COMPOSITION INCLUDING THERMOPLASTIC HOLLOW PARTICLE TECHNICAL FIELD

The present invention relates to a composition, preferably a cosmetic composition, and more preferably a skin cosmetic composition, for an aerosol, which includes thermoplastic hollow particle(s), for a keratin substance such as skin.

BACKGROUND ART

Cosmetic compositions such as skin-care and make-up compositions having matte-effect properties are generally used to solve sheen problems caused by excess sebum and to improve the long-term staying power of, for example, the make-up provided by the compositions, since the make-up has a tendency to degrade visually in the course of the day. They give the skin a matte appearance, resulting from the power to scatter light at the surface of the skin. They may also be used to fade out skin defects such as microreliefs, wrinkles, fine lines and pores or color variations.

Conventional compositions, known as matte-effect compositions, generally contain powders which can absorb sebum (cf. WO 2004/000212 or JP-T-2005-529976). Among the matte- effect powders of natural or synthetic origin which may be mentioned in particular are fillers such as talc, starch, mica, silica, Nylon powders, and poly-(methylmethacrylate). Fillers of this type have the drawback of not giving the skin a natural or transparent appearance, by giving a powdery or even plaster-like appearance and of accentuating defects in the skin. In addition, if the compositions include oil(s) or oily ingredient(s), the matte effects provided by the powders are in general deteriorated. Some of the conventional matte-effect compositions may be provided in the form of an aerosol with a spray device. However, the sebum-absorbing powders in the matte-effect compositions may clog the nozzle of the spray device. If the compositions include oil(s) or oily ingredient(s), the nozzle may be easily clogged by the powders which may be aggregated with the oil(s) or oily ingredient(s) which may function as a binder.

DISCLOSURE OF INVENTION

An objective of the present invention is to provide a composition, preferably a cosmetic composition, and more preferably a skin cosmetic composition, wherein the composition can provide both matte and transparent appearance, even if the composition includes oil(s) or oily ingredient(s), and the composition can be in the form of an aerosol by being sprayed with a spray device without causing clogging the nozzle of the spray device.

The above objective can be achieved by a composition, preferably a cosmetic composition, and more preferably a skin cosmetic composition, for an aerosol comprising:

(a) at least one thermoplastic hollow particle;

(b) at least one oil; and

(c) at least one propellant. The (a) thermoplastic hollow particle may be a hollow particle of expanded homopolymer or copolymer formed from a monomer or mixture of monomers selected from methacrylic acid esters, acrylic acid esters, vinylidene chloride, acrylonitrile, styrene and its derivatives, and butadiene and its derivatives. The (a) thermoplastic hollow particle may be a hollow particle of methyl (meth)acrylate homopolymer or copolymer, of copolymer of styrene and acrylonitrile, of copolymer of vinylidene chloride and acrylonitrile or vinyl chloride, or of expanded terpolymer of vinylidene chloride, acrylonitrile and methyl methacrylate. The (a) thermoplastic hollow particle may be a hollow particle of an expanded terpolymer of vinylidene chloride, acrylonitrile and methyl methacrylate.

The (a) thermoplastic hollow particle may have a particle size of from 20 μπι to 100 μπι. The (a) thermoplastic hollow particle may have a density ranging from 20 to 70 kg/m ³ .

The amount of the (a) thermoplastic hollow particle in the composition may be from 0.01 to 30% by weight, preferably from 0.05 to 20% by weight, and more preferably from 0.1 to 10% by weight, relative to the total weight of the composition.

The amount of the (b) oil in the composition may be from 0.1 to 50% by weight, preferably from 1 to 40% by weight, and more preferably from 5 to 30% by weight, relative to the total weight of the composition. The composition according to the present invention may comprise (d) at least one UV filter.

The composition according to the present invention may comprise (e) water.

The amount of (e) water in the composition may be from 1 to 90% by weight, preferably from 10 to 80%) by weight, and more preferably from 40 to 70%) by weight, relative to the total weight of the composition.

The composition according to the present invention may be in the form of a W/O emulsion. The present invention also relates to a cosmetic process for a keratin substance such as skin, comprising the steps of: applying the composition according to the present invention onto the keratin substance.

Another aspect of the present invention is an aerosol device, comprising

at least one nozzle;

at least one tube; and

at least one container comprising

a composition, preferably a cosmetic composition, and more preferably a skin cosmetic composition, comprising:

(a) at least one thermoplastic hollow particle; and

(b) at least one oil,

and

(c) at least one propellant,

wherein

the nozzle is connected with the container via the tube, and the composition in the container can be moved from the container to the nozzle via the tube to be sprayed from the nozzle.

BEST MODE FOR CARRYING OUT THE INVENTION

After diligent research, the inventors have discovered that it is possible to provide a composition, preferably a cosmetic composition, and more preferably a skin cosmetic composition, wherein the composition can provide both matte and transparent appearance, even if the composition includes oil(s) or oily ingredient(s), and the composition can be in the form of an aerosol by being sprayed with a spray device without causing clogging of the nozzle of the spray device.

Thus, the composition according to the present invention comprises:

(a) at least one thermoplastic hollow particle;

(b) at least one oil; and

(c) at least one propellant.

The composition according to the present invention can provide superior matte and transparent appearance effects. Furthermore, the composition according to the present invention can be sprayed via a nozzle of a spray device without causing clogging of the nozzle. Accordingly, the composition according to the present invention is suitable for an aerosol, and cosmetic uses for a keratin substance such as skin, in particular the face.

Hereafter, the present invention will be described in a detailed manner.

[Thermoplastic Hollow Particle]

The composition according to the present invention comprises at least one (a) thermoplastic hollow particle. If two or more (a) thermoplastic hollow particles are used, they may be the same or different.

The (a) thermoplastic hollow particle is made from at least one thermoplastic material. Two or more thermoplastic materials may be used. The thermoplastic material may soften at from 80 to 200°C, preferably from 90 to 190°C, and more preferably from 100 to 180°C.

The (a) thermoplastic hollow particle which can be used according to the invention may be prepared from ethylenically unsaturated monomers which are non-toxic and non-irritating to the skin. The (a) thermoplastic hollow particle used in the composition according to the present invention may be obtained, for example, according to the processes of European Patents and Patent Applications EP-056 219, EP-348 372, EP-486 080, EP-320 473, and EP- 112 807 and U.S. Pat. No. 3,615,972, the disclosures of which are hereby incorporated by reference.

