 6, 2016 |
Related U.S. Patent Documents
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Application
Number |
Filing Date |
Patent Number |
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13241860 |
Sep 23, 2011 |
9358200 |
|
|
15174117 |
|
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61385790 |
Sep 23, 2010 |
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Current U.S.
Class: |
1/1 |
Current CPC
Class: |
A61Q 1/10 20130101; A61K
8/19 20130101; A61K 8/29 20130101; A61Q 1/12 20130101; C07K 5/0827
20130101; C09C 3/12 20130101; A61K 8/26 20130101; A61K 8/585
20130101; A61K 8/0241 20130101; C09C 1/3684 20130101; A61K 8/64
20130101; A61Q 1/02 20130101; C07K 5/06026 20130101; C07F 7/1804
20130101; C07K 5/06191 20130101; A61K 2800/623 20130101; C01P
2004/61 20130101; C01P 2004/62 20130101; C07K 5/0806 20130101 |
International
Class: |
C07K 5/08 20060101
C07K005/08; C07F 7/18 20060101 C07F007/18; C07K 5/06 20060101
C07K005/06 |
Claims
1. A hydrophilic alkoxysilane derivative of an N-acyl dipeptide or
N-acyl tripeptide, wherein the acyl group is acetyl.
2. The hydrophilic alkoxysilane derivative according to claim 1,
wherein the alkoxy group is selected from the group consisting of
methoxy and ethoxy.
3. The hydrophilic alkoxysilane derivative according to claim 1,
wherein the derivative is a propyltrialkoxysilane derivative.
4. The hydrophilic alkoxysilane derivative according to claim 1,
wherein the derivative is
(N-acetylglycylpropyl)triethoxysilane.
5. The hydrophilic alkoxysilane derivative according to claim 1,
wherein the derivative is (N-acetylglycinamidepropyl)
trimethoxysilane.
6. The hydrophilic alkoxysilane derivative according to claim 1,
wherein the derivative is
(N-acetylleucinamidepropyl)triethoxysilane.
7. (N-acetylhydroxyprolyl)propyltriethoxysilane.
8. The hydrophilic alkoxysilane derivative according to claim 1,
comprising an amino acid residue selected from glycine and
hydroxyproline.
Description
CROSS-REFERENCE TO RELATED APPLICATIONS
[0001] This application is a continuation of co-pending U.S. patent
application Ser. No. 13/241,860, filed Sep. 23, 2011, which claims
the benefit of U.S. provisional patent Application No. 61/385,790,
filed on Sep. 23, 2010, the disclosures of which are incorporated
herein by reference.
BACKGROUND OF THE INVENTION
[0002] Surface treated pigments have been used to improve the
wetting and dispersion of pigments and fillers in inks, coatings,
resins and cosmetics. Passivation of the pigment and filler
surfaces to reduce chemical interaction with the vehicle is another
application of surface modifications. In cosmetics, surface
coatings of pigments and fillers offer the added benefits of
improvements in skin feel, easier spreading and blending on the
skin, reduction in irritation due to mechanical abrasion and
reduced drying of the skin from oil and moisture absorption.
[0003] Types of surface coatings used in cosmetic applications have
included fatty acids, lecithin, mineral waxes, e.g. polyethylene,
vegetable waxes, starches, peptides, polysaccharides, acyl amino
acids, titanate esters, fluorophosphates, silicones and silanes.
The modification of substrates with silanes is well-known in the
art and is described by Arkles in Chemtech, 7(12), 766, (1977),
which is herein incorporated by reference. Silane coupling agents
and reactive silicones are particularly useful surface treatments
for use in dispersed systems due to the formation of chemical bonds
between the treating compound and the pigment surface that prevents
solubilization of the coating during processing of the finished
product. Silane and silicone surface treated pigments have been
used in a variety of cosmetic formulations, including foundation,
mascara, eye liner, eye shadow, lip color and blush, in which the
powder is dispersed in a liquid phase. The most common hydrophilic
silane utilized is PEG.sub.6-9-silane
(methoxypoly(ethyleneoxy).sub.6-9propyltrimethoxysilane). However,
PEG.sub.6-9-silane can affect the formation of emulsions, causing
excessive pigment flotation. Further, the long-term oxidative
stability of PEG.sub.6-9-silane and degradation products of
ethyleneoxide derived materials have potential health effects that
may be of concern in some formulations.
