WO2009059872A1

WO2009059872A1 - Fragrancing composition comprising a combination of a benzotriazole compound, a uva screening agent of the dibenzoylmethane type and a particular uvb screening system

Info

Publication number: WO2009059872A1
Application number: PCT/EP2008/063779
Authority: WO
Inventors: Isabelle Bara
Original assignee: L'oreal
Priority date: 2007-11-09
Filing date: 2008-10-14
Publication date: 2009-05-14

Abstract

The invention relates to a fragrancing composition comprising, in a cosmetically acceptable medium: a) at least 2% by weight of a fragrancing substance relative to the total weight of the composition; b) at least one benzotriazole compound of formula (I); c) at least one UV-A screening agent of the dibenzoylmethane type; d) at least one UVB screening system constituted by (i) a mixture comprising at least one UV screening agent of the cinnamate type and at least one UV screening agent of the salicylate type; or (ii) an alkyl, β, β'-diphenylacrylate or alkyl α-cyano-β, β'-diphenylacrylate compound. The invention also relates to the use of the said combination of screening agents b), c) and d) in a fragrancing composition comprising, in a cosmetically acceptable medium, at least 2% by weight of a fragrancing substance relative to the total weight of the composition; as an agent for stabilizing the organoleptic properties of the composition against external attacking factors such as light or differences in temperature, in particular the colour and/or odour of the said composition. The invention also relates to a cosmetic process for fragrancing human keratin materials, especially the skin, the lips and the integuments, comprising the application to the keratin materials of the composition defined previously.

Description

Fragrancing composition comprising a combination of a benzotriazole compound, a UVA screening agent of the dibenzoylmethane type and a particular UVB screening system

The invention relates to a fragrancing composition comprising, in a cosmetically acceptable medium: a) at least 2% by weight of a fragrancing substance relative to the total weight of the composition; b) at least one benzotriazole compound of particular formula (I) that will be defined in detail hereinbelow; c) at least one UV-A screening agent of the dibenzoylmethane type; d) at least one UVB screening system constituted by (i) a mixture comprising at least one UV screening agent of the cinnamate type and at least one UV screening agent of the salicylate type; or

(ii) an alkyl β, β ' -diphenylacrylate or alkyl α-cyano-β, β ' -diphenylacrylate compound.

It is known that a fragrance is a combination of different odoriferous substances that evaporate at different periods. Each fragrance has what is known as a "head note", which is the odour that diffuses first when the fragrance is applied or when the container containing it is opened, a "heart or central note", which corresponds to the full fragrance (emitted for a few hours after the "head note"), and a "base note", which is the most persistent odour (emitted for a few hours after the "heart note") . The persistence of the base note corresponds to the remanence of the fragrance .

Human beings have since time immemorial sought to fragrance themselves and to fragrance the objects that surround them or the places that they frequent, both to mask strong and/or unpleasant odours and to give a good odour . It is common practice to incorporate fragrance into a certain number of products or compositions, in particular cosmetic and dermatological compositions such as eaux fraiches, eaux de toilette, eaux de parfum, aftershave lotions and care lotions.

A fragrance or a fragrancing composition should have a pleasant odour and a stable colour for a certain time corresponding to the time of use by the consumer. They should withstand various attacking factors such as light and differences in temperature. A screening system and/or an antioxidant system is generally added. However, certain screening systems are inefficient and/or have a tendency to denature the desired colour and/or fragrance.

Most of the coloured fragranced products comprise stabilizers such as UVA screening agents or UVB screening agents and antioxidants.

The role of stabilizers is to keep the organoleptic properties of the products stable with respect to various attacking factors such as UV and heat shocks. Stabilizers are known in the prior art for improving the resistance of these products with respect to these attacking factors.

Patent application WO 2005/123 013 discloses a combination of diethylaminohydroxybenzoylhexyl benzoate and of ethylhexyl methoxycinnamate, sold under the name Uvinul A + B, as a colour stabilizer in fragrancing compositions .

Patent application WO 2000/25730 also discloses the use of Tinogard AS or "Bumetrizole" for avoiding the photolytic degradation of cosmetic products, including fragrances . Patent application WO 2003/103 622 also discloses the use of Tinogard Q or "tris (tetramethylhydroxy- piperidinol) " for stabilizing fragrances, including eaux de toilette.

Patent WO 2005/042 828 mentions the combination of Tinogard Q with particular screening agents for the purpose of stabilizing fragrances and for avoiding the light-induced degradation of eaux de toilette.

Unfortunately, the UV screening agents or stabilizers recommended in the patent applications of the prior art are not entirely satisfactory, in particular for fragile fragrances that are rich in natural substances. Changes in the organoleptic properties are usually observed, such as, in particular, those of the odour and colour over time (assessed by sensory analysis such as the "sniff test" for the odour, and a test of visualization by the naked eye or with a spectrometer to quantify the changes in colour according to various colour change parameters, and according to exposure to different types of illumination) . In particular, yellowing or pinkening, associated with the degradation of the chemical substances, readily appear in the visual changes. It is also possible to see changes in the clarity of liquids, when these liquids are originally transparent, such as flocculations and precipitates of matter or cloudiness that impair the appearance of the products and that may harm the efficacy of the pumps, when the product is conditioned as a spray.

Thus, there is still a need to find novel fragrancing products that do not have the drawbacks of the products of the prior art, and especially the need for fragrancing products whose organoleptic properties such as the odour and the colour remain stable over time and under the effects of light or of differences in temperature . The Applicant has discovered, surprisingly, that this objective can be achieved by using a fragrancing composition comprising, in a cosmetically acceptable medium: a) at least 2% by weight of a fragrancing substance relative to the total weight of the composition; b) at least one benzotriazole compound of particular formula (I) that will be defined in detail hereinbelow; c) at least one UV-A screening agent of the dibenzoyl- methane type; d) at least one UVB screening system constituted by

(i) a mixture comprising at least one UV screening agent of the cinnamate type and at least one UV screening agent of the salicylate type; or

The combination of UV screening agents in accordance with the invention has the advantage of being colourless, unlike other known combinations of screening agents. It is perfectly suitable for protecting transparent compositions that are fundamentally colourless or that have a particular colour that should not be modified by the addition of a coloured screening agent.

