Note: Descriptions are shown in the official language in which they were submitted.
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Cosmetic Formulations Comprising Zn0 Nanoparticles
Inventors:
Valerie Andre
BASF Aktiengesellschaft
Richard W. Brotzman, Jr.
Nanophase Technologies Corporation
Cross-Reference to Related Patents
Particulate surfaces, and in particular nanoparticle surfaces, may be surface
treated by
star-graft copolymers to form uniform coatings according to the methods
disclosed in US
Patents 5,993,967 and 6,033,781, which are incorporated herein by reference.
Field of the Invention
Modern skin care formulations must meet high standards of efficacy, skin
compatibility and aesthetic appeal. It is commonly accepted that the
performance of a
cosmetic product is related to the entire formulation. Thus, an optimal
galenic formulation
that incorporated active ingredients is a necessary prerequisite to succeed in
the market. The
objective of topical formulations may be classified in two major areas: to
modulate or assist
the barrier function of the skin and to act as a delivery system for active
ingredients. This
patent focuses on the development of galenically interesting formulation
concepts used in
contemporary skin care products which combine, in particular, charged organic
moieties,
such as acrylate-based polymers, a- and (3-hydroxy acids, etc., and inorganic
zinc oxide and
titania.
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The present invention relates in particular to problems encountered when
particulate
zinc oxide, and in particular nanoparticulate zinc oxide, is formulated with
charged organic
moieties, such as acrylate-based polymers, a- and ~i-hydroxy acids, etc.
Contemporary skin
care formulations are dispersions. The charged organic moieties will reside in
the aqueous
phase of the dispersion and the inorganic ingredients, zinc oxide and titania,
reside in the oil
phase of the dispersion. In formulation the acrylate-based polymers, once
neutralized with a
cosmetically acceptable base such as triethanol amine or sodium hydroxide,
extend to thicken
the formulation by increasing the viscosity of the aqueous phase. Other
charged organic
moieties, such as a- and [3-hydroxy acids, may have other functions such as
enhancing
epithelial cell regeneration. However zinc ions from the particulate zinc
oxide migrate from
the oil phase to the aqueous phase and adversely interact with the charged
organic moieties to
either cause collapse of the acrylate-based polymers or the formation of
organic salts with
concomitant dissolution of the particulate inorganic.
Specifically excluded from the present invention are surface treatments for
all
inorganic, semi-metallic, and/or metallic oxide particles for all applications
except (a) the
products) per se, defined as surface treated Zn0 and/or Ti02 (titania), and
(b) the use of the
products) per' se in personal care formulations. Personal care formulations
are defined as
cosmetic or dermatological preparations for skin care, hair care, foot care,
sun care, oral care,
baby care, toiletries, color cosmetics, personal cleaning, and topical human
sunscreens.
Invention
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The present invention relates to the formation of surface treated zinc oxide
and titania
particles, and in particular zinc oxide and titania nanoparticles, with a
siloxane star-graft co-
polymer coating, comprising a looped and/or linear polymeric structure on a
star-graft
copolymer coating, on a particle surface to control the interfacial surface
interactions between
the particle and the oil phase of the cosmetic skin formulation. The siloxane
star-graft co-
polymer, that may or may not contain topological loops, is formed in the
"particle surface
proximity" by a heterogeneous polymerization reaction. The resulting surface
treatment will
passivate the zinc oxide surface to prevent ion leakage and render the surface
treated zinc
oxide compatible with charged organic moieties, such as acrylate-based
polymers and a- and
(3-hydroxy acids, etc. In addition the surface treatment on zinc oxide and
titania can be
tailored to render the surface treated particle thermodynamically compatible
with different oil
phase components of a cosmetic skin formulation.
Background of the Invention
The surface treatment of inorganic particles has been addressed over the years
by many
different techniques and chemical efforts. Some of the techniques are the
application of
coatings to the suxface of particles, using coupling agents on the surface of
the particles,
physically modifying the surface of the particles, chemically modifying the
innate
composition on the surface of the particles, and/or modifying the formulation
to
accommodate the particle - this latter is one of the least desirable methods
of controlling
particulate behavior in formulation as it limits formulation composition and
ingredients and
may alter essential formulation and product properties.
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The surfaces of zinc oxide and titania have been conventionally coated by
adsorption,
ion exchange, and covalent bonding. Adsorption and ion exchange require the
surface to
have the appropriate chemical characteristics. Reactions that enable covalent
bonding to
particle surfaces generally involve reactions with a surface-bound hydroxyl
group. These
coatings are thin surface treatments which afford a degree of formulation and
product
compatibility and for the best available technology no particulate
aggregation, but can not
prevent ion migration from reactive particles or affect ultimate control of
interfacial material
properties.
Description of Invention
The shortcomings of the existing art are overcome and additional advantages
are
provided through the provision of a surface treated zinc oxide and/or titania
nanoparticle
having a coating comprised of a star-graft siloxane copolymer to which are
polymerized
looped and/or linear polymer chains. Particulate surfaces, and in particular
nanoparticulate
surfaces, may be surface treated by siloxane star-graft copolymers to form
uniform coatings
according to the methods disclosed in US Patents 5,993,967 and 6,033,781 which
are
incorporated herein by reference. These uniform particulate surface treatments
enable
compatibility without particulate aggregation but they are subject to the
limitations
enumerated above. These star-graft copolymers may be formulated to have
pendant groups
that are reactive. It is to these reactive pendant groups that difunctional
monomers are graft
copolymerized to form looped and/or linear chains.
The star-graft copolymers may be applied to zinc oxide and/or titania
particles, and in
particular nanoparticles. The star-graft copolymer coatings are formed by
reacting specific
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monomers to form a siloxane-based polymer. The surface treatment encapsulates
the
nanoparticulate zinc oxide and/or titania. In general, a plurality of
nanoparticle zinc oxide
and/or titania is surface treated with the star-graft copolymer and the
surface treatment
encapsulates at least a portion of the particles discretely, preferably all of
the particles
discretely. The star-graft copolymer, disclosed in US 5,993,967 and 6,033,781,
comprises:
Si (w, x, y, z)
where w, x, y, and z are the mole percent tetrafunctional, trifunctional,
difunctional, and
monofunctional monomeric units, respectively and wherein w, x, y, and z ranges
of about 45-
75, 5-25, 5-45, and 5-10, respectively.
As disclosed in US Patents 5,993,967 and 6,033,781, a star-graft copolymer,
capable
of coating and encapsulating nanoparticles, required a relatively large
percentage of
tetrafunctional monomers to yield a high degree of branching. In addition, the
trifunctional
monomers directed coating conformation, difunctional monomers were the linear
polymer
segments, and monofunctional monomers controlled the overall size
Because difunctional monomers are polymerized to this star-graft polymer to
form
looped and/or linear polymer chains that extend from the particle surface into
the solvating
fluid or matrix structure, one skilled in the art would expect that a decrease
the
monofunctional monomer to enable the star-graft polymer surface treatment to
retain
functionality, and increase the difunctional monomers to form additional
linear polymer
segments would be yield the desired surface treatment. However to our
surprise, not only
was it necessary to decrease the monofunctional monomers to retain
functionality on the star-
graft polymer and to increase the difunctional monomers to form additional
linear chains, but
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the present invention further requires the star-graft copolymer to have a
significantly lower
degree of branching, with respect to surface treatments taught in US Patents
5,993,967 and
6,033,781- this is an unexpected and surprising result.
It is these looped and/or linear polymer chains that enable surface
treatments, what
would otherwise be thin coatings, to extend into the application medium and
control the
interfacial properties of the zinc oxide and/or titanic particle.
The present invention relates to a surface treated particle comprising a
plurality of
zinc oxide and/or titanic particles and a star-graft copolymer with looped
and/or linear
polymeric structure on a star-graft copolymer encapsulating at least a portion
of said
particles, said surface treatment comprising:
Si (x, y)
where x and y are the mole percent trifunctional and difunctional monomeric
units,
respectively.
In the preferred surface treated particle:
x is selected from the group of trifunctional monomers that have cosmetically
acceptable non-reactive ligands comprising of methyltrimethoxysilane, n-
propyltrimethoxysilane, isobutyltrimethoxysilane, n-hexyltrimethoxysilane, n-
octyltrimethoxysilane, n-octadecyltrimethoxysilane, phenyltrimethoxysilane,
and the
triethoxy-containing counterparts of these monomers; and
y is selected from the group of difunctional monomers that have cosmetically
acceptable non-reactive ligands comprising of dicyclohexyldimethoxysilane,
diethyldiethoxysilane, dimethyldichlorosilane, dimethyldiethoxysilane,
dimethyldimethoxysilane, diphenyldiethoxysilane, diphenyldimethoxysilane, di-n-
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hexyldichlorosilane, n-hexylmethyldichlorosilane, methyldodecyldiethoxysilane,
n-
octylmethyldimethoxysilane, and the diethoxy-containing counterparts of these
monomers.