[0004] The utilization of modified amino acids as surface
treatments for particulates, including pigments and fillers, is
well-known in cosmetic and personal care technology. Examples are
coated pigments and fillers with excellent skin feel and reduced
potential for skin abrasion, prepared by utilizing salts of acyl
amino acids such as aluminum N-myristoyl-L-glutamate (see U.S. Pat.
No. 4,606,914 of Miyoshi); platy pigments with improved tactile
properties, prepared by precipitation of acylamino acids such as
N-lauroyllysine on the surface of talcs (see, for example, U.S.
Pat. No. 5,326,392 of Miller); and skin treatments prepared by
treating pigments and fillers with combinations of N-acylamino
acids, N-acylamino acid salts and fatty acids (see U.S. Pat. No.
7,374,783 of Hasegawa). All of these coatings are produced by
adsorbing or precipitating amino acids on particles. For the most
part, these coatings are relatively hydrophobic since they are
derived from N-acyl substituted amino acids in which the acyl group
has six or more carbons, most often lauroyl (12 carbons). The use
of particles treated with these systems is restricted to oil based
color cosmetics, either anhydrous formulations or water-in-oil
emulsions, because particles with adsorbed hydrophobic amino acids
will not disperse in the continuous aqueous phase. The pigment
phase of the finished emulsion must be dispersed in the external
phase of the emulsion to allow the mass tone of the product to be
similar to that achieved on the skin after application.
[0005] There are many instances in which the benefits of amino acid
modified particles would be desirable in oil-in-water formulations.
However, amino acids simply adsorbed onto particulates tend to
destabilize oil-in-water emulsions. They also tend to coalesce
dispersed oil by physically bridging on the surface of the particle
by adsorption phenomena. Further, particles with adsorbed
hydrophilic amino acids tend to be intrinsically unstable at
water-oil interfaces since the amino acid tends to desorb from the
particle, at once changing the surface characteristics of the
particle and changing the aqueous environment by introducing
soluble amino acids which tend to be strong zwitter-ions.
[0006] While the immobilization of enzymes and amino acids has been
disclosed by Weetall (U.S. Pat. No. 3,652,761), these systems were
designed for fixed-bed catalysis, and the particle dimensions are
not suitable for the purpose of forming stable dispersions.
BRIEF SUMMARY OF THE INVENTION
[0007] The invention is directed to hydrophilic alkoxysilane
derivatives of N-acylamino acids, N-acyl dipeptides, and N-acyl
tripeptides, wherein the acyl group contains fewer than six carbon
atoms.
[0008] The invention also relates to particles of a mineral,
filler, or pigment having on its surface a coating of a hydrophilic
alkoxysilane derivative of an N-acylamino acid, N-acyl dipeptide,
or N-acyl tripeptide, wherein the acyl group contains fewer than
six carbon atoms.
[0009] The invention is further directed to oil-in-water
formulations containing a dispersion comprising particles of a
mineral, filler, and/or pigment having on its surface a coating of
a hydrophilic alkoxysilane derivative of an N-acylamino acid,
N-acyl dipeptide, or N-acyl tripeptide, wherein the acyl group
contains fewer than six carbon atoms.
[0010] Finally, the invention is directed to a pressed powder or
color cosmetic comprising particles of a mineral, filler, and/or
pigment having on its surface a coating of a hydrophilic
alkoxysilane derivative of an N-acylamino acid, N-acyl dipeptide,
or N-acyl tripeptide, wherein the acyl group contains fewer than
six carbon atoms.
DETAILED DESCRIPTION OF THE INVENTION
[0011] The present invention is directed to alkoxysilane
derivatives of N-acyl amino acids, N-acyl dipeptides, and N-acyl
tripeptides, in which the number of carbon atoms in the acyl
substitution is fewer than six carbons, preferably two carbons
(acetyl). The N-acyl amino acid, N-acyl dipeptide, and N-acyl
tripeptide is not limited, provided that the acyl substituent
contains fewer than six carbon atoms. If the acyl group contains
more than six carbon atoms, the resulting amino acid or di- or
tripeptide becomes hydrophobic. For example, exemplary amino acids
include N-acetylglycine, N-acetylproline, N-acetylhydroxyproline,
and N-acetyl leucine. Exemplary dipeptides include
N-acetylglycylglycine and N-acetylglycylserine, and an exemplary
tripeptide is N-acetylglycylglycylglycine.
