WO2023275142A1 - Fragranced cosmetic composition comprising at least one organic acid ester, an anthocyani(di)n dye and a fragrancing material - Google Patents

Fragranced cosmetic composition comprising at least one organic acid ester, an anthocyani(di)n dye and a fragrancing material Download PDF

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Publication number
WO2023275142A1
WO2023275142A1 PCT/EP2022/067896 EP2022067896W WO2023275142A1 WO 2023275142 A1 WO2023275142 A1 WO 2023275142A1 EP 2022067896 W EP2022067896 W EP 2022067896W WO 2023275142 A1 WO2023275142 A1 WO 2023275142A1
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group
hydroxyl
chosen
sugar
formula
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PCT/EP2022/067896
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French (fr)
Inventor
Christophe BOBIN
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L'oreal
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    • A—HUMAN NECESSITIES
    • A61—MEDICAL OR VETERINARY SCIENCE; HYGIENE
    • A61K—PREPARATIONS FOR MEDICAL, DENTAL OR TOILETRY PURPOSES
    • A61K8/00—Cosmetics or similar toiletry preparations
    • A61K8/18—Cosmetics or similar toiletry preparations characterised by the composition
    • A61K8/30—Cosmetics or similar toiletry preparations characterised by the composition containing organic compounds
    • A61K8/33—Cosmetics or similar toiletry preparations characterised by the composition containing organic compounds containing oxygen
    • A61K8/36—Carboxylic acids; Salts or anhydrides thereof
    • A61K8/365—Hydroxycarboxylic acids; Ketocarboxylic acids
    • A—HUMAN NECESSITIES
    • A61—MEDICAL OR VETERINARY SCIENCE; HYGIENE
    • A61K—PREPARATIONS FOR MEDICAL, DENTAL OR TOILETRY PURPOSES
    • A61K8/00—Cosmetics or similar toiletry preparations
    • A61K8/18—Cosmetics or similar toiletry preparations characterised by the composition
    • A61K8/30—Cosmetics or similar toiletry preparations characterised by the composition containing organic compounds
    • A61K8/33—Cosmetics or similar toiletry preparations characterised by the composition containing organic compounds containing oxygen
    • A61K8/37—Esters of carboxylic acids
    • A61K8/375—Esters of carboxylic acids the alcohol moiety containing more than one hydroxy group
    • A—HUMAN NECESSITIES
    • A61—MEDICAL OR VETERINARY SCIENCE; HYGIENE
    • A61K—PREPARATIONS FOR MEDICAL, DENTAL OR TOILETRY PURPOSES
    • A61K8/00—Cosmetics or similar toiletry preparations
    • A61K8/18—Cosmetics or similar toiletry preparations characterised by the composition
    • A61K8/30—Cosmetics or similar toiletry preparations characterised by the composition containing organic compounds
    • A61K8/63—Steroids; Derivatives thereof
    • A—HUMAN NECESSITIES
    • A61—MEDICAL OR VETERINARY SCIENCE; HYGIENE
    • A61Q—SPECIFIC USE OF COSMETICS OR SIMILAR TOILETRY PREPARATIONS
    • A61Q13/00—Formulations or additives for perfume preparations

Definitions

  • the present invention is directed towards proposing a novel fragranced cosmetic composition, notably for the field of fragrancing keratin materials and/or clothing, but also for caring for and/or making up keratin materials.
  • perfume it is common practice to incorporate perfume into a certain number of products or compositions, in particular cosmetic and dermatological compositions such as eaux fraiches, eaux de toilette, eaux de perfume, perfume elixirs or extracts, aftershave lotions, care fluids or two-phase lotions.
  • cosmetic and dermatological compositions such as eaux fraiches, eaux de toilette, eaux de perfume, perfume elixirs or extracts, aftershave lotions, care fluids or two-phase lotions.
  • perfumes are coloured by adding an effective amount of dyestuff to the formulation support (which is generally alcoholic or aqueous- alcoholic) rather than tinting or lacquering the bottle, which is a more expensive industrial operation.
  • formulation support which is generally alcoholic or aqueous- alcoholic
  • Dyestuffs that may be mentioned more particularly include water-soluble dyes that are natural or of natural origin.
  • water-soluble dyes natural anthocyanin dyes, belonging to the family of polyphenols or ortho-diphenols and flavonoids, have already been widely used in the pharmaceutical and food industries. These compounds are essentially the source of the mauve, red, blue and purple colours of flowers, leaves, fruit such as grapes, blackberries and plums, vegetables such as red cabbage, red radish or purple sweet potato, seeds and roots.
  • anthocyanin and anthocyanidin derivatives form during the preparation and ageing of wine, including flavanol/anthocyanin adducts with the presence of bridges bearing two carbon atoms originating from the oxidation of ethanol (He, J., Oliveira, et al. J. Agric. Food Chem, 58 (15), 8814-8819 (2010), de Freitas, V.; Mateus, N. Anal. Bioanal. Chem., 2011, 401 (5), 1463-1473 (2011), and Trouillas P. et al., Chem. Rev., 116, 4937-4982 (2016)).
  • fragranced compositions notably including dyes, comprising UV- screening agents as stabilizer, alone or in combination, in particular of the alkyl b,b’- diphenylacrylate or alkyl a-cyano-b,b’ -diphenyl aery late type, such as octocrylene, dibenzoylmethane derivatives, cinnamates or alternatively camphor and triazine derivatives, but also certain particular benzotriazole compounds, or screening agents of the aminobenzophenone type.
  • dyes comprising UV- screening agents as stabilizer, alone or in combination, in particular of the alkyl b,b’- diphenylacrylate or alkyl a-cyano-b,b’ -diphenyl aery late type, such as octocrylene, dibenzoylmethane derivatives, cinnamates or alternatively camphor and triazine derivatives, but also certain particular benzotriazole compounds, or screening agents of the amino
  • screening agents such as alkyl b,b’ -diphenylacrylate or alkyl a-cyano- b,b’ -diphenylacrylate compounds, for instance octocrylene, are not always satisfactory for stabilizing the tints while at the same time maintaining the odour of the perfumes.
  • octocrylene alkyl b,b’ -diphenylacrylate or alkyl a-cyano- b,b’ -diphenylacrylate compounds, for instance octocrylene
  • Synthetic screening agents such as ethylhexyl methoxycinnamate
  • Synthetic screening agents are also not satisfactory for stabilizing dyestuffs, in particular in terms of conservation of the colour intensity and/or of the chromaticity of the coloured solution with respect to light and/or over time
  • piperidinol derivatives have the drawback of causing yellowing in eaux de toilette and also a spurious odour with a “chemical” connotation.
  • Benzotriazole compounds in particular bumetrizole, are, for their part, difficult to dissolve in eaux de toilette and have a tendency to recrystallize over time, in addition to having low stabilizing power. Finally, aminobenzophenone screening agents give a yellow colour that is not desirable for pale-coloured fragranced formulations other than yellow.
  • sunscreens proposed to date such as ethylhexyl methoxycinnamate, are synthetic.
  • WO 2017/162 599 describes the stabilization of water-soluble natural dyes or dyes of natural origin using specific polymeric surfactants and/or fillers.
  • WO 2009/031 051 proposes to stabilize anthocyanin extracts with a stabilizing compound comprising a thiol group, in the food composition sector.
  • certain dyestuffs contained in coloured fragranced compositions may leave traces when they are applied to keratin materials and/or clothing, and in particular may have the drawback of staining clothing.
  • the need remains for coloured fragranced cosmetic compositions for which the evolution of the organoleptic properties, namely the odour and/or the colour, in particular at least the colour, is controlled over time, and this being achieved if possible by means of compounds which adhere to at least one of the twelve principles of green chemistry.
  • compositions whose formulation adheres to at least one of the twelve principles of green chemistry, in particular comprising ingredients derived from green chemistry.
  • the present invention is specifically directed towards meeting these needs.
  • the present invention relates to a fragranced composition, notably a cosmetic composition, comprising: a) at least one organic acid ester of formula (I), or a geometrical isomer thereof, organic or mineral acid or base salts thereof, or solvates thereof, in particular hydrates:
  • R 1 , R 4 and R 5 represent, independently of each other, a hydrogen atom or a hydroxyl group, preferably a hydrogen atom;
  • R 2 represents a hydrogen atom, a hydroxyl group or a (C 1 -C 6 )alkoxy group, preferably a (Ci- C4)alkoxy group, in particular methoxy;
  • R 3 represents a hydroxyl group or a (C 1 -C 6 )alkoxy group, preferably a hydroxyl group; and R 6 represents a group chosen from: i) (C 1 -C 6 )alkyl, preferably (C 1 -C 4 )alkyl, in particular methyl or ethyl, optionally substituted with one or more groups chosen from hydroxyl, amino, carboxyl and/or amido, preferably hydroxyl and/or carboxyl, ii) cycloalkyl, optionally substituted with one or more groups chosen from (Ci- Cio)alkyl, (C2-Cio)alkenyl, hydroxyl, amino, carboxyl and/or amido, preferably hydroxyl and/or carboxyl, and iii) glycosyl, b) at least one water-soluble dye that is natural or of natural origin chosen from anthocyani(di)ns and derivatives thereof; and c) at least one fragrancing substance
  • the inventors have found, surprisingly, that the combination of an organic acid ester of formula (I) as defined above, in a fragranced composition, with at least one fragrancing substance and at least one water-soluble dye that is natural or of natural origin of anthocyanidin or anthocyanidin derivative type allows efficient stabilization of said composition.
  • the composition according to the invention is stable, in the sense that the evolution of the colour of the composition remains low over time, even under conditions simulating accelerated ageing of the composition, notably in aqueous -alcoholic medium, and with respect to light.
  • the invention also relates to the use of an organic acid ester of formula (I), as a stabilizer in a fragranced composition, notably a cosmetic composition, notably an aqueous or aqueous-alcoholic composition, also comprising at least one water-soluble dye that is natural or of natural origin chosen from anthocyani(di)ns and derivatives thereof, and at least one fragrancing substance.
  • a fragranced composition notably a cosmetic composition, notably an aqueous or aqueous-alcoholic composition, also comprising at least one water-soluble dye that is natural or of natural origin chosen from anthocyani(di)ns and derivatives thereof, and at least one fragrancing substance.
  • a composition according to the invention is in particular intended for the cosmetic treatment of keratin materials.
  • the invention relates to a cosmetic process for treating keratin materials, in particular the skin, comprising at least one step of applying a composition according to the invention to said keratin materials.
  • the invention also relates to a cosmetic process for treating keratin materials, in particular the skin, or clothing, comprising at least one step of applying a fragranced composition according to the invention to said keratin materials and/or said clothing.
  • a composition according to the invention is notably intended to be used in order to fragrance keratin materials and/or clothing.
  • the invention also relates to a process for fragrancing keratin materials, notably the skin, and/or clothing, comprising the application of the composition as defined above to said keratin materials and/or to said clothing.
  • the composition may be applied by spraying, notably using a spray.
  • composition according to the invention is notably intended for use for caring for and/or making up keratin materials.
  • the invention also relates to a process for caring for and/or making up keratin materials, notably the skin, comprising the application of the composition as defined above to said keratin materials.
  • fragranced composition or ‘ fragrancing composition” is intended to denote any composition which leaves a perfume on keratin materials after application.
  • a perfume is the result of a combination of different odorous substances which each provide a specific diffusing odour or “note” and which respectively evaporate at different periods. More precisely, each perfume has what is known as a “ head note”, which is the odour that diffuses first when the perfume is applied or when the receptacle containing it is opened, a “ heart or body note”, which corresponds to the full fragrance (given off for a few hours after the “ head note”) and a “base note”, which is the most persistent odour (given off for several hours after the “ body note”). The persistence of the base note corresponds to the remanence of the perfume.
  • head note is the odour that diffuses first when the perfume is applied or when the receptacle containing it is opened
  • a “ heart or body note” which corresponds to the full fragrance (given off for a few hours after the “ head note”)
  • a “base note” which is the most persistent odour (given off for several hours after the “ body
  • keratin materials is notably intended to denote the skin, the lips, the hair, the scalp, the eyelashes and the eyebrows or else the nails, in particular the skin and/or the lips, and preferably the skin.
  • a fragranced composition according to the invention is said to be “coloured” .
  • coloured composition means a composition which appears to the human eye to have a colour of the visible spectrum, i.e. which appears to the eye as different from white or colourless, namely a composition which absorbs in the yellow, orange, red, purple, violet, blue and green ranges.
  • Such a composition may be opaque or clear, preferably clear.
  • the term “clear” means that the composition is transparent, i.e. it allows light to pass through and objects that are located behind it are seen in sharp definition.