The (a) thermoplastic hollow particle includes an internal cavity. The internal cavity of the (a) thermoplastic hollow particle may contain, for example, a gas which may be air, nitrogen or a hydrocarbon such as isobutane and isopentane.

Among the monomers used for preparing the (a) thermoplastic hollow particle, there may be mentioned methacrylic or acrylic acid esters such as methyl acrylate or methacrylate;

vinylidene chloride; acrylonitrile; styrene and its derivatives; butadiene and its derivatives; and mixtures thereof.

Thus, it may be preferable that the (a) thermoplastic hollow particle be a hollow particle of expanded homopolymer or copolymer formed from a monomer or mixture of monomers selected from methacrylic acid esters, acrylic acid esters, vinylidene chloride, acrylonitrile, styrene and its derivatives, and butadiene and its derivatives.

It is possible, for example, to use methyl acrylate or methacrylate polymers or copolymers, the copolymers formed from styrene and acrylonitrile and the copolymers of vinylidene chloride and acrylonitrile or vinyl chloride.

Thus, it may also be preferable that the (a) thermoplastic hollow particle be a hollow particle of methyl (meth)acrylate homopolymer or copolymer, of copolymer of styrene and acrylonitrile, or of copolymer of vinylidene chloride and acrylonitrile or vinyl chloride, or of expanded terpolymer of vinylidene chloride, acrylonitrile and methyl methacrylate.

More preferably, the (a) thermoplastic hollow particle used in the present invention is a hollow particle of an expanded copolymer of vinylidene chloride and acrylonitrile, or of vinylidene chloride, acrylonitrile and methyl methacrylate. These particles may be dry or hydrated.

In other words, it may be more preferable that the (a) thermoplastic hollow particle be a hollow particle of an expanded copolymer of vinylidene chloride and acrylonitrile, or an expanded terpolymer of vinylidene chloride, acrylonitrile and methyl methacrylate.

It is even more preferable that the (a) thermoplastic hollow particle be

Acrylonitrile/Methylmethacrylate/Vinylidene Chloride Copolymer.

The (a) thermoplastic hollow particle may have a particle size of from 20 μπι to 100 μπι, preferably from 25 μη to 70 μηι, and more preferably from 30 μηι to 50 μπι.

The (a) thermoplastic hollow particle may have a density ranging from 20 to 70 kg/m , preferably from 25 to 60 kg/m , and more preferably from 30 kg/m to 50 kg/m . The thickness of the wall forming the internal cavity of the (a) thermoplastic hollow particle may be from 0.01 to 1 μηι, preferably from 0.05 to 0.9 μηι, and more preferably from 0.1 to 0.8 μπι.

The (a) thermoplastic hollow particles which can be used in the present invention are, for example, microspheres of expanded terpolymer of vinylidene chloride, acrylonitrile and methyl methacrylate, sold under the brand name EXPANCEL by the company AkzoNovel and under the references 551DE40d42 (particle size approximately 40 μηι and density

approximately 42 kg/m ³ ), 920DE40d30 (particle size approximately 40 μιη and density approximately 30 kg/m ³ ), 920DE80d30 (particle size approximately 80 μπι and density approximately 30 kg/m ³ ), 461 WE40d36 (particle size approximately 40 μιη and density approximately 36 kg/m ³ ), 461WE20d36 (particle size approximately 20 μιη and density approximately 36 kg/m ³ ), and 921WE40d24 (particle size approximately 40 μπι and density approximately 24 kg/m ³ ). EXPALCEL 551DE40d42 is preferable. The amount of the (a) thermoplastic hollow particle(s) in the composition according to the present invention may be from 0.01 to 30% by weight, preferably from 0.05 to 20% by weight, and more preferably from 0.1 to 10% by weight, relative to the total weight of the

composition. [Oil]

The composition according to the present invention comprises at least one (b) oil. If two or more (b) oils are used, they may be the same or different. Here, "oil" means a fatty compound or substance which is in the form of a liquid or a paste (non-solid) at room temperature (25°C) under atmospheric pressure (760 mmHg). As the oils, those generally used in cosmetics can be used alone or in combination thereof. These oils may be volatile or non-volatile. The (b) oil may be a non-polar oil such as a hydrocarbon oil, a silicone oil, or the like; a polar oil such as a plant or animal oil and an ester oil or an ether oil; or a mixture thereof.

The (b) oil may be selected from the group consisting of oils of plant or animal origin, synthetic oils, silicone oils, hydrocarbon oils and fatty alcohols.

It is preferable that the (b) oil be selected from synthetic oils, hydrocarbon oils, and mixtures thereof, more preferably from ester oils, hydrocarbon oils and mixtures thereof, and even more preferably from ester oils. As examples of plant oils, mention may be made of, for example, linseed oil, camellia oil, macadamia nut oil, corn oil, mink oil, olive oil, avocado oil, sasanqua oil, castor oil, safflower oil, jojoba oil, sunflower oil, almond oil, rapeseed oil, sesame oil, soybean oil, peanut oil, and mixtures thereof. As examples of animal oils, mention may be made of, for example, squalene and squalane.

As examples of synthetic oils, mention may be made of alkane oils such as isododecane and isohexadecane, ester oils, ether oils, and artificial triglycerides. The ester oils are preferably liquid esters of saturated or unsaturated, linear or branched C ₁ - C ₂ 6 aliphatic monoacids or polyacids and of saturated or unsaturated, linear or branched C ₁ - C ₂₆ aliphatic monoalcohols or polyalcohols, the total number of carbon atoms of the esters being greater than or equal to 10. Preferably, for the esters of monoalcohols, at least one from among the alcohol and the acid from which the esters of the present invention are derived is branched.

Among the monoesters of monoacids and of monoalcohols, mention may be made of ethyl palmitate, ethyl hexyl palmitate, isopropyl palmitate, dicaprylyl carbonate, alkyl myristates such as isopropyl myristate or ethyl myristate, isocetyl stearate, 2-ethylhexyl isononanoate, isononyl isononanoate, isodecyl neopentanoate and isostearyl neopentanoate.

