Title of Invention

A SPRAYABLE OIL-IN-WATER EMULSION

Abstract A sprayable oil-in-water emulsion which is a sprayable sunscreen formulation comprising from 15% to 40% of an oil phase, from 5% to 30% of lipophilic UV filters, which filters are included in the oil-phase, from 0.3% to 3% of an alkyl glycol selected from the group consisting of 1,2-nonanediol, 1,2-decanediol, 1,2- dodecanediol, 1,2-heptanediol, 1,2-hexanediol and 1,2-octanediol, as well as addition products of 2 to 50 moles of ethylene oxide to fatty acids with 12 to 40 C-atoms, and polyalkylene glycol.
Full Text High Lipid Content Sprayable Emulsions
Field of the Invention
This invention relates to sprayable cil-in-water emulsions with a high content of oil
phase.
Background of the Invention
Sprays are attractive as a vehicle to apply liquid formulations on the skin such as in
skin care and cosmetic applications. Sprays are convenient to use and typically allow a
more controlled and even application of the formulation to the skin. Formulations for
use on the skin often are emulsion based, usually in the form of oil-in-water (O/W)
emulsions, allowing the presence of both lipophilic and hydrophilic components in one
formulation. In a number of instances an emulsion-based formulation requires a
relatively high amount of lipophilic components. This for example is the case where
the formulation needs to have high amounts of lipophilic actives, which in turn require
the presence of relatively high amounts of liquid oily components that are needed to
build a liquid oil phase. However, emulsions with high lipid phase content need
relatively high amounts of emulsifie:. This in turn results in an increase of viscosity
having the consequence that such formulations cannot be sprayed.
Also sunscreen formulations are frecuently formulated as oil-in-water emulsions.
Sunscreen formulations having a high SPF (Sun Protection Factor) are nowadays more
and more wanted by consumers because of increased awareness of skin damage and of
the long term effects of exposure of the skin to sunlight. Sunscreen formulations with
SPF values as high as SPF 50 and even higher are recommended for use on sensitive
skin types and for children. Such high SPF sunscreen formulations require the presence
of large amounts of UV filters. The largest choice of UV filters is amongst the
lipophilic filters, which also are the most effective and therefore are widely used in

sunscreen formulations. The choice of hydrophilic UV filters is limited and so is their
effectiveness so that increasing the amount of this type of filters is not sufficient to
reach high SPF value and moreover usually gives rise to white staining upon usage.
Inorganic pigments are another type of filters, the amounts of which could also be
increased, but this leads to problems of stability of the formulations and again of white
staining. Consequently sunscreen formulations with high SPF values can only be
obtained by adding larger amounts of lipophilic filters. This poses a special challenge
to sprayable formulations since increasing the; amount of lipophilic components in the
formulations requires more emulsifier, resulting in increased viscosity.
WO-03/013455 relates to light protecting cosmetic or dermatological emulsions, which
contain: (a) at least one benzotriazole derivative and (b) at least one grade of latex
particles having a mean particle size of 100 to 400 nm.
EP-A-1 206 933 relates to compositions containing caprylyl glycol or an analogue
thereof, and a preservative agent. It further relates to the use of caprylyl glycol or an
analogue thereof to increase the activity of preservative agents. EP-A-1 238 651
additionally relates to chemical compositions containing caprylyl glycol or an analogue
thereof, and a particular combination of preservative agents. It further relates to the use
of caprylyl glycol or an analog thereof to increase the activity of preservative agents,
more in particular of a combinatior of iodopropynyl butyl carbamate and
phenoxyethanol.
EP-A-1 005 851 discloses cosmetic or dermatological compositions useful for treating
Malassezia spp. infections, especially dandruff, comprising an alkynyl carbamate
derivative and polyol.
Hence there is a need to provide sprayable formulations that have a high content of
lipophilic components. In particular there is a need for sprayable formulations that
contain relatively high amounts of ipophilic ingredients, in particular of lipophilic
active ingredients. There is a more specific need to provide sprayable sunscreen
formulations that have a high SPF value. Providing such formulations is an object of
this invention.

Summary of the invention
Thus in one aspect this invention concerns a sprayable oil-in-water emulsion
comprising at least 15 % of oil phase, wherein the formulation contains at least 0.1 %
of an alkylglycol.
In a further aspect the invention concerns a sprayable oil-in-water emulsion comprising
at least 5 % of lipophilic active ingredients and wherein the emulsion contains at least
15 % of oil phase, wherein the formulation contains at least 0.1 % of an alkylglycol.
In a further aspect the invention concerns a sprayable oil-in-water emulsion which is a
sunscreen formulation comprising at least 5 % of lipophilic UV filters, wherein the
emulsion contains at least 15 % cf an oil phase, and wherein the formulation contains
at least 0.3 % of an alkylglycol. The sunscreen formulations of the invention may have
a high SPF value, e.g. an SPF ≥ 0, more preferably ≥50, or even ≥60.
Particular embodiments of this invention are those emulsions, including any emulsions
that contain active ingredients which can be UV filters or other active ingredients, that
contain at least 20%, or more in particular at least 25 %, or further in particular at least
30 % of lipid phase.
Other particular embodiments of this invention are those emulsions, including any
emulsions that contain active ingredients which can be UV filters or other active
ingredients, that contain at least 0.3 % of alkyl glycol, more in particular at least 0.3 %
of alkyl glycol.
In another aspect this invention concerns sprayable oil-in-water emulsions wherein the
emulsion contains from 15 % to 40%, in particular from 20 to 30 % of an oil phase, and
further comprising from 0.1 to 10%, in particular from 0.2 to 5%, more in particular
from 0.3 to 3% of an alkylglycol, preferably caprylyl glycol.