This discovery forms the basis of the invention.

The invention also relates to the use of a combination a) of at least one benzotriazole compound of particular formula (I) that will be defined in detail hereinbelow, b) of at least one UV-A screening agent of the dibenzoylmethane type and c) of at least one UVB screening system constituted by:

(i) a mixture comprising at least one UV screening agent of the cinnamate type and at least one UV screening agent of the salicylate type; or (ii) an alkyl β, β ' -diphenylacrylate or alkyl α-cyano-β, β ' -diphenylacrylate compound, in a fragranced composition comprising, in a cosmetically acceptable medium, at least 2% by weight of a fragrancing substance; as a stabilizer for the organoleptic properties, in particular the colour and/or the odour, of the said composition with respect to external attacking factors such as light or differences in temperature .

The invention also relates to a process for stabilizing the organoleptic properties, in particular the colour and/or the odour, of a fragrancing composition, comprising, in a cosmetically acceptable medium, at least 2% by weight of a fragrancing substance relative to the total weight of the composition, characterized in that it consists in incorporating into the composition a combination a) of at least one benzotriazole compound of particular formula (I) that will be defined in detail hereinbelow, b) of at least one UV-A screening agent of the dibenzoylmethane type and c) of at least one UVB screening system constituted by :

(ii) an alkyl β, β ' -diphenylacrylate or alkyl α-cyano-β, β ' -diphenylacrylate compound as defined previously .

A subject of the invention is also a cosmetic process for fragrancing human keratin materials and especially the skin, the lips, the hair, the scalp, the eyelashes, the eyebrows and the nails, comprising the application to the keratin materials of the composition as defined above . The term "fragrancing composition" means any composition that leaves a fragrance on keratin materials after application.

The term "fragrancing substance" means any fragrance or aroma capable of fragrancing the skin and human keratin materials in general comprising the skin, the hair, the scalp, the lips; the nails.

The amount of fragrancing substance (s) will more preferentially be from 3% to 50% by weight, better still from 5% to 30% by weight and even better still 10% to 20% by weight relative to the total weight of the composition.

In the composition of the invention, the term "cosmetically acceptable medium" means a non-toxic medium that can be applied to human keratin materials comprising the skin (including the interior of the eyelids) , the lips, the nails, the hair, the scalp, the eyelashes and the eyebrows.

Fragrances and aromas of natural or synthetic origin, and mixtures thereof, may be used in the composition of the invention as fragrancing substance. Examples of fragrances and aromas of natural origin that may be mentioned include extracts of flowers (lily, lavender, rose, jasmine or ylang-ylang) , of stalks and of leaves

(patchouli, geranium or bitter orange) , of fruit (coriander, aniseed, cumin or juniper) , of fruit peel

(bergamot, lemon or orange) , of roots (angelica, celery, cardamom, iris or sweet flag) , of wood (pine wood, sandalwood, guaiacwood, cedar wood or rosewood) , of herbs and grasses (tarragon, lemongrass, sage or thyme) , of needles and branches (spruce, fir, pine or dwarf pine), and of resins and balms (galbanum, elemi, benzoin, myrrh, olibanum or opopanax) . Examples of fragrancing substances of synthetic origin that may be mentioned include compounds of the ester, ether, aldehyde, ketone, aromatic alcohol and hydrocarbon type.

Esters that may be mentioned in particular include benzyl acetate, benzyl benzoate, phenoxyethyl isobutyrate, p-tert-butylcyclohexyl acetate, citronellyl acetate, citronellyl formate, geranyl acetate, linalyl acetate, dimethylbenzylcarbinyl acetate, phenylethyl acetate, linalyl benzoate, benzyl formate, ethylmethylphenyl glycinate, alkylcyclohexyl propionate, styrallyl propionate and benzyl salicylate.

An ether that may be mentioned is benzyl ethyl ether.

Examples of aldehydes that may be mentioned include linear alkanals containing from 8 to 18 carbon atoms, citral, citronellal, citronellyloxyacetaldehyde, cyclamenaldehyde, hydroxycitronellal, lilial and bourgeonal .

Examples of ketones that may be mentioned include ionones such as α-isomethylionone and methyl cedryl ketone.

Among the aromatic and especially terpenic alcohols that may be mentioned are anethole, citronellol, eugenol, isoeugenol, geraniol, linalool, phenylethyl alcohol and terpineol.

Hydrocarbons that may especially be mentioned include terpenes. These compounds are often in the form of a mixture of two or more of these odoriferous substances.

Moreover, it is also possible to use essential oils or flavour components, for instance essential oils of sage, of camomile, of clove, of balm, of mint, of cinnamon tree leaves, of lime tree blossom, of juniper, of vetiver, of olibanum, of galbanum, of labdanum and of lavandin.

Essential oil of bergamot, dihydromercenol, lilial, lyral, citronellol, phenylethyl alcohol, α-hexyl- cinnamaldehyde, geraniol, benzylacetone, cyclamenalde- hyde, linalool, ambroxane, indol, hedione, sandelice, essential oils of lemon, mandarin and orange, allylamine glycolate, cyclovertal, essential oil of lavandin, essential oil of sage, β-damascone, essential oil of geranium, cyclohexyl salicylate, phenylacetic acid, geranyl acetate, benzyl acetate and rose oxide are preferably used as fragrancing substance, alone or as a mixture.

According to one preferred embodiment of the invention, a mixture of different fragrancing substances that together generate a note that is pleasant to the user is used. Among the known olfactive notes, examples that may be mentioned include hesperidium fragrances, aromatics, floral fragrances, musks, fruity fragrances, spices, oriental fragrances, marine fragrances, aquatic notes, chypre fragrances, woody fragrances and ferns, and mixtures thereof.