Esters of C ₄ -C ₂₂ dicarboxylic or tricarboxylic acids and of C ₁ -C ₂₂ alcohols, and esters of monocarboxylic, dicarboxylic or tricarboxylic acids and of non-sugar C ₄ -C ₂₆ dihydroxy, trihydroxy, tetrahydroxy or pentahydroxy alcohols may also be used. Mention may especially be made of: diethyl sebacate; isopropyl lauroyl sarcosinate;

diisopropyl sebacate; bis(2-ethylhexyl) sebacate; diisopropyl adipate; di-n-propyl adipate; dioctyl adipate; bis(2-ethylhexyl) adipate; diisostearyl adipate; bis(2-ethylhexyl) maleate; triisopropyl citrate; triisocetyl citrate; triisostearyl citrate; glyceryl trilactate; glyceryl trioctanoate; trioctyldodecyl citrate; trioleyl citrate; neopentyl glycol diheptanoate; diethylene glycol diisononanoate.

As ester oils, one can use sugar esters and diesters of C ₆ -C ₃₀ and preferably C ₁₂ -C ₂₂ fatty acids. It is recalled that the term "sugar" means oxygen-bearing hydrocarbon-based compounds containing several alcohol functions, with or without aldehyde or ketone functions, and which comprise at least 4 carbon atoms. These sugars may be monosaccharides, oligosaccharides or polysaccharides. Examples of suitable sugars that may be mentioned include sucrose (or saccharose), glucose, galactose, ribose, fucose, maltose, fructose, mannose, arabinose, xylose and lactose, and derivatives thereof, especially alkyl derivatives, such as methyl derivatives, for instance methylglucose. The sugar esters of fatty acids may be chosen especially from the group comprising the esters or mixtures of esters of sugars described previously and of linear or branched, saturated or unsaturated C ₆ -C ₃₀ and preferably C ₁₂ -C ₂₂ fatty acids. If they are unsaturated, these compounds may have one to three conjugated or non-conjugated carbon-carbon double bonds. The esters according to this variant may also be selected from monoesters, diesters, triesters, tetraesters and polyesters, and mixtures thereof.

These esters may be, for example, oleates, laurates, palmitates, myristates, behenates, cocoates, stearates, linoleates, linolenates, caprates and arachidonates, or mixtures thereof such as, especially, oleopalmitate, oleostearate and palmitostearate mixed esters, as well as pentaerythrityl tetraethyl hexanoate.

More particularly, use is made of monoesters and diesters and especially sucrose, glucose or methylglucose monooleates or dioleates, stearates, behenates, oleopalmitates, linoleates, linolenates and oleostearates.

An example that may be mentioned is the product sold under the name Glucate® DO by the company Amerchol, which is a methylglucose dioleate. As examples of preferable ester oils, mention may be made of, for example, diisopropyl adipate, dioctyl adipate, 2-ethylhexyl hexanoate, ethyl laurate, cetyl octanoate, octyldodecyl octanoate, isodecyl neopentanoate, myristyl propionate, 2-ethylhexyl 2-ethylhexanoate, 2- ethylhexyl octanoate, 2-ethylhexyl caprylate/caprate, methyl palmitate, ethyl palmitate, isopropyl palmitate, dicaprylyl carbonate, isopropyl lauroyl sarcosinate, isononyl

isononanoate, ethylhexyl palmitate, isohexyl laurate, hexyl laurate, isocetyl stearate, isopropyl isostearate, isopropyl myristate, isodecyl oleate, glyceryl tri(2-ethylhexanoate),

pentaerythrithyl tetra(2-ethylhexanoate), 2-ethylhexyl succinate, diethyl sebacate, and mixtures thereof. As examples of artificial triglycerides, mention may be made of, for example, capryl caprylyl glycerides, glyceryl trimyristate, glyceryl tripalmitate, glyceryl trilinolenate, glyceryl trilaurate, glyceryl tricaprate, glyceryl tricaprylate, glyceryl tri(caprate/caprylate) and glyceryl tri(caprate/caprylate/linolenate).

As examples of silicone oils, mention may be made of, for example, linear

organopolysiloxanes such as dimethylpolysiloxane, methylphenylpolysiloxane,

methylhydrogenpolysiloxane, and the like; cyclic organopolysiloxanes such as

cyclohexasiloxane, octamethylcyclotetrasiloxane, decamethylcyclopentasiloxane,

dodecamethylcyclohexasiloxane, and the like; and mixtures thereof.

Preferably, the silicone oil is chosen from liquid polydialkylsiloxanes, especially liquid polydimethylsiloxanes (PDMS) and liquid polyorganosiloxanes comprising at least one aryl group.

These silicone oils may also be organomodified. The organomodified silicones that can be used according to the present invention are silicone oils as defined above and comprise in their structure one or more organofunctional groups attached via a hydrocarbon-based group. Organopolysiloxanes are defined in greater detail in Walter Noll's Chemistry and Technology of Silicones (1968), Academic Press. They may be volatile or non- volatile.

When they are volatile, the silicones are more particularly chosen from those having a boiling point of between 60°C and 260°C, and even more particularly from:

(i) cyclic polydialkylsiloxanes comprising from 3 to 7 and preferably 4 to 5 silicon

atoms. These are, for example, octamethylcyclotetrasiloxane sold in particular under the name Volatile Silicone® 7207 by Union Carbide or Silbione® 70045 V2 by Rhodia, decamethylcyclopentasiloxane sold under the name Volatile Silicone® 7158 by Union Carbide, Silbione® 70045 V5 by Rhodia, and

dodecamethylcyclopentasiloxane sold under the name Silsoft 1217 by Momentive

Performance Materials, and mixtures thereof. Mention may also be made of cyclocopolymers of the type such as dimethylsiloxane/methylalkylsiloxane, such as Silicone Volatile® FZ 3109 sold by the company Union Carbide, of formula:

Mention may also be made of mixtures of cyclic polydialkylsiloxanes with organosilicon compounds, such as the mixture of octamethylcyclotetrasiloxane and tetratrimethylsilylpentaerythritol (50/50) and the mixture of

octamethylcyclotetrasiloxane and oxy- 1,1'-bis(2,2,2',2',3,3'- hexatrimethylsilyloxy)neopentane; and

linear volatile polydialkylsiloxanes containing 2 to 9 silicon atoms and having a viscosity of less than or equal to 5x10 ^-6 m ² /s at 25°C. An example is

decamethyltetrasiloxane sold in particular under the name SH 200 by the company Toray Silicone. Silicones belonging to this category are also described in the article published in Cosmetics and Toiletries, Vol. 91, Jan. 76, pp. 27-32, Todd & Byers, Volatile Silicone Fluids for Cosmetics. The viscosity of the silicones is measured at 25°C according to ASTM standard 445 Appendix C. Non-volatile polydialkylsiloxanes may also be used. These non-volatile silicones are more particularly chosen from polydialkylsiloxanes, among which mention may be made mainly of polydimethylsiloxanes containing trimethylsilyl end groups.