In another aspect this invention concerns sprayable oil-in-water emulsions, wherein the
emulsion contains from 15 % to 40 %, in particular from 20 to 30 % of an oil phase,
comprising :
(a) from 5 to 30 %, in particular from 10 to 30%, more in particular from 10 to 30%,
further in particular from 10 to 20% of one or more lipophilic active ingredients, which
active ingredients are included in the oil phase;
(b) from 0.1 to 10%, in particular from 0.2 to 5%, more in particular from 0.3 to 3% of
an alkylglycol, preferably caprylyl glycol.
In another aspect, this invention concerns sprayable oil-in-water emulsion which are
sunscreen formulations, wherein the emulsion contains from 15 % to 40%, in particular
from 20 to 30 % of an oil phase, comprising:
(a) from 5 to 30 %, in particular frc m 10 to 30%, more in particular from 10 to 30%,
further in particular from 10 to 20% of lipophilic UV filters, which filters are included
in the oil phase;
(b) from 0.1 to 10%, in particular from 0.2 to 5%, more in particular from 0.3 to 3% of
an alkylglycol, preferably caprylyl glycol.
A preferred alkyl glycol is caprylyl glycol, also referred to as 1,2-octanediol.
Detailed description of the invention
As used in this specification and claims, any % is weight by weight, unless indicated
otherwise. The symbol "≥" means greater or equal to.
The term 'sprayable' means that the composition can be applied by a standard spraying
device used in consumer products. In particular, sprayable emulsions have a viscosity
of 100 to 2000 cps in particular frc m 100 to 1000 cps, measured with a spindle rotation
rheometer at a constant shear rate of 60 s-1, equipped with a spindle appropriate for
these viscosity ranges.

The alkyl glycol for use in the emulsions of the invention in particular can be C6-14
alkyl glycols, more in particular C8-12 alkyl glycols, further in particular C8 alkyl
glycols, preferably caprylyl glycol, .vhich is a.so referred to as 1,2-octanediol.
Examples of alkyl glycols comprise 2,3-octanediol, 1,2-nonanediol, 1,2-decanediol,
1,2-dodecanediol, 1,2-heptanediol, 1,2-hexanediol, 3,4-octanediol and the like. Of
particular interest are those alkyl glycols wherein one hydroxyl group is substituted at
an end carbon and the other on the carbon atom adjacent thereto.
The term 'oil phase' covers the sum of all lipophilic components. These may comprise
oils, fats, waxes, lipophilic active ingredients, lipophilic polymers, etc.
Oil Phase
The oil-in-water emulsions of the present invention contain an oil phase that may
comprise suitable oils which are skin-compatible components or component mixtures
that are non water-mixable such as, "or example, silicone oils, natural oils, fatty acid
esters, mono-, di- or triglycerides, or other oils, or mixtures thereof. Preferably, the oils
are liquid at ambient temperature, in particular are liquid at 25 °C. They can contain
certain amounts of solid lipid components (e.g fats or waxes) as long as the complete
oily mixture is liquid at ambient temperature or at the temperature mentioned above.
Oils, which can be incorporated in the oil phase comprise natural oils, or natural oil
derivatives, in particular of vegetable origin. Examples are almond oil, soybean oil,
sunflower oil, safflower oil, corn oil, canola oil, borage oil, evening primrose oil,
grapeseed oil, wheat germ oil, avoca to oil, jojoba oil, kernel oil, sesame oil, walnut oil,
linseed oil, palm oil, olive oil, macacamia oil, castor oil, rapeseed oil, peanut oil,
coconut oil, and tumip seed oil.
The oil phase in the emulsions may also contain mono-, di or triglycerides, including
mixtures thereof. These can be the natural oils mentioned above but may also comprise
oil components isolated from natural oils, for example triglycerides or triglyceride
mixtures isolated from natural oils, or mono-, di or triglycerides having been prepared

chemically. The mono-, di or triglycerides may be derived from saturated or
unsaturated, linear or branch chair ed, substi:uted or unsubstituted fatty acids or fatty
acid mixtures. In particular such glycerides comprise the mono-, di- or tri-C6-30 fatty
acid glycerides, more in particular the mono-, di- or tri-C8-24 fatty acid glycerides,
specifically the mono-, di-or tri-C2-22 fatty acid glycerides. Also included are mixed
glyceride esters, i.e. di- or triglyceride esters with two or three different fatty acids.
Mixtures of mono-, di- and triglyoeridcs include technical mixtures derived from
fractions of fatty acids obtained by hydrolysis from fractions of oils or fats. An example
of the latter is a technical mixture of C12-18 fatty acid mono-, di- and triglycerides.
Examples of glyceride oils are mono-, di-or triglycerides derived from palmitic, palmic,
oleic, lauric, myristic, stearic, hydroxystearic, behenic acid, or mixtures thereof.
Of particular interest are the trigycerides, including triglyceride mixtures, and also
including mixed esters, i.e. tri-esters of glycerine with different fatty acids. Examples
are glyceryl tristearate, glyceryl trioleate, glyceryl tripalmitate, glyceryl trimyristate,
glyceryl tribehenate, glyceryl trilaurate.
Interesting mono- or diglycerides are the mono- or di-C12-24 fatty acid glycerides,
specifically the mono- or di-C16-20 fatty acid glycerides, for example glyceryl
monostearate, glyceryl distearate glyceryl laurate, glyceryl dilaurate, glyceryl
palmitate, glyceryl dipalmitate.
The oil phase in the emulsions may also comprise alkyl esters of fatty acids, wherein
the alkyl group in the latter may be linear or branch chained, saturated or unsaturated,
substituted or unsubstituted, and may have from 1 to 30 carbon atoms, in particular
from 1 to 22 carbon atoms. The arty acids in said alkyl esters may be linear or branch
chained, saturated or unsaturated substituted or unsubstituted C6-30 fatty acids or fatty
acid mixtures, in particular C6-24 fatty acids, more in particular C8-22 fatty acids,
preferably C12-18 fatty acids. The alkyl groups in said esters are derived preferably from
fatty alcohols as well as of mixtures thereof, in particular C1-24 fatty alcohols, more in
particular C6-22 fatty alcohols, preferably C8-18 fatty alcohols. Fatty alcohol mixtures for