  • a conventional commercial untinted, transparent borosilicate, soda-lime or neutral glass test tube such as a test tube made of Pyrex ® or Duran ® glass, 16 cm tall and 1.6 cm in diameter is taken and is filled to 14 cm of said tube (the bottom of the meniscus of the composition in the tube is located 14 cm from the bottom of the tube), and a page of published international patent application (in A4 format) is placed behind it at a distance of 1 cm; and by placing the eyes at a distance (reading focal length relative to the test tube) of between 20 cm and 40 cm, such as 30 cm, and perpendicular to the middle of the composition of said tube (about 7 cm from the bottom of said tube), an evaluation is made as to whether or not it is possible to read distinctly said page of the published international patent application, notably the first page, through the composition in said tube.
  • the tester has good vision, or that he is equipped with spectacles, contact lenses or any other optical devices that he normally wears for reading.
  • Use may be made, for example, of patent application WO 2018/104 428 and evaluate the sharpness, i.e. the ability to read the 31 lines of page 13 to perform the test or, better still, to perform the reading test on the first page.
  • dye or “ dyestuff ’ is intended to denote any compound that is capable of colouring the fragranced composition, i.e. any compound which absorbs in the visible spectrum, in particular so as to appear to the human eye to have a colour such as yellow, orange, red, violet, blue or green.
  • a fragranced coloured composition may be in any form that is suitable for its application to keratin materials and/or clothing. It may notably be in liquid or solid form, for example in powder form.
  • powder means a composition in pulverulent form, which is preferably essentially free of dust.
  • the particle size distribution of the particles is such that the weight content of particles which have a size of less than or equal to 50 pm (content of fines), preferably less than or equal to 10 pm (content of fines) is advantageously less than or equal to 5%, preferably less than 2% and more particularly less than 1% (particle size evaluated using a Retsch AS 200 Digit particle size analyser; oscillation height: 1.25 mm/screening time: 5 minutes).
  • the particle size is between 10 pm and 500 pm.
  • the powder of solid natural material(s) may be screened to obtain particles with upper limit sizes corresponding to the orifices or mesh sizes of the screen particularly between 35 and 80 mesh (US).
  • the size of the particles of the powder of solid natural material(s) is fine. According to the invention, this more particularly means a particle size of less than or equal to 900 pm.
  • the powder is constituted of fine particles between 7 and 700 pm and better still between 100 nm and 500 pm in size.
  • ‘‘ fragrancing substance ” means any odorous starting material or aroma that is capable of giving off a pleasant odour, in particular as defined in the continuation of the text.
  • ‘fragrancing” , “ odorous ” or “ odoriferous ” substances are synonymous.
  • a composition according to the invention is generally suitable for application to keratin materials, in particular topical application to the skin, and thus generally comprises a physiologically acceptable medium, i.e. a medium that is compatible with the skin.
  • a cosmetically acceptable medium i.e. a medium which has a pleasant colour, odour and feel and which does not cause any unacceptable discomfort, i.e. stinging, tautness or redness, liable to discourage the user from applying this composition.
  • a “ stabilizer ” is intended to denote a compound that is capable of stabilizing the fragranced composition comprising same, in particular in terms of conservation of its organoleptic properties with respect to external attacking factors, notably to light, or temperature or oxygen differences, in particular the colour and/or the odour of said composition.
  • a (C x -C z )alkyl group represents a linear or branched hydrocarbon-based chain comprising from x to z carbon atoms.
  • a (C 1 -C 6 )alkyl group represents a linear or branched hydrocarbon-based chain comprising from 1 to 6 carbon atoms.
  • a (C x -C z )alkenyl group represents a linear or branched hydrocarbon-based chain comprising from x to z carbon atoms, and comprising one or more conjugated or non-conjugated unsaturations, preferably only one unsaturation.
  • a (C 2 -C 10 )alkenyl group represents a linear or branched hydrocarbon-based chain comprising from 2 to 10 carbon atoms and comprising one or more unsaturations.
  • a (C x -C z )alkoxy group represents a radical -O-(C x -C z )alkyl in which the (C x -C z )alkyl group is as defined previously.
  • cycloalkyl means a fused or non-fused, more preferentially fused, saturated or unsaturated, preferably saturated, non-aromatic, monocyclic or polycyclic carbocycle (cyclic hydrocarbon-based group), preferably of between 2 and 5 rings, comprising from 5 to 42 carbon atoms, in particular comprising from 6 to 10 carbon atoms.
  • aryl means a monocyclic or fused or non-fused polycyclic carbocycle comprising from 6 to 22 carbon atoms, and in which at least one ring is aromatic; preferentially, the aryl radical is a phenyl, biphenyl, naphthyl, indenyl, anthracenyl or tetrahydronaphthyl, preferably phenyl.
  • glycosyl group is intended to denote a monovalent radical obtained from a monosaccharide or polysaccharide by replacement of one of the hemiacetal hydroxyl groups of said monosaccharide or polysaccharide with a covalent bond with the compound bearing the group.
  • the term “natural ” is intended to denote any compound obtained directly from the earth or the soil, or from plants or animals, via, where appropriate, one or more physical processes, for instance milling, refining, distillation, purification or filtration, or else from a biotechnological process, notably obtained from microbiological or cell cultures, for example from fungi or from bacteria.
  • the “natural ” dyes or pigments are compounds that are present in nature and that can be reproduced by chemical (semi)synthesis.
  • the term “of natural origin” is intended to denote any compound obtained from a natural substance which has undergone one or more associated chemical or industrial treatments, giving rise to changes which do not affect the essential qualities of this substance.
  • additional chemical or industrial treatments bringing about modifications which do not affect the essential qualities of a natural compound, mention may be made of those permitted by the controlling bodies, such as Ecocert (Reference system for organic and ecological cosmetic products, January 2003), or defined in recognized handbooks in the field, such as Cosmetics and Toiletries Magazine, 2005, volume 120, 9:10.
  • a compound is considered to be natural or of natural origin when it is predominantly composed of natural constituents, i.e. when the weight ratio of natural constituents to non-natural constituents which make up the compound is greater than 1.
  • the ester of formula (I) is a “ green ” compound, that is to say that it adheres to at least one of the twelve principles of green chemistry.
  • geometrical isomer is understood to denote any molecule whose constitution is identical to that of formula (I) defined above, but in which the spatial organization of the atoms is different.
  • they may be conformational stereoisomers, i.e. compounds which differ in their rotation around a single bond, or configurational stereoisomers, in particular enantiomers or diastereoisomers.
  • anionic counterion means an anion or an anionic group derived from an organic or mineral acid salt which counterbalances the cationic charge of the dye; more particularly, the anionic counterion is chosen from: i) halides such as chloride or bromide; ii) nitrates; iii) sulfonates, including C 1 -C 6 alkylsulfonates: Alk-S(O) 2 O- such as methylsulfonate or mesylate and ethylsulfonate; iv) arylsulfonates: Ar-SO) 2 O- such as benzenesulfonate and toluenesulfonate or tosylate; v) citrate; vi) succinate; vii) tartrate; viii) lactate; ix) alkyl sulfates: Alk-O-S(O)O- such as methyl sulfate and ethyl s
  • addition salts that may be used in the context of the invention are notably chosen from addition salts with a cosmetically acceptable base such as the basifying agents as defined below, for instance alkali metal hydroxides such as sodium hydroxide, potassium hydroxide, aqueous ammonia, amines or alkanolamines.
  • a cosmetically acceptable base such as the basifying agents as defined below, for instance alkali metal hydroxides such as sodium hydroxide, potassium hydroxide, aqueous ammonia, amines or alkanolamines.
  • organic or mineral acid or base salt is intended to denote a salt obtained between an ionic form of an ester of formula (I) and a corresponding counterion.
  • a salt is obtained by addition of an organic or mineral acid or base, which is notably cosmetically acceptable, to the ester of formula (I).
  • mineral bases include hydroxides or carbonates of alkali metals or alkaline-earth metals, such as sodium, potassium, calcium, ammonium, magnesium, lithium or sodium.
  • organic bases include amines or alkanolamines.
  • acids examples include hydrochloric acid, hydrobromic acid, sulfuric acid, alkylsulfonic acids, arylsulfonic acids, citric acid, succinic acid, tartaric acid, lactic acid, alkoxysulfinic acids, aryloxysulfinic acids, phosphoric acid and acetic acid.
  • solvate is intended to denote the form of the ester of formula (I) when it is associated with a solvent.
  • the solvates include conventional solvates formed during the process for the preparation of the ester of formula (I). Examples of solvates are those obtained in the presence of water or of a linear or branched alcohol, in particular ethanol or isopropanol.
  • a fragranced composition according to the invention comprises at least one organic acid ester of formula (I), or a geometrical isomer thereof, an organic or mineral acid or base salt thereof, or a solvate thereof, in particular hydrates:
  • R 1 , R 4 and R 5 represent, independently of each other, a hydrogen atom or a hydroxyl group, preferably a hydrogen atom;
  • R 2 represents a hydrogen atom, a hydroxyl group or a (C 1 -C 6 )alkoxy group, preferably a (C 1 - C 4 )alkoxy group, in particular methoxy;
  • R 3 represents a hydroxyl group or a (C 1 -C 6 )alkoxy group, preferably a hydroxyl group; and R 6 represents a group chosen from: i) (C 1 -C 6 )alkyl, preferably (C 1 -C 4 )alkyl, in particular methyl or ethyl, optionally substituted with one or more groups chosen from hydroxyl, amino, carboxyl and/or amido, preferably hydroxyl and/or carboxyl, ii) cycloalkyl, optionally substituted with one or more groups chosen from (C 1 - C 10 )alkyl, (C 2 -C 10) alkenyl, hydroxyl, amino, carboxyl and/or amido, preferably hydroxyl and/or carboxyl, and iii) glycosyl.
  • R 6 represents a (C 1 -C 6 )alkyl group i), as defined above.
  • R 6 represents a saturated or unsaturated, preferably saturated, non-aromatic monocyclic cycloalkyl group ii), comprising from 5 to 7 carbon atoms and optionally substituted with one or more (C 1 -C4)alkyl groups and/or with one or more groups chosen from hydroxyl, amino, carboxyl and/or amido, preferably hydroxyl and/or carboxyl.
  • the cycloalkyl group is cyclohexyl, optionally substituted with 1 to 5 hydroxyl and/or carboxyl groups.
  • the cycloalkyl group is cyclohexyl and is optionally substituted with one or more groups chosen from hydroxyl, amino, carboxyl and/or amido, preferably hydroxyl and/or carboxyl. More particularly, the cycloalkyl group is cyclohexyl, optionally substituted with 1 to 5 hydroxyl and/or carboxyl groups.
  • R 6 represents a polycyclic cycloalkyl group ii), preferably comprising between 2 and 5 fused rings, comprising from 12 to 32 carbon atoms and being optionally substituted; in particular, the cycloalkyl is a polycyclic group comprising between 4 and 5 fused rings, said rings being 3-, 5- or 6- membered and containing 16 to 20 carbon atoms, better still 17 or 18 carbon atoms, said cycloalkyl being optionally substituted with one or more linear or branched (C 1 -C 10 )alkyl or linear or branched (C 1 -C 10 )alkenyl groups.
  • the cycloalkyl is a polycyclic group comprising between 4 and 5 fused rings, said rings being 3-, 5- or 6- membered and containing 16 to 20 carbon atoms, better still 17 or 18 carbon atoms, said cycloalkyl being optionally substituted with one or more linear or branched (C 1 -C 10 )alkyl or linear
  • the organic acid ester is of formula (I) in which:
  • R 1 , R 4 and R 5 represent hydrogen atoms
  • R 2 represents a hydroxyl group or a (C 1 -C 6 )alkoxy group, preferably a (C 1 -C 4 )alkoxy group, in particular methoxy;
  • R 3 represents a hydroxyl group or a (C 1 -C 6 )alkoxy group
  • R 6 represents a group chosen from i) (C 1 -C 6 )alkyl, preferably (C 1 -C 4 )alkyl, and also the geometrical isomers thereof, the organic or mineral acid or base salts thereof, and the solvates thereof such as hydrates.
  • ester of formula (I) is of formula (I') below:
  • R 6 is as defined above.
  • R 7 represents a hydrogen atom or a C 1 -C 6 alkyl group.
  • the organic acid ester may more particularly be of formula (I') in which R 6 represents a (C 1 -C 6 )alkyl and preferably (C 1 -C 4 )alkyl group, preferably an ethyl group; and R 7 is a (C 1 -C 6 )alkyl and preferably (C 1 -C 4 )alkyl group, preferably a methyl group.
  • ethyl ferulate is preferred.
  • the organic acid ester may more particularly be of formula (I') in which R 6 represents a saturated monocyclic cycloalkyl group comprising from 5 to 7 carbon atoms, optionally substituted with one or more groups, preferably between 1 and 4 groups, chosen from hydroxyl and/or carboxyl; and R 7 is a hydrogen atom.
  • chlorogenic acid is preferred.
  • the organic acid ester may more particularly be of formula (I') in which R 6 represents a polycyclic group comprising between 3 and 5 saturated fused rings, comprising between 16 and 20 carbon atoms, substituted with at least one, preferably at least two, (C 1 -C 4 )alkyl groups, preferably ethyl, and with at least one, preferably one, branched (C 8 -C 10 )alkenyl or (C 8 -C 10 )alkyl group, and R 7 is a (C 1 -C 6 )alkyl and preferably (C 1 -C 4 )alkyl group, preferably a methyl group.