The benzotriazole compounds in accordance with the invention correspond to formula (I) below:

in which: Ri represents a Ci-Ci₂ alkyl radical, a Ci-C₅ alkoxy radical, a Ci-C₅ alkoxycarbonyl, a C₅-C₇-cycloalkyl, a C₆-Ci₀ aryl, an aralkyl radical or a group SO₃M, R₃ denotes hydrogen, a Ci-Ci₂ alkyl radical, a Ci-C₅ alkoxy radical, a halogen, preferably Cl, or a hydroxyl group;

M denotes an alkali metal, alkaline-earth metal or ammonium cation, preferably Na⁺; m denotes 1 or 2; n is 0 or 1 ; if m = 1, then R₂ is hydrogen, a Ci-Ci₂ alkyl group that is unsubstituted or substituted with a phenyl; a C₆-Ci₀ aryl; if m = 2, then R₂ is a direct bond, a radical -(CH₂)_p- with p being an integer from 1 to 3.

The alkyl radicals are linear or branched and are chosen, for example, from methyl, ethyl, n-propyl, isopropyl, n-butyl, sec-butyl, tert-butyl, amyl, isoamyl, heptyl, octyl, isooctyl, nonyl, decyl and dodecyl .

Ci-C₅ alkoxy radicals that may be mentioned include: methoxy, ethoxy, n-propoxy, n-butoxy, n-pentoxy, 1-methylpropoxy, 3-methylbutoxy, 2, 2-dimethylpropoxy .

The C₅-C₇ cycloalkyls are, for example, cyclopentyl, cycloheptyl or, preferably, cyclohexyl.

The alkylphenyls are, for example, phenylpropyl, phenylethyl and, preferably, benzyl.

The benzotriazole compounds of formula (I) are known per se and their structures are described in patent application WO 00/25730.

Among the compounds of formula (I), mention may be made especially of the following compounds: (i) sodium benzotriazolylbutylphenol sulfonate of formula (1)

for instance the product sold under the name Tinoguard HS by the company Ciba-Geigy.

(ii) Benzotriazolyldodecyl-p-cresol of formula (2) :

for instance the product sold under the name Tinoguard TL by the company Ciba-Geigy.

(iii) Bumetrizole of formula (3) :

for instance the product sold under the name Tinoguard AS by the company Ciba-Geigy.

The compound Bumetrizole of formula (4) will be used more particularly. The compound (s) of the benzotriazole type of formula (I) in accordance with the invention is (are) preferably present in the compositions according to the invention in a content ranging from 0.01% to 0.1% of the final composition, more preferentially from 0.01% to 0.05% by weight and even more particularly from 0.01% to 0.03% by weight relative to the total weight of the composition. These proportions will be adapted to the nature of the fragrance (s) used.

Among the screening agents of cinnamate type in accordance with the invention, mention may be made especially, in a non-limiting manner, of:

Ethylhexyl methoxycinnamate sold especially under the trade name Parsol MCX by DSM Nutritional Products,

Inc . ,

Isopropyl methoxycinnamate,

Isoamyl methoxycinnamate sold under the trade name Neo Heliopan E 1000 by Symrise,

Cinoxate,

DEA methoxycinnamate,

Diisopropyl methylcinnamate,

Glyceryl ethylhexanoate dimethoxycinnamate .

Among the cinnamate screening agents mentioned above, use will be made most particularly of ethylhexyl methoxycinnamate, sold under the trade name Parsol MCX by the company DSM Nutritional Products or Uvinul MC 80 by the company BASF; this screening agent corresponds to formula (B) below:

(B)

Among the screening agents of the dibenzoylmethane type in accordance with the invention, mention may be made especially, in a non-limiting manner, of: - 2-methyldibenzoylmethane,

- 4-methyldibenzoylmethane,

- 4-isopropyldibenzoylmethane,

- 4-tert-butyldibenzoylmethane,

- 2, 4-dimethyldibenzoylmethane, - 2 , 5-dimethyldibenzoylmethane,

- 4,4' -diisopropyldibenzoylmethane,

- 4,4' -dimethoxydibenzoylmethane,

- 4-tert-butyl-4 ' -methoxydibenzoylmethane,

- 2-methyl-5-isopropyl-4 ' -methoxydibenzoylmethane, - 2-methyl-5-tert-butyl-4 ' -methoxydibenzoylmethane,

- 2 , 4-dimethy1-4 ' -methoxydibenzoylmethane,

- 2, 6-dimethyl-4-tert-butyl-4 ' -methoxydibenzoylmethane .

Among the dibenzoylmethane derivatives mentioned above, use will be made most particularly of 4- (tert-butyl) -

4 ' -methoxydibenzoylmethane or butylmethoxydibenzoyl- methane, sold under the trade name Parsol 1789 by the company DSM Nutritional Products, or Eusolex 9020 by the company Merck; this screening agent corresponds to formula (C) below:

Among the screening agents of the salicylate type in accordance with the invention, mention may be made especially, for example, of:

Homosalate sold under the name Eusolex HMS by Rona/EM Industries, Ethylhexyl salicylate sold under the name Neo Heliopan OS by Symrise,

Dipropylene glycol salicylate sold under the name Dipsal by Scher, TEA salicylate sold under the name Neo Heliopan TS by Symrise .

Among the salicylates mentioned above, use will be made most particularly of ethylhexyl salicylate sold under the name Neo Heliopan OS by Symrise, of formula (D) below:

The alkyl β, β ' -diphenylacrylates and alkyl α-cyano- β, β ' -diphenylacrylates that may be used according to the present invention are preferably chosen from those corresponding to formula (II) below:

in which:

- R₄ and R₅, which may be identical or different, are in a meta or para position and are chosen from: hydrogen; a Ci-C₈ alkoxy radical with a straight or branched chain; a Ci-C₄ alkyl radical with a straight or branched chain;

- R₆ represents a Ci-Ci₂ alkyl radical with a straight or branched chain; - R₇ represents a hydrogen atom or a -CN radical.