Among these polydialkylsiloxanes, mention may be made, in a non-limiting manner, of the following commercial products:

the Silbione ^® oils of the 47 and 70 047 series or the Mirasil ^® oils sold by Rhodia, for instance the oil 70 047 V 500 000;

the oils of the Mirasil ^® series sold by the company Rhodia;

the oils of the 200 series from the company Dow Corning, such as DC200 with a viscosity of 60 000 mm ² /s; and

the Viscasil ^® oils from General Electric and certain oils of the SF series (SF 96, SF 18) from General Electric.

Mention may also be made of polydimethylsiloxanes containing dimethylsilanol end groups known under the name dimethiconol (CTFA), such as the oils of the 48 series from the company Rhodia.

Among the silicones containing aryl groups, mention may be made of polydiarylsiloxanes, especially polydiphenylsiloxanes and polyalkylarylsiloxanes such as phenyl silicone oil.

The phenyl silicone oil may be chosen from the phenyl silicones of the following formula:

in which

R ₁ to R ₁₀ , independently of each other, are saturated or unsaturated, linear, cyclic or branched C ₁ -C ₃₀ hydrocarbon-based radicals, preferably C ₁ -C ₁₂ hydrocarbon-based radicals, and more preferably C ₁ -C ₆ hydrocarbon-based radicals, in particular methyl, ethyl, propyl or butyl radicals, and

m, n, p and q are, independently of each other, integers from 0 to 900 inclusive, preferably 0 to 500 inclusive, and more preferably 0 to 100 inclusive,

with the proviso that the sum n+m+q is other than 0.

Examples that may be mentioned include the products sold under the following

the Silbione® oils of the 70 641 series from Rhodia;

the oils of the Rhodorsil® 70 633 and 763 series from Rhodia; the oil Dow Corning 556 Cosmetic Grade Fluid from Dow Corning; the silicones of the PK series from Bayer, such as the product PK20;

certain oils of the SF series from General Electric, such as SF 1023, SF 1154, SF 1250 and SF 1265.

As the phenyl silicone oil, phenyl trimethicone (R ₁ to R ₁₀ are methyl; p, q, and n = 0; m=l in the above formula) is preferable.

The organomodified liquid silicones may especially contain polyethyleneoxy and/or polypropyleneoxy groups. Mention may thus be made of the silicone KF-6017 proposed by Shin-Etsu, and the oils Silwet® L722 and L77 from the company Union Carbide.

Hydrocarbon oils may be chosen from:

linear or branched, optionally cyclic, C ₆ -C ₁ lower alkanes. Examples that may be mentioned include hexane, undecane, dodecane, tridecane, and isoparaffins, for instance isohexadecane, isododecane and isodecane; and

linear or branched hydrocarbons containing more than 16 carbon atoms, such as liquid paraffins, liquid petroleum jelly, polydecenes and hydrogenated

polyisobutenes such as Parleam®, and squalane.

As preferable examples of hydrocarbon oils, mention may be made of, for example, linear or branched hydrocarbons such as isohexadecane, isododecane, squalane, mineral oil (e.g., liquid paraffin), paraffin, vaseline or petrolatum, naphthalenes, and the like; hydrogenated .

polyisobutene, isoeicosan, and decene/butene copolymer; and mixtures thereof.

The term "fatty" in the fatty alcohol means the inclusion of a relatively large number of carbon atoms. Thus, alcohols which have 4 or more, preferably 6 or more, and more preferably 12 or more carbon atoms are encompassed within the scope of fatty alcohols. The fatty alcohol may be saturated or unsaturated. The fatty alcohol may be linear or branched.

The fatty alcohol may have the structure R-OH wherein R is chosen from saturated and unsaturated, linear and branched radicals containing from 4 to 40 carbon atoms, preferably from 6 to 30 carbon atoms, and more preferably from 12 to 20 carbon atoms. In at least one embodiment, R may be chosen from C ₁₂ -C ₂₀ alkyl and C ₁₂ -C ₂₀ alkenyl groups. R may or may not be substituted with at least one hydroxyl group.

As examples of the fatty alcohol, mention may be made of lauryl alcohol, cetyl alcohol, stearyl alcohol, isostearyl alcohol, behenyl alcohol, undecylenyl alcohol, myristyl alcohol, octyldodecanol, hexyldecanol, oleyl alcohol, linoleyl alcohol, palmitoleyl alcohol, arachidonyl alcohol, erucyl alcohol, and mixtures thereof.

It is preferable that the fatty alcohol be a saturated fatty alcohol.

Thus, the fatty alcohol may be selected from straight or branched, saturated or unsaturated C -C ₃₀ alcohols, preferably straight or branched, saturated C ₆ -C ₃₀ alcohols, and more preferably straight or branched, saturated C ₁₂ -C ₂₀ alcohols.

The term "saturated fatty alcohol" here means an alcohol having a long aliphatic saturated carbon chain. It is preferable that the saturated fatty alcohol be selected from any linear or branched, saturated C ₆ -C ₃₀ fatty alcohols. Among the linear or branched, saturated C ₆ -C ₃₀ fatty alcohols, linear or branched, saturated C ₁₂ -C ₂₀ fatty alcohols may preferably be used. Any linear or branched, saturated C ₁₆ -C ₂₀ fatty alcohols may be more preferably used.