  • R 6 represents a polycyclic group comprising between 3 and 5 saturated fused rings, comprising between 16 and 20 carbon atoms, substituted with at least one, preferably at least two, (C 1 -C 4 )alkyl groups, preferably ethyl, and with at least one, preferably one, branched (C 8 -C
  • oryzanol and in particular Gamma-oryzanol, is particularly preferred.
  • the compounds of formulae (I) and (I') in accordance with the invention are preferably chosen from natural compounds or compounds of natural origin. They are preferably “green” compounds.
  • esters of formula (I) or (I') mention may be made of methyl ferulate, ethyl ferulate, chlorogenic acid, isopropyl ferulate or ferulic acid esters of sterols, such as oryzanol, notably gamma-oryzanol.
  • the ferulic acid esters may be obtained by esterification of ferulic acid, which is itself obtained, for example, by biosynthesis via methoxylation of caffeic acid using the enzyme caffeic acid-0 -methyl transferase , or by extraction from a plant extract, in particular wheat bran, for example using concentrated bases such as sodium hydroxide and potassium hydroxide.
  • Gamma-Oryzanol may be obtained by extraction using an organic solvent, notably from rice bran.
  • the compounds of formula (I) or (I') defined above may optionally be introduced into a fragranced composition according to the invention in the form of a plant extract.
  • a plant extract For example, Gamma-oryzanol may be used in the form of a rice bran extract.
  • Chlorogenic acid may be used in the form of an extract of green coffee, blackcurrant, sunflower, artichoke, honeysuckle, plum, apple, potato, sweet potato, blueberry, arnica or damask rose.
  • a certain number of compounds of formula (I) or (I') are also commercially available, for instance Gamma-oryzanol available under the trade name Oryzanol ® from the company Tsuno Rice Fine Chemicals, Gamma Oryzanol ® from the company Ikeda or Oryzanolgamma V ® from the company Ichimaru Pharcos, ethyl ferulate under the reference Ethyl Ferulate, Natural or COS by the company Gfn Selco, also available from Sigma-Aldrich, and chlorogenic acid under the reference Eucommia Leaves Extract Chlorogenic Acid 98% by the company Guilin Layn Natural Ingredients.
  • a composition according to the invention comprises an organic acid ester chosen from ethyl ferulate, oryzanol and in particular Gamma-oryzanol, chlorogenic acid, and mixtures thereof.
  • a fragranced composition according to the invention may comprise from 0.01% to 5.0% by weight, in particular from 0.03% to 2.0% by weight, preferably from 0.05% to 1.0% by weight and more preferentially from 0.1% to 0.8% by weight of organic acid ester(s) of formula (I), relative to the total weight of said composition.
  • the ester of formula (I) may be used in the form of a plant extract also known as a “ crude raw material ”, comprising one or more compounds of formula (I) as defined previously.
  • a fragranced composition according to the invention may comprise, for example, from 2.0% to 20% by weight of plant extract containing at least one organic acid ester of formula (I), relative to the total weight of said composition.
  • Water-soluble anthocyani(di)n dye which is natural or of natural origin
  • a fragranced composition according to the invention comprises at least one water-soluble dye that is natural or of natural origin, chosen from anthocyani(di)ns and derivatives thereof.
  • water-soluble dye denotes any natural or synthetic, generally organic dye, which is soluble in an aqueous phase or in water-miscible solvents.
  • a dye is water-soluble when its solubility in water, measured at 25 °C, is at least equal to 0.01 g/L.
  • anthocyani(di)ns and derivatives refers to any natural dye belonging to the flavonoid family in the broad sense, comprising a phenyl benzopyrylium cation. More precisely, the anthocyanidins, also known as “anthocyanidols”, cover “anthocyanidins”, i.e.
  • phenyl benzopyrylium cation as defined below including a hydroxyl group on the carbon atom in position 3 of ring C (corresponding to the radical R3 of formulae (IIA) and (lie)) and “anthocyanins” comprising an -O-Sugar group on the carbon atom in position 3 of ring C (corresponding to the radical R3 of formulae (IIA), (HB), (He) and (IID)).
  • anthocyani(di)n derivatives
  • heterosides derived from the condensation of a sugar or “saccharide” with the anthocyani(di)n molecule (non-carbohydrate molecule referred to as an “aglycone”), optionally bearing one or more acyl groups, and/or cosmetically acceptable salts thereof.
  • the heteroside derivatives of the anthocyani(di)ns are also known as anthocyans, anthocyanosides or anthocyanins.
  • acyl means that at least one hydroxyl group of a sugar undergoes the condensation (esterification) of a hydroxyl group with a carboxyl group of another molecule (i.e. of a carboxylic acid notably of formula (I) or (I') as defined previously) to form an ester bond.
  • the anthocyani(di)n natural dyes of the invention comprise in their chemical structures a phenyl benzopyrylium cation (II), notably 2-phenylchromenylium or 2- phenylbenzopyrilyum or 3-phenylchromenylium, preferably 2-phenylchromenylium having the following formula, and also the optical isomers thereof, the geometrical isomers thereof, the tautomers thereof, the organic or mineral acid or base salts thereof, and the solvates thereof such as hydrates:
  • a phenyl benzopyrylium cation II
  • 2-phenylchromenylium or 2- phenylbenzopyrilyum or 3-phenylchromenylium preferably 2-phenylchromenylium having the following formula, and also the optical isomers thereof, the geometrical isomers thereof, the tautomers thereof, the organic or mineral acid or base salts thereof, and the solvates thereof such as hydrates:
  • - ring A comprises at least one hydroxyl or -O-Sugar group, particularly two hydroxyl groups or one hydroxyl group and one -O-Sugar group, preferably located on the carbon atoms in position 5 and/or 7;
  • - ring B is connected to ring C on carbon atoms 2, 3 or 4, particularly on the carbon atoms in position 2 or 3, preferably on carbon atom 2; ring B comprises at least one hydroxyl group, particularly at least two hydroxyl groups, or at least one hydroxyl group and at least one (Ci- C 6 )alkoxy group; and
  • - ring C preferably comprises, in position 3, a hydroxyl or -O-Sugar group.
  • O-Sugar means a monosaccharide radical or a polysaccharide radical consisting of 2 to 5 saccharide units, in particular from 2 to 3 and preferably 2 saccharide units connected to the rest of the molecule via an oxygen atom.
  • the anthocyani(di)ns are substituted glycoside salts and acyl glycosides of 2-phenylbenzopyrylium.
  • the anthocyani(di)ns are of formula (IIA) below, and also the optical or geometrical isomers thereof, the tautomers thereof, the organic or mineral acid or base salts thereof, and the solvates thereof such as hydrates:
  • R3 represents a hydrogen atom or hydroxyl (OH), or -O-Sugar, preferably hydroxyl or -O- Sugar;
  • O-Sugar denoting a monosaccharide radical or a polysaccharide radical consisting of 2 to 5 saccharide units, in particular from 2 to 3 and preferably 2 saccharide units connected to the rest of the molecule via an oxygen atom; in particular, Sugar is as defined below, notably glucoside;
  • R 5 and R 7 which may be identical or different, represent a hydrogen atom or a (C 1 -C 6 )alkyl, (C 1 -C 6 )alkoxy or hydroxyl group, preferably a hydroxyl group;
  • - R 6 represents a hydrogen atom or a (C 1 -C 6 )alkyl, (C 1 -C 6 )alkoxy, (di)(C 1 -C 6 )(alkyl)amino, hydroxyl or -O-Sugar group, preferably hydrogen;
  • - R’ 3 represents a hydrogen atom or a (C 1 -C 6 )alkyl, (C 1 -C 6 )alkoxy such as methoxy, hydroxyl or -O-Sugar group; preferably a hydrogen atom or a (Ci-COalkoxy such as methoxy, or hydroxyl group;
  • - R’4 represents a hydrogen atom or a (C 1 -C 6 )alkyl, (C 1 -C 6 )alkoxy, hydroxyl or -O-Sugar group, preferably a hydroxyl group;
  • - R’ 5 represents a hydrogen atom or a (C 1 -C 6 )alkyl, (C 1 -C 6 )alkoxy such as methoxy, hydroxyl or -O-Sugar group; preferably a hydrogen atom or a (Ci-COalkoxy such as methoxy, or hydroxyl group, more preferentially a hydrogen atom; and - Q " represents an anionic counterion.
  • the sugar is attached to the oxygen atom of the -O- Sugar via carbon atom Ci of the 3- or 4-membered monosaccharide of the following -Sugar radical:
  • R a representing a hydrogen atom, a (C 1 -C 4 )alkyl group such as methyl or a (poly)hydroxy(C 1 -C 4 )alkyl group such as hydroxymethyl or 1,2-dihydroxy ethyl, the hydroxyl group(s) of the (poly)hydroxy(C 1 -C 4 )alkyl group being substituted with A as defined below; it being understood that the radical R a is in position C5 if the sugar unit is in pyranose form or in position C4 if it is in furanose form;
  • R e represents a hydrogen atom or a group -CH2-O-A, preferably hydrogen
  • R d represents a group of formula (I”):
  • R 1 to R 5 are as defined in formula (I); preferably, R d represents a caffeyl or 3, 4-dihydroxy styryl, ferulyl or 3-methoxy-4- hydroxystyryl, sinapyl or 3,5-dimethoxy-4-hydroxystyryl, 4-coumaryl or 4-hydroxystyryl group.
  • the “Sugar” radical represents a monosaccharide which may be acylated; more particularly, said sugar is chosen from pentoses such as ribose, arabinose, xylose, lyxose, ribulose or xylulose; hexoses such as allose, altrose, galactose, glucose, gulose, idose, mannose, talose, fructose, psicose, sorbose, arabinose or tagatose, and deoxyhexoses, such as fucose or rhamnose.
  • pentoses such as ribose, arabinose, xylose, lyxose, ribulose or xylulose
  • hexoses such as allose, altrose, galactose, glucose, gulose, idose, mannose, talose, fructose, psicose, sorbose, arabi
  • said “Sugar” radical represents a group which may be acylated chosen from glucose, rhamnose, xylose, galactose, arabinose and fructose, preferentially D-glucose, D-rhamnose, L-rhamnose, D-xylose, D-galactose, arabinose and fructose, and more preferentially D-glucose.
  • the dye comprises at least one -O-Sugar group in which the “Sugar” radical represents a monosaccharide which may be acylated chosen from pentoses such as ribose, arabinose, xylose, lyxose, ribulose or xylulose; hexoses such as allose, altrose, galactose, glucose, gulose, idose, mannose, tallose, fructose, psicose, sorbose, arabinose or tagatose; and deoxyhexoses such as fucose or rhamnose; the monosaccharide may be of D or L configuration, preferentially of D configuration; more particularly, said “Sugar” radical represents a group which may be acylated chosen from glucose, rhamnose and xylose, preferentially D-glucose, D-rhamnose and D-xylose, and more preferentially D- glucose
  • the -O-Sugar radical represents a monosaccharide radical chosen from -O-S 1 to -O-S 5 :
  • -O-S 1 to -O-S 5 in which one or more hydroxyl groups may be replaced with a group R d - C(O)-O-, with R d as defined previously, preferably (C 1 -C 4 )alkyl optionally substituted with a carboxyl group, such as methyl or styryl, the phenyl group of which is optionally substituted with one or more groups chosen from hydroxyl and/or (C 1 -C 4 )alkoxy such as methoxy, preferably a replacement of the hydroxyl, notably of the hydroxyl in the position of carbon C 6 of -O-S 1 and C5 of -O-S 5 ; more particularly, the -O-Sugar radical represents - O-S 1 , -O-S 4 or -O-S 5 , particularly -O-S 1 or -O-S4, and preferentially -O-Sugar represents: [Chem 9]
  • O-glucoside O-galactoside O-arabinoside preferably chosen from O-galactoside and O-glucoside, it being understood that for -O-glucoside, -O-galactoside and -O-arabinoside, a hydroxyl group may be replaced with a group -R d -C(O)-O-, with R d as defined previously, preferably (C 1 -C 4 )alkyl optionally substituted with a carboxyl group, such as methyl or styryl, the phenyl group of which is optionally substituted with one or more groups chosen from hydroxyl and/or (C 1 -C 4 )alkoxy such as methoxy, preferably the replacement of the hydroxyl, notably of the hydroxyl in the position of carbon C 6 of -O-glucoside and -O-galactoside.
  • the -O-Sugar radical represents a polysaccharide radical constituted of 2 to 5 saccharide units, in particular 2 to 3, and preferably 2 saccharide units, linked together via an oxygen atom (oxy) by 1 ⁇ 4 bonding, i.e. Ci of one saccharide unit ⁇ C 4 of the other saccharide unit, or by 1 ⁇ 3 bonding, i.e. Ci of one saccharide unit ⁇ C 3 of the other saccharide unit, or by 1 ⁇ 6 bonding, i.e.