Among the alkyl β, β ' -diphenylacrylates and alkyl α-cyano-β, β ' -diphenylacrylates that may be used according to the present invention, 2-ethylhexyl α-cyano-β, β ' -diphenylacrylate, also known as Octocrylene, is more particularly preferred, and is known as being a lipophilic screening agent that absorbs in the UVB range. It is commercially available and sold especially under the name Uvinul N 539 by the company BASF. It corresponds to the following formula:

^' Φ

^XC=C-COOCH₂CHC₄H₉

<K I I

CN C₂H₅

in which φ denotes a phenyl radical.

Preferably, the total amount of screening agents: a) benzotriazole compound of formula (I), b) dibenzoyl- methane, c) screening agents constituting the UVB screening system, present in the composition of the invention will range from 0.1% to 2% by weight and preferably from 0.3% to 1% by weight relative to the total weight of the composition.

According to one particularly preferred form of the invention, the weight ratio of the combination of dibenzoylmethane screening agent/UVB screening system to the benzotriazole compound ranges from 1/1 to 100/1 and preferably from 10/1 to 25/1.

These proportions and weight ratios are adapted to the nature of the fragrance (s) used. According to one particular form of the invention, the cosmetically acceptable medium in accordance with the present invention contains at least one volatile alcohol and/or one volatile silicone oil and optionally water. Preferentially, this medium of the composition contains water in an amount preferably ranging from

0.01% to 50% and more preferentially from 0.5% to 25% by weight relative to the total weight of the composition.

The term "volatile alcohol" means any compound comprising at least one alcohol function and having a vapour pressure at 2O⁰C of greater than 17.5 mmHg.

For the purposes of the invention, the term "oil" means a water-insoluble fatty substance that is liquid at room temperature and atmospheric pressure.

For the purposes of the invention, the term "volatile silicone oil" means any silicone compound that is capable of evaporating on contact with the skin or keratin fibre in less than one hour, at room temperature and atmospheric pressure. The volatile compound is a volatile cosmetic compound, which is liquid at room temperature, especially having a non^¬ zero vapour pressure, at room temperature and atmospheric pressure, especially a vapour pressure ranging from 0.13 Pa to 40 000 Pa (10^~3 to 300 mmHg), in particular ranging from 1.3 Pa to 13 000 Pa (0.01 to 100 mmHg) and more particularly ranging from 1.3 Pa to 1300 Pa (0.01 to 10 mmHg) .

The volatile alcohols in accordance with the present invention are preferably chosen from Ci-C₅ lower monoalcohols, which may be chosen from methanol, ethanol, propanol, isopropanol, n-butanol, isobutanol and t-butanol, and more particularly ethanol. The volatile alcohol (s) is (are) preferably present in amounts ranging from 40% to 80% and more preferentially in amounts ranging from 55% to 80% by weight relative to the total weight of the composition.

Examples of volatile silicone oils that may be mentioned include linear or cyclic volatile silicone oils, especially those with a viscosity ≤ 6 centistokes

(6xlO^~6 m²/s) and especially containing from 2 to 10 silicon atoms, these silicones optionally comprising alkyl or alkoxy groups containing from 1 to 22 carbon atoms. As volatile silicone oils that may be used in the invention, mention may be made especially of octamethylcyclotetrasiloxane, decamethyIcyclopenta- siloxane, dodecamethylcyclohexasiloxane, heptamethyl- hexyltrisiloxane, heptamethyloctyltrisiloxane, hexa- methyldisiloxane, octamethyltrisiloxane, decamethyl- tetrasiloxane and dodecamethylpentasiloxane, and mixtures thereof.

The volatile silicone oil (s) is (are) preferably present in concentrations ranging from 40% to 98.5% and preferably ranging from 10% to 80% by weight relative to the total weight of the composition.

The composition of the invention may also comprise any additive usually used in the field of fragrances, chosen especially from antioxidants, cosmetic or dermatological active agents, for instance emollients or softeners, such as sweet almond oil, apricot kernel oil, moisturizers, for instance glycerol, calmatives, for instance α-bisabolol, allantoin and aloe vera; vitamins, essential fatty acids, insect repellents, propellants, peptizers, dyestuffs, nacres and glitter flakes, and mixtures thereof. The composition of the invention may also contain adjuvants that are common in cosmetics or dermatology, such as hydrophilic or lipophilic gelling agents, preserving agents (for example phenoxyethanol and parabens) , solvents, fillers and bactericides. The amounts of these various adjuvants are those conventionally used in the field under consideration, for example from 0.01% to 20% of the total weight of the composition.

Examples of antioxidants that may be mentioned include BHA (tert-butyl-4-hydroxyanisole) , BHT (2, 6-di-tert- butyl-p-cresol) , tocopherols, for instance vitamin E and derivatives thereof such as tocopheryl acetate.

The composition according to the invention may especially comprise at least one dyestuff such as pulverulent dyestuffs, liposoluble dyes and water- soluble dyes. The combination of UV screening agents in accordance with the invention will also play a protective role on these dyes, so as to avoid any degradation of the colour associated either directly with the reaction of light or of temperature on these dyes, or the interaction of the fragrancing substances or of its derived products originating from degradation on the said dyes.

The pulverulent dyestuffs may be chosen from pigments and nacres.

The pigments may be white or coloured, mineral and/or organic, and coated or uncoated. Among the mineral pigments that may be mentioned are titanium dioxide, optionally surface-treated, zirconium oxide, zinc oxide or cerium oxide, and also iron oxide, chromium oxide, manganese violet, ultramarine blue, chromium hydrate and ferric blue. Among the organic pigments that may be mentioned are carbon black, pigments of D & C type, and lakes based on cochineal carmine or on barium, strontium, calcium or aluminium.