In the most preferred surface treated particle:
x is selected from the group of n-octyltrimethoxysilane, n-
octyltriethoxysilane,
phenyltrimethoxysilane and phenyltriethoxysilane; and
y is selected from the group of diphenyldiethoxysilane and
diphenyldimethoxysilane.
The values of x and y in the above silicon-based polymers have ranged from 1-
50 and
50-99, respectively. Preferably the values of x and y in the above silicon-
based polymers
have ranged from 1-40 and 60-99, respectively. Most preferably the values of x
and y in the
above silicon-based polymers have ranged from 10-30 and 70-90, respectively.
The surface treatment is applied to zinc oxide and/or titania particles, and
in particular
nanoparticles. The nanoparticle mean particle size range is from about 1 nm to
about 900
nm. The preferred nanoparticle mean particle size range is from about 2 nm to
about 500 nm.
The most preferred nanoparticle mean particle size range is from about 5 nm to
about 100
nm.
As an alternative to processing methods disclosed in US Patents 5,993,967 and
6,033,71, the preferred method of preparing the surface treated zinc oxide
and/or titania
comprises mixing the particulate comprising substantially spherical
nanocrystalline particles
with surface treatment precursors. The siloxane star-graft copolymer, that
contains loops
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and/or linear polymer chains, is formed in the "particle surface proximity" by
a
heterogeneous polymerization reaction. The mixture is carried out at a
temperature, in an
environment, and for a time that is effective for the star-graft copolymer to
coat the
nanocrystalline particle and the difunctional precursors to polymerize to form
the looped
and/or linear chain surface treatment morphology. Volatile by-products may be
driven off as
the surface treated powder is heated. The nanoparticles and the coating
precursor are added
in quantities effective to enable chemically passive surface treatments that
prevent ion
leakage and render the surface treated zinc oxide compatible with charged
organic moieties,
such as acrylate-based polymers, a- and (3-hydroxy acids. The amount of
coating precursor
used is directly related to the particle surface area or the particle size.
Detailed Description of the Invention
In accordance with the principles of the present invention, a surface
treatment of zinc
oxide and/or titania particles, and in particular the surface treated
nanoparticles, with looped
and/or linear polymeric structure on a star-graft polymer coating on a
particle surface and
method for making the same are provided. To passivate the zinc oxide surface
to prevent ion
leakage and render the surface treated zinc oxide compatible with charged
organic moieties,
such as acrylate-based polymers, a- and (3-hydroxy acids, etc., the surface
treatment contains
predominantly phenyl chemistry. In addition the surface treatment on zinc
oxide and titania
can be tailored to render the surface treated particle thermodynamically
compatible with
different oil phase components of a cosmetic skin formulation, by judicious
selection of non-
phenyl containing precursors.
The surface treatment is applied to zinc oxide and/or titania particles, and
in particular
nanoparticles. The nanoparticle mean particle size range is from about 1 nm to
about 900
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nm. The preferred nanoparticle mean particle size range is from about 2 nm to
about 500 nm.
The most preferred nanoparticle mean particle size range is from about 5 nm to
about 100
nm.
The values of x and y in the above silicon-based polymers have ranged from 1-
50 and
50-99, respectively. Preferably the values of x and y in the above silicon-
based polymers
have ranged from 1-40 and 60-99, respectively. Most preferably the values of x
and y in the
above silicon-based polymers have ranged from 10-30 and 70-90, respectively.
Various combinations are employed to control the branching of the siloxane
backbone, the degree of looped and/or linear chains, and its chemical nature,
that is, the
degree of thermodynamic compatibility with specific oil phase components of a
cosmetic
skin formulation. Additionally the chemical nature of the difunctional
monomers are selected
to transform what would otherwise be thin coatings, into loops and/or linear
chains that
extend into the oil phase components of a cosmetic skin formulation medium.
The invention also relates to a method of protecting human skin or human hair
from
ultraviolet radiation comprising treating said skin or hair with an effective
protecting
concentration of a surface treated particle comprising a plurality of zinc
oxide and/or titania
particles and a star-graft copolymer with looped and/or linear polymeric
structure on a star-
graft copolymer encapsulating at least a portion of said particles, said
surface treatment
comprising:
Si (x, y)
where x and y are mole percent trifunctional and difunctional monomeric units,
respectively
and wherein x and y are about 1-50 and 50 - 99, respectively, wherein:
x is selected from the group of trifunctional monomers that have cosmetically
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acceptable non-reactive ligands comprising of methyltrimethoxysilane, n-
propyltrimethoxysilane, isobutyltrimethoxysilane, n-hexyltrimethoxysilane, n-
octyltrimethoxysilane, n-octadecyltrimethoxysilane, phenyltrimethoxysilane,
and the
triethoxy-containing counterparts of these monomers;
y is selected from the group of difunctional monomers that have cosmetically
acceptable non-reactive ligands comprising of dicyclohexyldimethoxysilane,
diethyldiethoxysilane, dimethyldichlorosilane, dimethyldiethoxysilane,
dimethyldimethoxysilane, diphenyldiethoxysilane, diphenyldimethoxysilane, di-n-
hexyldichlorosilane, n-hexylmethyldichlorosilane, methyldodecyldiethoxysilane,
n-
octylmethyldimethoxysilane, and the diethoxy-containing counterparts of these
monomers,
where the products) per se, defined as surface treated Zn0 and/or Ti02, are
used in personal
care formulations.
In a preferred variant of the method the surface treatment comprising:
Si (x, y)
wherein x and y are about 10-30 and 70-90, respectively, wherein:
x is selected from the group of n-octyltrimethoxysilane, n-
octyltriethoxysilane,
phenyltrimethoxysilane and phenyltriethoxysilane, and
y ' is selected from the group of n-octyltrimethoxysilane, n-
octyltriethoxysilane.
According to one variant of the method the said effective protecting
concentration
ranges between 0.1 % and 25% by weight, preferably between 0.1 % and 10%,
particularly
preferably between 1 % and 7%, based on the total weight of the personal care
formulation.
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In a preferred variant of the method the said personal care formulation
comprises
surface treated zinc oxide and/or titanium dioxide particles alone or together
with compounds
which absorb in the LTV region and are known for cosmetic and pharmaceutical
preparations.
Accordingly, the present invention also relates to sunscreen-containing
personal care
formulations for protecting human skin or human hair from ultraviolet
radiation, which
comprises, in a cosmetically and pharmaceutically suitable carrier, an
effective protecting
concentration of a surface treated particle comprising a plurality of zinc
oxide and/or titania
particles and a star-graft copolymer with looped and/or linear polymeric
structure on a star-
graft copolymer encapsulating at least a portion of said particles, said
coating polymer
comprising:
Si (x,y)
where x and y are the mole percent trifunctional and difunctional monomeric
units,
respectively, and wherein x is about 1-50 and y is about 50-99, respectively,
wherein:
x is selected from the group of trifunctional monomers that have cosmetically
acceptable non-reactive ligands comprising of methyltrimethoxysilane, n-
propyltrimethoxysilane, isobutyltrimethoxysilane, n-hexyltrimethoxysilane, n-
octyltrimethoxysilane, n-octadecyltrimethoxysilane, phenyltrimethoxysilane,
and the
triethoxy-containing counterparts of these monomers;
y is selected from the group of difunctional monomers that have cosmetically
acceptable non-reactive ligands comprising of dicyclohexyldimethoxysilane,
diethyldiethoxysilane, dimethyldichlorosilane, dimethyldiethoxysilane,
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dimethyldimethoxysilane, diphenyldiethoxysilane, diphenyldimethoxysilane, di-n-
hexyldichlorosilane, n-hexylmethyldichlorosilane, methyldodecyldiethoxysilane,
n-
octylmethyldimethoxysilane, and the diethoxy-containing counterparts of these
monomers.
Particular preference is given to personal care formulations wherein the said
surface
treatment comprising:
Si (x, y)
wherein x and y are about 10-30 and 70-90, respectively, wherein:
x is selected from the group of n-octyltrimethoxysilane, n-
octyltriethoxysilane,
phenyltrimethoxysilane and phenyltriethoxysilane, and
y is selected from the group of n-octyltrimethoxysilane, n-
octyltriethoxysilane.