  • - p and q are independently equal to 0, 1, 2, 3 or 4 with p + q being equal to 1, 2, 3 or 4, particularly equal to 1, 2 or 3; preferentially, p + q is equal to 1 or 2; preferably, p is equal to 0 and q is equal to 1 or else q is equal to 0 and p is equal to 1 ;
  • the -Sugar” radical represents a disaccharide which may be acylated, chosen from: lactose, diglucoside or gentiobiose (6-0- ⁇ -D-glucosyl-D-glucose), maltulose, palatinose, lactulose, amygdalose, turanose, cellobiose, isomaltose, rutinose (6- O- ⁇ -L-rhamnosyl-D-glucose), sophorose (2-O- ⁇ -D-xylosyl-D-glucose), sambubiose (2-0- b-D-xylosyl-D-glucose), maltose, xylosylrutinose and glycosylrutinose; and particularly chosen from mtinose, sophorose, diglugoside or gentiobiose, sambubiose, xylosylrutinose and glycosylmt
  • -O-Sugar represents a monosaccharide radical chosen from -O-S 6 to -O-
  • R 8 represents a hydrogen atom
  • R d -C(O)- with R d representing an aryl group optionally substituted with one or more hydroxyl groups such as hydroxyphenyl (4-hydroxyphenyl) or aryl(C 2 -C 4 )alkenyl, notably styryl, the phenyl group of which is optionally substituted with one or more groups chosen from hydroxyl and/or (Ci-C 4 )alkoxy such as methoxy;
  • R d represents a group of formula (I”) as defined previously, more particularly caffeyl or 3,4-dihydroxystyryl, ferulyl or 3-methoxy-4-hydroxystyryl, sinapyl or 3,5- dimethoxy-4-hydroxystyryl, 4-coumaryl or 4-hydroxystyryl, more preferentially R d -C(O)- a caffeoyl (3,4-dihydroxystyrylcarbonyl), feruloyl
  • R 9 and Rio which may be identical or different, preferably different, represent a hydrogen atom
  • R d -C(O)- with R d representing a group from among: ii) aryl optionally substituted with one or more hydroxyl groups such as hydroxyphenyl (4-hydroxyphenyl) or iii) aryl(C2- C4)alkenyl, notably styryl, the phenyl group of which is optionally substituted with one or more groups chosen from hydroxyl and/or (C 1 -C 4 )alkoxy ; in particular, R d represents a group of formula (II”) as defined previously, more particularly methoxy (3,4-dihydroxystyryl or 3- methoxy-4-hydroxystyryl, sinapyl), more preferentially R d -C(O)- represents a 4- hydroxyphenyl (p-hydroxyphenyl), caffeoyl or feruloyl (3-methoxy-4- hydroxyst
  • -O-Sugar represents a group chosen from:
  • R 8 and R 9 as defined previously, and more particularly defined in Table 1 below: [Table 1] and more preferentially Cy3 and Pn3; with “O-Sugar” as defined previously, preferably chosen from S 1 , S 4 , Sugar’ and Sugar”.
  • R 3 represents a group -O-Sugar -O-S 1 or -O-S 4 , preferably -O-S 1 such as glucoside
  • R5 represents a disaccharide -O-Sugar”, particularly -O-S 6 to -O-S 8 , more particularly -O- S 6 ’ to -O-S 8 ’.
  • the compounds comprising acylated or non-acylated Pg, Cy, Dp, Pn, Pt, Mv are found in natural extracts of plants, notably of red cabbage.
  • the anthocyani(di)ns of formula (II) as defined previously are chosen from those of formula (IIB) below, and also the optical or geometrical isomers thereof, the tautomers thereof, the organic or mineral acid or base salts thereof, and the solvates thereof such as hydrates:
  • R3 represents a hydroxyl group or a (C 1 -C 4 )alkoxy group such as methoxy; and R 8 , R 9 and Rio and Q- are as defined previously.
  • Compounds 1 to 10 are found in natural extracts of plants, notably of violet sweet potato.
  • Compounds 11 to 22 are found in natural extracts, notably of red radish.
  • the anthocyani(di)ns of formula (II) as defined previously are chosen from those of formula (lie) below, and also the optical or geometrical isomers thereof, the tautomers thereof, the organic or mineral acid or base salts thereof, and the solvates thereof such as hydrates:
  • R3’ represents a hydroxyl group or a (C 1 -C 4 )alkoxy group such as methoxy, preferably a hydroxyl group; and R3 is as defined previously, and preferably represents a hydroxyl or -O-Sugar group as defined previously, preferably -O-S 1 and more particularly -O-glucoside, and R 7 represents a hydroxyl group or an -O-Sugar group as defined previously, preferably -O-S 8 , more particularly -O-S 8 ’ with R 8 preferably representing a group R d -C(O)- with R d representing a (C 1 -C 4 )alkyl group optionally substituted with a carboxyl and/or hydroxyl group such as acetyl [CH 3 -C(O)-], oxalyl [HO-C(O)-C(O)-], malonyl [HO-C(O)-CH 2 -C(O)-] and succiny
  • anthocyani(di)ns of formula (II) as defined previously are chosen from those of formula (IID) below, and also the optical or geometrical isomers thereof, the tautomers thereof, the organic or mineral acid or base salts thereof, and the solvates thereof such as hydrates:
  • R3’ represents a hydrogen atom or a hydroxyl group or (C 1 -C 4 )alkoxy group such as methoxy; R 8 and Q- are as defined previously; preferably, R 8 represents a group chosen from sinapoyl, feruloyl and 4-coumaroyl.
  • the various anthocyani(di)n compounds of the invention differ notably in the number and position of the hydroxyl and/or (C 1 -C 4 )alkoxy groups, notably methoxy groups, attached to their position 3, 5, 6, 7, 3’, 4’ and/or 5’.
  • the colour of the anthocyani(di)ns of the invention ranges from yellow, orange or red to purple or even blue.
  • pelargonidol has an orange-red colour, cyanidol a red colour, peonidol a pink colour, delphinidol a blue-violet colour, petunidol a violet colour and malvidol a mauve colour (see, for example, Critical Reviews in Analytical Chemistry, J. M. Bueno et ah, “Analysis and Antioxidant Capacity of Anthocyanin Pigments. Part II: Chemical Structure, Color, and Intake of Anthocyanins” 42: 126-151, (2012)).
  • These dyes may notably be characterized by the following CAS numbers: 134-01-1, 134- 04-3, 528-53-0, 528-28-5, 643-84-5, 1429-30-7, 11029-12-2, etc., and defined by the “CTFA - International Color Handbook” , Third Edition, CTFA, pages 856-857.
  • the natural anthocyani(di)ns of the invention are derived from extracts of plants or plant parts.
  • said extracts will be assimilated in their entirety as compound b).
  • the anthocyanidin dye(s) of the invention are present in the form of extracts from plants, notably chosen from extracts of blueberry, blackberry, loganberry, black grape, blood orange, a ⁇ j ai berry, chokeberry, aubergine, cranberry, purple potato, purple sweet potato, plum, sloe, cornflower (wild lowbush blueberry, not to be confused with cornflower), mallow, red grape (and red wine), strawberry, raspberry and black raspberry, banana, cranberry, red radish, potato, apple (notably the skin or peel), elderberry, peach, pear, fig, cherry, onion, notably red onion, redcurrant, red cabbage, rhubarb, blackcurrant, violet (purple) carrot, passionfruit, stringbean, pomegranate, grape, black rice, black bean, blue and purple maize, blue and purple maize grain, and blue and purple maize leaves. They give their colour both to autumn leaves and to red fruit.
  • These natural dyestuffs may be used in a form dissolved in an aqueous phase.
  • the water-soluble dyes that are natural or of natural origin, that are suitable for use in the invention are derived from extracts of bacteria, fungi, algae or plants, used in their entirety or partially.
  • Extracts of plants or plant parts such as the fruit, including citrus fruit, vegetables, trees and shrubs. Mixtures of these extracts may also be used.
  • water-soluble dye(s) that are natural or of natural origin may be introduced into a fragranced composition according to the invention in the form of a natural extract.
  • Such extracts may be obtained by extraction of various plant parts, for instance the root, the wood, the bark, the leaf, the flower, the fruit, the seed, the pod or the peel.
  • extracts of plants mention may be made of extracts of cornflower, of mallow flower, of rose petals, of hibiscus or of black rice envelope.
  • extracts of fruit mention may be made of extracts of blueberry, of blackberry, of plum, of cherry, of blood orange or of black grape. [Table 4]
  • extracts of vegetables mention may be made of extracts of red radish, of red cabbage, of aubergine, of purple sweet potato or of purple potato, of red onion, of purple maize and of black or violet (purple) carrot, preferably of purple sweet potato.
  • the extracts of vegetables are chosen from extracts of red radish, of red cabbage, of purple sweet potato or of purple potato, of red onion and of black or violet (purple) carrot, preferably of purple sweet potato.
  • All the enantiomers, diastereoisomers and geometrical isomers of the dyes defined above may be suitable for use as water-soluble dye that is natural or of natural origin, and also the racemic mixtures.
  • the water-soluble anthocyanin dye(s) b) that are natural or of natural origin, in particular obtained from natural extract(s), which is suitable for use in the invention may be in any form enabling its dissolution in the fragranced composition, in particular in aqueous, alcoholic or aqueous -alcoholic medium. It may notably be in powder or liquid form, preferably in powder form.
  • anthocyani(di)ns and derivatives thereof are commercially available, for instance the anthocyanin powder from red cabbage sold under the name 600008 Vitiva DD from the company Vitiva, from black radish D 600549 from the company Vitiva, and from black carrot (Black Carrot Powder EV-9 Blue sold by Secna).
  • the amount of water-soluble anthocyani(di)n dye(s) that are natural or of natural origin present in a composition according to the invention is able to vary significantly with regard to the hue or the chromatic intensity sought by its presence.
  • the natural anthocyani(di)n dye(s), and/or the natural extract(s), used as ingredient b) the composition according to the invention preferably represent from 0.0001% to 20% by weight relative to the total weight of the composition(s) containing the anthocyani(di)n dye(s) or the extract(s).
  • the content in the fragrancing composition containing same preferably ranges from 0.0001% to 5% by weight, preferably from 0.001% to 3.0% by weight, more preferentially from 0.01% to 1.0% by weight and even more preferentially from 0.1% to 0.5% by weight of anthocyani(di)n dye(s) relative to the total weight of said composition.
  • the content in the fragranced composition of the anthocyani(di)n dye(s) b) in the form of extract(s) particularly ranges from 0.01% to 20% by weight, more particularly from 0.1% to 10% by weight, preferably from 0.2% to 8.0% by weight, more preferentially from 0.3% to 3.0% by weight, even more preferentially from 0.4% to 2.0% by weight and better still from 0.5% to 1% by weight of extract(s) b) in said composition.
  • the total amount of water-soluble dye(s) that are natural or of natural origin chosen from anthocyani(di)ns and derivatives thereof contained in the composition ranges from 1 to 300 ppm (parts per million) and more particularly from 1 to 200 ppm.
  • a content of water-soluble dye(s) that are natural or of natural origin of the type such as anthocyani(di)n or anthocyani(di)n derivative of less than or equal to 300 ppm in the fragranced coloured composition makes it possible to prevent the formation of marks during its application, in particular on clothing, irrespective of the dyestuff used.
  • the water-soluble dye(s) that are natural or of natural origin chosen from anthocyani(di)ns and derivatives thereof may be introduced into the fragranced composition of the invention in the form of a natural extract.
  • a fragranced composition according to the invention may comprise from 0.05% to 15% by weight of natural extract comprising a water-soluble dye that is natural or of natural origin chosen from anthocyani(di)ns and derivatives thereof, relative to the total weight of said composition.
  • a composition according to the invention comprises one or more anthocyani(di)n dye(s) in a content ranging from 0.0001% to 20% by weight relative to the total weight of the composition containing the anthocyani(di)n dye(s) or the extracts containing same, preferably:
  • the content in the fragrancing composition ranges from 0.0001% to 5% by weight, preferably from 0.001% to 3.0% by weight, more preferentially from 0.01% to 1.0% by weight and even more preferentially from 0.1% to 0.5% by weight of anthocyani(di)n dye(s) relative to the total weight of said composition;
  • the content of extract(s) b) in the composition ranges from 0.01% to 20% by weight, particularly from 0.1% to 10% by weight, more particularly from 0.2% to 8.0% by weight, for example from 0.3% to 3.0% by weight, notably from 0.4% to 2.0% by weight and better still from 0.5% to 1% by weight of extract(s) b) in said composition.
  • a fragranced composition according to the invention comprises at least one fragrancing substance.