use in these esters for example, may be obtained by high-pressure hydrogenation of technical mixtures of the methyl esters derived from fats or oils.
Examples of oil components of the ester type are the following: decyl oleate, coco caprylate/-caprate, hexyl laurate, myristyl isostearate, myristyl oleate, cetyl isostearate, cetyl oleate, cetyl stearate, cetyl behenate, cetyl palmitate, cetearyl behenate, isostearyl myristate, isostearyl palmitate, isostearyl stearate, isostearyl isostearate, isostearyl oleate, isostearyl behenate, oleyl myristate, oleyl isostearate, oleyl oleate, oleyl erucate, oleyl palmitate, oleyl stearate, oleyl isostearate, oleyl oleate, oleyl behenate, erucyl isostearate, erucyl oleate, palmityl stearate, stearyl heptanoate, stearyl octanoate, stearyl stearate, stearyl isostearate, stearyl behenate, stearyl oleate, myristyl myristate, myristyl palmitate, myristyl stearate, myristyl isostearate, myristyl oleate, behenyl behenate, behenyl isostearate, behenyl oleate,
.Interesting oil components of the ester type are the esters from linear C6-22-fatty acids with branched C1-12 alkanols, in particular with 2-ethylhexanol (e.g. the stearate of the latter commercially available under the trade name Cetiol™ 868); esters from branched C6-22-fatty acids with linear C1-12 alkanols; esters from C12-30-hydroxy fatty acids with linear or branched C6-22-fatty alcohols; esters from linear or branched fatty acids with multifunctional alcohols (e.g. propylene glycol, dimerdiol oder trimertriol) or with Guerbet alcohols; esters from C6-22-fatty alcohols or Guerbet alcohols with aromatic carboxylic acids, in particular with benzoic acids; esters from C2-C12-dicarboxylic acids with linear or branched alcohols having 1 to 22 carbon atoms (e.g. dioctyl maleates); esters of linear or branched fatty acids with poly-alcohols (e.g. propylene glycol, dimerdiol or trimertriol) or with Guerbet alcohols. As used herein the Guerbet alcohols may be based on fatty alcohols having 6 to 18, in particular 8 to 10 carbon atoms.
Other oil components that may be used comprise fatty alcohols in particular any saturated or unsaturated, straight or branch chained fatty alcohols, including mixtures thereof. Fatty alcohols comprise, for example, C12-C50-fatty alcohols, in particular the C12-C24-fatty alcohols-, more in particular the C16-C22-fatty alcohols that are derived from natural fats, oils or waxes such as, for example, myristyl alcohol, l-pentadecanol,


































cetylalcohol, 1-heptadecanol, steary. alcohol, l-nonadecanol, arachidyl alcohol, 1-
heneicosanol, behenyl alcohol, brasidyl alcohol, lignoceryl alcohol, ceryl alcohol,
myricyl alcohol, lauryl alcohol, capryl alcohol, caprinyl alcohol, cetyl alcohol,
palmoleyl alcohol, isostearyl alcohol, oleyl alcohol, elaidyl alcohol, petroselinyl
alcohol, arachidyl alcohol, gadoleyl alcohol, erucyl alcohol, including mixtures thereof
such as cetearyl alcohol, C12/13 fatty alcohol, as well as Guerbet alcohols.
Mixtures of fatty alcohols can evi iently also be used, including fatty alcohol fractions
obtained from the reduction of the corresponding fatty acid fractions derived from
naturally occurring oils or fats such as the natural oils or fats mentioned above.
Further oil components comprise fatty acids in particular C14-C40-fatty acids, and
hydroxy fatty alcohols, in particular C12-C30-hydroxy fatty alcohols. Other oil
components, which can be used comprise mineral and paraffin oils and synthetic oils,
either aliphatic or aromatic, as well as mixtures thereof.
Further oil components that can be added are the Guerbet alcohols which may be based
on fatty alcohols having 6 to 18, in particular 8 to 10 carbon atoms.
Still further oil components that are hydrocarbons comprise, for example, squalane,
squalene, paraffine oils, isohexadecane, isoeicosane or polydecene as well as
dialkylcyclohexanes.
Still further oil components are silicone oils such as, for example cyclic silicones,
dialkyl- or alkylarylsiloxanes e.g., cyclomethicone, dimethyl polysiloxane and
methylphenyl polysiloxane, as well as the alkoxylated and quaternized analogs thereof.
Appropriate non-volatile silk one oils are e.g. polyalkylsiloxanes,
polyalkylarylsiloxanes and polyethersiloxane-copolymers. A particularly suitable
silicone oil can be a dimethy,polysiloxane having trimethylsiloxy groups at both
molecular terminals, a methylphenylpolysiloxane having trimethylsiloxy groups at both
molecular terminals, a copolymer of methylphenylsiloxane and dimethylsiloxane
having trimethylsiloxy groups at both molecular terminals, a cyclic dimethylsiloxane.
or a cyclic methylphenylsiloxane.

Preferred silicone oils comprise cyclic dimethylsilicones, i.e. the cyclomethicones, e.g.
tetracyclomethicone, pentacyclonethicone, and linear dimethylsilicones, i.e. the
dimethicones, including any mix ture of these.
The oil phase may also contain certain amounts of solid or semi-solid lipophilic
components such as fats and waves, which are materials that are liquid above ambient
temperature, in particular above 25 °C. Fats comprise triglyceride materials from
natural origin or synthetic. Waxes comprise synthetic or natural waxes. The latter
comprise Japan wax, Ouricury v ax, montan wax, castor wax, carnauba wax, candelilla
wax, beeswax, ceresin wax and ozokerite waxes. Synthetic waxes comprise petroleum-
based waxes such as paraffin, petrolatum, polyalkylene glycol waxes, e.g. polyethylene
wax.
Waxes also encompass materials, which are the higher homologues of the materials
mentioned hereinabove as oils, for example the higher esters, the higher mono-, di- and
triglycerides, the higher alkanols (in particular the higher fatty alcohols), higher
alkanediols (in particular hydroxy fatty alcohols), the higher fatty acids. As further
useful components there can be mentioned silicone waxes.
The aqueous phase
The water phase in the O/W emulsions of this invention may be pure water but usually
contains one or more hydrophilic components. The latter can be lower alkanols,
polyols, water-soluble active ingredients, preservatives and moisturizers, chelating
agents, etc.
Emulsifier
The O/W emulsions of this invention additionally contain one or more emulsifiers
suitable for making oil-in-water emulsions. These emulsifiers may be anionic, cationic,