[0012] Although there is no limitation on the length of the alkoxy
group, preferred alkoxy groups include methoxy and ethoxy.
Preferred compounds according to the invention contain three alkoxy
groups (which may be the same or different, such as dimethoxyethoxy
or diethoxymethoxy), although compounds containing two alkoxy
groups are also within the scope of the invention.
[0013] The compounds of the invention are preferably
alkylalkoxysilane derivatives, such as methylalkoxy, ethylalkoxy,
and propylalkoxy, propylalkoxy being presently preferred. Other
alkyl group lengths are also within the scope of the invention, but
are not presently preferred for economic reasons. Accordingly, in
preferred embodiments, the compounds are propyltrialkoxysilane
derivatives of N-acyl amino acids, N-acyl dipeptides, or N-acyl
tripeptides, such as propyltrimethoxysilane and
propyltriethoxysilane derivatives. For example, exemplary compound
according to the invention include
N-acetylglycylglycylglycylpropyltriethoxysilane and
N-acetylglycylglycylpropyltriethoxysilane.
[0014] Exemplary silane modified amino acids, which have been found
to enhance dispersion of particles in aqueous phases, include:
##STR00001##
[0015] The method of preparing these materials is not critical and
the compounds may be prepared by any effective method known in the
art or to be developed. Preferred methods include carbodiimide
coupling, resulting in amide formation, or the formation of an
alkali metal salt of the amino acid and reaction with a halogenated
alkylsilane, resulting in ester formation. Ester formation is
advantageous because the need for strong dehydrating reagents such
as carbodiimides, which tend to be skin sensitizing agents, is
eliminated. For example, the compounds may be prepared by a
coupling reaction between a haloalkoxysilane and the salt of the
appropriate N-acyl amino acid, N-acyl dipeptide, or N-acyl
tripeptide. For instance, (N-Acetylglycylpropyl)triethoxysilane may
be prepared via the reaction of 3-iodopropyltriethoxysilane with
N-acetylglycine.
[0016] The invention is also directed to particles (such as
particles of minerals, pigments, or fillers) that have been treated
with the alkoxysilane derivatives of N-acylaminoacids, N-acyl
dipeptides, or N-acyl tripeptides to create relatively hydrophilic
particle surfaces. In other words, the treated particles have on
their surface a coating of a hydrophilic alkoxysilane derivative of
an N-acyl amino acid, N-acyl dipeptide, or N-acyl tripeptide
according to the invention. The modification may be performed as
described by Arkles in Chemtech, 7(12), 766, (1977), which is
herein incorporated by reference. These treated particles according
to the invention wet preferentially in water, rendering the
resulting pigments or fillers suitable for use in water-based
formulations, including gels and oil-in-water emulsions. The
covalent bonding of hydrophilic amino acids or analogous di- and
tripeptides on particles provides for the formation of stable
oil-water systems, especially emulsion interfacial systems, without
deterioration. In order to function as stable dispersions, the
treated particles of this invention preferably are no greater than
about 200 microns in the largest dimension and no less than about
0.01 microns in the smallest dimension.
[0017] The particles according to the invention are particularly
useful in cosmetics. Particles utilized in cosmetics include both
filler materials, such as mica, talc, sericite, silica,
fluorophlogopite, borosilicate flakes, alumina, and kaolin,
inorganic pigments, such as iron oxides, titanium dioxide, ferric
ammonium ferrocyanide, chromium oxide, chromium hydroxide, zinc
oxide, and ultramarines, and organic pigments, such as carmine, and
the FDA certified lakes of Red 6, Red 7, Red 21, Red 27, Red 33,
Red 36, Red 40, Yellow 5, Yellow 6, Yellow 10, and Blue 1. These
types of particles are meant to be exemplary, not limiting, and it
is within the scope of the invention to treat other types of
particles (both those useful in cosmetics and those that are not),
as well.
[0018] The invention is also directed to oil-in-water formulations,
such as, without limitation, concealers or foundations, containing
dispersions comprising particles of a mineral, filler, and/or
pigment having on its surface a coating of an alkoxysilane
derivative of an N-acyl amino acid, N-acyl dipeptide, or N-acyl
tripeptide according to the invention. Another potential benefit of
hydrophilic amino acid modified particles (or the analogous di- and
tri-peptides) is that they may contribute to skin care as natural
moisturizing factors when utilized alone or in combination with
unbound hydrophilic amino acids and formulated into foundations or
concealers. Further, the invention is directed to pressed powder
and color cosmetics, including those suitable for eye area use,
containing such treated particles. The additional components of the
oil-in-water formulations and cosmetics, and methods for their
preparation, are well known in the art and need not be
described.