The cosmetic and dermatological preparations according to the invention can
comprise cosmetic active ingredients, auxiliaries and/or additives, for
example, coemulsifiers,
fats and waxes, stabilizers, thickeners, biogenic active ingredients, film
formers, fragrances,
dyes, pearlizing agents, preservatives, pigments, electrolytes (e.g. magnesium
sulfate) and pH
regulators.
Suitable coemulsifiers are, preferably, known W/O and also O/W emulsifiers,
such as,
for example, polyglycerol esters, sorbitan esters or partially esterified
glycerides. Typical
examples of fats are glycerides; waxes which may be mentioned are inter alia
beeswax,
paraffin wax or microcrystalline waxes, optionally in combination with
hydrophilic waxes.
Stabilizers which may be used axe metal salts of fatty acids, such as, for
example,
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magnesium, aluminum and/or zinc stearate. Examples of suitable thickeners are
crosslinked
polyacrylic acids and derivatives thereof, polysaccharides, in particular
xanthan gum, guar
guar, agar agar, alginates and tyloses, carboxymethylcellulose and
hydroxyethylcellulose, and
also fatty alcohols, monoglycerides and fatty acids, polycrylates, polyvinyl
alcohol and
polyvinylpyrrolidone. The term biogenic active ingredients means, for example,
plant
extracts, protein hydrolyzates and vitamin complexes. Customary film formers
are, for
example, hydrocolloids, such as chitosan, microcrystalline chitosan or
quaternary chitosan,
polyvinylpyrrolidone, vinylpyrrolidone/vinyl acetate copolymers, polymers of
the acrylic
acid series, quaternary cellulose derivatives and similar compounds. Examples
of suitable
preservatives are formaldehyde solution, p-hydroxybenzoate or sorbic acid.
Examples of
suitable pearlizing agents are glycol distearic esters, such as ethylene
glycol distearate, but
also fatty acids and fatty acid monoglycol esters. Dyes which may be used are
the substances
suitable and approved for cosmetic purposes, as listed, for example, in the
publication
"I~osmetische Farbemittel" [Cosmetic Colorants] from the Farbstofflcommission
der
Deutschen Forschungsgemeinschaft [Dyes Commission of the German Research
Council],
published by Verlag Chemie, Weinheim, 1984. These dyes are usually used in a
concentration of from 0.001 to 0.1 % by weight, based on the total mixture.
It is likewise advantageous to add customary antioxidants to the preparations
for the
purposes of the present invention. According to the invention, all
antioxidants which are
customary or suitable for cosmetic and dermatological applications may be used
as favorable
antioxidants.
The antioxidants are advantageously chosen from the group consisting of amino
acids
(e.g. glycine, histidine, tyrosine, tryptophan) and derivatives thereof,
imidazoles (e.g.
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urocanic acid) and derivatives thereof, peptides, such as D,L-carnosine, D-
carnosine, L-
carnosine and derivatives thereof (e.g. anserine), carotenoids, carotenes
(e.g. a-carotene, f3-
carotene, lycopene) and derivatives thereof, retinoids, such as, for example,
retinol, retinal
and/or retinoic acid and the respective esters, a-lipoic acid and derivatives
thereof (e.g.
dihydrolipoic acid), aurothioglucose, propylthiouracil and other thiols (e.g.
thioredoxin,
glutathione, cysteine, cystine, cystamine and the glycosyl, N-acetyl, methyl,
ethyl, propyl,
amyl, butyl and lauryl, palmitoyl, oleyl, y-linoleyl, cholesteryl and glyceryl
esters thereof)
and salts thereof, dilauryl thiodipropionate, distearyl thiodipropionate,
thiodipropionic acid
and derivatives thereof (esters, ethers, peptides, lipids, nucleotides,
nucleosides and salts),
and sulfoximine compounds (e.g. buthionine sulfoximines, homocysteine
sulfoximine,
buthionine sulfones, penta-, hexa-, heptathionine sulfoximine) in very low
tolerated doses
(e.g. pmol to ~.mol/kg), and also (metal) chelating agents (e.g. a-hydroxy
fatty acids, palmitic
acid, phytic acid, lactoferrin), a-hydroxy acids (e.g. citric acid, lactic
acid, malefic acid),
humic acid, bile acid, bile extracts, bilirubin, biliverdin, EDTA, EGTA and
derivatives
thereof, unsaturated fatty acids and derivatives thereof (e.g. y-linolenic
acid, linoleic acid,
oleic acid), folic acid and derivatives thereof, 2-aminopropionic acid
diacetic acid,
flavonoids, polyphenols, catechins, ubiquinone and ubiquinol and derivatives
thereof, vitamin
C and derivatives (e.g. ascorbyl palmitate, Mg ascorbyl phosphate, ascorbyl
acetate),
tocopherols and derivatives (e.g. vitamin E acetate), and coniferyl benzoate
of benzoin resin,
rutinic acid and derivatives thereof, ferulic acid and derivatives thereof,
butylhydroxytoluene,
butylhydroxyanisole, nordihydroguaiacic acid, nordihyrdoguaiaretic acid,
trihydroxybutyrophenone, uric acid and derivatives thereof, mannose and
derivatives thereof,
zinc and derivatives thereof, (e.g. ZnO, ZnSO4), selenium and derivatives
thereof (e.g.
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selenomethionine), stilbene and derivatives thereof (e.g. silbene oxide, trans-
stilbene oxide)
and the derivatives (salts, esters, ethers, sugars, nucleotides, nucleosides,
peptides and lipids)
of said active ingredients which are suitable according to the invention.
The amount of antioxidants (one or more compounds) in the preparations is
preferably
0.001 to 30% by weight, particularly preferably 0.05 to 20% by weight, in
particular 0.1 to
10% by weight, based on the total weight of the preparation.
If vitamin E and/or derivatives thereof are the antioxidant or antioxidants,
it is
advantageous to choose their respective concentrations from the range 0.001 to
10% by
weight, based on the total weight of the formulation.
If vitamin A and/or derivatives thereof or carotenoids are the antioxidant or
antioxidants, it is advantageous to choose the respective concentration
thereof from the range
0.001 to 10% by weight, based on the total weight of the formulation.
If the cosmetic or dermatological preparation for the purposes of the present
invention
is a solution or emulsion or dispersion, the solvents used may be:
water or aqueous solutions; oils, such as triglycerides of capric acid or of
caprylic
acid, but preferably castor oil; fats, waxes and other natural and synthetic
fatty substances,
preferably esters of fatty acids with alcohols of low carbon number, e.g. with
isopropanol,
propylene glycol or glycerol, or esters of fatty alcohols with alkanoic acids
of low carbon
number or with fatty acids; alcohols, diols or polyols of low carbon number,
and ethers
thereof, preferably ethanol, isopropanol, propylene glycol, glycerol, ethylene
glycol, ethylene
glycol monoethyl or monobutyl ether, propylene glycol monomethyl, monoethyl or
monobutyl ether, diethylene glycol monomethyl or monethyl ether and analogous
products.
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In particular, mixtures of the above mentioned solvents are used. In the case
of
alcoholic solvents, water may be a further constituent.
The oil phase of the emulsions, oleogels or hydrodispersions or
lipodispersions for the
purposes of the present invention is advantageously chosen from the group of
esters of
saturated and/or unsaturated, branched and/or unbranched alkanecarboxylic
acids with a
chain length of from 3 to 30 carbon atoms and saturated and/or unsaturated,
branched and/or
unbranched alcohols with a chain length of from 3 to 30 carbon atoms, from the
group of
esters of aromatic carboxylic acids and saturated and/or unsaturated, branched
and/or
unbranched alcohols with a chain length of from 3 to 30 carbon atoms. Such
ester oils can
then advantageously be chosen from the group consisting of isopropyl
myristate, isopropyl
palmitate, isopropyl stearate, isopropyl oleate, n-butyl stearate, diisopropyl
adipate, n-hexyl
laurate, n-decyl oleate, glyceryl stearate, isooctyl steaxate, isononyl
stearate, isononyl
isononanoate, 2-ethylhexyl palmitate, 2-ethylhexyl laurate, 2-hexyldecyl
stearate, 2-
octyldodecyl palmitate, oleyl oleate, oleyl erucate, erucyl oleate, erucyl
erucate, and
synthetic, semisynthetic and natural mixtures of said esters, e.g. jojoba oil.
In addition, the oil phase can advantageously be chosen from the group of
branched
and unbranched hydrocarbons and hydrocarbon waxes, silicone oils, dialkyl
ethers, the group
of saturated or unsaturated, branched or unbranched alcohols, and fatty acid
triglycerides,
namely the triglycerol esters of saturated and/or unsaturated, branched and/or
unbranched
alkanecarboxylic acids with a chain length of from 8 to 24, in particular 12-
18, carbon atoms.