amphoteric or non-ionic emulsifie s, including mixtures thereof. Preferred are non-
ionic emulsifiers.
Suitable anionic emulsifiers include the fatty acid soaps, e.g. sodium, potassium and
triethanolamine soaps, wherein the fatty acid moiety may contain from 10 to 20 carbon
atoms. Other suitable anionic emulsifiers include the alkyl sulfonates, alkyl sulfates,
alkylaryl sulfonates, alkyl polyethoxy ether sulfonates, alkylphenol polyethoxy ether
sulfonates, mono- or diesters of s ilfosuccinic acid, in particular the alkali metal,
ammonium or substituted ammorium salts thereof. The alkyl group may 10 to 30
carbon atoms and the polyethoxylated anionic emulsifiers may contain from 1 to 50 and
in particular 2 to 25 ethylene oxide units.
Suitable cationic emulsifiers are quaternary ammonium, morpholinium and pyridinium
salts, in particular the tetraalkylammonium, halides such as the
alkyltrimethylammonium halides, wherein the alkyl group may 10 to 30 carbon atoms.
Particular non-ionic emulsifiers comprise :
(1) Addition products of 2 to 50 moles of ethylene oxide and/or 0 to 20 moles
propylene oxide to linear fatty alcohols having 8 to 40 C-atoms, to fatty acids
with 12 to 40 C-atoms an 1 to alkylphenols with 8 to 15 C-atoms in the alkyl rest.
(2) C12/18-fatty acid mono- and -diesters of addition products of 1 to 50 moles of
ethylene oxide and glycenine.
(3) Glycerine mono- and -diesters and sorbitan mono- and -diesters of saturated and
unsaturated fatty acids w th 6 to 22 C-atoms and their ethylene oxide addition
products.
(4) Alkyl mono- and -oligoglycosides with 8 to 22 C-atoms in the alkyl rest and the
ethoxylated analogs thereof.
(5) Addition products of 7 to 60 moles of ethylene oxide to castor oil and/or
hardened castor oil.
(6) Polyol- and in particular polyglycerine esters, such as e.g. polyol poly-12-
hydroxystearate, polyg ycerine polyricinoleate, polyglycerine diisostearate or

polyglycerine dimerate. Also applicable are mixtures of compounds of several of
these substance classes.
(7) Addition products of 2 to 15 moles of ethylene oxide to castor oil and/or
hardened castor oil.
(8) Partial esters derived from linear, branch chained, unsaturated or saturated C6-
C22-fatty acids, ricinoleic acid as well as 12-hydroxystearic acid and glycerine,
polyglycerine, pentaerythrite, dipentaerythrit, sugar alcohols (e.g. sorbitol),
alkylglucosides (e.g. methylglucoside, butylglucoside, laurylglucoside) as well as
polyglucosides (e.g. cellulose), or mixed esters such as e.g. glyceryl
stearate/citrate and glyceryl stearate/lactate.
(9) Wool wax alcohols.
(10) Polysiloxane-polyalkyl-polyether-copolymers and derivatives thereof.
(1.1) Mixed esters from pentaery hrite, fatty acids, citric acid and fatty alcohols and/or
mixed esters of fatty acids vith 6 to 22 C-atoms with methylglucose and polyo-
les, respectively glycerine or polyglycerine.
(12) Polyalkylene glycols, including block copolymers of ethylene oxide and
propylene oxide.
Theaddition products of ethylene oxide and/or of propylene oxide and fatty alcohols,
fatty acids, alkylphenoles, glycerme mono- and -diesters as well as sorbitan mono- and
-diesters of fatty acids or of castor oil are known and commercially available products.
Usually these are mixtures of homologues of which the average degree of alkoxylation
corresponds to the ratio of starting quantities of ethylene oxide and/or propylene oxide
and substrate, with which the addition reaction is conducted.
Examples of suitable zwitterionic emulsifiers include alkyldimethylamine oxides, the
alkyl group having from 6 to 16 carbon atoms.
The emulsions may comprise from about 1% to 10%, preferably from about 2% to 5%,
of emulsifier.

Active ingredients
The emulsions of the invention may contain active ingredients for application to the
skin. Examples of active agents comprise anti-microbial agents, e.g. anti-bacterials and
antifungals, anti-inflammatory agen:s, anti-irritating compounds, anti-itching agents,
moisturising agents, skin caring ingredients, plant extracts, vitamins, and the like.
Examples of such ingredients comprise complexes of PVP and hydrogen peroxide,
anti-inflammatories as, plant extracts, bisabolol, panthenol, tocopherol, actives for anti-
stinging, anti-irritants, anti-dandrufts, for anti-ageing e.g. retinol, melibiose etc. Other
suitable actives are e.g. allantoin, A.oe barbadensis, Avena sativa, beta-carotene,
bisabolol, Borago officinalis, Cham Emilia recutita, dichlorophenyl imidazoldioxolan,
ethyl panthenol, farnesol, ferulic acid, Ginkgo biloba, heliotropine, hydrolyzed wheat
protein, Juniperus communis, lactis proteinum, lactose, linalool, lysine, mannitol,
Mentha piperita, menthol, menthyl lactate, olgflur, Oryza sativa, panthenol, Prunus
amygdalus dulcis, retinyl palmitate, Ricinus communis, Rosmarinus officinalis,
salicylic acid, sodium carboxymethy1 betaglucan, sodium cocoyl amino acids, sodium
hyaluronate, sodium palmitoyl proline, thymus vulgaris, tocopherol, tocopheryl acetate,
tyrosine, valine, etc.
The active ingredients can be present, depending on the nature of the ingredients and
their application, in various concentrations, but usually are present in a quantity in the
range of from 0.01 - 10 % (w/w), preferably from 0.1-7 % (w/w) and more
preferably from 1 -5 % (w/w) expressed to the total weight of the emulsion.
The emulsions according to this invention can be used as anti-perspirants or deodorants
wherein one or both phases of the e: nulsion contain actives that have deodorizing and
/or anti-perspirant properties. Actives that can be used to this purpose are anti-
perspirant agents such as, for example, aluminium chlorohydrates, aluminium-
zirconium-chlorohydrate as well as zinc salts. Other such agents comprise aluminium
hydroxylactates as well as acid aluminium/zirconium salts. A particularly suitable
chlorohydrate is the compound of formula [Al2(OH)5Cl]-2.5 H2O. Further such agents
are aluminium-zirconium-tetrachlorohydroxy-glycine-complexes. Esterase inhibitors