[0019] The invention will now be described in conjunction with the
following, non-limiting examples.
EXAMPLES
Preparation Examples
Example 1
Preparation of (N-Acetyl-glycylpropyl)triethoxysilane
[0020] A 5 L, 4-neck flask equipped with a heating mantle, a
mechanical stirrer, a pot thermometer, an addition funnel, and a
short Vigreux column with a distillation head connected to a
nitrogen bubbler was charged with 2500 g of ethanol and 146.4 g of
N-acetylglycine. This mixture was stirred at room temperature for
15 minutes. 110.5 g of potassium ethoxide were added while
maintaining the pot temperature below 50.degree. C. The mixture was
heated to a pot temperature of 80.degree. and 362.7 g of
3-iodopropyltriethoxysilane was added. Ethanol was removed by
distillation until the pot temperature rose to 90.degree. C. to
95.degree. C. The reaction was followed by GC and heating continued
for .about.100 hours until less than 10% of the
3-iodopropyltriethoxysilane remained. The flask and the contents
were allowed to cool to room temperature and then filtered to give
a clear to slightly hazy solution with 25-30% solids. A sample of
solution was stripped of solvent at 120.degree. C. and 1 mm vacuum
to remove all solvents and unreacted starting materials. The
product was purified by wiped film distillation at 190.degree. C.
at 0.5 mm. IR and NMR results were consistent with the target
structure.
Example 2
Preparation of (N-Acetyl-4-hydroxyprolyl)propyltriethoxysilane
[0021] A 5 L, 4-neck flask equipped with a heating mantle, a
mechanical stirrer, a pot thermometer, an addition funnel, and a
short Vigreux column with a distillation head connected to a
nitrogen bubbler was charged with 2500 g of ethanol and 432.9 g of
N-acetylhydroxyproline. This mixture was stirred at room
temperature for 15 minutes. 220.9 g of potassium ethoxide were
added while maintaining the pot temperature below 40.degree. C. The
pot temperature was slowly heated to 80.degree. C. and 500 ml of
ethanol were removed and discarded. At a pot temperature of
80.degree. C., 31.1 g of potassium iodide and 602 g of
chloropropyltriethoxysilane were added. An additional 500 ml of
ethanol was removed by distillation and retained. The pot
temperature gradually rose from 80.degree. C. to 90.degree. C.
during removal of ethanol. The reaction was followed by GC, and
heating was continued until less than 5% of the
3-chloropropyltriethoxysilane remained. The retained ethanol was
charged back to the flask and the contents were allowed to cool to
room temperature. The mixture was filtered to give .about.3 kg of a
clear to slightly hazy amber solution with 25-30% solids. The
density of the solution at 25.degree. C. was 0.87 g/cm.sup.3. A
sample of solution was stripped of solvent at 60.degree. C. and 1
mm vacuum to give gel-like solids. IR and NMR results were
consistent with the target structure.
Example 3
Preparation of (N-Acetyl-leucinamidepropyl)triethoxysilane
[0022] A 1 L, 4-neck flask equipped with a heating mantle, a
magnetic stirrer, a pot thermometer, an addition funnel, and a
dry-ice condenser connected to a nitrogen bubbler was charged with
125 ml of dimethylformamide and 25 g of N-acetylleucine. This
mixture was stirred at room temperature for 15 minutes. 14.9 g of
dicyclohexylcarbodiimide in 10 portions were added. Pot temperature
rose 10.degree. C. The mixture was stirred for 60 minutes and the
pot temperature returned to 24.degree. C. 32 g of
3-aminopropyltriethoxysilane was added over 45 minutes as the pot
temperature rose 15.degree. C. The mixture was stirred for an
additional 4 hours. The flask was heated to 40.degree. C. and the
dimethylformamide was removed under vacuum. 300 ml of toluene were
added and the mixture was heated to 40.degree. C. and then allowed
to stir overnight without heating. The mixture was filtered. The
solids were washed with 100 ml of toluene and the volatiles were
stripped from the combined filtrates to give the product as a pale
yellow solid. IR and NMR results were consistent with the target
structure. The product formed a 13% solution in ethanol after
warming to 30.degree. C. with a density of 0.763.