The fatty acid triglycerides can, for example, be chosen advantageously from
the group of
synthetic, semisynthetic and natural oils, e.g. olive oil, sunflower oil,
soybean oil, peanut oil,
rapeseed oil, almond oil, palm oil, coconut oil, palm kernel oil and the like.
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Any mixtures of such oil and wax components are also to be used advantageously
for
the purposes of the present invention. It may in some instances also be
advantageous to use
waxes, for example cetyl palmitate, as the sole lipid component of the oil
phase.
The oil phase is advantageously chosen from the group consisting of 2-
ethylhexyl
isostearate, isohexadecane, octyldodecanol, isotridecyl isononanoate,
isoeicosane, 2-
ethylhexyl cocoate, C12-Cis-alkyl benzoate, caprylic/capric acid triglyceride,
dicaprylyl ether.
Mixtures of C12-Cis-alkyl benzoate and 2-ethylhexyl isostearate, mixtures of
C12-Cis-
alkyll benzoate and isotridecyl isononanoate, and mixtures of C12-Cis-alkyl
benzoate, 2-
ethylhexyl isostearate and isotridecyl isononanoate are particularly
advantageous.
Of the hydrocarbons, paraffin oils, squalane and squalene are to be used
advantageously for the purposes of the present invention.
Advantageous oil components are also, for example, butyloctyl salicylate (for
example that available under the trade name Hallbrite BHB from CP Hall),
hexadecyl
benzoate and butyloctyl benzoate and mixtures thereof (Hallstar AB) and/or
diethylhexyl
naphthalate (Hallbrite TQ).
The oil phase can also advantageously have a content of cyclic or lineax
silicone oils,
or consist entirely of such oils, although it is preferred to use an
additional content of other oil
phase components apart from the silicone oil or the silicone oils.
Advantageously, cyclomethicone (octamethylcyclotetrasiloxane) is used as
silicone
oil to be used according to the invention. However, other silicone oils can
also be used
advantageously for the purposes of the present invention, for example
hexamethylcyclotrisiloxane, polydimethylsiloxane, poly(methylphenylsiloxane).
17
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Mixtures of cyclomethicone and isotridecyl isononanoate, and of cyclomethicone
and
2-ethylhexyl isostearate are also particularly advantageous.
Solid sticks comprise, for example, natural or synthetic waxes, fatty alcohols
or fatty
acid esters. Preference is given to using lip care sticks, and stick
formulations for deodorizing
the body.
Customary basic substances which are suitable for use as cosmetic sticks for
the
purposes of the present invention are liquid oils (e.g. paraffin oils, castor
oil, isopropyl
myristate), semisolid constituents (e.g. petroleum jelly, lanolin), solid
constituents (e.g.
beeswax, ceresin and microcrystalline waxes and ozocerite), and high-melting
waxes (e.g.
carnauba wax, candelilla wax).
Suitable propellants for cosmetic and/or dermatological preparations for the
purposes
of the present invention which can be sprayed from aerosol containers are the
customary
known readily volatile, liquefied propellants, for example hydrocarbons
(propane, butane,
isobutane), which can be used on their own or in a mixture with one another.
Compressed air
can also be used advantageously.
The person skilled in the art is of course aware that there are propellant
gases which
are nontoxic per se which would in principle be suitable for realizing the
present invention in
the form of aerosol preparations, but which nevertheless have to be avoided
due to a harmful
effect on the environment or other accompanying phenomena, in particular
fluorocarbons and
chlorofluorocarbons (CFCs).
Cosmetic preparations for the purposes of the present invention may also be in
the
form of gels which, besides an effective content of active ingredient
according to the
invention and solvents customarily used therefore, preferably water, also
comprise organic
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thickeners, e.g. gum arabic, xanthan gum, sodium alginate, cellulose
derivatives, preferably
methylcellulose, hydroxymethylcellulose, hydroxyethylcellulose,
hydroxypropylcellulose,
hydroxpropylmethylcellulose or inorganic thickeners, e.g. aluminum silicates,
such as, for
example, bentonites, or a mixture of polyethylene glycol and polyethylene
glycol stearate or
distearate. The thickener is present in the gel, for example, in an amount
between 0.1 and
30% by weight, preferably between 0.5 and 15% by weight. The cosmetic and
pharmaceutical preparations comprising light protection agents are generally
based on a
carrier which comprises at least one oil phase. Preparations based solely on
aqueous
components are, however, also possible. Accordingly, suitable preparations are
oils, oil-in-
water and water-in-oil emulsions, creams and pastes, lip-protection stick
compositions or
grease-free gels.
Gels used according to the invention usually comprise alcohols of low carbon
number,
e.g. ethanol, isopropanol, 1,2-propanediol, glycerol and water or an
abovementioned oil in the
presence of a thickener, which in the case of oily-alcoholic gels is
preferably silicon dioxide
or an aluminum silicate, and in the case of aqueous-alcoholic or alcoholic
gels is preferably a
polyacrylate.
The total proportion of auxiliaries and additives can be 1 to 80% by weight,
preferably
6 to 40% by weight, and the nonaqueous proportion ("active substance") can be
20 to 80% by
weight, preferably 30 to 70% by weight, based on the compositions. The
compositions can be
prepared in a manner known per se, i.e. for example by hot, cold, hot-hot/cold
or PIT
emulsification. This is a purely mechanical process, and no chemical reaction
takes place.
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Such sunscreen preparations can accordingly be in liquid, paste or solid form,
for
example as water-in-oil creams, oil-in-water creams and lotions, aerosol foam
creams, gels,
oils, marking pencils, powders, sprays or alcohol-aqueous lotions.
According to the application technology requirements the surface treated
particles
(Zn0 and/or Ti02) can be added either to the Qil or to the aqueous phase of
the cosmetic
preparation.
Finally, it is possible additionally to use further substances known per se
which absorb
in the UV region, provided they axe stable in the overall system of the
combination of UV
filters to be used according to the invention.
The majority of light protection agents in the cosmetic and pharmaceutical
preparations used to protect the human epidermis consists of compounds which
absorb UV
light in the UV-B region, i.e. in the range from 2~0 to 320 nm and UV-A
region, i.e. in the
range from 320 to 400 nm. For example, the proportion of the UV-A absorbers to
be used
according to the invention is 10 to 90% by weight, preferably 20 to 50% by
weight, based on
the total amount of UV-B and LJV-A absorbing substances.
Suitable UV filter substances which are used in combination with the
formulations to
be used according to the invention are any UV-A and UV-B filter substances.
Examples
which may be mentioned are:
No. Substance CAS No.