can be added as further deodorizing agents, i.e. agents such as trialkyl citrates such as
trimethylcitrate, tripropyl citrate, triisopropyl citrate, tributyl citrate and in particular
triethyl citrate. Further esterase inhib tors are sterol sulfates or-phosphates, such as,
for example, lanosterine-, cholesterine-, campesterine-, stigmasterine- and sitosterine
sulfate respectively -phosphate, dicarboxylic acids and their esters, such as, for
example, glutaric acid, glutaric acid nonoethylester, glutaric acid diethylester, adipinic
acid, adipinic acid monoethylester, adipinic acid diethylester, malonic acid and malonic
acid diethylester, hydroxycarbonic acids and their esters such as, for example, citric
acid, malonic acid, tartaric acid or taitaric acid diethylester.
Antibacterial active ingredients that influence the growing conditions and eradicate
perspiration decomposing bacteria, of impede their growth, can also be present in the
lipid and/or aqueous phase. Examples of such ingredients are phenoxyethanol,
Ghlorohexidine gluconate and 5-chloro-2-(2,4-dichlorophenoxy)-phenol.
The emulsions according to the inver tion can also be used in sunscreen applications
and in that instance take the form of sunscreen sprays. In these products, the lipid
and/or aqueous phase contains one of more sunscreen filters which are for example
organic substances that are capable of absorbing ultraviolet radiation and to set free the
absorbed energy as longer-wave radiation.
UVB-filters can be oil or water-soluble. As oil-soluble substances there can be
mentioned for example:
• 3-Benzylidene campher respectively 3-benzylidene norcampher and derivatives
thereof, e.g. 3-(4-methylbenzylidene) campher;
• 4-Aminobenzoic acid derivatives respectively 4-(dimethylamino)benzoic acid-2-
ethylhexyl esters, 4-(dimethylamino)benzoic acid-2-octyl esters and 4-
(dimethylamino)benzoic acid arm/lesters;
• Esters of cinnamonic acid, in particular 4-methoxycinnamonic acid-2-
ethylhexylester, 4-methoxycinnamonicacid propylester, 4-methoxycinnamonic acid
isoamyl ester, 2-cyano-3,3-pheny;cinnamonic acid-2-ethylhexyl ester (octocrylene);

• Esters of salicylic acid, respe;tively salicylic acid-2-ethylhexylester, salicylic acid-
4-isopropylbenzyl ester, salicylic acid homomenthyl ester;
• Derivatives of benzophenones, in particular 2-hydroxy-4-methoxybenzophenone,
2-hydroxy-4-methoxy-4'-methylbenzophenone, 2,2'-dihydroxy-4-
methoxybenzophenone;
• Esters of benzalmalonic acid, in particular 4-methoxybenzmalonic acid di-2-
ethylhexyl ester;
• Triazine derivatives, such as, for example, 2,4,6-trianiIino-(p-carbo-2'-ethyl-1'-
hexyloxy)-1,3,5-triazine and octyltriazone;
• Propane-1,3-diones, such as for example, 1-(4-tert.butylphenyl)-3-(4'-
methoxyphenyl)propane-1,3 -dione;
• Ketotricyclo(5.2.1.0)decane -derivatives.
Water-soluble UV-filter are for example:
• 2-Phenylbenzimidazol-5-sulfonic acid and its alkali-, alkaline earth-, ammonium-,
alkylammonium-, alkanolammonium- and glucammonium salts;
• Sulfonic acid derivatives of benzophenones, in particular 2-hydroxy-4-
mcthoxybenzophenone-5-sulfonic acid and its salts;
• Sulfonic acid derivatives of 3-benzylidene campher, e.g. 4-(2-oxo-3-bornylidene
methyl)benzol-sulfonic acid and 2-methyl-5-(2-oxo-3-bornylidene)sulfonic acid
and its salts.
Typical UV-A-Filters that can be used are derivatives of benzoylmethane, such as, for
example, 1-(4'-tert.butylphenyl)-3-(4,-methoxyphenyl)propane-1,3-dione, 4-tert.-butyl-
4'-methoxydibenzoylmethane (Parsol 1789), or l-phenyl-3-(4'-isopropylphenyl)-
propane-1,3-dione. Mixtures of UV-A and UV-B-filters can be evidently used too.
Of particular interest are the so-called, broadband filters. One type of such filters are the
water-soluble filters, more specifically the benzotriazoles, in particular the
benzotriazole derivate known as 2,2'-methyIene-bis- (6-(2H- benzotriazole-2-yl)-4-
(1,1,3,3-tetramethylbutyl)-phenol) [INCI: Bisoctyltriazol], which is commercially