Branched C ₁₆ -C ₂₀ fatty alcohols may be even more preferably used. As examples of saturated fatty alcohols, mention may be made of lauryl alcohol, cetyl alcohol, stearyl alcohol, isostearyl alcohol, behenyl alcohol, undecylenyl alcohol, myristyl alcohol, octyldodecanol, hexyldecanol, and mixtures thereof. In one embodiment, cetyl alcohol, stearyl alcohol, octyldodecanol, hexyldecanol, or a mixture thereof (e.g., cetearyl alcohol) as well as behenyl alcohol, can be used as a saturated fatty alcohol.

According to at least one embodiment, the fatty alcohol used in the composition according to the present invention is preferably chosen from octyldodecanol, hexyldecanol and mixtures thereof. The amount of the (b) oil(s) in the composition according to the present invention may range from 0.1 to 50% by weight, preferably from 1 to 40% by weight, and more preferably from 5 to 30% by weight, relative to the total weight of the composition.

[Propellant]

The composition according to the present invention includes at least one (c) propellant. If two or more (c) propellants are used, they may be the same or different.

For the purposes of the invention, the term "propellant" means any compound that is gaseous at a temperature of 20°C and at atmospheric pressure, and that can be stored under pressure in liquid or gaseous form in an aerosol container.

The (c) propellant may be, for example, any liquefiable gas normally used in aerosol devices, such as dimethyl ether, C3-C5 alkanes, 1,1-difluoroethane, mixtures of dimethyl ether and of C ₃ -C ₅ alkanes, and mixtures of 1,1-difluoroethane and of dimethyl ether and/or of C ₃ -C ₅ alkanes. C ₃ -C ₅ alkanes, for example, propane, n-butane, isobutane, and mixtures thereof, such as liquefied petroleum gas (LPG), may be used as propellant. In one embodiment,

compressed air may be used as the (c) propellant. In another embodiment, carbon dioxide, nitrous oxide, or nitrogen may be used as the (c) propellant.

The (c) propellant(s) may be present in the composition according to the present invention in a content ranging from 1 to 90% by weight, preferably ranging from 2 to 85% by weight, and more preferably from 3 to 80% by weight, relative to the total weight of the composition. [UV Filter]

The composition according to the present invention may include at least one (d) UV filter. If two or more (d) UV filters are used, they may be the same or different. The (d) UV filter may be solid or liquid, preferably liquid. The terms "solid" and "liquid" mean solid and liquid, respectively, at 25°C under 1 atm. The (d) UV filter may be made from at least one organic or inorganic material, preferably at least one organic material. Thus, the (d) UV filter is preferably an organic UV filter. The organic UV filter may be selected from the group consisting of anthranilic derivatives; dibenzoylmethane derivatives; cinnamic derivatives; salicylic derivatives; camphor derivatives; benzophenone derivatives; β,β-diphenylacrylate derivatives; triazine derivatives; benzotriazole derivatives; benzalmalonate derivatives; benzimidazole derivatives; imidazoline derivatives; bis-benzoazolyl derivatives; p-aminobenzoic acid (PABA) and derivatives thereof; benzoxazole derivatives; screening polymers and screening silicones; dimers derived from a-alkylstyrene; 4,4-diarylbutadienes; octocrylene and derivatives thereof, guaiazulene and derivatives thereof, rutin and derivatives thereof, flavonoids, biflavonoids, oryzanol and derivatives thereof, quinic acid and derivatives thereof, phenols, retinol, cysteine, aromatic amino acids, peptides having an aromatic amino acid residue, and mixtures thereof.

Mention may be made, as examples of the organic UV filter, of those denoted below under their INCI names, and mixtures thereof.

- Anthranilic derivatives: Menthyl anthranilate, marketed under the trademark "Neo Heliopan MA" by Haarmann and Reimer.

- Dibenzoylmethane derivatives: Butyl methoxydibenzoylmethane, marketed in particular under the trademark "Parsol 1789" by Hoffmann- La Roche; and isopropyl dibenzoylmethane.

- Cinnamic derivatives: Ethylhexyl methoxycinnamate, marketed in particular under the trademark "Parsol MCX" by Hoffmann-La Roche; isopropyl methoxycinnamate; isopropoxy methoxycinnamate; isoamyl methoxycinnamate, marketed under the trademark "Neo

Heliopan E 1000" by Haarmann and Reimer; cinoxate (2-ethoxyethyl-4-methoxy cinnamate); DEA methoxycinnamate; diisopropyl methylcinnamate; and glyceryl ethylhexanoate dimethoxycinnamate.

- Salicylic derivatives: Homosalate (homomentyl salicylate), marketed under the trademark "Eusolex HMS" by Rona/EM Industries; ethylhexyl salicylate, marketed under the trademark

"Neo Heliopan OS" by Haarmann and Reimer; glycol salicylate; butyloctyl salicylate; phenyl salicylate; dipropyleneglycol salicylate, marketed under the trademark "Dipsal" by Scher; and TEA salicylate, marketed under the trademark "Neo Heliopan TS" by Haarmann and Reimer.

- Camphor derivatives, in particular, benzylidenecamphor derivatives: 3-benzylidene camphor, manufactured under the trademark "Mexoryl SD" by Chimex; 4-methylbenzylidene camphor, marketed under the trademark "Eusolex 6300" by Merck; benzylidene camphor sulfonic acid, manufactured under the trademark "Mexoryl SL" by Chimex; camphor benzalkonium methosulfate, manufactured under the trademark "Mexoryl SO" by Chimex; terephthalylidene dicamphor sulfonic acid, manufactured under the trademark "Mexoryl SX" by Chimex; and polyacrylamidomethyl benzylidene camphor, manufactured under the trademark "Mexoryl SW" by Chimex.