(=acid)
1 4-Aminobenzoic acid 150-13-0
2 3-(4'-Trimethylammonium)benzylidenebornan-2-one52793-97-2
methylsulfate
3 3,3,5-Trimethylcyclohexyl salicylate 11 ~-56-9
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(homosalate)
4 2-Hydroxy-4~-methoxy-benzophenone 131-57-7
(oxybenzone)
2 Phenylbenzimidazole-5-sulfonic acid and 27503-81-7
its potassium,
sodium and triethanolamine salts
6 3,3'-(1,4-Phenylenedimethine)-bis(7,7-dimethyl-2-90457-82-2
oxobicyclo[2.2.1]heptane-1-methanesulfonic
acid) and its salts
7 Polyethoxyethyl4-bis(polyethoxy)aminobenzoate113010-52-9
8 2-Ethylhexyl4-dimethylaminobenzoate 21245-02-3
9 2-Ethylhexyl salicylate 118-60-5
2-Isoamyl4-methoxycinnamate 71617-10-2
11 2-Ethylhexyl 4-methoxycinnamate 5466-77-3
12 2-Hydroxy-4-methoxy-benzophenone-5-sulfonic 4065-45-6
acid (sulisobenzone) and the sodium salt
13 3-(4'-Sulfobenzylidene)bornan-2-one and salts58030-58-6
14 3-Benzylidenebornan-2-one 16087-24-8
1-(4'-Isopropylphenyl)-3 phenylpropane-1,3- 63260-25-9
dione
16 4-Isopropylbenzyl salicylate 94134-93-7
17 2,4,6-Trianiline(o-carbo-2'-ethylhexyl-1'-oxy)-1,3,588122-99-0
triazine
18 3-Imidazol-4-ylacrylic acid and its ethyl 104-98-3
ester
19 Ethyl2--cyano-3,3-diphenylacrylate 5232-99-5
2'-Ethylhexyl2-cyano-3,3-diphenylacrylate 6197-30~
21 Menthyl o-aminobenzoate or: 134-09-8
5-methyl-2-( 1-methylethyl)-2-aminobenzoate
22 Glyceryl p-aminobenzoate or: 136-44-7
1-glyceryl 4-aminobenzoate
23 2,2'-Dihydroxy~-methoxybenzophenone (dioxybenzone)131-53-3
24 2-Hydroxyl-methoxy-4-methylbenzophenone (mexenone)1641-17-4
Triethanolamine salicylate 2174-16-5
26 Dimethoxyphenylglyoxalic acid or: 4732-70-1
sodium 3,4-dimethoxyphenylglyoxalate
27 3-(4'Sulfobenzylidene)bornan-2-one and its 56039-58-8
salt
28 4-tert-Butyl-4'-methoxydibenzoylmethane 70356-09-1
29 2,2',4,4'-Tetrahydroxybenzophenone 131-SS-5
2,2'-Methylenebis[6(2H-benzotriazol-2 yl)-4-(1,1,3,3-103597-45-1
tetramethylbutyl)phenol]
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31 2,2'-(1,4-Phenylene)-bis-1H-benzimidazole-4,6-180898-37-7
disulfonic acid, Na salt
32 2,4-bis[4-(2-Ethylhexyloxy)-2 hydroxy]phenyl-6-(4-187393-00-6
methoxyphenyl)-(1,3,5)-triazine
33 3-(4-Methylbenzylidene)camphor 36861-47-9
34 Polyethoxyethyl4-bis(polyethoxy)paraaminobenzoate113010-52-9
35 2,4-Dihydroxybenzophenone 131-56-6
36 2,2'-Dihydroxy-4,4'-dimethoxybenzophenone-5,5'-disodium3121-60-6
sulfonate
37 Benzoic acid, 2-[4-(diethylamino)-2-hydroxybenzoyl]-,302776-68-7
hexylester
38 2-(2H-Benzotriazol-2-yl)-4-methyl-6-[2-methyl-3-[1,3,3,3-155633-54-8
tetramethyl-1- [(trimethylsilyl)oxy] disiloxanyl]propyl]phenol
39 1,1-[(2,2'-Dimethylpropoxy)carbonyl]-4,4-diphenyl-1,3-363602-15-7
butadiene
Polymeric or polymer-bonded filter substances can also be used according to
the
invention.
The cosmetic and dermatological preparations according to the invention can
additionally advantageously comprise inorganic pigments based on metal oxides
and/or other
metal compounds which are insoluble or sparingly soluble in water, selected
from the group
consisting of the oxides of iron (e.g. Fe203), zirconium (Zr02), silicon
(Si02), manganese
(e.g. Mn0), aluminum (A1a03), cerium (e.g. Ce203), mixed oxides of the
corresponding
metals, and mixtures of such oxides.
For the purposes of the present invention, it is particularly advantageous,
although not
obligatory, for the inorganic pigments to be in coated form, i.e. to have been
surface-treated.
This surface treatment may involve for example providing the pigments with a
thin
hydrophobic layer by a method known per se, as described in DE-A-33 14 742.
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To protect human hair from UV rays, the light protection agent formulations
according to the invention can be incorporated into shampoos, lotions, gels,
hairsprays,
aerosol foam creams or emulsions in concentrations of from 0.1 to 10% by
weight, preferably
to 7% by weight. The respective formulations can inter alia be used for
washing, coloring
and for styling hair.
The formulations to be used according to the invention are usually notable for
a
particularly high absorbance in the UV-A radiation region with a sharp band
structure.
Moreover, they are readily soluble in cosmetic oils and can easily'be
incorporated into
cosmetic formulations. The emulsions prepared with the formulations are
particularly notable
for their high stability, the formulations I themselves are notable for their
high photostability,
and the preparations prepared therewith are notable for their pleasant feel on
the skin.
The UV filter action of the formulations according to the invention can also
be
utilized for stabilizing active ingredients and auxiliaries in cosmetic and
pharmaceutical
formulations.
The preparations according to the invention are notable for particularly high
absorbance in the UV-A radiation region with a sharp band structure and high
light protection
factors.
Example 1 General Batch Process for Surface Treating Zinc Oxide and/or Titania
Particles
The method comprises introducing zinc oxide and/or titania particles
comprising a
plurality of nanoparticles into a surface treatment vessel that is capable of
mixing and heating
its contents under a controlled environment. Example of suitable surface
treatment vessels
comprise a Buchi Rotovap (small scale available from Brinkrnann Instruments),
V-blender
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(commercial scale available from Patterson-Kelley), ribbon-blender (commercial
scale
available from Jaygo), rotary oven (commercial scale available from Thermal
Processing
Solutions), and a fluidized bed (commercial scale available from Littleford
Day).
a) The particles are introduced into the surface treatment vessel using
methods known to
those skilled in the art. Oxygen is removed from the vessel, typically by
vacuum
followed by inert gas flush, and the plurality of nanoparticles is mixed by
methods
such as, but not limited to, rotating the vessel or by rotating elements
within the
vessel. The particles are substantially spherical nanocrystalline
nanoparticles and
readily flow using standard unit operation methodologies. Particle mixing is
carried
out at a temperature, in an environment, and for a time that is effective at
exposing
particulate surface area to the environment of the surface treatment vessel
enabling
conditioning of the particle surface. Mixing may occur continuously, or at
programmed intervals, and at a range of mixing rates. Mixing may occur at room
temperature or at temperatures above or below room temperature depending on
the
chemistry of the surface treated particles. The degree of mixing may be used
to
control the bulk density of the final product - greater mixing yields a higher
bulk
density particulate product.
b) Particle surface conditioning comprises, but is not limited to, removing
material
sorbed to the particle surface, adding dopants to the particle surface, or a
combination
of conditioning steps. Particle surface conditioning may be accomplished by,
but is
not limited to, the following unit operations: vacuum treatment, plasma
treatment,
washing or flushing or fluidizing with a gas, fluid washing, reactive gas or
fluid
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treatment, etc. In all instances reactive by-products and residues are removed
prior to
the application of surface treatment precursors.
c) Subsequent to particle surface conditioning, the particles are mixed with
surface
treatment precursors and heated in an environment, to a pre-determined
temperature,
and for a time effective for the star-graft copolymer to coat the
nanocrystalline zinc
oxide and/or titania particle and the difunctional precursors to polymerize to
form the
looped and/or linear chains on the star-graft copolymer. During surface
treatment
particulate mixing enables continuous surface exposure and promotes
application of a
uniform surface treatment to the plurality of particles. The nanoparticles and
the
coating precursor are added in relative quantities effective to enable a
personal care
application. The amount of coating precursor used is directly related to the
particle
surface area or the particle size.
d) Surface treatment sequences may include, but are not limited by, the
followings
process sequences: particle conditioning followed by surface treatment as in
b) and c)
above, multiple particle conditioning steps followed by surface treatment,
particle
conditioning followed by multiple surface treatment steps, sequential particle
conditioning - surface treatment - particle conditioning - surface treatment
steps, and
others imagined by those skilled in the art.
e) The particles may comprise a single composition or multiple compositions.
f) Methods of introducing the surface treatment precursors may include, but
are not
limited by, fluid spray or vapor flow, employing any metered technique known
to
those skilled in the art.
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g) The surface treatment precursors may be introduced as a precursor mixture,
as a
precursor mixture followed by a single precursor, or by sequential single
precursor
additions.
h) The surface treated particles are dried, if wet, cooled to room
temperature, if reaction
occurs at elevated temperature, and removed from the surface treatment vessel.
Example 2 Batch Process for Surface Treating Zinc Oxide
The following process description is for preparing surface treated zinc oxide
particles.
The surface treated zinc oxide is an active physical sunscreen ingredient for
cosmetic
formulations.