The nacres may be chosen from white nacreous pigments such as mica coated with titanium or with bismuth oxychloride, coloured nacreous pigments such as titanium mica with iron oxides, titanium mica with, especially, ferric blue or chromium oxide, titanium mica with an organic pigment of the abovementioned type, and also nacreous pigments based on bismuth oxychloride.

The soluble dyes are, for example: caramel, Yellow 5, Acid Blue 9/Blue 1, Green 5, Green 3/Fast Green FCF 3, Orange 4, Red 4/Food Red 1, Yellow 6, Acid Red 33/Food Red 12, Red 40, cochineal carmine (CI 15850, CI 75470), Ext. Violet 2, Red 6-7, Ferric Ferrocyanide, Ultramarines, Acid Yellow 3/Yellow 10, Acid Blue 3, Yellow 10.

The liposoluble dyes are, for example, Sudan red, D&C Red 17, D&C Green 6, β-carotene, soybean oil, Sudan brown, D&C Yellow 11, D&C Violet 2, D&C Orange 5, quinoline yellow and annatto.

The invention applies not only to fragrancing products but also to products for caring for or treating the body, the skin, the face, the lips, the nails, including the hair and the scalp, containing an odoriferous substance. The composition according to the invention may thus constitute a fragrancing composition for caring for or treating keratin materials, and may especially be in the form of an eau fraiche, an eau de toilette, an eau de parfum, an aftershave lotion, a care lotion, a silicone-based or hydrosilicone-based care oil, hygiene products such as shower gels, bath products, shampoos or scrubs. It may also be in the form of a fragrancing two-phase or three-phase lotion

(eau de toilette phase/hydrocarbon-based oil and/or silicone oil and/or fluoro oil phase) .

A subject of the invention is also a cosmetic process for fragrancing human keratin materials and especially the skin, the lips and the integuments, comprising the application to the keratin materials of the composition as defined above.

The composition according to the invention may be manufactured by the known processes, generally used in the field of fragranced compositions.

The compositions according to the invention may be conditioned in the form of bottles. They may also be applied in the form of fine particles using pressurization devices. The devices in accordance with the invention are well known to those skilled in the art and comprise non-aerosol pumps or "atomizers", aerosol containers comprising a propellant, and also aerosol pumps using compressed air as propellant. These devices are described in patents US 4 077 441 and US 4 850 517.

The compositions conditioned in aerosol form in accordance with the invention generally contain conventional propellants, for instance hydrofluoro compounds, dichlorodifluoromethane, difluoroethane, dimethyl ether, isobutane, n-butane, propane or trichlorofluoromethane .

The fragrancing compositions according to the invention may be in any galenical form conventionally used for topical application and especially in the form of aqueous or aqueous-alcoholic solutions, oil-in-water (O/W) or water-in-oil (W/O) or multiple (triple: W/O/W or 0/W/O) emulsions, aqueous gels, dehydrated anhydrous products such as loose or compact fragrancing powders, or dispersions of an oily phase in an aqueous phase with the aid of lipid vesicles of ionic type (liposomes) and/or nonionic type. These compositions are prepared according to the usual methods.

In addition, the compositions according to the invention may be more or less fluid and may have the appearance of a cream, an ointment, a milk, a lotion, a serum, a paste or a mousse. They may also be in solid form, for example in stick form.

When the composition according to the invention comprises an oily phase, it preferably contains at least one oil, especially a physiologically acceptable oil. It may also contain other fatty substances.

As oils that may be used in the composition of the invention, examples that may be mentioned include:

- hydrocarbon-based oils of animal origin, such as perhydrosqualene; hydrocarbon-based oils of plant origin, such as liquid triglycerides of fatty acids containing from 4 to 10 carbon atoms, for instance heptanoic or octanoic acid triglycerides, or alternatively, for example, sunflower oil, corn oil, soybean oil, marrow oil, grapeseed oil, sesameseed oil, hazelnut oil, apricot oil, macadamia oil, arara oil, castor oil, avocado oil, caprylic/capric acid triglycerides, for instance those sold by the company Stearineries Dubois or those sold under the names Miglyol 810, 812 and 818 by the company Dynamit Nobel, jojoba oil and shea butter oil; - synthetic esters and ethers, especially of fatty acids, for instance the oils of formulae RiCOOR₂ and RiOR₂ in which Ri represents a fatty acid residue containing from 8 to 29 carbon atoms and R₂ represents a branched or unbranched hydrocarbon-based chain containing from 3 to 30 carbon atoms, for instance Purcellin oil, isononyl isononanoate, isopropyl myristate, 2-ethylhexyl palmitate, 2-octyldodecyl stearate, 2-octyldodecyl erucate or isostearyl isostearate; hydroxylated esters, for instance isostearyl lactate, octyl hydroxystearate, octyldodecyl hydroxystearate, diisostearyl malate or triisocetyl citrate; fatty alcohol heptanoates, octanoates or decanoates; polyol esters, for instance propylene glycol dioctanoate, neopentyl glycol diheptanoate and diethylene glycol diisononanoate; and pentaerythritol esters, for instance pentaerythrityl tetraisostearate; linear or branched hydrocarbons, of mineral or synthetic origin, such as volatile or non-volatile liquid paraffins, and derivatives thereof, petroleum jelly, polydecenes, and hydrogenated polyisobutene such as Parleam oil;

- fatty alcohols containing from 8 to 26 carbon atoms, for instance cetyl alcohol, stearyl alcohol and a mixture thereof (cetylstearyl alcohol) , octyldodecanol, 2-butyloctanol, 2-hexyldecanol, 2-undecylpentadecanol, oleyl alcohol or linoleyl alcohol;

- fluoro oils that are partially hydrocarbon- based and/or silicone-based, for instance those described in document JP-A-2 295 912; silicone oils, for instance volatile or non^¬ volatile polymethylsiloxanes (PDMS) with a linear or cyclic silicone chain, which are liquid or pasty at room temperature, especially cyclopolydimethylsiloxanes

(cyclomethicones) such as cyclohexasiloxane; polydimethylsiloxanes comprising alkyl, alkoxy or phenyl groups, which are pendent or at the end of a silicone chain, these groups containing from 2 to 24 carbon atoms; phenylsilicones, for instance phenyl trimethicones, phenyl dimethicones, phenyltrimethyl- siloxydiphenylsiloxanes, diphenyl dimethicones, diphenylmethyldiphenyltrisiloxanes or 2-phenylethyl trimethylsiloxy silicates, and polymethylphenyl- siloxanes; mixtures thereof.