- Benzophenone derivatives: Benzophenone- 1 (2,4-dihydroxybenzophenone), marketed under the trademark "Uvinul 400" by BASF; benzophenone-2 (Tetrahydroxybenzophenone), marketed under the trademark "Uvinul D50" by BASF; Benzophenone-3 (2-hydroxy-4- me hoxybenzophenone) or oxybenzone, marketed under the trademark "Uvinul M40" by BASF; benzophenone-4 (hydroxymethoxy benzophonene sulfonic acid), marketed under the trademark "Uvinul MS40" by BASF; benzophenone-5 (Sodium hydroxymethoxy

benzophenone Sulfonate); benzophenone-6 (dihydroxy dimethoxy benzophenone); marketed under the trademark "Helisorb 11 " by Norquay; benzophenone- 8, marketed under the trademark "Spectra-Sorb UV-24" by American Cyanamid; benzophenone-9 (Disodium dihydroxy dimethoxy benzophenonedisulfonate), marketed under the trademark "Uvinul DS- 49" by BASF; benzophenone- 12, and n-hexyl 2-(4-diethylamino-2-hydroxybenzoyl)benzoate.

- β,β-Diphenylacrylate derivatives: Octocrylene, marketed in particular under the trademark "Uvinul N539" by BASF; and Etocrylene, marketed in particular under the trademark "Uvinul N35" by BASF. - Triazine derivatives: diethylhexyl butamido triazone, marketed under the trademark

"Uvasorb HEB" by Sigma 3V; 2,4,6-tris(dineopentyl 4'-aminobenzalmalonate)-s-triazine.

- Benzotriazole derivatives, in particular, phenylbenzotriazole derivatives: 2-(2H- benzotriazole-2-yl)-6-dodecyl-4-methylphenol, branched and linear; and those described in USP 5240975.

- Benzalmalonate derivatives: Dineopentyl 4'-methoxybenzalmalonate, and

polyorganosiloxane comprising benzalmalonate functional groups, such as polysilicone-15, marketed under the trademark "Parsol SLX" by Hoffmann-LaRoche.

- Benzimidazole derivatives, in particular, phenylbenzimidazole derivatives:

Phenylbenzimidazole sulfonic acid, marketed in particular under the trademark "Eusolex 232" by Merck, and disodium phenyl dibenzimidazole tetrasulfonate, marketed under the trademark "Neo Heliopan AP" by Haarmann and Reimer.

- Imidazoline derivatives: Ethylhexyl dimethoxybenzylidene dioxoimidazoline propionate.

- Bis-benzoazolyl derivatives: The derivatives as described in EP-669,323 and U.S. Pat. No. 2,463,264.

- Para-aminobenzoic acid and derivatives thereof: PABA (p-aminobenzoic acid), ethyl PABA, Ethyl dihydroxypropyl PABA, pentyl dimethyl PABA, ethylhexyl dimethyl PABA, marketed in particular under the trademark "Escalol 507" by ISP, glyceryl PABA, and PEG-25 PABA, marketed under the trademark "Uvinul P25" by BASF.

- Benzoxazole derivatives: 2,4-bis[5-l(dimethylpropyl)benzoxazol-2-yl-(4-phenyl)imino]- 6- (2-ethylhexyl)imino-l,3,5-triazine, marketed under the trademark of Uvasorb K2A by Sigma 3V.

- Screening polymers and screening silicones: The silicones described in WO 93/04665.

- Dimers derived from a-alkylstyrene: The dimers described in DE-19855649.

- 4,4-Diarylbutadiene derivatives: 1,1-dicarboxy(2,2'-dimethylpropyl)-4,4-diphenylbutadiene.

- Guaiazulene and derivatives thereof: Guaiazulene and sodium guaiazulene sulfonate.

- Rutin and derivatives thereof: Rutin and glucosylrutin.

- Flavonoids: Robustin (isoflavonoid), genistein (flavonoid), tectochrysin (flavonoid), and hispidone (flavonoid).

- Biflavonoids: Lanceolatin A, lanceolatin B, and hypnumbiflavonoid A.

- Oryzanol and derivatives thereof: Γ-oryzanol.

- Quinic acid and derivatives thereof: Quinic acid.

- Phenols: Phenol.

- Retinols: Retinol.

- Cysteines: L-cysteine.

- Peptides having an aromatic amino acid residue: Peptides having tryptophan, tyrosine or phenylalanine.

The preferred organic UV filter may be selected from:

butyl methoxydibenzoylmethane, ethylhexyl methoxycinnamate, homosalate, ethylhexyl salicylate, octocrylene, phenylbenzimidazole sulfonic acid, benzophenone-3, benzophenone-4, benzophenone-5, n-hexyl 2-(4-diethylamino-2-hydroxybenzoyl)benzoate, 4- methylbenzylidene camphor, terephthalylidene dicamphor sulfonic acid, disodium phenyl dibenzimidazole tetrasulfonate, ethylhexyl triazone, bis-ethylhexyloxyphenol methoxyphenyl triazine, diethylhexyl butamido triazone, 2,4,6-tris(dineopentyl 4'-aminobenzalmalonate)-s- triazine, 2,4,6-tris(diisobutyl 4'-aminobenzalmalonate)-s-triazine, methylene bis- benzotriazolyl tetramethylbutylphenol, polysilicone-15, dineopentyl 4'- methoxybenzalmalonate, 1 , 1 -dicarboxy(2,2'-dimethylpropyl)-4,4-diphenylbutadiene, 2,4- bis [5- 1 (dimethylpropyl)benzoxazol-2-yl-(4-phenyl)imino] -6-(2-ethylhexyl)imino- 1,3,5- triazine, and their mixtures. A more preferable organic UV filter is butyl methoxydibenzoylmethane (Avobenzone) .

In a preferred embodiment, the (d) UV filter is an organic liquid UV filter. The material of the organic liquid UV filter is not limited as long as it is organic. If two or more organic liquid UV filters are used, the material(s) of the organic liquid UV filters may be the same as or different from each other.

Amongst the organic liquid UV filter, we can mention:

- Cinnamic derivatives: Ethylhexyl methoxycinnamate, marketed in particular under the trademark "Parsol MCX" by Hoffmann-La Roche; isopropyl methoxycinnamate; isopropoxy methoxycinnamate; isoamyl methoxycinnamate, marketed under the trademark "Neo

Heliopan E 1000" by Haarmann and Reimer; cinoxate (2-ethoxyethyl-4-methoxy cinnamate); DEA methoxycinnamate; diisopropyl methylcinnamate; and glyceryl ethylhexanoate dimethoxycinnamate .