Example 4
Preparation of (N-Acetylglycinamidepropyl) trimethoxysilane
[0023] A 3 L, 4-neck flask equipped with a heating mantle, a
mechanical stirrer, a pot thermometer, an addition funnel, and a
dry-ice condenser connected to a nitrogen bubbler was charged with
300 ml of dimethylformamide and 58.5 g of acetylglycine. This
mixture was stirred at room temperature for 20 minutes. 56.1 g of
dicyclohexylcarbodiimide in 10 portions were added, and the pot
temperature rose 12.degree. C. The mixture was stirred for 60
minutes and the pot temperature returned to 25.degree. C. 44.8 g of
3-aminopropyltrimethoxysilane were added over 45 minutes as the pot
temperature rose 20.degree. C. The mixture was stirred for an
additional 4 hours. The flask was heated to 40.degree. C. and the
dimethylformamide was removed under vacuum. 400 ml of THF were
added to the pot and that mixture was heated to 40.degree. C. and
then allowed to stir overnight without heating. The mixture was
filtered at room temperature. The solids were washed with 100 ml of
THF and the volatiles were stripped from the combined filtrates to
give the product as a pale yellow solid. IR and NMR results were
consistent with the target structure. The product formed a 5%
solution in methanol at 25.degree. C. with a density of 0.799.
Preparation of Particles and Analysis
Preparation of Treated Particles
Example 5
Preparation of Treated Yellow Iron Oxide
[0024] 2 grams of (N-acetyl-4-hydroxyprolyl)propyltriethoxysilane
(prepared in Example 2) were added to 2000 ml of an 80%
isopropanol/20% distilled water solution with stirring. The silane
was allowed to hydrolyze at ambient conditions for 2 hours. 100
grams of yellow iron oxide were added and stirring continued for
one hour. The suspension was filtered and the filtrate was heated
to 80.degree. C. for 4 hours. The resulting powder was milled using
a hammer mill through a 0.027'' screen.
Example 6
Preparation of Treated Red Iron Oxide, Black Iron Oxide, and
Titanium Dioxide
[0025] 2 grams of (N-acetyl-4-hydroxyprolyl)propyltriethoxysilane
(prepared in Example 2) were sprayed onto 100 grams of dry red iron
oxide under agitation in a tumbling mixer. The powder was agitated
for one hour at ambient conditions and then heated to 80.degree. C.
for four hours. After cooling, the treated powder was
deagglomerated by milling with a hammer mill through a 0.035''
screen. Black iron oxide and titanium dioxide treated particles
were prepared in an analogous fashion.
Example 7
Preparation of Treated Sericite
[0026] 2 grams of (N-acetyl-4-hydroxyprolyl)propyltriethoxysilane
(prepared in Example 2) were sprayed onto to 100 grams of sericite
under agitation in a tumbling mixer. The powder was agitated for
one hour at ambient conditions and then heated to 80.degree. C. for
four hours. After cooling, the treated powder was milled using a
hammer mill through a 0.067'' screen.
Analysis of Treated Pigment Particles
[0027] The four treated pigments (yellow iron oxide, red iron
oxide, black iron oxide, and titanium dioxide) were analyzed and
compared with a variety of comparative materials in order to
determine the effect of surface modification on the pigment
particles.
[0028] Aqueous Dispersion (Visual):
[0029] 0.3 grams of each treated pigment were added to 15 ml
deionized water. Behavior was observed without stirring and the
results tabulated in Table 1.
TABLE-US-00001 TABLE 1 Visual Evaluation of Treated Pigment
Particles Yellow Iron Red Iron Black Iron Titanium Oxide Oxide
Oxide Dioxide control (untreated) wets, falls to falls to bottom
falls to bottom bloom bottom PEG.sub.6-9 Silane self disperses self
disperses slight bloom self disperses PEG-8 wets slowly; falls wets
slowly; falls wets slowly; falls wets slowly; falls to bottom;
slight to bottom; slight to bottom to bottom; slight bloom bloom
bloom Aminopropyl Silane wets slowly bloom blooms 50% slight bloom;
settles wets slowly; slight bloom Na2 self disperses self disperses
sl bloom self disperses Carboxyethylsilanetriol Na Propionate wets
slowly; very wets slowly; settles wets slowly; settles wets slowly;
very slight bloom slight bloom N-Acetyl falls to bottom falls to
bottom falls to bottom falls to bottom Hydroxyproline N-Acetyl self
disperses self disperses slight bloom self disperses Hydroxyprolyl
propyltriethoxysilane
[0030] It can be seen in Table 1 that all of the pigments with
hydrophilic modification de-agglomerated and dispersed without
stirring to some extent. PEG.sub.6-9 silane
(methoxy(polyethyleneoxy).sub.6-9propyltrimethoxysilane), sodium
carboxyethylsilanetriol, and
(N-acetylhydroxyprolyl)propyltriethoxysilane treated pigments
dispersed completely, some particles remaining in suspension for
over one month.