The product is prepared by the batch process detailed in Example 1.
a) 8-kg of zinc oxide nanoparticles, with a surface area of 14-m2/g, is
weighed into a
plastic bag and manually charged into a clean, 2-ft3 V-blender. Oxygen is
removed
by evacuating the V-blender to full vacuum level followed by vacuum relief of
the V-
blender with nitrogen. The evacuation and relieve cycle is repeated twice.
b) With the V-blender filled with inert gas, the V-blender is rotated at 5
RPM, and the V-
blender is constantly flushed with nitrogen to condition the particles by
removing
sorbed materials.
c) Diphenyldimethoxysilane (168 g) and octyltriethoxysilane (42 g) monomers
axe
homogeneously mixed using a paddle mixer to form approximately a Si(0, 20, 80,
and
0) surface treatment precursor mixture (210 g total weight).
d) Subsequent to particle surface conditioning, the surface treatment
precursor mixture is
introduced into the V-blender through a nozzle by inert pressure displacement
and
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sprayed on the particles as the particles are mixing at room temperature. The
temperature continues to ramp to 105 to.115°C. Particle mixing and
vapor-phase
transport enable surface treatment precursors to wet the particles and react
to coat the
nanocrystalline zinc oxide. The temperature is maintained at 105 to
115°C for 1-hour.
e) The surface treated zinc oxide is dried by pulling a vacuum, while purging
the vessel
with inert gas, N2, on the surface treatment vessel. Vacuum removes un-reacted
surface treatment precursors and reaction by-products. At the same time the
temperature of the vessel is cooled to room temperature. The surface treated
zinc
oxide is removed from the vessel at room temperature.
The surface treatment on the zinc oxide product, when added to cosmetic
formulation,
prevents ion leakage and renders the surface treated zinc oxide compatible
with charged
organic moieties, such as acrylate-based polymers, a- and (3-hydroxy acids. No
other known
commercial product or known surface treatment on zinc oxide particles enables
the observed
chemically passive behavior.
The above batch process may be scaled to surface treat larger amounts of
particles or
rendered continuous, as will be recognized by persons skilled in the art, by
employing
continuous mixing and heating equipment and appropriate process modifications.
.
Example 3 Specific Surface Treatment Examples
1) Physical sunscreen ingredients - Si(20, 80) / octyltriethoxysilane,
diphenyldimethoxysilane; 4.3 wt% surface treatment precursor mixture applied
to
Zn0 (23 m2lg).
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2) Physical sunscreen ingredients - Si(20, 80) / octyltriethoxysilane,
diphenyldimethoxysilane; approximately 9.4 wt% surface treatment precursor
mixture
applied to Ti02 (50 ma/g).
Example 4 - Cosmetic Formulations
Surface treated zinc oxide nanoparticles, produced by methods disclosed above,
were
incorporated into the oil in water formulations given in Tables 1-20 using the
procedure
following each respective table.
Table 1- Formulation 1
Weight INCI - Names
%
Phase A
1,5 Steareth-2
0,5 Steareth-21
3,0 Cetearyl Alcohol
0,2 Bees wax
20,0 Cetearyl Ethylhexanoate
5,0 Surface Treated Zinc Oxide
Phase B
0,3 Acrylates/Clo-C3o Alkyl Acrylate Crosspolymer
ad 100 Deionized Water
0,04 Triethanolamine
Procedure: Formulation 1
1. Heat Phase A ingredients to 80°C
2. Stir Phase A at 11000 rpm using a homogenizer for 3 minutes
3. Mix Phase B ingredients and heat them to 80°C.
4. Add Phase B to Phase A to form Mixture 1
5. Stir Mixture 1 at 11000 rpm using a homogenizer for 30sec-lmin
6. Cool Mixture 1 to room temperature under gentle planetary mixing
7. Stir Mixture 1 at 11000 rpm using a homogenizer for 30sec-lmin
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Table 2 - Formulation 2
Weight % 1NCI - Names
Phase A
1,5 Steareth-2
0,5 Steareth-21
3,0 Cetearyl Alcohol
0,2 Bees wax
20,0 Cetearyl Ethylhexanoate
5,0 Surface Treated Zinc Oxide
Phase B
0,2 Acrylates/C10-30 Alkyl Acrylate Cross olymer
45,77 Deionized Water
0,04 Triethanolamine
Phase C
0,1 Acrylates/Acrylamide Copolymer, Mineral
Oil, Polysorbate
85, Triethanolamine
22,88 ~ Deionized Water
Procedure: Formulation 2
1. Heat Phase A ingredients to 80°C
2. Stir Phase A at 15000 rpm using a homogenizer for 3 minutes
3. Mix Phase B ingredient and heat them to 80°C
4. Mix Phase C ingredients and heat them to 80°C
5. Mix Phase B and Phase C to form Mixture 1
6. Add Mixture 1 to Phase A to form Mixture 2.
7. Stir Mixture 2 at 11000 rpm using a homogenizer for 30sec-lmin
8. Cool Mixtuxe 2 to room temperature under gentle planetary mixing
9. Stir Mixture 1 at 11000 rpm using a homogenizer for 30sec-lmin
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Table 3 - Formulation 3
Weight % INCI - Names
Phase A
8,0 Dibutyl Adipate
8,0 Cla-C15 Alkyl Benzoate
12,0 Cocoglycerides
1,0 Sodium Cetearyl Sulfate
4,0 Lauryl Glucoside and Polyglyceryl-2 Dipolyhydroxystearate
and Glycerin
2,0 Ceteraryl Alcohol
5,0 Surface Treated Zinc Oxide
Phase B
3,0 Glycerin
0,05 pisodium EDTA
0,2 Allantoin
0,3 Carbomer
ad 100 Demineralized Water
0,04 Triethanolamine
Phase C
0,5 DMDM Hydantoin
Procedure: Formulation 3
1. Heat Phase A ingredients to 80°C
2. Stir Phase A at 11000 rpm using a homogenizer for 3 minutes
3. Mix Phase B ingredients and heat them to 80°C
4. Mix Phase B and Phase A to form Mixture 1
5. Stir Mixture 1 at 11000 rpm using a homogenizer for 30sec-lmin
6. Cool Mixture 1 to room temperature under gentle planetary mixing.
7. Mix Phase C to Mixture 1 at 11000 rpm using a homogenizer for 30sec-
1 min
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Table 4 - Formulation 4
INCI - Names
Phase A
7,50 Ethylhexyl Methoxycinnamate
1,50 Polysorbate 20
3,00 Sodium Lauryl Lactylate
1,00 PEG - 40 Hydrogenated Castor Oil
1,00 Butyrospermum Parlcii (Shea Butter)
6,50 Cia-Cis Alkyl Benzoate
Phase B
5,00 Surface Treated Zinc Oxide
Phase C
4,00 Glycerin
1,00 Panthenol, Propylene Glycol
0,30 Xanthan gum . .
0,10 Disodium EDTA
2,00 Urea
2,00 Hydroxyethyl Acrylate/Sodium Acryloyldimethyl
Taurate
Copolymer, Squalane, Polysorbate 60
ad 100 l~emineralized Water
Phase D
0,50 ~,actic acid
0,50 Phenoxyethanol, Methylparaben, Butylparaben,
F~thylparaben, Pro ylparaben, Isobutylparaben
Procedure: Formulation 4
1. Heat Phase A ingredients to 80°C
2. Add Phase B with Phase A and mix to form Mixture 1 using a
homogenizer at 15000 rpm for 3 minutes
3. Mix Fhase C ingredients and heat them to 80°C
4. Mix Mixture 1 and Phase C to form Mixture 2 using a homogenizer at
11000 rpm for 3 minutes
5. Add Phase D ingredients to Mixture 2 to form Mixture 3 using a
homogenizer at 11p00 rpm 30sec-lmin
6. Cool Mixture 3 to room temperature under gentle planetary mixing
7. Stir Mixture 1 at 11000 rpm using a homogenizer for 30sec-lmin
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Table 5 - Formulation 5
Weight % INCI - Names
Phase A
1,00 ' Ceteareth - 25
2,00 Ceteareth - 6, Stearyl Alcohol
2,00 PEG -14 Dimethicone
3,60 Cetearyl Alcohol
6,00 Ethylhexyl Methoxycinnamate
2,00 Dibutyl Adipate
5,00 Surface Treated Zinc Oxide
Phase B
1,00 Panthenol
5,00 Glycerin
ad100 Demineralized Water
Phase C
4,00 Caprylic/Capric Tri lyceride, Sodium Acrylates
Copolymer
Phase D
0,50 Phenoxyethanol, Methylparaben, Butylparaben,
Ethylparaben, Propylparaben, Isobutylparaben
Procedure: Formulation 5
1. Heat Phase A ingredients to 80°C
2. Stir Phase A at 11000 rpm using a homogenizes for 3 minutes
3. Heat Phase B ingredients to 80°C
4. Add Phase B with Phase A and mix to form Mixture 1 using a
homogenizes at 11000 rpm for 30sec-lminute.