available under the tradename Tinosorb™ M from CIBA Chemicals. Another useful
benzotriazole derivate is 2-(2H-benzotriazole-2-yl)-4-methyl-6-[2-methyl-3-[1,3,3,3-
tetramethyl-1-[(trimethylsilyl)oxy]disiIoxanyl]propyl]-phenol(CAS-No.: 155633-54-8)
also indicated by the INCI name drometrizole trisiloxane and is available from Chimex
under the tradename Mexoryl™ XL. These benzotriazole derivatives can be
conveniently incorporated in th( water phase at a pH >4.5.
Other useful water-soluble UV fiters are the sulfonated UV filters such as 3,3'-(1,4-
phenylenedimethylene) bis (7,7-limethyl-2-oxo-bicyclo-[2.2.1]hept-1- yl
methanesulfonic acid, and its sodium, potassium or its triethanolammonium salt, and
the sulfonic acid itself, indicated by the INCI name terephthalidene dicamphor sulfonic
acid (CAS No. 90457- 82-2), which is available, for example, under the trade name
Mexoryl™ SX from Chimex.
Oil-soluble broadband filters are the asymmetrically substituted triazine derivatives. Of
particular interest is 2,4- Bis-{[4-(2-ethyl-hexyloxy)-2-hydroxy]-phenyl}-6-(4-
methoxyphenyl)-1,3,5-triazine (IMCI: anisotriazine), that is commercially available
under the tradename Tinosorb™ S from CIBA Chemicals.
A further advantageous water-soluble UV filter is 3,3'-(1,4- phenylenedimethylene) bis
(7,7-dimethyl-2-oxo-bicyclo-[2,2,1]hept-1-ylmethanesulfonic acid, as well its sodium,
potassium or its triethanolammonium salt, with the INCI name terephthalidene
dicamphor sulfonic acid (CAS No. 90457- 82-2), which is available, for example,
under the trade name Mexoryl® SX from Clumex.
Specific embodiments in accordance with this invention are sprayable oil-in-water
emulsions, which are sunscreen formulations, having an SPF≥40, in particular ≥50, or
≥60, comprising an oil-in-water emulsion wherein the emulsion contains from 15% to
40%, in particular from 20 to 30% of an oil phase, said emulsions comprising:
(a) from 5 to 30%, in particular from 10 to 30%, more in particular from 10 to 30%,
further in particular from 10 to 20% of lipophilic UV filters, which filters are included
in the oil phase;


(b) from 0.1 to 10%, in particular from 0.2 to 5%, more in particular from 0.3 to 3% of
an alkylglycol, preferably caprylyl glycol.
Further embodiments of this invention are sprayable oil-in-water emulsions, which are
sunscreen formulations, having an SPF ≥40, in particular ≥50, or ≥60, wherein the
emulsion contains from 15 % to 40%, in particular from 20 to 30 % of an oil phase,
comprising :
(a) from 5 to 30 %, in particular from 10 to 30%, more in particular from 10 to 30%,
further in particular from 10 to 20% of lipophilic UV filters, which filters are included
in the oil phase;
(b) from 1 to 10%, in particular from 1 to 5%, more in particular from 2 to 5% of
hydrophilic UV filters;
(c) from 0.1 to 10%, in particular from 0.2 to 5%, more in particular from 0.3 to 3% of
an alkylglycol, preferably caprylyl glycol at least 0.3 % of an alkylglycol.
Further embodiments of this invention are sprayable oil-in-water emulsions, which are
sunscreen formulations, having an SPF ≥40, in particular ≥50, wherein the emulsion
contains from 15 % to 40%, in particular from 20 to 30 % of an oil phase, said
emulsions comprising:
(a) from 5 to 30 %, in particular fom 10 to 30%, more in particular from 10 to 30%,
further in particular from 10 to 20 % of lipophilic UV filters, which filters are included
in the oil phase;
(b) from 1 to 10%, in particular from 1 to 5%, more in particular from 2 to 5% of
hydrophilic UV filters;
(c) from 0.5% to 15%, in particular from 1 to 10%, more in particular from 1 to 5% of
an inorganic pigment, in particular titanium dioxide or coated titanium dioxide;
(d) from 0.1 to 10%, in particular from 0.2 to 5%, more in particular from 0.3 to 3% of
an alkylglycol, preferably capryly glycol.
Further embodiments of this invention are sprayable sunscreen formulations having an
SPF ≥40, in particular ≥50, composing an oil-in-water emulsion wherein the emulsion
contains from 15 % to 40%, in particular from 20 to 30 % of an oil phase, comprising:

(a) from 5 to 30 %, in particular from 10 to 30%, more in particular from 10 to 30%,
further in particular from 10 to 20% of lipophilic UV filters, which filters are included
in the oil phase;
(b) from 1 to 10%, in particular from 1 to 5%, more in particular from 2 to 5% of
hydrophilic UV filters;
(c) from 0.5% to 15%, in particular from 1 to 10%, more in particular from 1 to 5% of
an inorganic pigment, in particular titanium dioxide or coated titanium dioxide;
(d) from 0.1 to 15%, in particular from 0.5% to 10%, more in particular from 1 to 10%
of latex particles, in particular of hollow latex particles;
(e) from 0.1 to 10%, in particular :rom 0.2 to 5%, more in particular from 0.3 to 3% of
an alkylglycol, preferably capryly glycol.
Spray formulations having an SPF ≥40, in particular ≥50 preferably contain both a
benzotriazole and an asymmetrically substituted triazine derivative, in particular both
the components Tinosorb™ M ar d Tinosorb™ S.
Apart from the above-mentioned soluble UV filter substances, there can also be added
insoluble sunscreen pigments, namely finely dispersed metal oxides or metal salts.
Examples of appropriate metal o tides in particular are zinc oxide and titanium dioxide
as well as oxides of iron, zirconium, silicon, manganese, aluminium and cerium as well
as mixtures thereof/Salts that can be used comprise silicates (talcum), barium sulfate
or zinc stearate. The particle size of these pigments is sufficiently small, e.g. less than
100 nm, in particular between 5 and 50 nm and more in particular between 15 and 30
nm. The particles can be spherical but can have other shapes too such as ellipsoidal or
similar shapes. The surface of the pigments may have been treated, e.g. hydrophilized
or made hydrophobic. Typical e camples are coated titanium dioxide, e.g. Titanium
dioxide T 805 (available from Eegussa)or Eusolex® T 2000 (Merck). Silicones can be
used as hydrophobic coating agents, in particular trialkoxyoctyl silanes or simethicones.
So-called micro- or nanopigments are particularly attractive for use in sunscreen
products.