[0031] Deposition of the polar compounds alone on the pigment
surfaces did not produce the instant dispersion effect that results
from surface treatment with silanes having the polar compounds as a
functional group. The dry treated pigments were de-agglomerated to
some extent due to the milling steps in the treatment process, but
the effect was negated by particle size reduction steps of all
samples used for dispersion testing. The greater surface area can
actually appear to slow the wetting process, but the results of the
viscosity tests described below show that wetting of the treated
particles improved compared to the untreated pigments. The dramatic
dispersion of the hydrophilic treatments seen in visual evaluation
was confirmed by the quantitative measurements.
[0032] Dispersion Viscosity (Butylene Glycol):
[0033] Dispersions of the pigments were prepared by wetting in
butylene glycol with stirring for one hour, followed by three
passes over a three roll mill. Viscosity was measured using a
Brookfield viscometer using standard spindles at 20 RPM. Different
spindle sizes were used in different viscosity ranges. The results
are tabulated in Table 2. Lower viscosity at equal concentration
and degree of dispersion (particle size) indicates better
wetting.
TABLE-US-00002 TABLE 2 Dispersion Viscosity of Treated Pigment
Particles Pigment, % in Butylene Glycol Yellow Iron Red Iron Black
Iron Titanium Treatment Oxide 45% Oxide 50% Oxide 50% Dioxide 50%
control (untreated) 73,400 cps 24,500 cps 10,950 cps 11,150 cps
(spindle #7) (spindle #6) (spindle #6) (spindle #6) PEG.sub.6-9
Silane 1,610 cps 2,100 cps 3,970 cps 12,150 cps (spindle #3)
(spindle #4) (spindle #4) (spindle #6) Aminopropyl 675 cps 4,100
cps 9,000 cps 4,700 cps Silane (spindle #3) (spindle #4) (spindle
#4, 5) (spindle #4) Na Carboxyethyl- 540 cps 2,690 cps 6,500 cps
415 cps silanetriol (spindle #3) (spindle #4) (spindle #4, 5)
(spindle #3) N-Acetyl Hydroxyprolyl 520 cps 3,120 cps 5,940 cps
2,870 cps) propyltriethoxysilane (spindle #3) (spindle #4) (spindle
#4, 5) (spindle #3)
[0034] It can be seen that all of the hydrophilic treated pigments
improved wetting and dispersion in butylene glycol relative to the
untreated pigment, except, surprisingly, PEG.sub.6-9 silane on
titanium dioxide. (N-acetyl-hydroxyprolyl)propyltriethoxysilane
treated pigments performed comparably to the other hydrophilic
treatments. Dispersion viscosity measurements indicated that
PEG.sub.6-9silane, sodium carboxyethylsilanetriol, and
(N-acetyl-hydroxyprolyl)propyltriethoxysilane treated iron oxides
exhibited the best wetting. Sodium carboxyethylsilanetriol and
(N-acetyl-hydroxyprolyl)propyltriethoxysilane treatments were the
most effective treatment for titanium dioxide.
Formulation and Cosmetics Preparation and Analysis
Example 8
Preparation and Analysis of Oil-in-Water Concealers
[0035] Five anionic oil-in-water emulsion concealers containing 20%
pigment and filler were prepared using the components shown in
Table 3. One formulation was prepared using pigments treated with
(N-acetyl-4-hydroxyprolyl)propyltriethoxysilane (as prepared in
Example 2), and three comparative formulations were prepared using
pigments treated with PEG.sub.6-9 silane, aminopropylsilane, or
sodium carboxyethylsilanetriol. A fifth formulation was prepared as
a control using untreated pigments. In each case, water phase
ingredients were added in order to the finishing beaker while
homogenizing at low speed. Following Veegum addition, the phase was
heated to 85-90.degree. C. for 15 minutes, then other additions
were performed at 75.degree. C. The oil phase ingredients were
combined and stirred at 75-80.degree. C. until homogenous. The oil
phase was added to the water phase with homogenization.