  • Perfumes are compositions notably containing the starting materials described in S. Arctander, Perfume and Flavor Chemicals ( Montclair , N.J., 1969), in S. Arctander, Perfume and Flavor Materials of Natural Origin ( Elizabeth , N.J., 1960 ) and in Flavor and Fragrance Materials - 1991, Allured Publishing Co., Wheaton, III.
  • a fragranced composition according to the invention preferably comprises at least one fragrancing substance chosen from essential oils, perfumes and aromas of synthetic or natural origin, and mixtures thereof.
  • They may be natural products, such as essential oils, absolutes, resinoids, resins, concretes, and/or synthetic products, such as terpene or sesquiterpene hydrocarbons, alcohols, phenols, aldehydes, ketones, ethers, acids, esters, nitriles or peroxides, which may be saturated or unsaturated, and aliphatic or cyclic.
  • an essential oil is an odorous product, generally of complex composition, obtained from a botanicahy defined plant starting material, either by steam distillation, or by dry distillation, or by an appropriate mechanical process without heating (cold pressing).
  • the essential oil is generally separated from the aqueous phase via a physical process which does not result in any significant change in the composition.
  • the choice of the method for obtaining essential oils depends mainly on the starting material: its original state and its characteristics, its intrinsic nature.
  • the “ essential oil/plant starting material” yield may be extremely variable depending on the plant: 15 ppm to more than 20%. This choice determines the characteristics of the essential oil, in particular viscosity, colour, solubility, volatility, and richness or poorness in certain constituents.
  • Steam entrainment corresponds to vaporization, in the presence of steam, of a sparingly water-miscible substance.
  • the raw material is placed in contact with boiling water or steam in an alambic.
  • the steam entrains the essential oil vapour, which is condensed in the condenser and recovered as a liquid phase in a Florentine vase (or essence jar), where the essential oil is separated from the water by settling.
  • the aqueous distillate that remains after the steam distillation, once the separation of the essential oil has been performed, is known as the “ aromatic water” or “ hydrolate ” or “distilled floral water”.
  • Production by dry distillation consists in obtaining the essential oil by distillation of woods, barks or roots, without addition of water or steam, in a closed chamber designed so that the liquid is recovered at the bottom.
  • Cade oil is the best known example of a product obtained in this way.
  • the method of production by cold pressing applies only to citrus fruits (Citrus spp.) via mechanical processes at room temperature.
  • the principle of the method is as follows: the zests are tom into pieces and the contents of the secretory sacs that have been broken are recovered by a physical process.
  • the conventional process consists in exerting an abrasive action on the entire surface of the fruit under a stream of water. After removal of the solid waste, the essential oil is separated from the aqueous phase by centrifugation.
  • the majority of industrial installations allow simultaneous or sequential recovery of the fruit juices and of the essential oil.
  • Essential oils are generally volatile and liquid at room temperature, which distinguishes them from “set” oils. They are more or less coloured and their density is generally less than that of water. They have a high refractive index and most of them deflect polarized light. They are liposoluble and soluble in the usual organic solvents, distillable with steam, and very sparingly soluble in water.
  • essential oils that may be used according to the invention, mention may be made of those obtained from plants belonging to the following botanical families: Abietaceae or Pinaceae, for example conifers; Amaryllidaceae; Anacardiaceae; Anonaceae, for example ylang ylang; Apiaceae, for example Umbelliferae, in particular dill, angelica, coriander, sea fennel, carrot or parsley; Araceae; Aristolochiaceae; Asteraceae, for example yarrow, artemisia, camomile, helichrysum; Betulaceae; Brassicaceae; Burseraceae, for example frankincense; Caryophyllaceae; Canellaceae; Cesalpiniaceae, for example copaifera (copaiba balsam); Chenopodaceae; Cistaceae, for example rock rose; Cyperaceae; Dipterocarpaceae; Ericaceae, for
  • fragrancing substances are notably: geraniol, geranyl acetate, famesol, bomeol, bomyl acetate, linolool, linalyl acetate, linalyl propionate, linalyl butyrate, tetrahydrolinolool, citronellol, citronellyl acetate, citronellyl formate, citronellyl propionate, dihydromyrcenol, dihydromyrcenyl acetate, tetrahydromyrcenol, terpineol, terpinyl acetate, nopol, nopyl acetate, nerol, neryl acetate, 2-phenylethanol, 2-phenylethyl acetate, benzyl alcohol, benzyl acetate, benzyl salicylate, styrallyl acetate, benzyl benzoate, amyl salicy
  • a fragranced composition according to the invention preferably comprises a fragrancing substance chosen from essential oils, perfumes and aromas of synthetic or natural origin, and mixtures thereof.
  • a mixture of different fragrancing substances that generate in common a note that is pleasant to the user is used.
  • the fragranced composition comprises at least 1% by weight of a mixture of fragrancing substances, in particular of at least two different fragrancing substances, relative to the total weight of the composition, and preferably at least three different fragrancing substances.
  • the fragrancing substances will preferably be chosen such that they produce notes (head, heart and base) in the following families: citrine, aromatic, floral notes, in particular pink flowers and white flowers, spicy, woody, investigating, chypre, fougere, leathery, musk.
  • the amount of fragrancing substance(s) present in a composition according to the invention is able to vary significantly with regard to the odour or the odour intensity sought by its presence.
  • a fragranced composition according to the invention may comprise from 0.0001% to 10% by weight, particularly from 0.001% to 8.0% by weight, more particularly from 0.01% to 5.0% by weight and preferentially from 0.1% to 1.0% by weight of fragrancing substance(s), relative to the total weight of said composition.
  • the fragrancing substances may be introduced into a fragranced composition in accordance with the invention in the form of a perfume concentrate.
  • the perfume concentrate may be a concrete or an absolute, preferably an absolute.
  • a fragranced composition according to the invention particularly comprises from 1.0% to 50% by weight of perfume concentrate, more particularly from 2.0% to 40% by weight, preferentially from 5.0% to 30% by weight and more preferentially from 10% to 20% by weight, for example 15% by weight, relative to the total weight of the composition.
  • a fragranced composition according to the invention is preferably a cosmetic composition, i.e. a composition that is cosmetically acceptable so as to be applied to keratin materials, notably human keratin materials, without impairing them.
  • a fragranced composition according to the invention is in the form of a cosmetic cream, milk or gel.
  • a fragranced composition according to the invention is of oil-in- water type, and is preferably in the form of an oil-in-water emulsion.
  • a fragranced composition according to the invention is an alcoholic composition, i.e. a composition comprising at least one alcohol as solvent(s), or an aqueous-alcoholic composition, i.e. a composition comprising a mixture of water and of alcohol as solvents.
  • the composition comprises as solvent(s) (bio)ethanol, pentylene glycol, or a mixture of these compounds optionally in the presence of water.
  • a fragranced composition according to the invention may comprise a mixture of water and alcohol (notably (bio)ethanol) in an alcohol/water mass ratio of less than or equal to 25/75, preferably less than or equal to 20/80, in particular less than 15/85, notably ranging from 15/85 to 25/75, for example ranging from 15/85 to 20/80.
  • alcohol notably (bio)ethanol
  • a fragranced composition according to the invention may comprise a mixture of water, alcohol (notably (bio)ethanol) and perfume concentrate (water/alcohol (notably (bio)ethanol)/perfume concentrate) in a mass ratio ranging from 40/55/5 notably for after-shave lotions to 25/70/5 for colognes and up to 5/65/30 for eaux de perfumes and perfumes.
  • alcohol notably (bio)ethanol
  • perfume concentrate water/alcohol (notably (bio)ethanol)/perfume concentrate
  • a fragranced composition according to the invention may be an alcoholic or aqueous-alcoholic composition.
  • the composition according to the invention is aqueous-alcoholic.
  • the alcohols that are most particularly suitable for use in the invention are chosen from i) monoalcohols containing from 2 to 6 carbon atoms such as ethanol and isopropanol, and ii) glycols containing from 2 to 8 carbon atoms such as ethylene glycol, propylene glycol, 1 ,3- butylene glycol and dipropylene glycol.
  • the alcohols are of natural origin.
  • a fragranced composition according to the invention comprises as solvent(s) water, (bio)ethanol, pentylene glycol, or a mixture of at least two of these compounds.
  • a fragranced composition according to the invention may comprise a content of alcohols, notably of (bio)ethanol, ranging from 0.5% to 99.5% by weight, particularly from 5% to 97% by weight, more particularly from 15% to 95% by weight, better still from 25% to 93%, preferably from 40% to 92% by weight, more preferentially from 50% to 90% by weight, even more preferentially from 60% to 88% by weight and better still from 70% to 85% by weight, relative to the total weight of the composition. More preferentially, the amount of alcohol, notably of (bio)ethanol, is less than 75% as pure alcohol.
  • a fragranced composition according to the invention may comprise a content of alcohols, notably of (bio)ethanol, of less than or equal to 20% by weight, preferably less than 15% by weight, in particular ranging from 0.1% to 20% by weight, more particularly from 0.5% to 15%, for example from 0.5% to 10% by weight, relative to the total weight of the composition.
  • alcohols notably of (bio)ethanol
  • a fragranced composition according to the invention may be an aqueous composition, i.e. a composition comprising water as solvent(s), or an aqueous- alcoholic composition, i.e. a composition comprising a mixture of water and of alcohol as solvents.
  • a fragranced composition according to the invention may comprise, besides water, at least one water-soluble solvent different from the alcohols defined above.
  • water-soluble solvent denotes a compound that is liquid at room temperature and water-miscible (miscibility with water of greater than 50% by weight at a temperature ranging from 20°C to 25°C and atmospheric pressure).
  • the water-soluble solvents that may be used in the composition of the invention may also be volatile.
  • a fragranced composition according to the invention may be anhydrous, i.e. it comprises less than 2% by weight of water, preferably less than 1% by weight of water, preferentially less than 0.5% by weight of water, or even is totally free of water.
  • a fragranced composition according to the invention may also comprise at least one C2-C32 polyol.
  • polyol should be understood as meaning any organic molecule including at least three free hydroxyl (-OH) groups.
  • a polyol in accordance with the present invention is present in liquid form at room temperature.
  • a polyol that is suitable for use in the invention may be a compound of linear, branched or cyclic, saturated or unsaturated alkyl type, bearing on the alkyl chain at least three -OH functions and in particular at least four -OH functions.
  • the polyols that are advantageously suitable for formulating a composition according to the present invention are those notably containing from 2 to 32 carbon atoms and preferably 3 to 16 carbon atoms.
  • the polyol may be chosen, for example, from pentaerythritol, trimethylolpropane, glycerol, polyglycerols, in particular glycerol oligomers, preferably diglycerol, and mixtures thereof.
  • a fragranced composition according to the invention may comprise one or more fatty substances that are liquid at room temperature and/or a fatty substance that is solid at room temperature such as waxes, pasty fatty substances, gums and mixtures thereof.
  • room temperature means a temperature equal to 25 °C.
  • the fatty substances that are suitable for use in the present invention are liquid at room temperature and at atmospheric pressure.
  • the oils may be polar or non-polar, of different chemical nature, alone or as a mixture.
  • polar oils that may be mentioned include: hydrocarbon-based plant oils with a high content of triglycerides consisting of fatty acid esters of glycerol, for example like wheat germ oil, com oil, sunflower oil, shea oil, castor oil and sweet almond oil; synthetic esters and ethers; saturated C12 to C26 fatty alcohols; and mixtures thereof.
  • non-polar oils may be chosen in particular from silicone oils such as volatile or non-volatile, linear or cyclic polydimethylsiloxanes, which are liquid at room temperature (20°C ⁇ 5°C) and atmospheric pressure, and linear or branched hydrocarbons of synthetic or mineral origin.
  • solid fatty substances examples include waxes, notably hydrocarbon-based waxes or silicone waxes, of natural or synthetic origin, insofar as they are compatible with the other components of the composition, and insofar as they do not impair the properties, notably the olfactory and colour properties, of the fragranced composition.
  • the fatty substances are plant oils.
  • Plant oils that may be mentioned include sunflower oil, virgin olive oil or refined sesame oil.
  • a fragranced composition according to the invention may also comprise one or more anionic, cationic, nonionic, zwitterionic or amphoteric surfactants.
  • Nonionic surfactants that may be mentioned most particularly include fatty acid esters of sugars, notably those chosen from the group comprising esters or mixtures of esters of C8- C 22 fatty acid and of sucrose, of maltose, of glucose or of fructose, and esters or mixtures of esters of C14-C22 fatty acid and of methylglucose.
  • esters or mixtures of esters of fatty acid and of sucrose, maltose, glucose or fructose include sucrose monostearate, sucrose distearate and sucrose tristearate, and mixtures thereof, and an example of esters or mixtures of esters of fatty acid and of methylglucose that may be mentioned is methylglucose polyglyceryl-3 distearate, sold by the company Goldschmidt under the name Tego-Care 450.
  • the fragranced composition according to the invention may comprise one or more co-emulsifiers.
  • This or these co-emulsifiers may be chosen, for example, from C 16 -C 22 fatty alcohols or esters of C3-C6 polyols with C14-C22 fatty acids, and mixtures thereof.