Other components that can be added are latex particles, in particular latex particles
having a mean particle size of 100 o 400 nm. Of particular interest are the hollow latex
particles described in US-5,663,213 corresponding to EP-A-0 761 201. Particularly
preferred are those latex particles that are made of styrene/acrylate copolymers and
which are available under the tradename 'Alliance SunSphere™' from Rohm & Haas.
These commercial products usually have a content of 'active' (i.e. of pure latex) of
about 25 to 27 weight-% and when used in the emulsions of this invention the quantity
of commercial product needs to be recalculated in function of the quantity of the latex
particles present therein.
Apart from both groups of primary light protecting filters that are mentioned above
there can also be used secondary light protecting factors. These pertain to the class of
anti-oxidants and their activity is based on the interruption or decrease of the
photochemical processes caused by solar radiation upon penetration in the skin.
Typical examples of secondary light protecting agents are amino acids such as for
example glycine, histidine, tyrosine and tryptophane, including derivatives of amino
acids; imidazoles (for example urocnic acid) and derivatives thereof; peptides such as
D,L-camosine, D-carnosine, L-carnosine and derivatives thereof (e.g. anserin). Further
agents that can be used are carotinoices, carotenes (for example α-carotene, β-Carotene
and lycopene) and derivatives thereol; chlorogenic acid and its derivatives; lipoic acid
and derivatives thereof (e.g. dihydrol: poic acid), aurothioglucose, propylthiouracil and
other thioles (for example thioredoxine, glutathione, cysteine, cystamine and glycosyl-,
N-acetyl-, methyl-, ethyl-, propyl-, amyl-, butyl- and lauryl-, palmitoyl-, oleyl-, γ-
linoleyl-, cholesteryl- and glyceryl esters) and their salts. Further examples are dilauryl
thiodipropionate, distearyl thiopropio late, thiodipropionic acid and derivatives thereof
(for example esters, ethers, peptides, lipids, nucleotides, nucleosides and salts),
sulfoximine compounds (for example buthionins sulfoximine, homocysteine
sulfoximine, butionine sulfone, penta- hexa-, and heptathione sulfoximine). These
secondary agents usually are formulatsd at very low concentrations (e.g. pmol to
μmol/kg),

Other secondary agents (usually in small concentrations, as mentioned above) are
chelating agents (for example α-hydroxy fatty acids, palmeate acid, phytic acid,
lactoferrin), α-hydroxy acids (for example citric acid, lactic acid, malic acid), humic
acid, bile acid, bile extracts, bilirubin, biliverdin, EDTA, EGTA and derivatives
thereof; unsaturated fatty acids anc derivatives thereof such as for example γ-linolenic
acid, linoleic acid, oleic acid, folic acid and derivatives thereof, ubiquinones and
ubiquinol and derivatives thereof, vitamin C and derivatives thereof (e.g. ascorbyl
palmitate, Mg ascorbylphosphate, ascorbyl acetate), tocopherol and derivatives thereof
(for example vitamin E acetate), vitamin A and derivatives thereof (e.g. vitamin A
palmitate), coniferyl benzoates of benzoic acid, rutinic acid and derivatives thereof, α-
glycosyl rutin, ferula acid, furfurylidene glucitol, carnosine, butyl hydroxytoluene, butyl
hydroxyanisol, nordihydroguaiac re sin acid, nordihydroguaiaret acid,
trihydroxybutyrophenone, ureic acid and derivatives thereof, mannose and derivatives
thereof, superoxide-dismutase, zinc and derivatives thereof such as zinc oxide, zinc
sulphate, selenium and derivatives thereof (e.g. seleno-methionine); stilbene and
derivatives thereof (e.g. stilbene oxide, trans stilbene oxide); and any appropriate
derivatives of these UV filters.
The sprayable emulsions of this invention can also be used as self-tanning sprays. In
that instance there can be added dihydroxy acetone.
The lipid and/or aqueous phase can :urther contain one or more moisturizers, which
may be present in quantities of 1 -20 % (w/w). preferably of 5 -15 % (w/w), and more
preferably 5 -10 % (w/w) - relative :o the tota, amount of the emulsion.
Suitable moisturizers are a.o. amino acids, pynolidone carbonic acid, lactic acid and its
salts, lactitol, urea and urea derivatives, ureic acid, glucosamine, creatinine, hydrolysis
products of collagen, chitosan or chilosan salts/'-derivatives , and in particular polyols
and polyol derivatives such as ethylene glycol, propylene glycol, butylene glycol,
pentylene glycol, hexylene glycol, erythrite, 1,2,6-hexanetriol, polyethylene glycols
such as PEG-4, PEG-6, PEG-8, PEG-10, PEG-12, PEG-14, PEG-16, PEG-18, PEG-20,
PEG-135, PEG-150, sugar and sugar derivatives (a.o. fructose, glucose, maltose,

maltitol, mannite, inosite, sorbite, sorbityl silandiol, sucrose, trehalose, xylose, xylite,
glucuronic acid and its salts), etroxylated sorbitol, honey and hydrogenated honey,
hydrogenated starch hydrolysates, as well as mixtures of hydrogenated wheat protein,
hydrolyzed milk protein, lecithir, pythantriol, hyaluronic acid and salts thereof, and
PEG-20-acetate copolymers. Particularly preferred moisturizers are glycerine,
diglycerine and triglycerine.
The emulsions of the invention may contain perfume oils which can be mixtures of
synthetic or natural odorous substances exuacted from blossoms (lilly, lavender, rose,
jasmine, neroli, ylang-ylang), from stems and leaves (geranium, patchouli, petitgrain),
from fruits (anis, coriander, caraway, juniper), from cortex (bergamot, lemon, orange),
from roots (macis, angelic, celery, cardamon, costus, iris, calmus), from wood (pine,
sandelwood, guajak, cedar, rose, from herbs and grass (tarragon, lemongrass, sage,
thyme), from needles and branches (spruce, fir, pine, mountain pine), from resins and
balms (galbanum, elemi, benzoine, myrrh, olibanum).
The emulsions of this invention may contain one or more preservatives. Preservatives
are useful for substantially preventing microbial decomposition. Examples of
preservatives include phenoxyethanol, iodopropyl butylcarbamate (IPBC), sodium
benzoate, and parabens such as methyl-paraben, ethylparaben, and propylparaben.
Other examples of preservatives, are listed on pages 1654- 55 of the International
Cosmetic Ingredient Dictionary and Handbook, eds. Wenninger and McEwen (CTFA,
7th ed., 1997), hereinafter referred to as the "Cosmetic Handbook." The compositions
may comprise from about 0.01,% to about 10%, by weight (more preferably, from about
0.5% to about 5%, by weight) of preservative.
Antioxidants and/or chelating agents may also be used to increase shelf life and
stability of the compositions. Antioxidant compounds and their derivatives include, but
are not limited to, water-soluble antioxidants such as sulfhydryl compounds and their
derivatives (e.g., sodium metabisulfite and N-acetyl-cystein), lipoic acid and
dihydrolipoic acid, resveratrol, acetyl-cysteine or lactoferrin, ascorbic acid and ascorbic
acid derivatives (e.gvascorbyl balmitate and ascorbyl polypeptide). Oil-soluble