TABLE-US-00003 TABLE 3 Formulation for Oil-in-Water Concealer % by
Ingredient INCI* Name weight Water Phase Deionized Water 50.37
Tween 60 Polysorbate 60 0.10 Laponite XLG Sodium Lithium Magnesium
0.30 Silicate Veegum reg Magnesium Aluminum Silicate 0.70 Titanium
Dioxide Titanium Dioxide 16.00 Yellow Iron Oxide Iron Oxides 1.60
Red Iron Oxide Iron Oxides 0.60 Black Iron Oxide Iron Oxides 0.16
Talc Talc 1.64 Butylene Glycol 6.00 CMC7H3SF (Aqualon) Cellulose
Gum 0.10 Tween 60 (Croda) Polysorbate 60 0.40 Methylparaben 0.25
Amphisol K (DSM) Potassium Cetyl Phosphate 2.00 Oil Phase DE 12
(Gelest) Polydiethylsiloxane 12.00 Ceraphyl 368 (ISP) Ethylhexyl
Palmitate 5.00 Span 60 (Croda) Sorbitan Stearate 1.00 Cerasynt SD
(ISP) Glyceryl Stearate 1.50 Propylparaben 0.10 Glydant (Lonza)
DMDM Hydantoin 0.18 100.00 *INCI = International Nomenclature of
Cosmetic Ingredients
[0036] Performance of the treated pigments in the formulations was
analyzed visually. Dispersion quality was evaluated by the presence
or absence of undispersed color, detected by pressing a drop of the
finished emulsion between two microscope slides and checking for
spots of color. Time required to wet the particles was used to
compare ease of wetting. "Rapid" means pigment dispersion and color
development commenced immediately after addition of the powders to
the water phase. "Slow" refers to the presence of unwet
agglomerates even after five minutes of mixing. "Intermediate"
refers to a delay of 45-90 seconds between pigment addition and
disappearance of dry particles. Color development (intensity) in
the final product and presence or absence of color flotation during
processing were observed and photographed for later analysis.
Viscosity and emulsion stability of the final products were also
monitored. Data for untreated pigments and those having control
treatments are compared against pigments treated with (N-acetyl
hydroxyprolyl)propyltriethoxysilane and the results are shown in
Table 4.
TABLE-US-00004 TABLE 4 Analysis of Concealer Formulations Parameter
Color development.sup.1 Treatment Dispersion (Intensity) Wetting
Flotation control (untreated) undispersed 1 slow white pigment
PEG.sub.6-9 Silane complete 4 rapid white/ yellow/black Aminopropyl
Silane undispersed 2 slow white TiO.sub.2 Na complete 5 rapid
yellow > Carboxyethylsilanetriol 60.degree. C. N-Acetyl
Hydroxyprolyl complete 3 intermediate none propyltriethoxysilane
.sup.1On a scale of 1 to 5, 1 being the lowest
[0037] The data clearly demonstrate the hydrophilicity and
dispersibility in water of the
(N-acetyl-hydroxyprolyl)propyltriethoxysilane treated pigments.
[0038] Surprisingly,
(N-acetyl-4-hydroxyprolyl)propyltriethoxysilane treatment resulted
in the most consistent wetting of the different pigments. The
formula containing (N-acetyl-4-hydroxyprolyl)propyltriethoxysilane
treated pigments exhibited good dispersion with no visible
agglomerates and none of the color flotation that usually indicates
poor wetting of an individual colorant. The formula spread evenly
over the skin to leave a comfortable layer on the delicate
under-eye area that hid dark circles and other imperfections. The
emulsion was stable under accelerated aging and long term
testing.
[0039] Interaction of the treated surfaces with other raw materials
may be the cause of the variable results observed with the other
treatments in the actual formulation. Surface activity of the PEG
group of the PEG.sub.6-9 silane may affect the formation of the
emulsion, causing excessive pigment flotation, and appears to
influence wetting of some thickening agents. The anionic nature of
sodium carboxyethylsilanetriol does stabilize pigment dispersions,
but the effect of the added electrolyte on other raw materials,
particularly gellants, may be the cause of emulsion instability or
color flotation. Accordingly, the inventive materials provide
results that are not achieved by prior art materials.