In the list of oils mentioned above, the term "hydrocarbon-based oil" means any oil mainly comprising carbon and hydrogen atoms, and possibly ester, ether, fluoro, carboxylic acid and/or alcohol groups.

The other fatty substances that may be present in the oily phase are, for example, fatty acids containing from 8 to 30 carbon atoms, for instance stearic acid, lauric acid, palmitic acid and oleic acid; waxes, for instance lanolin wax, beeswax, carnauba wax or candelilla wax, paraffin wax, lignite wax or microcrystalline waxes, ceresin or ozokerite, and synthetic waxes, for instance polyethylene waxes and Fischer-Tropsch waxes; silicone resins such as trifluoromethyl-Cl-4-alkyl dimethicone and trifluoropropyl dimethicone; and silicone elastomers, for instance the products sold under the name KSG by the company Shin-Etsu, under the name Trefil, BY29 or EPSX by the company Dow Corning, or under the name Gransil by the company Grant Industries.

These fatty substances may be chosen in a varied manner by a person skilled in the art so as to prepare a composition having the desired properties, for example in terms of consistency or texture.

The emulsions generally contain at least one emulsifier chosen from amphoteric, anionic, cationic and nonionic emulsifiers, used alone or as a mixture. The emulsifiers are chosen in an appropriate manner according to the continuous phase of the emulsion to be obtained (W/0 or 0/W) . When the emulsion is a multiple emulsion, it generally comprises an emulsifier in the primary emulsion and an emulsifier in the external phase into which the primary emulsion is introduced.

As emulsions that may be used for the preparation of the W/O emulsions, examples that may be mentioned include alkyl esters or ethers of sorbitan, of glycerol or of sugars; silicone surfactants, for instance dimethicone copolyols, such as the mixture of cyclomethicone and of dimethicone copolyol, sold under the names DC 5225 C and DC 3225 C by the company Dow Corning, and alkyldimethicone copolyols such as the laurylmethicone copolyol sold under the name Dow Corning 5200 Formulation Aid by the company Dow Corning, cetyldimethicone copolyol sold under the name Abil EM 9OR by the company Goldschmidt and the mixture of polyglyceryl-4 isostearate/cetyldimethicone copolyol/hexyl laurate sold under the name Abil WE 09R by the company Goldschmidt. One or more co-emulsifiers may also be added thereto, which may be chosen advantageously from the group comprising branched-chain fatty acid esters of polyols, and especially branched- chain fatty acid esters of glycerol and/or of sorbitan, for example polyglyceryl isostearate, such as the product sold under the name Isolan GI 34 by the company Goldschmidt, sorbitan isostearate, such as the product sold under the name Arlacel 987 by the company ICI, and sorbitan glyceryl isostearate, such as the product sold under the name Arlacel 986 by the company ICI, and mixtures thereof.

As emulsifying agents that may be used for the preparation of 0/W emulsions, examples that may be mentioned include nonionic emulsifiers such as oxyalkylenated (more particularly polyoxyethylenated) fatty acid esters of polyols, for example polyethylene glycol stearates, for instance PEG-100 stearate, PEG-50 stearate and PEG-40 stearate; and mixtures thereof, such as the mixture of glyceryl monostearate and of polyethylene glycol stearate (100 EO) sold under the name Simulsol 165 by the company SEPPIC; oxyalkylenated fatty acid esters of sorbitan comprising, for example, from 20 to 100 EO, for example those sold under the trade names Tween 20 or Tween 60 by the company Uniqema; oxyalkylenated (oxyethylenated and/or oxypropylenated) fatty alcohol ethers; sugar esters, for instance sucrose stearate; and mixtures thereof, for instance the mixture of glyceryl stearate and of PEG-100 stearate, sold under the name Arlacel 165 by the company Uniqema.

Co-emulsifiers may be added to these emulsifiers, for instance fatty alcohols containing from 8 to 26 carbon atoms, for instance cetyl alcohol, stearyl alcohol and the mixture thereof (cetearyl alcohol) , octyldodecanol, 2-butyloctanol, 2-hexyldecanol, 2-undecylpentadecanol or oleyl alcohol.

Emulsions free of emulsifying surfactants or containing less than 0.5% of emulsifying surfactants relative to the total weight of the composition may also be prepared, by using suitable compounds, for example polymers having emulsifying properties, such as the polymers sold under the names Carbopol 1342 and Pemulen by the company Noveon; or polymers and copolymers of 2- acrylamido 2-methylpropane sulfonic acid, optionally crosslinked and/or neutralized, such as the poly (2- acrylamido 2-methylpropane sulfonic acid) sold by the company Clariant under the name Hostacerin AMPS (CTFA name: ammonium polyacryldimethyltauramide) or polymers in emulsion form such as the product sold under the name Sepigel 305 by the company SEPPIC (INCI name: polyacrylamide/C13-C14 isoparaffin/laureth-7) ; particles of ionic or nonionic polymers, more particularly particles of anionic polymer such as, especially, isophthalic acid or sulfoisophthalic acid polymers, and in particular the phthalate/sulfoisophthalate/glycol copolymers (for example diethylene glycol/phthalate/isophthalate/ 1, 4-cyclohexanedimethanol (INCI name: diglycol/CHDM/ isophthalates/SIP copolymer) sold under the names Eastman AQ polymer (AQ35S, AQ38S, AQ55S and AQ48 Ultra) by the company Eastman Chemical.