antioxidants include, but are not limited to, butylated hydroxytoluene, retinoids (e.g.
retinol and retinyl palmitate), tocopherols; (e.g., tocopherol acetate), tocotrienols, and
ubiquinone. Natural extracts containing antioxidants comprise extracts containing
flavonoids and isoflavonoids and their derivatives (e.g., genistein and diadzein),
extracts containing resveratrol and the like. Examples of such natural extracts include
grape seed, green tea, pine bark, propolis, and legume extracts. Other examples of
antioxidants may be found on pages 1612-13 of the Cosmetic Handbook. The
compositions of the present invention may comprise the antioxidant in an amount of
from about 0.001% to about 20%, by weight (e.g., from about 0.01% to about 10% by
weight) of the composition.
Chelating agents may also be added for example to assist the stabilization of the
emulsions of this invention. Examples of chelating agents include EDTA and
derivatives thereof (e.g., disodium EDTA and dipotassium EDTA), Iniferine ™,
lactoferrin, and citric acid. Other examples of chelating agents are listed on page 1626
of the Cosmetic Handbook. The emulsions of the present invention may comprise the
chelating agent in an amount of from about 0.001% to about 20%, by weight (e.g., from
about 0. 01% to about 10% by weight) of the composition.
The emulsions of the invention are prepared following art-known procedures to prepare
oil-in-water emulsions. In generat, the oil and the water phases are prepared separately
whereupon the oil phase is added to the water phase or vice versa, upon vigorous
stirring as to form the emulsion. If desired, additional components may be added to the
emulsion. If desired, the emulsification process may be done at increased temperature,
e.g. at a temperature above 50 °C, or above 70 °C.
The sprayable emulsions of this invention may find use in instances where high lipid
content is required, e.g. emulsions with relatively high amounts of active ingredients
that are lipophilic, e.g. sunscreen formulations with high SPF, or sprays aimed at
delivering oils.
The following examples are given to illustrate the invention and not to limit it thereto.





We Claim:
1. A sprayable oil-in-water emulsion which is a sprayable sunscreen
formulation comprising from 15% to 40% of an oil phase, from 5% to
30% of lipophilic UV filters, which filters are included in the oil-phase,
from 0.3% to 3% of an alkyl glycol selected from the group consisting
of 1,2-nonanediol, 1,2-decariediol, 1,2-dodecanediol, 1,2-heptanediol,
1,2-hexanediol and 1,2-octanediol, as well as addition products of 2 to
50 moles of ethylene oxide to fatty acids with 12 to 40 C-atoms, and
polyalkylene glycol.
2. The sprayable emulsion as claimed in claim 1 wherein said emulsion
comprises from 20% to 30% of said oil phase.
3. The sprayable emulsion as claimed in claim 1 or 2 wherein said
emulsion comprises, from 10% to 20% of liphophilic UV filters.
4. The emulsion as claimed in claims 1 or 2 having an SPF ≥ 40, more
preferably ≥ 50 or even ≥ 60
5. The emulsion as claimed in any of claims 1 to 4 wherein the alkylglycol
is caprylyl glycol.

A sprayable oil-in-water emulsion which is a sprayable sunscreen formulation
comprising from 15% to 40% of an oil phase, from 5% to 30% of lipophilic UV
filters, which filters are included in the oil-phase, from 0.3% to 3% of an alkyl
glycol selected from the group consisting of 1,2-nonanediol, 1,2-decanediol, 1,2-
dodecanediol, 1,2-heptanediol, 1,2-hexanediol and 1,2-octanediol, as well as
addition products of 2 to 50 moles of ethylene oxide to fatty acids with 12 to 40
C-atoms, and polyalkylene glycol.

Documents:

778-kol-2004-granted-abstract.pdf

778-kol-2004-granted-claims.pdf

778-kol-2004-granted-correspondence.pdf

778-kol-2004-granted-description (complete).pdf

778-kol-2004-granted-examination report.pdf

778-kol-2004-granted-form 1.pdf

778-kol-2004-granted-form 18.pdf

778-kol-2004-granted-form 2.pdf

778-kol-2004-granted-form 26.pdf

778-kol-2004-granted-form 3.pdf

778-kol-2004-granted-form 5.pdf

778-kol-2004-granted-reply to examination report.pdf

778-kol-2004-granted-specification.pdf

778-kol-2004-granted-translated copy of priority document.pdf


Patent Number 231363
Indian Patent Application Number 778/KOL/2004
PG Journal Number 10/2009
Publication Date 06-Mar-2009
Grant Date 04-Mar-2009
Date of Filing 30-Nov-2004
Name of Patentee JOHNSON & JOHNSON CONSUMER FRANCE.S.A.S.
Applicant Address 1, RUE CAMILLE DESMOULINS, 92787 ISSY-LES-MOULINEAUX-CEDEX 9
Inventors:
# Inventor's Name Inventor's Address
1 ISABELLE TISCHENBACH 5 RUE DE L'ECHO, 27400 LOUVIERS
2 ANNE-SOPHIE BRILLOUET 2 AVENUE F. MITTERRAND, 27400 LOUVIERS
PCT International Classification Number A61K 7/40,A61K 7/42
PCT International Application Number N/A
PCT International Filing date
PCT Conventions:
# PCT Application Number Date of Convention Priority Country
1 03293000.0 2003-12-01 EPO