5. Mix Phase C to Mixture 1 to form Mixture 2 using a homogenizes at
11000rpm for 30 sec-lminute
6. Add Phase D ingredients to Mixture 2 while cooling to room
temperature under gentle planetary mixing
7. Stir Mixture 1 at 11000 rpm using a homogenizes for 30sec-lmin
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Table 6 - Formulation 6
Weight % INCI - Names
Phase A
3,0 Steareth-21
2,0 Cetearyl Alcohol
6,0 Ethylhexyl Methoxycinnamate
2,0 C12-Cis-Alkyl Benzoate
5,0 Surface Treated Zinc Oxide
3,0 VP/Eicosene Copolymer
Phase B
5,0 Glycerin
2,0 Hydroxyethyl Acrylates/Sodium Acryloyl
ad 100 Deionized Water
3,0 Potassium Cetyl Phos hate
0,1 Disodium EDTA
Phase C
0,5 Phenoxyethanol, Methylparaben, Ethylparaben,
I Butylparaben, Pro ylparaben
Procedure: Formulation 6
1. Heat Phase A and Phase B ingredients separately to 80°C
2. Homogenize Phase A and Phase B separately
3. Add Phase B to Phase A and homogenize for 3 minutes
4. Add Phase C to Phase A/B and homogenize
S. Cool Mixture 4 to room temperature under gentle planetary mixing
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Table 7 - Formulation 7'
Weight INCI - Names
%
Phase A
3,0 Steareth-21
2,0 Cetearyl Alcohol
6,0 Ethylhexyl Methoxycinnamate
2,0 C12-Cis-Alkyl Benzoate
5,0 Surface Treated Zinc Oxide
3,0 VP/Eicosene Copolymer
Phase B
5,0 Glycerin
2,0 Acrylates/Clo-C3o Alkylacrylate Crosspolymer
ad 100 Deionized Water
0,04 Triethanolamine
3,0 Potassium Cetyl Phosphate
0,1 Disodium EDTA
Phase C
0,5 Phenoxyethanol, Methylparaben, Ethylparaben,
Butylparaben, Propylparaben
Procedure: Formulation 7
1. Heat Phase A and Phase B ingredients separately to 80°C
2. Homogenize Phase A and Phase B separately
3. Add Phase B to Phase A and homogenize for 3 minutes
4. Add Phase C to Phase A/B and homogenize
5. Cool Mixture 4 to room temperature under gentle planetary mixing
34
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Table 8 - Formulation 8
Weight INCI - Names
%
Phase A
3,0 Steareth-21
2,0 Cetearyl Alcohol
6,0 Ethylhexyl Methoxycinnamate
2,0 Isohexadecane
3,0 Surface Treated Zinc Oxide
3,0 VP/Eicosene Copolymer
Phase B
5,0 Glycerin
0.3 Acrylates/Clo-C3o Alkylacrylate Cross olymer
ad 100 Deionized Water
0,06 Triethanolamine
3,0 Potassium Cetyl Phosphate
0,1 Disodium EDTA
Phase C
0,5 Phenoxyethanol, Methylparaben, Ethylparaben,
Butylparaben, Propylparaben
Procedure: Formulation 8
1. Heat Phase A and Phase B ingredients separately to 80°C
2. Homogenize Phase A and Phase B separately
3. Add Phase B to Phase A and homogenize for 3 minutes
4. Add Phase C to Phase A/B and homogenize
S. Cool Mixture 4 to room temperature under gentle planetary mixing
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Table 9 - Formulation 9
Weight INCI - Names
%
Phase A
8,0 Dibutyl Adipate
8,0 C12-Cls-Alkyl Benzoate
12,0 Cocoglycerides
1,0 Sodium Cetearyl Sulfate
4,0 Lauryl Glucoside, Polyglyceryl-2 Dipolyhydroxystearate
2,0 Cetearyl Sulfate
5,0 Surface Treated Zinc Oxide
Phase B
3,0 Glycerin
0,05 Disodium EDTA
0,2 Allantoin
0,3 Carbomer
ad 100 Deionized Water
0,04 Triethanolamine
3,0 Potassium Cetyl Phosphate
Phase C
0,5 DMDM Hydantoin
Procedure: Formulation 9
1. Heat Phase A and Phase B ingredients separately to 80°C
2. Homogenize Phase A and Phase B separately
3. Add Phase B to Phase A and homogenize for 3 minutes
4. Add Phase C to Phase A/B and homogenize
5. Cool Mixture 4 to room temperature under gentle planetary mixing
36
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Table 10 - Formulation 10
Weight INCI - Names
%
Phase A
8,0 Dibutyl Adipate
8,0 C12 -Cls-Alkyl Benzoate
12,0 Cocoglycerides
1,0 Sodium Cetearyl Sulfate
4,p Lauryl Glucoside, Polyglyceryl-2 Dipolyhydroxystearate
2,0 Cetearyl Alcohol
5,0 Surface Treated Zinc Oxide
2,0 Ethylhexyl Triazone
Phase B
3,0 Glycerin
0,05 Disodium EDTA
0,2 Allantoin
0,3 Carbomer
ad 100 Deionized Water
0,04 Triethanolamine
3,4 Potassium Cetyl Phosphate
Phase C
0,5 DMDM Hydantoin
Procedure: Formulation 10
1. Heat Phase A and Phase B ingredients separately to 80°C
2. Homogenize Phase A and Phase B separately
3. Add Phase B to Phase A and homogenize for 3 minutes
4. Add Phase C to Phase A/B and homogenize
5. Cool Mixture 4 to room temperature under gentle planetary mixing
37
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Table 11- Formulation 11
Weight INCI - Names
%
Phase A
3,0 Steareth-21
2,0 Cetearyl Alcohol
3,0 Ethylhexyl Methoxycinnamate
3,0 Octocrylene
2,0 C12-Cls-Alkyl Benzoate
5,0 Surface Treated Zinc Oxide
3,0 VP/Eicosene Copolymer
Phase B
5,0 Glycerin
2,0 Acrylates/Clo-C3o Alkylacrylate Cross olymer
ad 100 Deionized Water
0,04 Triethanolamine
3,0 Potassium Cetyl Phosphate
0,1 Disodium EDTA
Phase C
0,5 Phenoxyethanol, Methylparaben, Ethylparaben,
Butyl araben, Propyl araben
Procedure: Formulation 11
1. Heat Phase A and Phase B ingredients separately to 80°C
2. Homogenize Phase A and Phase B separately
3. Add Phase B to Phase A and homogenize for 3 minutes
4. Add Phase C to Phase AB and homogenize
5. Cool Mixture 4 to room temperature under gentle planetary mixing
38
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Table 12 - Formulation 12
Weight INCI - Names
%
Phase A
3,0 Steareth-21
2,0 Cetearyl Alcohol
4,0 Ethylhexyl Methoxycinnamate
2,0 2-(4-Ethoxy-anilinomethylene)-propanedioic
acid diethyl
ester
2,0 Ci2-Cis-Alkyl Benzoate
5,0 Surface Treated Zinc Oxide
3,0 VPIEicosene Copolymer
Phase B
5,0 Glycerin
2,0 AcrylateslClo-C3o Alkylacrylate Crosspolymer
.