Emulsifier-free emulsions stabilized with silicone particles or metal oxide particles such as TiO₂ or the like may also be prepared.

As fillers that may be used in the composition of the invention, examples that may be mentioned, besides pigments, include silica powder; talc; polyamide particles and especially those sold under the name Orgasol by the company Atochem; polyethylene powders; powders of natural organic materials such as starch powders, especially corn starch, wheat starch or rice starch, which may be crosslinked or non-crosslinked, such as the powders of starch crosslinked with octenyl succinate anhydride, sold under the name Dry-Flo by the company National Starch; microspheres based on acrylic copolymers, such as those based on a copolymer of ethylene glycol dimethacrylate/lauryl methacrylate sold by the company Dow Corning under the name Polytrap; expanded powders such as hollow microspheres, and especially the microspheres sold under the name Expancel by the company Kemanord Plast or under the name Micropearl F 80 ED by the company Matsumoto; silicone resin microbeads such as those sold under the name Tospearl by the company Toshiba Silicone; and mixtures thereof. These fillers may be present in amounts ranging from 0 to 20% by weight and preferably from 1% to 10% by weight relative to the total weight of the composition.

The invention will now be described with reference to the following examples, which are given as non-limiting illustrations. In these examples, unless otherwise indicated, the amounts are expressed as weight percentages. The following fragranced formulations were prepared; the amounts are indicated as weight percentages :

EXAMPLES Ia, Ib, Ic

COMPARATIVE TESTS OF STABILITY OF THE ODOUR AND COLOUR

Principle

The principle of these tests consists in exposing the test products to an irradiating light source whose spectral distribution is fully defined and whose emitted energy is fully quantified. The light sources commonly used are xenon lamps emitting through:

- a platinized quartz filter, which diverts the infrared radiation and eliminates it via the top of the device, and a glass filter, which, by absorbing the short ultraviolet radiation, makes it possible to simulate the radiation received behind a display glass.

Equipment

A CPS Sun-test machine is used:

- the lighting provided by a xenon lamp between 300 and 800 nm is set at 765 W/m² (value set by the manufacturer) ,

- the optical filtration is provided by a quartz filter with IR coating and special glazing glass) .

The colour of each bottle before and after exposure to the light from the Sun-test machine after 16 hours at room temperature is observed with the naked eye.

A "sniff test" olfactory test is also performed with a panel of 5 individuals on the samples at T₀ at 45⁰C and after 2 months at 45⁰C.

Summary table of the tests:

Composition la(*) lb(*) Ic

(invention)

Fragrance concentrate 15% 15% 15%

Ethanol 65% 65% 65%

Dyes qs qs qs

35/65 mixture of n-hexyl 2-(4- 0.6 - - diethylamino-2- hydroxybenzoyl) benzoate and of ethylhexyl methoxycinnamate (Uvinul A + B)

Ethylhexyl methoxycinnamate - 1 0.4

(Parsol MCX) Butylmethoxydibenzoylmethane 0.2 0.3 0.1

(Parsol 1789) Ethylhexyl salicylate 0.1 - 0.08

(Neo Heliopan OS)

Bumetrizole - compound (4) - - 0.03 (Tinoguard AS)

Water qs 100% qs 100% qs 100%

(*) outside the invention

35/65 mixture of n-hexyl 2- (4-diethylamino-2- hydroxybenzoyl) benzoate and of ethylhexyl methoxycinnamate (Uvinul A + B)

Results :

Test Ia

Result at T₀: production of a beige-coloured fragrance of pleasant odour.

The mixture Uvinul A+B/Parsol 1789/ethylhexyl salicylate is coloured. The colour of the desired fragrance was pale pink.

Result of the sun test at 16 hours: good resistance of the beige colour.

Observation after 2 months at 45⁰C: acceptable change in the odour. No change in the beige colour.

The stability of the desired initial colour is not achievable with this combination of screening agents.

Test Ib:

Result at T₀: production of a pale pink fragrance of pleasant odour. O Q

Result of the sun test at 16 hours: degradation of the colour = decolourization

Observation after 2 months at 45⁰C: very marked impairment of the odour and of the colour, changing to beige.

Test Ic (according to the invention) :

Result at T₀: production of a pink fragrance of pleasant odour.

Result of the sun test at 16 hours: maintenance of the initial pink colour.

Observation after 2 months at 45⁰C: very slight change in odour and maintenance of the initial pink colour.

It is observed that composition Ic according to the invention comprising the colourless combination of Bumetrizole/ethylhexyl methoxycinnamate/butylmethoxy- dibenzoylmethane/ethylhexyl salicylate has a stable odour and colour on exposure to light and after storage at 45⁰C, unlike compositions Ia and Ib (outside the invention) .

EXAMPLES 2a, 2b, 2c

Composition 2a(*) 2b(*) 2c

(invention)

Fragrance concentrate 15% 15% 15%

Ethanol 65% 65% 65%

Dyes qs qs qs

35/65 mixture of n-hexyl 2-(4- 0.6 - - diethylamino-2- hydroxybenzoyl) benzoate and of ethylhexyl methoxycinnamate

(Uvinul A + B)

Ethylhexyl methoxycinnamate (Parsol MCX) Butylmethoxydibenzoylmethane 0.2 0.2 0.2 (Parsol 1789)

Octocrylene - - 0.6

(Uvinul N539) Ethylhexyl salicylate 0.1

(Neo Heliopan OS)

Bumetrizole - compound (4) - - 0.03 (Tinoguard AS)

Water qs 100% qs 100% qs 100%

(*) outside the invention

Results :

Test 2a

Result at T₀: production of a beige-coloured fragrance of pleasant odour.