  • co-emulsifiers that may be mentioned include cetyl alcohol, stearyl alcohol, cetearyl alcohol (mixture of cetyl alcohol and of stearyl alcohol), glyceryl stearate, and mixtures thereof, and preferably cetyl alcohol.
  • a fragranced composition may comprise from 0.01% to 10% by weight, more particularly from 0.1% to 5% by weight and preferentially from 1% to 3% by weight of surfactant(s) relative to the total weight of the fragranced composition.
  • a fragranced composition according to the invention may also comprise at least one preserving agent.
  • preservative or “preserving agent” means any cosmetically or pharmaceutically acceptable compound which can prevent microbial growth (or the growth of microorganisms) which may take place in cosmetic or pharmaceutical compositions, from the moment of their preparation, while they are in storage and up to the time of their conventional use by consumers.
  • Preserving agents that may notably be mentioned include the preserving agents described in Cosmetics, Kirk-Othmer Encyclopedia of Chemical Technology. John Wiley & Sons, Inc., Martin M. Rieger; 5.2 preservatives & table 3, 04/12/2000, https://doi.org/10.1002/0471238961.0315191318090507.a01.
  • the preserving agent(s) are chosen from organic preserving agents bearing an aromatic group.
  • a fragranced composition according to the invention may also comprise at least one preserving agent, notably chosen from i) benzene -based carboxylic acids optionally substituted on the phenyl group with one or more groups chosen from hydroxyl, (Ci- Cio)alkyl and (Ci-Cio)alkylcarbonyl, and also the base salts thereof, notably of alkali metals and alkaline-earth metals, ii) hydroxybenzoic acid esters optionally substituted on the phenyl group with one or more groups chosen from (Ci-Cio)alkyl such as parabens, notably methylparaben and ethylparaben and propylparaben, and iii) aromatic alcohols.
  • at least one preserving agent notably chosen from i) benzene -based carboxylic acids optionally substituted on the phenyl group with one or more groups chosen from hydroxyl, (Ci- Cio)alkyl and (Ci
  • the preserving agent(s) other than a) are chosen from i) and in particular benzoic acid [CAS No. 65-85-0] and also the base salts thereof, notably of alkali metals and alkaline-earth metals; and also salicylic acid optionally substituted with a (Ci-Cx)alkylcarbonyl group, preferably salicylic acid.
  • the preserving agent(s) are notably chosen from aryl(C 1 - C 6 )alkanols and aryloxy(C 1 -C 6 )alkanols, such as phenylethanol, parabens, such as propylparaben, methylparaben, butylparaben, ethylparaben and isobutylparaben, benzyl alcohol and/or chlorophenesin.
  • a fragranced composition according to the invention may also comprise at least one organic or mineral alkaline agent, for example an amine, in particular a (C 2 -C 6 )alkanolamine, in particular 2-amino-2-methyl-l -propanol, or a mineral alkaline agent, for instance alkali metal or alkaline-earth metal hydroxides, such as sodium hydroxide.
  • organic or mineral alkaline agent for example an amine, in particular a (C 2 -C 6 )alkanolamine, in particular 2-amino-2-methyl-l -propanol
  • a mineral alkaline agent for instance alkali metal or alkaline-earth metal hydroxides, such as sodium hydroxide.
  • the composition comprises one or more chelating agents.
  • chelating agent means a ligand or chelating agent which makes it possible to form a metal complex with a chelated cation or metal atom.
  • the chelating agent is electron-donating and the chelated species is electron-deficient.
  • a “chelate” differs from a simple “complex” in that the metal cation is attached to the chelating ligand or chelating agent via at least two coordination bonds. The metal is thus “gripped” between the chemical functions of the ligand.
  • the number of metal-ligand bonds of a ligand molecule defines the “denticity”: such coordinates or ligands are referred to as being bidentate, tridentate or tetradentate.
  • the central atom is bonded to the neighbouring atoms via at least two bonds, forming a ring structure, a chelate ring.
  • the chelate rings that are the most stable are 5- and 6-membered chelate rings. By means of this effect, chelates are more stable complexes than the complexes of monodentate ligands including the same chemical functions.
  • chelating agents are chosen from aminocarboxylic acids, for example ethylenediaminetetraacetic acid (EDTA), aminotriacetic acid, diethylenetriaminepentaacetic acid, and the salts thereof, in particular the alkaline salts, for instance disodium EDTA or dipotassium EDTA, aminopolycarboxylic acids, for instance ethylenediaminedisuccinic acid (EDDS), and salts thereof, in particular alkaline salts, or alternatively one or more phosphate-based chelating agents such as alkali metal metaphosphates such as sodium metaphosphate, alkali metal hexametaphosphates such as sodium hexametaphosphate, tetra- alkaline pyrophosphates such as tetrapotassium pyrophosphate, acids containing phosphorus, such as phytic acid, and salts thereof, in particular alkali metal or alkaline-earth metal salts, such as ethylenediaminetetram
  • the composition of the invention comprises one or more metal salts, metal complexes, metal oxides, metal oxoanions, and the hydrates and supported forms thereof.
  • a composition according to the invention comprises one or more metal salts. More particularly, the metal(s) are of oxidation state I or II, more particularly II, preferably chosen from 1) Cu, 2) Fe, 3) Zn, 4) Mg and 5) Mn.
  • metal salt means a compound other than alloys, i.e. the salt is formed from a metal combined with certain non-metallic elements.
  • metal salts derives from oxidative attack.
  • the metal is oxidized to a cationic species and then combines with an anionic species to give a salt.
  • This formation takes place by applying redox principles and the redox reaction (chemical reaction during which an electron transfer takes place in which the atom that captures the electrons is known as the “oxidizing agent”; the atom that yields the electrons is the “reducing agent”); or via chemical exchange reactions between one salt and another salt or an acid, in the presence or absence of atmospheric oxygen. These reactions are known to those skilled in the art.
  • the salts according to the invention are soluble in water to a proportion of at least 0.0001 g/L.
  • the metal salts according to the invention may be introduced in solid form into the compositions or may originate from a natural, mineral or spring water that is rich in these ions, or alternatively from seawater (notably the Dead Sea). They may also originate from mineral compounds, such as plant extracts containing same (cf., for example, FR 2814943).
  • the term “mett” or “ coordination compounds” mean systems in which the metal ion, the central atom, is chemically bonded to one or more electron donors (ligands).
  • a ligand comprising various coordinating groups gives metal compounds corresponding to coordination sphere principles with a given number of electrons (internal complexes or chelates), as described in Ullmann’s Encyclopedia of Industrial Chemistry, “ Metal complex dyes”, 2005, pages 1-42.
  • metal complex means: i) metallic dyes or “ metal-complex dyes”, which are complexed dyes derived from azo, azomethine, hydrazono or formazan dyes (free, bidentate, tridentate, tetradentate) such as those described in Ullmann’s Encyclopedia of Industrial Chemistry, “Metal complex dyes”, 2005, pages 1-42, which preferentially comprise Cu and Mg; ii) compounds of the “ aza[18]annulene ” type, also known as “(metallo)porphyrins” and “ phthalocyanines ” which contain 4 and 8 nitrogen atoms, respectively, included in the perimeter of the macrocycle, as described in the book “Co/or Chemistry” , H.
  • the metal ion is then at the centre of said macrocycle bonded by coordination with two hydrogen atoms to the nitrogen atoms of pyrroles, the metal also possibly being stabilized with one or more bidentate or non-bidentate ligands, the metal ion preferentially being Mg 2+ or Cu 2+ ; the metal complex is particularly:
  • metalloporphyrin formed from a backbone bearing 4 pyrrole groups that are connected at their a, a’ position via 4 methine groups and contain 16 sp 2 hybridized atoms, complexing a metal such as Cu or Mg, or
  • phthalocyanines which are tetraaza analogues of tetrabenzoporphyrins, such as Monastral Fast Blue B (C.I. Pigment Blue 15); Monastral Fast Blue G (C.I. Pigment Blue 16) (see “ Color Chemistry”, H. Zollinger, 3rd Ed., Wiley-VCH, 2003, chapter 5, Aza[18]annulenes, page 140); the sulfonyl derivatives Sirius Light Turquoise Blue G (C.I. Direct Blue 86, copper phthalocyanine tetrasulfonic acid) and “phthalocyanines” as described in Ullmann’s Encyclopedia of Industrial Chemistry, “Phthalocyanines”, 2005, pages 1-34, which comprise Cu and Si.
  • Monastral Fast Blue B C.I. Pigment Blue 15
  • Monastral Fast Blue G C.I. Pigment Blue 16
  • Sirius Light Turquoise Blue G C.I. Direct Blue 86, copper phthalocyanine tetra
  • metal oxide(s) means compounds of general formula A x O y with A representing a metal element, x being greater than or equal to 1 and less than or equal to 4, and y being greater than or equal to 1 and less than or equal to 12.
  • metal oxoanion(s) means compounds of general formula Z z A x O y with A representing a metal element, Z representing an alkali metal such as Li, Na or K or a hydrogen atom or an ammonium ion, z being greater than or equal to 1 and less than or equal to 6, x being greater than or equal to 1 and less than or equal to 4, and y being greater than or equal to 1 and less than or equal to 12.
  • supported form(s) means the forms in which the metal derivative b) is impregnated onto a material known as a “support”.
  • the optional supports for these metal derivatives may be chosen from charcoal, silica, alumina, optionally charged polymers comprising counter-anions or counter-cations (counter-cation or counter-anion of the metallic species).
  • the polymers may be polyethylene glycol (PEG).
  • the metal salt(s) are chosen from the (poly)hydroxyalkyl(Ci-Ci 6 )carboxylates of metals of oxidation state II, notably Fe II, Cu II, Zn II, Mg II and Mn II (poly)hydroxyalkyl(Ci-Ci 6 )carboxylates.
  • the metal salt(s) are chosen from Cu gluconate, Fe gluconate, Zn gluconate or Mg gluconate, gluconates of metals of oxidation state II such as Fe, Cu, Zn or Mg gluconates, and lactates of metals of oxidation state II such as Fe, Cu, Zn or Mg lactates.
  • the metal salts are Fe, Cu, Mg or Zn gluconate, preferably Fe and Cu gluconate.
  • a fragranced composition according to the invention may also comprise at least one aqueous pH buffer, namely at least one compound which makes it possible to maintain a constant pH in aqueous solution.
  • aqueous pH buffer(s) that are particularly suitable for use in the invention may be chosen from benzoic acid, maleic acid, fumaric acid, succinic acid and the salts thereof, in particular the alkali metal or alkaline-earth metal salts, for example sodium benzoate.
  • a fragranced composition according to the invention may also comprise one or more related dyestuffs, different from the water-soluble anthocyani(di)ns that are natural or of natural origin, defined above.
  • This (or these) dyestuff(s) are preferably chosen from particulate dyestuffs, liposoluble dyes and water-soluble dyes, and mixtures thereof.
  • water-soluble dyes that are suitable for use in the invention, mention may be made notably of synthetic or natural water-soluble dyes, for instance FDC Red 4, DC Red 6, DC Red 22, DC Red 28, DC Red 30, DC Red 33, DC Orange 4, DC Yellow 5, DC Yellow 6, DC Yellow 8, FDC Green 3, DC Green 5, FDC Blue 1, betanine (beetroot), carmine, copper chlorophyllin, methylene blue, caramel, sandalwood, gardenia, spirulina and riboflavin.
  • liposoluble dye denotes any natural or synthetic, generally organic dye, which is soluble in an oily phase or in solvents that are miscible with a fatty substance.
  • liposoluble dyes that are suitable for use in the invention, mention may notably be made of synthetic or natural liposoluble dyes, for instance DC Red 17, DC Red 21, DC Red 27, DC Green 6, DC Yellow 11, DC Violet 2, DC Orange 5, Sudan red, carotenes (b-carotene, lycopene), xanthophylls (capsanthin, capsorubin, lutein), palm oil, Sudan brown, quinoline yellow, annatto and curcumin.
  • the colouring particulate materials may be pigments, nacres and/or particles with metallic tints.
  • pigments is intended to denote white or coloured, mineral or organic solid particles.
  • Pigments are naturally insoluble in the liquid hydrophilic and lipophilic phases usually employed in cosmetics. Alternatively, they may be rendered insoluble by formulation in lake form, where appropriate.
  • the pigment has little or no solubility in aqueous -alcoholic media.
  • the pigments may be white or colored, mineral and/or organic, and coated or uncoated.
  • mineral pigments that may be mentioned are metal oxides, in particular titanium dioxide, optionally surface-treated, zirconium oxide, zinc oxide or cerium oxide, and also iron oxide, titanium oxide or chromium oxide, manganese violet, ultramarine blue, chromium hydrate and ferric blue.
  • 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 aluminum.
  • nacres denotes coloured particles of any form, which may or may not be iridescent, notably produced by certain molluscs in their shell, or alternatively synthesized, and which have a colour effect via optical interference.