- Salicylic derivatives: Homosalate (homomentyl salicylate), marketed under the trademark "Eusolex HMS" by Rona/EM Industries; ethylhexyl salicylate, marketed under the trademark "Neo Heliopan OS" by Haarmann and Reimer; glycol salicylate; butyloctyl salicylate; phenyl salicylate; dipropyleneglycol salicylate, marketed under the trademark "Dipsal" by Scher; and TEA salicylate, marketed under the trademark "Neo Heliopan TS" by Haarmann and Reimer.

- β,β-Diphenylacrylate derivatives: Octocrylene, marketed in particular under the trademark "Uvinul N539" by BASF; and Etocrylene, marketed in particular under the trademark "Uvinul N35" by BASF.

- Polyorganosiloxane comprising benzalmalonate functional groups, such as polysilicone-15, marketed under the trademark "Parsol SLX" by Hoffmann-LaRoche.

The preferred organic liquid UV filter(s) may be selected from:

ethylhexyl methoxycinnamate, homosalate, ethylhexyl salicylate, octocrylene, and bis- ethylhexyloxyphenol methoxyphenyl triazine.

The (c) UV filter(s) may be present in the composition according to the present invention in a content ranging from 1 to 30% by weight, preferably ranging from 5 to 25% by weight, and more preferably from 10 to 20% by weight, relative to the total weight of the composition. [Water]

The composition according to the present invention may comprise (e) water.

The amount of (e) water is not limited, and may be from 1 to 90% by weight, preferably from 10 to 80%) by weight, and more preferably from 40 to 70% by weight, relative to the total weight of the composition according to the present invention.

[Filler] The composition according to the present invention may include at least one filler. If two or more fillers are used, they may be the same or different.

It is preferable that the filler be capable of absorbing and/or adsorbing an oil or a liquid fatty substance, for instance sebum (from the skin). This oil-absorbing filler may also advantageously have a BET specific surface area of greater than or equal to 300 m ² /g, preferably greater than 500 m ² /g and preferentially greater than 600 m ² /g, and especially less than 1500 m /g. The BET specific surface area is determined according to the BET (Brunauer-Emmet-Teller) method described in the Journal of the American Chemical Society, vol. 60, page 309, February 1938 and corresponding to the international standard ISO 5794/1 (appendix D). The BET specific surface area corresponds to the total specific surface area (thus including micropores) of the powder.

The filler may be characterized in that it has an oil uptake of greater than or equal to 1 ml/g, preferably greater than or equal 1.5 ml/g, especially ranging from 1.5 ml/g to 20 ml/g, or even ranging from 1.5 ml/g to 15 ml/g. It preferably has an oil uptake of greater than or equal to 2 ml/g, especially ranging from 2 ml/g to 20 ml/g, or even ranging from 2 ml/g to 15 ml/g.

The filler may be chosen more particularly from silicas, silica silylates (in particular hydrophobic silica aerogel particles), polyamide (in particular Nylon-6) powders, powders of acrylic polymers, especially of polymethylmethacrylate, of polymethyl methacrylate/ethylene glycol dimethacrylate, of polyallyl methacrylate/ethylene glycol dimethacrylate or of ethylene glycol dimethacrylate/lauryl methacrylate copolymer; perlites; magnesium carbonate, silicone elastomers or silicone resins, and mixtures thereof.

The filler may be present in the composition according to the present invention in a content ranging from 0.01 to 10% by weight, preferably ranging from 0.1 to 5% by weight, and more preferably from 0.5 to 2% by weight, relative to the total weight of the composition.

[Optional Ingredients]

The composition according to the present invention may also comprise one or more standard cosmetic adjuvants chosen from, for example, fillers, softeners, humectants, opacifiers, stabilizers, emollients, silicones, antifoams, fragrances, preserving agents, surfactants such as nonionic, cationic, anionic and amphoteric surfactants, active agents, colouring agents, cationic, anionic, amphoteric polymers, propellants, or any other ingredient usually used in cosmetics and/or dermatology.

Needless to say, a person skilled in the art will take care to select the optional adjuvant(s) added to the composition according to the present invention such that the advantageous properties intrinsically associated with the composition according to the present invention are not, or are not substantially, adversely affected by the envisaged addition.

[Cosmetic Composition]

The composition according to the present invention may preferably be used as a cosmetic composition. Thus, the composition according to the present invention may be intended for application onto a keratin substance. Keratin substance here means a material containing keratin as a main constituent element, and examples thereof include the skin, scalp, nails, lips, hair and the like. It is preferable that the composition according to the present invention be used for a cosmetic process for the keratin substance, in particular skin. Thus, it is preferable that the composition according to the present invention be a skin cosmetic composition. It is more preferable that the composition according to the present invention be a skin-care or make-up composition, in particular a UV screening composition, if the composition includes at least one UV filter. The composition according to the present invention may be in the form of an O/W emulsion or a W/O emulsion, if the composition includes water. It is preferable that the composition according to the present invention be in the form of a W/O emulsion.

The composition according to the present invention may preferably be in the form of an aerosol. Thus, the composition according to the present invention may be contained in an aerosol device.

[Process] The present invention also relates to a cosmetic process for a keratin substance such as skin, comprising the steps of:

applying the composition according to the present invention as explained above onto the keratin substance. The keratin substance can be in a dry state or in a wet state before applying the composition according to the present invention.

The composition according to the present invention to be applied onto the keratin substance may be in the form of an aerosol.

It is preferable that the composition according to the present invention not be rinsed off after being applied onto the keratin substance.

[Aerosol Device]

The present invention also relates to an aerosol device, comprising

at least one nozzle;

at least one tube; and

at least one container comprising

a composition, preferably a cosmetic composition, and more preferably a skin cosmetic composition, comprising:

(a) at least one thermoplastic hollow particle; and

(b) at least one oil,

and

(c) at least one propellant,

wherein

the nozzle is connected with the container via the tube, and

the composition in the container can be moved from the container to the nozzle via the tube to be sprayed from the nozzle.

The above aerosol device is well known in the field of cosmetics.

In one embodiment, the aerosol device according to the present invention comprises a single container which contains a mixture of a composition comprising the (a) thermoplastic hollow particle(s) and the (b) oil(s), and of the (c) propellant(s), as well as the other ingredients, if present, of the composition according to the present invention.