ad 100 Deionized Water
0,04 Triethanolamine
3,0 Potassium Cetyl Phosphate
0,1 Disodium EDTA
Phase C
0,5 Phenoxyethanol, Methylparaben, Ethylparaben,
Butyl araben, Propylparaben
Procedure: Formulation 12
1. Heat Phase A and Phase B ingredients separately to 80°C
2. Homogenize Phase A and Phase B separately
3. Add Phase B to Phase A and homogenize for 3 minutes
4.' Add Phase C to Phase A/B and homogenize
5. Cool Mixture 4 to room temperature under gentle planetary mixing
39
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Table 13 - Formulation 13
Weight % INCI - Names
Phase A
3,0 Steareth-21
2,0 Cetearyl Alcohol
4,0 Ethylhexyl Methoxycinnamate
2,0 Drometrizole Trisiloxane
2,0 Cia -Cis-Alkyl Benzoate
5,0 Surface Treated Zinc Oxide
3,0 VP/Eicosene Co olymer
Phase B
5,0 Glycerin
2,0 Acrylates/Clo-C3o Alkylacrylate Crosspolymer
ad 1 Qp IDeionized Water
O,Q4 Triethanolamine
3,0 Potassium Cetyl Phos hate
4,1 Disodium EDTA
Phase C
Q,5 Phenoxyethanol, Methylparaben, Ethylparaben,
Butylparaben, Pro y1 araben
_
Procedure: Formulation 13
1. Heat Phase A and Phase $ ingredients separately to SQ°C
2. Homogenize Phase A and Phase B separately
3. Add Phase B t9 Phase A and homogenize for 3 minutes
4. Add Phase C to Phase A/$ and homogenize
5. Cool Mixture 4 to room temperature under gentle planetary mixing
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Table 14 - Formulation 14
Weight INCI - Names
%
Phase A
3,0 Ethylhexyl Methoxycinnamate
1,0 Diethylamino Hydroxybenzoyl Hexyl Benzoate
3,0 Cia-Cis-Alkyl Benzoate
0,5 Bees wax
3,0 Ceteareth-6, Stearyl Alcohol
1,0 Cetearyth-25
3,0 Cetearyl Alcohol
5,0 Caprylic/Capric Triglyceride
3,0 Surface Treated Zinc Oxide
2,0 Surface Treated Titanium Dioxide
Phase B
2,0 Hydroxyethylacrylate l sodium acrylodimethyltaurate
copolymer & Squalane& Polysorbate 60
ad 100 Deionized Water
Phase C
0,5 Benzyl Alcohol, Methylchloroisothiazolinone,
Methylisothiazolinone
Procedure: Formulation 14
1. Heat Phase A and Phase B separately to about 80°C
2. Homogenize Phase A and Phase B at 11000 rpm using a homogenizer for 3
minutes
3. Stir Phase B into Phase A and homogenize
4. Cool Mixture 3 to room temperature under gentle planetary mixing
5. Stir in Phase C and homogenize
41
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Table 15 - Formulation 15
Weight INCI - Names
%
Phase A
3,0 Ethylhexyl Methoxycinnamate
1,0 Diethylamino Hydroxybenzoyl Hexyl Benzoate
3,0 Cia -Cis-Alkyl Benzoate
0,5 Bees wax
3,0 Ceteareth-6, Stearyl Alcohol
1,0 Cetearyth-25
3,0 Cetearyl Alcohol
5,0 Isohexadecane
3,0 Surface Treated Zinc Oxide
2,0 Surface Treated Titanium Dioxide
Phase B
0,3 Carbomer
0,04 Triethanolamine
ad 100 Deionized Water
Phase C
0,5 Benzyl Alcohol, Methylchloroisothiazolinone,
Methylisothiazolinone
Procedure: Formulation 15
1. Heat Phase A and Phase B separately to about 80°C
2. Homogenize Phase A and Phase B at 11000 rpm using a homogenizer for 3
minutes
3. Stir Phase B into Phase A and homogenize
4. Cool Mixture 3 to room temperature under gentle planetary mixing
5. Stir in Phase C and homogenize
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Table 16 - Formulation 16
Weight 1NCI - Names
%
Phase A
4,0 Glyceryl Stearate, PEG-100 Stearate
3,0 Ethylhexyl Methoxycinnamate
1,0 Diethylamino Hydroxybenzoyl Hexyl Benzoate
0,5 Lecithin
0,5 Polyglyceryl Dimer Soyate
Phase B
0,25 Iron Oxides Braun 70 E 172
2,25 Trimethylolpropane Triisostearate
Phase C
5,5 Cyclopentasiloxane, Cyclohexasiloxane
4,0 Ethylhexyl Palmitate
1,5 Simmondsia Chinensis (Jojoba) Seed Oil
2,0 Propylene Glycol Dicaprylate/Dicaprate
1,5 Sweet Almond (Prunus Amygdalus Dulcis) Oil
5,0 Surface Treated Titanium Dioxide
0,5 Tocopheryl Acetate
1,0 Butyros ermum Parkii (Shea Butter)
0,5 Polyglyceryl-2 Dipolyhydroxystearate
Phase D
5,0 Propylene Glicol
0,5 Poloxamer 188
0,1 Disodium EDTA
ad 100 Deionized Water
Phase E
2,00 Hydroxyethylacrylate / sodium acrylodimethyltaurate
copolymer & Squalane& Polysorbate 60
Phase F
1,0 Phenonip, Phenoxyethanol, Methylpaxaben,
Ethylparaben,
Butylparaben, Propylparaben, Isobutyl araben
0,2 Bisabolol
Procedure: Formulation 16
1. Heat Phase A, B, C and Phase D separately to about 70°C
2. Homogenize Phase B over a roller mill
3. Mix Phase B into Phase A and homogenize
4. Homogenize Phase C and stir into Phase A and B and homogenize at
12000 rpm
5. Dissolve Phase D and stir into combined Phase A,B and C and homogenize
6. Stir in Phase E and homogenize smoothly
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7. Cool down to 40°C under stirring
8. Add Phase F and homogenize
44
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Table 17 - Formulation 17
Weight INCI - Names
%
Phase A
1,5 Steareth-2
0,5 Steareth-21
3,0 Cetearyl Alcohol
0,2 Bees wax
20,0 Cetearyl Ethylhexanoate
Phase B
0,3 Acrylates/Clo-C3o Alkyl Acrylate Crosspolymer
ad 100 Deionized Water
0,04 Triethanolamine
Phase C
5,0 Surface Treated Zinc Oxide
Procedure: Formulation 17
1. Heat Phase A ingredients to 80°C
2. Stir Phase A at 11000 rpm using a homogenizer for 3 minutes
3. Mix Phase B ingredients and heat them to 80°C.
4. Add Phase C to Phase B and homogenize
5. Add Phase B/C to Phase A and homogenize
6. Cool Mixture to room temperature under gentle planetary mixing
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Table 18 - Formulation 18
Weight 1NCI - Names
%
Phase A
3,0 Diethylamino Hydroxybenzoyl Hexyl Benzoate
2,5 Di-C12-Ci3 Allcyl Malate
p,5 Tocopherylacetate
1,0 Sodium Cetearyl Sulfate
4,0 Polyglyceryl-3 Methyl Glucose Distearate
1,0 VP/Eicosene Copolymer
1,0 Glycerin
5,0 CapryliclCapric Triglyceride
3,0 Surface Treated Zinc Oxide
Phase B
2,0 Hydroxyethylacrylate / sodium acrylodimethyltaurate
copolymer & Squalane& Polysorbate 60
ad 100 ~ Deionized Water
Procedure: Formulation 18
1. Heat Phase A and Phase B ingredients separately to 80°C
2. Stir in Phase B into Phase A and homogenize
3. Cool Mixture to room temperature under gentle planetary mixing
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Table 19 - Formulation 19
Weight% INCI-Names
Phase A
3,0 Avobenzone
2,5 Di-C12-Ci3 Alkyl Malate
0,5 Tocopherylacetate
1,0 Sodium Cetearyl Sulfate
4,0 Polyglyceryl-3 Methyl Glucose Distearate
1,0 VP/Eicosene Copolymer
1,0 Glycerin
5,0 Caprylic/Capric Triglyceride
3,0 Surface Treated Zinc Oxide
Phase B
2,0 Hydroxyethylacrylate / sodium acrylodimethyltaurate
copolymer & Squalane& Polysorbate 60
ad 100 ~ Deionized Water
Procedure: Formulation 19
1. Heat Phase A and Phase B ingredients separately to 80°C
2. Stir in Phase B into Phase A and homogenize
3. Cool Mixture to room temperature under gentle planetary mixing
47
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Table 20 - Formulation 20
Weight 1NCI - Names
%
Phase A
8,0 Dibutyl Adipate
8,0 C12 -Cls-Alkyl Benzoate
12,0 Cocoglycerides
1,0 Sodium Cetearyl Sulfate
4,0 Lauryl Glucoside, Polyglyceryl-2 Dipolyhydroxystearate
2,0 Cetearyl Alcohol
5,0 Surface Treated Zinc Oxide
2,0 l,1-[(2,2'-Dimethylpropoxy)carbonyl]-4,4-diphenyl-1,3-
butadiene
Phase B
3,0 Glycerin
0,05 Disodium EDTA
0,2 Allantoin
0,3 Carbomer
ad 100 Deionized Water
0,04 Triethanolamine
3,0 Potassium Cetyl Phosphate
Phase C
0,5 DMDM Hydantoin
Procedure: Formulation 20
1. Heat Phase A and Phase B ingredients separately to 80°C
2. Homogenize Phase A and Phase B separately
3. Add Phase B to Phase A and homogenize for 3 minutes
4. Add Phase C to Phase AB and homogenize
5. Cool Mixture 4 to room temperature under gentle planetary mixing
48
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The above examples are O/W dispersions used as sun care formulations. However
the
disclosed invention is not limited by these examples, may be extended to other
skin care
formulations containing all acceptable cosmetic ingredients for all personal
care
formulations.
While particular elements, embodiment, and applications of the present
invention
have been shown and described, it will be understood, of course, that the
invention is not
limited thereto since modifications may be made by those skilled in the art,
particularly in
light of the forgoing teachings. It is therefore contemplated by the appended
claims to cover
such modifications as incorporate those features which come within the spirit
an scope of the
invention.
49