  • the nacres may be chosen from nacreous pigments such as titanium mica coated with an iron oxide, titanium mica coated with bismuth oxychloride, titanium mica coated with chromium oxide, titanium mica coated with an organic dye and also nacreous pigments based on bismuth oxychloride.
  • the nacres may more particularly have a yellow, pink, red, bronze, orange, brown, gold and/or coppery color or tint.
  • particles with a metallic tint means any compound whose nature, size, structure and surface finish allow it to reflect the incident light, notably in a non-iridescent manner.
  • the particles with a metallic tint that may be used in the invention may be chosen in particular from particles of at least one metal and/or of at least one metal derivative, particles including a single-material or multi-material organic or mineral substrate, at least partially covered with at least one coat with a metallic tint comprising at least one metal and/or at least one metal derivative, and mixtures of said particles. These particles are different from metal ions.
  • metals that may be present in said particles, mention may be made, for example, of Ag, Au, Cu, Al, Ni, Sn, Mg, Cr, Mo, Ti, Zr, Pt, Va, Rb, W, Zn, Ge, Te and Se, and mixtures or alloys thereof.
  • Ag, Au, Cu, Al, Zn, Ni, Mo and Cr, and mixtures or alloys thereof are preferred metals.
  • metal derivatives denotes compounds derived from metals, notably oxides, fluorides, chlorides and sulfides.
  • the related dyestuffs are natural or of natural origin.
  • These related dyestuffs may be present in a content ranging from 0.01% to 30% by weight relative to the total weight of the composition and in particular from 0.02% to 20% by weight relative to the total weight of the composition.
  • a fragranced composition according to the invention may also comprise any additive usually used in the field of fragrances, for instance emollients or softeners, in particular sweet almond oil, apricot kernel oil, moisturizers, in particular glycerol, calmatives, in particular a-bisabolol, allantoin and Aloe vera vitamins and derivatives thereof, essential fatty acids, insect repellents, propellants, peptizers, fillers, cosolvents, UV-screening agents, stabilizers or preserving agents other than the organic acid esters of formula (I) as defined according to the invention, and mixtures thereof.
  • emollients or softeners in particular sweet almond oil, apricot kernel oil, moisturizers, in particular glycerol, calmatives, in particular a-bisabolol, allantoin and Aloe vera vitamins and derivatives thereof, essential fatty acids, insect repellents, propellants, peptizers, fillers, cosolvents, UV-
  • these additives When they are present in the composition of the invention, these additives may be present in an amount ranging from 0.001% to 10% by weight and better still from 0.01% to 5% by weight relative to the total weight of the composition.
  • a composition according to the invention may be obtained via any method known to those skilled in the art for the formulation of coloured fragranced compositions.
  • a fragranced composition according to the invention may be obtained by simple mixing, at room temperature, namely at a temperature ranging from 20°C to 25°C, of the compounds constituting the composition.
  • a fragranced composition according to the invention results from mixing between a colouring solution comprising one or more anthocyani(di)n dyes, on the one hand, and a fragranced solution comprising the ester of formula (I), on the other hand.
  • Said colouring solution thus comprises at least one water-soluble dye that is natural or of natural origin chosen from anthocyani(di)ns and derivatives thereof, in particular as defined above, in a physiologically acceptable medium, in particular in aqueous or aqueous-alcoholic medium.
  • Said fragranced solution comprises, for its part, at least one fragrancing substance, in particular as defined above, and at least one ester of formula (I) as defined above, in a physiologically acceptable medium, in particular an aqueous -alcoholic medium.
  • Said fragranced solution may itself result from mixing between an intermediate fragranced solution, comprising at least one fragrancing substance, in particular as defined above, in a physiologically acceptable medium, in particular in aqueous -alcoholic medium, and an ester of formula (I) as defined above, directly or which is in solution in a physiologically acceptable medium, in particular an aqueous -alcoholic medium.
  • ester(s) of formula (I) may be introduced, directly or in solution, into a fragranced composition, also comprising at least one fragrancing substance and at least one water-soluble dye that is natural or of natural origin chosen from anthocyani(di)ns and derivatives thereof, in a physiologically acceptable medium.
  • the invention applies not only to fragrancing products but also to cosmetic products for caring for or treating keratin materials, in particular the skin, including the scalp, and the lips, containing an odorous substance.
  • a composition according to the invention may thus constitute a cosmetic composition for fragrancing, caring for or treating keratin materials, and may notably be in the form of an eau fraiche, eau de toilette, eau de perfume, aftershave lotion, care lotion, or silicone or hydrosilicone care oil. It may also be in the form of a fragranced two-phase lotion (eau de toilette phase/hydrocarbon-based oil and/or silicone oil phase), a body milk or a shampoo.
  • the compositions according to the invention may be packaged in the form of bottles.
  • a fragrancing composition according to the invention may be diffused by various systems, such as sprays, aerosols or piezoelectric devices.
  • the devices in accordance with the invention are well known to those skilled in the art and comprise pump-bottles or “sprays”, aerosol containers comprising a propellant and aerosol pumps using compressed air as propellant. These devices are notably described in patents US 4 077 441 and US 4 850 517.
  • compositions conditioned as aerosols in accordance with the invention generally contain conventional propellants, for instance dimethyl ether, isobutane, n-butane or propane.
  • propellants for instance dimethyl ether, isobutane, n-butane or propane.
  • the compositions according to the invention are lotions and preferably have a viscosity ranging from 10 to 120 DU, more preferentially from 30 to 120 DU and even more preferentially from 40 to 80 DU; the viscosity being measured using a Rheomat TVe-05 viscometer, at 25°C, rotation speed 200 rpm, spindle No. 1, 10 minutes.
  • a fragranced composition according to the invention may also be in the form of a body milk or in the form of a shampoo.
  • the stability of the compositions is evaluated by observation of the change in colour over time, visually and using a spectrocolorimeter (L*, a*, b*) Konica Minolta CM 3600A, and by olfactory evaluation of the change in the notes of the fragranced composition.
  • compositions are poured into 50 mL borosilicate glass bottles and are then observed after storage for 2 months, at atmospheric pressure and under various conditions: a) in an oven, at a temperature of 45°C. Storage of the compositions for two months at 45°C simulates accelerated ageing of the product corresponding to a shelf life of 3 years; b) in natural light and at room temperature, namely between 20°C and 25 °C, and then: b.l) 16 hours in an Atlas brand SunTest CPS+ ageing device, equipped with a xenon lamp, irradiating light source whose spectral distribution is close to that of sunlight, delivering an energy of 765 W/m 2 , simulating exposure to neon lights in a shop; or b.2) 2 weeks in an oven at a temperature of 45 °C, simulating an extreme condition for the perfume; c) in the refrigerator, at a temperature of 4°C; d) at room temperature, namely between 20°C and 25 °C, protected
  • the intensity difference DL between a reference composition and a composition tested after storage under the conditions mentioned above may be calculated from the L*a*b values according to the following formula:
  • the colouring solutions C1 to C3 are prepared using the weight proportions detailed in Table 5 below. The values are expressed as weight percentages relative to the total weight of the colouring solution.
  • the colouring compositions are prepared by dissolving the dyes in the appropriate solvent or mixture of solvents.
  • the required amount of dye is weighed out in a beaker.
  • the amount of solvents ethanol, water, propylene glycol and/or pentylene glycol
  • the mixture is left stirring by magnetic stirring for 20 minutes.
  • fragranced compositions PI, P2 and P3 according to the invention and a fragranced composition P4 outside the invention are prepared using the weight proportions as detailed in Table 6 below.
  • the values are expressed as weight percentages relative to the total weight of the fragranced composition.
  • compositions PI to P3 0.5 g of Gamma-oryzanol, chlorogenic acid and ethyl ferulate are respectively added and the mixture is then left under magnetic stirring for 10 minutes, so as to obtain a fragranced solution.
  • Composition P4 is prepared according to the same protocol, with the exception of the addition of organic acid ester (without Gamma-oryzanol, chlorogenic acid or ethyl ferulate).
  • composition P4 outside the invention not comprising any organic acid ester, becomes colourless after ageing. It is thus seen that despite the presence of ethanol in large amount (predominant amount of ingredient in the composition), the composition according to the invention conserves for a longer time its base colour originating from anthocyani(di)n natural dyes due to the presence of the organic acid ester of formula (I) according to the invention.
  • the fragranced composition according to the invention is more stable over time and with respect to external attacking factors such as light, than a composition not in accordance with the invention.

Abstract

The present invention relates to a fragranced composition comprising: a) at least one organic acid ester of formula (I), or a geometrical isomer thereof, an organic or mineral acid or base salt thereof, or a solvate thereof, in particular hydrates: (I) b) at least one water-soluble dye that is natural or of natural origin chosen from anthocyani(di)ns and derivatives thereof; and c) at least one fragrancing substance.

Description

Description
FRAGRANCED COSMETIC COMPOSITION COMPRISING AT LEAST ONE ORGANIC ACID ESTER, AN ANTHOCYANI(DI)N DYE AND A FRAGRANCING MATERIAL
Technical field
The present invention is directed towards proposing a novel fragranced cosmetic composition, notably for the field of fragrancing keratin materials and/or clothing, but also for caring for and/or making up keratin materials.
In general, the formulation of environmentally friendly cosmetic products has become a major challenge for meeting new consumer expectations, in particular regarding natural and/or eco-friendly products, i.e. products whose design and development take into account their environmental impacts.
It is thus common practice to seek to replace synthetic compounds present in cosmetic compositions with natural ingredients and/or ingredients of natural origin.
These considerations have notably given rise to the development of green chemistry, also known as sustainable chemistry or ecological chemistry, which envisages the implementation of principles for reducing and eliminating the use or generation of environmentally unfriendly substances.
The guiding principle of “Green Chemistry”, put forward in 1991, is to reduce or eliminate at source the use of hazardous substances in the design of new products.
These environmental problems concern all cosmetic products, notably fragranced compositions.
Human beings have always sought to perfume themselves and to perfume the objects surrounding them or their environments, both to mask strong and/or unpleasant odours and to give a nice odour.
It is common practice to incorporate perfume into a certain number of products or compositions, in particular cosmetic and dermatological compositions such as eaux fraiches, eaux de toilette, eaux de parfum, perfume elixirs or extracts, aftershave lotions, care fluids or two-phase lotions.
For aesthetic and manufacturing cost reasons, perfumes are coloured by adding an effective amount of dyestuff to the formulation support (which is generally alcoholic or aqueous- alcoholic) rather than tinting or lacquering the bottle, which is a more expensive industrial operation.
Dyestuffs that may be mentioned more particularly include water-soluble dyes that are natural or of natural origin.
Among these water-soluble dyes, natural anthocyanin dyes, belonging to the family of polyphenols or ortho-diphenols and flavonoids, have already been widely used in the pharmaceutical and food industries. These compounds are essentially the source of the mauve, red, blue and purple colours of flowers, leaves, fruit such as grapes, blackberries and plums, vegetables such as red cabbage, red radish or purple sweet potato, seeds and roots.
It is generally accepted that it is when they are in a dilute form in aqueous media that these compounds give the most intense and in this respect the chromatic colour that is the most particularly interesting for the cosmetic field.
Unfortunately, the use of natural dyes and in particular of anthocyanins and anthocyanidins, in the form of aqueous solutes, poses difficulties notably in terms of colour stability, with regard to certain perfumes dedicated to incorporating them, generally formulated in alcoholic or aqueous -alcoholic medium, in particular when the ethanol content is high, i.e. greater than 15% by weight.
In addition, it is known, for example in the wine sector, and this being even at a lower amount of alcohol (i.e. a content of less than or equal to 15% by weight of alcohol), that the anthocyanin and anthocyanidin dyes that are dissolved and in suspension undergo numerous chemical reactions, notably electrophilic substitutions on the electron-rich ring A (hemiacetal form) of the flavylium cation and nucleophilic additions on ring C which is the electrophilic pyrylium ring of said flavylium cation (Fulcrand, H. et al, Am. J. Enol. Vitic, 57 (3), 289-297 (2006). Cheynier, V. et al. Am. J. Enol. Vitic. 57 (3), 298-305 (2006)). A wide variety of anthocyanin and anthocyanidin derivatives form during the preparation and ageing of wine, including flavanol/anthocyanin adducts with the presence of bridges bearing two carbon atoms originating from the oxidation of ethanol (He, J., Oliveira, et al. J. Agric. Food Chem, 58 (15), 8814-8819 (2010), de Freitas, V.; Mateus, N. Anal. Bioanal. Chem., 2011, 401 (5), 1463-1473 (2011), and Trouillas P. et al., Chem. Rev., 116, 4937-4982 (2016)). These chemical transformations have the effect of changing the colour of the starting anthocyans and anthocyanidins. It has even been observed that by increasing the ethanol content, the stability of anthocyanins and anthocyanidins, notably of malvidin 3- monoglucoside, acetosyringone or syringaldehyde, decreases very significantly (Dufour C. and Sauvaitre L, J. Agric. Food. Chem., 48, 1784-1788 (2000)).