In the aerosol device for the present invention, the nozzle is connected with the container via the tube. In one embodiment, one end of the tube is connected with the nozzle, and the other end of the tube is immersed into the mixture of the composition and the (c) propellant in the container.

Due to the presence of the (c) propellant(s), the composition including the (a) thermoplastic hollow particle(s) and the oil(s) in the container is pushed to move from the container to the nozzle via the tube. The moved composition can be sprayed from the nozzle toward the keratin substance such as skin.

The aerosol device may comprise a push button which is linked with the nozzle. A user of the aerosol device can push the button to spray the composition via the nozzle.

According to another embodiment, the aerosol device may have two compartments which are formed by, for example an inner bag in the container. The (a) thermoplastic hollow particle(s) and the (b) oil(s) as well as the other ingredients, if present, of the composition according to the present invention are introduced into the inner bag, while the (c) propellant is introduced between the inner bag and the container at a sufficient pressure to make the composition come out in the form of a spray through the nozzle. In this case, as the (c) propellant, for example, compressed air may be used. In this case, the (c) propellant is preferably used at a pressure of between 1 and 12 bar, and better still between 9 and 11 bar. Such an aerosol device is sold, for example, under the name EP Spray by the company EP- Spray System SA.

The composition according to the present invention can be discharged from the aerosol device as an aerosol by being sprayed from the nozzle. Even after spraying for a long time, the nozzle of the aerosol device cannot be clogged.

The composition according to the present invention to be applied onto the keratin substance may be in the form of an aerosol or a spray.

EXAMPLES

The present invention will be described in a more detailed manner by way of examples.

However, these examples should not be construed as limiting the scope of the present invention. The examples below are presented as non-limiting illustrations in the field of the present invention.

[Examples 1-3]

The following compositions according to Examples 1-3 shown in Table 1, were prepared by mixing the ingredients shown in Table 1. The numerical values for the amounts of the ingredients shown in Table 1 are all based on "% by weight" as active raw materials. Table 1

[Comparative Examples 1-7]

The following compositions according to Comparative Examples 1-7 shown in Table 2, were prepared by mixing the ingredients shown in Table 2. The numerical values for the amounts of the ingredients shown in Table 2 are all based on "% by weight" as active raw materials.

[Comparative Examples 8-14]

The following compositions according to Comparative Examples 8-14 shown in Table 3, were prepared by mixing the ingredients shown in Table 3. The numerical values for the amounts of the ingredients shown in Table 3 are all based on "% by weight" as active raw materials.

[Evaluations]

The compositions according to Examples 1-3 and Comparative Examples 1-14 were evaluated as follows.

(Matte)

Each of the compositions according to Examples 1-3 and Comparative Examples 1-14 was applied onto a substrate sheet (contrast card) such that the composition formed a layer with a thickness of 100 μηι. After leaving the substrate at room temperature for 24 hours, the gloss intensity was measured by a glossmeter (CM-2600d, Konica Minolta) by reflection intensity at 60 degree of incidence angle. The gloss intensity was categorized in accordance with the following criteria. High: < 50

Mid: 50-80

Low: > 80

The results are shown in Tables 1 to 3.

(Transparency)

Each of the compositions according to Examples 1-3 and Comparative Examples 1-14 was applied onto a transparent PET sheet (BYK sheet) such that the composition formed a layer with a thickness of 25μιη. After leaving the substrate at room temperature for 24 hours, the light transmittance (%) was measured by a hazemeter (BYK guardner Haze guard plus, Toyo Seiki). The light transmittance was categorized in accordance with the following criteria.

High: > 90

Mid: 90-85

Low: < 85

The results are shown in Tables 1 to 3. (Results)

The compositions according to Examples 1-3 which comprise thermoplastic hollow particles (acrylonitrile/methylmethacrylate/vinylidene chloride copolymer) were able to provide superior matte and transparent appearance although they include oil (isononyl isononanoate). Accordingly, the compositions according to Examples 1-3 were found to have good cosmetic properties for, in particular, the skin. In addition, it can be understood from Examples 1-3 that even a small amount of the thermoplastic hollow particles can provide superior matte and transparent appearance. The compositions according to Comparative Examples 1-4, 7 and 10-12 include

polymethylsilsesquioxane, methylmethacrylate crosspolymer, Nylon®- 12, synthetic wax, boron nitride, silica (and) dimethicone, and kaolin, respectively, instead of the thermoplastic hollow particles in Examples 1-3, and therefore, the compositions according to Comparative Examples 1-4, 7 and 10-12 could not provide superior matte effects. The compositions according to Comparative Examples 5, 6, 8 and 9 include corn starch, trimethylsiloxysilicate, silica, and silica silylate, respectively, instead of the thermoplastic hollow particles in Examples 1-3, and therefore, the compositions according to Comparative Examples 5, 6, 8 and 9 could provide some matte effects. However, the matte effects provided by the compositions according to Comparative Examples 5, 6, 8 and 9 were inferior to those provided by the compositions according to Examples 1-3.

The composition according to Comparative Example 13 includes titanium dioxide, instead of the thermoplastic hollow particles in Examples 1-3, and therefore, the composition according to Comparative Example 13 could not provide transparency.

The composition according to Comparative Example 14 includes zinc oxide, instead of the thermoplastic hollow particles in Examples 1-3, and therefore, the matte and transparency provided by the composition according to Comparative Examples 14 were inferior to those provided by the compositions according to Comparative Examples 1-3.

[Spray Test]

The compositions according to Examples 1-3 are subjected to a spray test using a

conventional spray device.

Each of the compositions according to Examples 1-3 (30%) is mixed with n-butane as a propellant (70%)The mixture is charged into a container. Then, the container is installed in an aerosol device such that a nozzle of the device is connected with the container via a tube. Specifically, one end of the tube is connected with the nozzle, and the other end of the tube is immersed into the mixture of the composition and the propellant in the container.

The composition was discharged from the aerosol device as an aerosol by being sprayed from the nozzle. After spraying for 30 seconds, the nozzle was not clogged.

The composition was discharged from the aerosol device as an aerosol by being sprayed from the nozzle as above every day for 1-3 months. The nozzle was not clogged.