The mixture Uvinul A+B/Parsol 1789/ethylhexyl salicylate is coloured. The desired colour of the fragrance was pale pink.

Result of the sun test at 16 hours: good resistance of the beige colour.

Test 2b:

Result at T₀: production of a pale pink fragrance of pleasant odour.

Result of the sun test at 16 hours: degradation of the colour = decolourization . Observation after 2 months at 45⁰C: very marked impairment in the odour and the colour, which turns beige .

Test 2c (according to the invention) : Result at T₀: production of a pink fragrance of pleasant odour.

Result of the sun test at 16 hours: maintenance of the initial pink colour. Observation after 2 months at 45⁰C: very slight change in odour and maintenance of the initial pink colour.

It is observed that composition 2c according to the invention comprising the colourless combination of Bumetrizole/Octocrylene/butylmethoxydibenzoylmethane proves to be very efficient in terms of stabilizing the odour and the colour and does not impair the initial colours of the formula, unlike compositions 2a and 2b (outside the invention) .

Claims

1. Fragrancing composition comprising, in a cosmetically acceptable medium: a) at least 2% by weight of a fragrancing substance relative to the total weight of the composition; b) at least one benzotriazole compound of formula (I) below:

in which:

Ri represents a Ci-Ci₂ alkyl radical, a Ci-C₅ alkoxy radical, a Ci-C₅ alkoxycarbonyl, a C₅-C₇-cycloalkyl, a

C₆-Ci₀ aryl, an aralkyl radical or a group SO₃M,

R₃ denotes hydrogen, a Ci-Ci₂ alkyl radical, a Ci-C₅ alkoxy radical, a halogen, preferably Cl, or a hydroxyl group;

M denotes an alkali metal, alkaline-earth metal or ammonium cation, preferably Na⁺; m denotes 1 or 2; n is 0 or 1; if m = 1, then R₂ is hydrogen, a Ci-Ci₂ alkyl group that is unsubstituted or substituted with a phenyl; a C₆-Ci₀ aryl; if m = 2, then R₂ is a direct bond, a radical -(CH₂)_p- with p being an integer from 1 to 3; c) at least one UV-A screening agent of the dibenzoylmethane type; d) at least one UVB screening system constituted by (i) a mixture comprising at least one UV screening agent of the cinnamate type and at least one UV screening agent of the salicylate type; or

2. Composition according to Claim 1, in which the amount of fragrancing substance is from 3% to 50% by weight, better still from 5% to 30% and even better still from 10% to 20% by weight relative to the total weight of the composition.

3. Composition according to Claim 1 or 2, in which the compound of formula (I) is chosen from the following compounds:

(i) Sodium benzotriazolylbutylphenol sulfonate of formula (1)

( i i ) Benz otriaz olyldodecyl-p-cresol of formula ( 2 ^'

( i i i ) Bumetri z ole of formula ( 3 ) :

4. Composition according to any one of Claims 1 to 3, in which the compound of formula (I) is Bumetrizole of formula (3) :

5. Composition according to any one of Claims 1 to 4, in which the cinnamate compound is ethylhexyl methoxycinnamate of formula (B) below:

6. Composition according to any one of Claims 1 to 5, in which the dibenzoylmethane compound is 4- (tert- butyl) -4' -methoxydibenzoylmethane or butylmethoxy- dibenzoylmethane of formula (C) below:

7. Composition according to Claim 6, in which the salicylate compound is ethylhexyl salicylate of formula (D) below:

8. Composition according to any one of Claims 1 to 7, in which the alkyl β, β ' -diphenylacrylate or alkyl α-cyano-β, β ' -diphenylacrylate compound corresponds to formula (II) below:

in which:

- R₄ and R₅, which may be identical or different, are in a meta or para position and are chosen from: hydrogen; a Ci-C₈ alkoxy radical with a straight or branched chain; a Ci-C₄ alkyl radical with a straight or branched chain; - R₆ represents a Ci-Ci₂ alkyl radical with a straight or branched chain;

- R₇ represents a hydrogen atom or a -CN radical.

9. Composition according to Claim 8, in which the compound of formula (II) is 2-ethylhexyl α-cyano-β, β ' - diphenylacrylate, also known as Octocrylene, having the following formula:

in which φ denotes a phenyl radical.

10. Composition according to any one of Claims 1 to 9, in which the cosmetically acceptable medium contains at least one volatile alcohol and/or a volatile silicone oil and optionally water.

11. Composition according to Claim 10, in which the volatile alcohols are chosen from Ci-C₅ lower monoalcohols and more particularly ethanol.

12. Composition according to any one of Claims 1 to 11, characterized in that it is in the form of an eau fraiche, an eau de toilette, an eau de parfum, an aftershave lotion, a care lotion, a silicone-based or hydrosilicone-based care oil, a hygiene product; a fragrancing two-phase or three-phase lotion; which is conditioned in the form of a bottle or in the form of a non-aerosol pump or an aerosol container.

13. Use of a combination of at least one benzotriazole compound of formula (I), of at least one UV-A screening agent of the dibenzoylmethane type; of at least one UVB screening system as defined in the preceding claims, in a fragrancing composition comprising, in a cosmetically acceptable medium, at least 2% by weight of a fragrancing substance relative to the total weight of the composition; as an agent for stabilizing the organoleptic properties of the composition against external attacking factors, especially light or differences in temperature, in particular the colour and/or odour of the said composition.

14. Process for stabilizing the organoleptic properties, especially the colour and/or odour of a fragrancing composition, comprising, in a cosmetically acceptable medium, at least 2% by weight of a fragrancing substance relative to the total weight of the composition, characterized in that it consists in adding to the composition a combination of at least one benzotriazole compound of formula (I), of at least one UV-A screening agent of the dibenzoylmethane type; of at least one UVB screening system as defined in the preceding claims.

15. Cosmetic process for fragrancing human keratin materials, comprising the application to the keratin materials of the composition as defined in Claims 1 to 13.