Example 9
Preparation and Analysis of Pressed Powder Foundation
[0040] A pressed powder foundation was prepared using the
components shown in Table 5 by combining the powder phase in a
tumbling mixer equipped with a high speed agitator. When
homogenous, the oils were combined and added to the batch with
agitation until dispersed. The powder was pressed into suitable
pans at 750 psi. The product exhibited excellent affinity for the
skin, applying smoothly with a soft, silky feel to give full, yet
natural looking coverage that lasted all day.
TABLE-US-00005 TABLE 5 Formulation for Pressed Powder Foundation
Ingredient Surface treatment % Powder Phase Mica (N-Acetyl- 20.00
hydroxyprolyl)propyltriethoxysilane Yellow Iron Oxide (N-Acetyl-
2.00 hydroxyprolyl)propyltriethoxysilane Red Iron Oxide (N-Acetyl-
0.80 hydroxyprolyl)propyltriethoxysilane Black Iron Oxide
(N-Acetyl- 0.35 hydroxyprolyl)propyltriethoxysilane Talc (N-Acetyl-
55.84 hydroxyprolyl)propyltriethoxysilane Zinc Stearate 3.00 Nylon
-12 5.00 Benzoic Acid 0.10 Oil Phase Octyldodecyl Stearate 2.50
Polydiethylsiloxane 1.50 100.00
Example 10
Pressed Powder Eye Shadow
[0041] A pressed powder eye shadow was prepared using the
components shown in Table 6 by combining the powder phase in a
tumbling mixer equipped with a high speed agitator. When
homogenous, the oils were combined and added to the batch with
agitation until dispersed. The powder was pressed into suitable
pans at 850 psi. The product applied smoothly with a soft, silky
feel to the delicate eye area. Due to the affinity of the
(N-acetyl-4-hydroxyprolyl)propyltriethoxysilane treated pigments
for the skin, the eye shadow exhibited long wear and resistance to
creasing.
TABLE-US-00006 TABLE 6 Pressed Powder Eye Shadow Formulation
Ingredient Surface treatment % Powder Phase Mica (N-Acetyl- 30.00
hydroxyprolyl)propyltriethoxysilane Yellow Iron Oxide (N-Acetyl-
3.00 hydroxyprolyl)propyltriethoxysilane Red Iron Oxide (N-Acetyl-
3.00 hydroxyprolyl)propyltriethoxysilane Black Iron Oxide
(N-Acetyl- 4.00 hydroxyprolyl)propyltriethoxysilane Talc (N-Acetyl-
47.90 hydroxyprolyl)propyltriethoxysilane Zinc Stearate 3.00
Nylon-12 5.00 Benzoic Acid 0.10 Oil Phase Octyldodecyl Stearate
2.50 Polydiethylsiloxane 1.50 100.00
Example 10
Preparation and Analysis of Eyeliner
[0042] A water based eyeliner was prepared by dispersing
(N-acetyl-4-hydroxyprolyl)propyltriethoxysilane treated black iron
oxide in the water phase of the emulsion with only low speed
homogenization to give fine pigment particle size with full color
development. The eyeliner drew a fine line behind the eye lashes
that adhered well throughout the day. The formulation of the
eyeliner is shown in Table 7.
TABLE-US-00007 TABLE 7 Formulation of Eyeliner Ingredient %
Deionized Water 69.49 Butylene Glycol 6.00 Methylparaben 0.30
TrisAmino (Dow) [Tromethamine] 1.00 Deionized Water 4.00 Shellac
(Mantrose-Haeuser) 1.00 Hydroxyethylcellulose 0.50 Black Iron Oxide
treated with (N-acetyl-4- 10.00 hydroxyprolyl)propyltriethoxysilane
Wax Phase White Beeswax 4.00 Carnauba Wax 0.50 Cetyl Alcohol 1.25
Sorbitan Stearate 1.00 Hydrogenated Polyisobutene 0.50
Propylparaben 0.10 DMDM Hydantoin 0.36 100.00
[0043] It will be appreciated by those skilled in the art that
changes could be made to the embodiments described above without
departing from the broad inventive concept thereof. It is
understood, therefore, that this invention is not limited to the
particular embodiments disclosed, but it is intended to cover
modifications within the spirit and scope of the present invention
as defined by the appended claims.
* * * * *