Added to this, mention should also be made of the known conventional degradations on anthocyanin and anthocyanidin dyes notably due to atmospheric oxygen oxidation and thermal or photochemical reactions, in the presence or absence of acids, and/or during storage, further impairing the colour of said dyes (Yesi Armalina, et al. Asian Journal of Pharmaceutical Research and Development. 8(5): 75-81, (2020); Furtado P. et al. J. Photochem. and Photobiol. A: Chemistry, Vol. 75, 2, 113-118, (1 Nov. 1993), Castaneda- Ovando, A et al., A Review. Food Chem., 113 (4), 859- 759, 871 (2009), Jackman, R.L et al., J. Food Biochem., Ill, 11 (3), 201-247. 772 (1987), Cavalcanti, R.N. et al., Food Res. Int. 44 (2), 499-509 (2011), V. Gerard, /. Agric. Food Chem., DOI:
10.1021/acs.jafc.9b01672; April 2019; J. Agric. Food Chem. 66, 6790-6798 (2018)). It has been proposed in the agrifood sector to add to the dyes, for example, ascorbic acid, lysine, glutathione and derivatives, or even to cover with a coating of “candy” type, or even to encapsulate the food comprising anthocyanin and anthocyanidin dyes in order to stabilize the colour of said dyes (V. Gerard, J. Agric. Food Chem., DOI: 10.1021/acs.jafc.9b01672 (April 2019), JP 5632555 B 1, US 8623429 B2, WO 2015/017606 Al and WO 2013/010967 Al). These compositions do not comprise any fragrancing substance.
Thus, there is great interest in seeking to stabilize the colour developed in cosmetic formulations, notably fragranced formulations and in particular in aqueous-alcoholic medium, starting with dyes of natural origin such as anthocyani(di)n dyes, and to do so not only over time but also when exposed to light and/or heat and/or atmospheric oxygen. In addition, any interaction of the fragrancing products with the anthocyanin and anthocyanidin dyes, changing the odours over time, should be avoided, whether or not such interaction is in the presence of heat and/or light.
Prior art
In order to ensure the stability of fragranced formulations, it has already been proposed to incorporate therein a filtering system and/or an antioxidant system.
Thus, a certain number of documents in the cosmetics field, notably EP 1 897 592 and WO 2005/042 828, propose fragranced compositions, notably including dyes, comprising UV- screening agents as stabilizer, alone or in combination, in particular of the alkyl b,b’- diphenylacrylate or alkyl a-cyano-b,b’ -diphenyl aery late type, such as octocrylene, dibenzoylmethane derivatives, cinnamates or alternatively camphor and triazine derivatives, but also certain particular benzotriazole compounds, or screening agents of the aminobenzophenone type.
Firstly, these prior art documents are not in any way directed towards the use of water- soluble natural dyes or dyes of natural origin belonging to the ortho-diphenol family and thus do not take into account the specificities of these dyes.
Moreover, the screening and/or antioxidant systems proposed in these documents have certain drawbacks.
In particular, certain screening agents such as alkyl b,b’ -diphenylacrylate or alkyl a-cyano- b,b’ -diphenylacrylate compounds, for instance octocrylene, are not always satisfactory for stabilizing the tints while at the same time maintaining the odour of the perfumes. The reason for this is that certain screening agents may leave an unpleasant odour in the formulation. Synthetic screening agents, such as ethylhexyl methoxycinnamate, are also not satisfactory for stabilizing dyestuffs, in particular in terms of conservation of the colour intensity and/or of the chromaticity of the coloured solution with respect to light and/or over time, and piperidinol derivatives have the drawback of causing yellowing in eaux de toilette and also a spurious odour with a “chemical” connotation.
Benzotriazole compounds, in particular bumetrizole, are, for their part, difficult to dissolve in eaux de toilette and have a tendency to recrystallize over time, in addition to having low stabilizing power. Finally, aminobenzophenone screening agents give a yellow colour that is not desirable for pale-coloured fragranced formulations other than yellow.
Besides the potential problems mentioned above associated with their presence, generally speaking, the sunscreens proposed to date, such as ethylhexyl methoxycinnamate, are synthetic.
However, as mentioned previously, an ever-increasing number of users are in search of coloured fragranced compositions that are “ less chemical” and more environmentally friendly. These users may perceive synthetic compounds negatively, notably as compounds that are harmful to their health and to the environment. Thus, coloured fragranced compositions comprising synthetic sunscreens are not entirely satisfactory to consumers who favour natural compounds or compounds of natural origin over synthetic compounds. What is more, these coloured fragranced compositions generally do not respect the principles of green chemistry.
There is thus every interest in finding a means for stabilizing the colour of fragrancing compositions, if possible with natural products or products of natural origin.
Moreover, it has already been sought to specifically stabilize water-soluble natural dyes or dyes of natural origin, notably of anthocyan type, in cosmetic or food compositions.
In this respect, WO 2017/162 599 describes the stabilization of water-soluble natural dyes or dyes of natural origin using specific polymeric surfactants and/or fillers. Also, WO 2009/031 051 proposes to stabilize anthocyanin extracts with a stabilizing compound comprising a thiol group, in the food composition sector.
However, said documents do not in any way concern the formulation of fragrancing compositions.
Finally, certain dyestuffs contained in coloured fragranced compositions may leave traces when they are applied to keratin materials and/or clothing, and in particular may have the drawback of staining clothing.
Disclosure of the invention
The need thus remains to find novel fragranced formulations coloured with natural dyes or dyes of natural origin, notably aqueous or aqueous -alcoholic formulations, which remain stable over time and under the effects of light and of oxygen.
In particular, the need remains for coloured fragranced cosmetic compositions for which the evolution of the organoleptic properties, namely the odour and/or the colour, in particular at least the colour, is controlled over time, and this being achieved if possible by means of compounds which adhere to at least one of the twelve principles of green chemistry.
In addition, there is a need for such compositions whose formulation adheres to at least one of the twelve principles of green chemistry, in particular comprising ingredients derived from green chemistry.
Finally, the need remains to propose coloured fragranced cosmetic compositions which leave few or no traces, in particular on clothing, when they are used.
The present invention is specifically directed towards meeting these needs.
Summary of the invention Thus, according to a first of its aspects, the present invention relates to a fragranced composition, notably a cosmetic composition, comprising: a) at least one organic acid ester of formula (I), or a geometrical isomer thereof, organic or mineral acid or base salts thereof, or solvates thereof, in particular hydrates:
[Chem 1]
Figure imgf000007_0001
in which formula (I):
R1, R4 and R5 represent, independently of each other, a hydrogen atom or a hydroxyl group, preferably a hydrogen atom;
R2 represents a hydrogen atom, a hydroxyl group or a (C1-C6)alkoxy group, preferably a (Ci- C4)alkoxy group, in particular methoxy;
R3 represents a hydroxyl group or a (C1-C6)alkoxy group, preferably a hydroxyl group; and R6 represents a group chosen from: i) (C1-C6)alkyl, preferably (C1-C4)alkyl, in particular methyl or ethyl, optionally substituted with one or more groups chosen from hydroxyl, amino, carboxyl and/or amido, preferably hydroxyl and/or carboxyl, ii) cycloalkyl, optionally substituted with one or more groups chosen from (Ci- Cio)alkyl, (C2-Cio)alkenyl, hydroxyl, amino, carboxyl and/or amido, preferably hydroxyl and/or carboxyl, and iii) glycosyl, b) at least one water-soluble dye that is natural or of natural origin chosen from anthocyani(di)ns and derivatives thereof; and c) at least one fragrancing substance.
The inventors have found, surprisingly, that the combination of an organic acid ester of formula (I) as defined above, in a fragranced composition, with at least one fragrancing substance and at least one water-soluble dye that is natural or of natural origin of anthocyanidin or anthocyanidin derivative type allows efficient stabilization of said composition.
Specifically, as emerges from the examples given below, the composition according to the invention is stable, in the sense that the evolution of the colour of the composition remains low over time, even under conditions simulating accelerated ageing of the composition, notably in aqueous -alcoholic medium, and with respect to light.
Thus, according to another of its aspects, the invention also relates to the use of an organic acid ester of formula (I), as a stabilizer in a fragranced composition, notably a cosmetic composition, notably an aqueous or aqueous-alcoholic composition, also comprising at least one water-soluble dye that is natural or of natural origin chosen from anthocyani(di)ns and derivatives thereof, and at least one fragrancing substance.
A composition according to the invention is in particular intended for the cosmetic treatment of keratin materials.
Thus, according to another of its aspects, the invention relates to a cosmetic process for treating keratin materials, in particular the skin, comprising at least one step of applying a composition according to the invention to said keratin materials.
The invention also relates to a cosmetic process for treating keratin materials, in particular the skin, or clothing, comprising at least one step of applying a fragranced composition according to the invention to said keratin materials and/or said clothing.
It is understood that the cosmetic treatment processes targeted in the present patent application are non-therapeutic.
A composition according to the invention is notably intended to be used in order to fragrance keratin materials and/or clothing.
Thus, according to another of its aspects, the invention also relates to a process for fragrancing keratin materials, notably the skin, and/or clothing, comprising the application of the composition as defined above to said keratin materials and/or to said clothing. Advantageously, the composition may be applied by spraying, notably using a spray.
Also, the composition according to the invention is notably intended for use for caring for and/or making up keratin materials. Thus, according to another of its aspects, the invention also relates to a process for caring for and/or making up keratin materials, notably the skin, comprising the application of the composition as defined above to said keratin materials.
In the context of the present invention, and unless otherwise indicated, the following definitions apply:
For the purposes of the present invention, the term ‘‘ fragranced composition” or ‘ fragrancing composition” is intended to denote any composition which leaves a perfume on keratin materials after application.
A perfume is the result of a combination of different odorous substances which each provide a specific diffusing odour or “note” and which respectively evaporate at different periods. More precisely, each perfume has what is known as a “ head note”, which is the odour that diffuses first when the perfume is applied or when the receptacle containing it is opened, a “ heart or body note”, which corresponds to the full fragrance (given off for a few hours after the “ head note”) and a “base note”, which is the most persistent odour (given off for several hours after the “ body note”). The persistence of the base note corresponds to the remanence of the perfume.
For the purposes of the present invention, the term “ keratin materials” is notably intended to denote the skin, the lips, the hair, the scalp, the eyelashes and the eyebrows or else the nails, in particular the skin and/or the lips, and preferably the skin.
In other words, a fragranced composition according to the invention is said to be “coloured” . The term “ coloured composition” means a composition which appears to the human eye to have a colour of the visible spectrum, i.e. which appears to the eye as different from white or colourless, namely a composition which absorbs in the yellow, orange, red, purple, violet, blue and green ranges. Such a composition may be opaque or clear, preferably clear.
For the purposes of the present invention, the term “clear” means that the composition is transparent, i.e. it allows light to pass through and objects that are located behind it are seen in sharp definition.
In particular, to evaluate the transparency of a composition according to the invention, a conventional commercial untinted, transparent borosilicate, soda-lime or neutral glass test tube such as a test tube made of Pyrex® or Duran® glass, 16 cm tall and 1.6 cm in diameter is taken and is filled to 14 cm of said tube (the bottom of the meniscus of the composition in the tube is located 14 cm from the bottom of the tube), and a page of published international patent application (in A4 format) is placed behind it at a distance of 1 cm; and by placing the eyes at a distance (reading focal length relative to the test tube) of between 20 cm and 40 cm, such as 30 cm, and perpendicular to the middle of the composition of said tube (about 7 cm from the bottom of said tube), an evaluation is made as to whether or not it is possible to read distinctly said page of the published international patent application, notably the first page, through the composition in said tube. It is understood that the tester has good vision, or that he is equipped with spectacles, contact lenses or any other optical devices that he normally wears for reading. Use may be made, for example, of patent application WO 2018/104 428 and evaluate the sharpness, i.e. the ability to read the 31 lines of page 13 to perform the test or, better still, to perform the reading test on the first page.
The term “dye” or “ dyestuff ’ is intended to denote any compound that is capable of colouring the fragranced composition, i.e. any compound which absorbs in the visible spectrum, in particular so as to appear to the human eye to have a colour such as yellow, orange, red, violet, blue or green.
As visual colour and absorption wavelength associated with said colour, mention may be made of the following colours: “yellow” = λmax greater than 400 nm up to 440 nm limits inclusive, “orange” = λmax greater than 440 nm up to 490 nm limits inclusive, “red” = λmax greater than 490 nm up to 520 nm limits inclusive, “purple” = λmax greater than 520 nm up to 560 nm limits inclusive, “violet” = λmax greater than 560 nm up to 580 nm limits inclusive, “blue” = λmax greater than 580 nm up to 620 nm limits inclusive, “blue-green” = λmax greater than 620 nm up to 650 nm limits inclusive, and “green” = λmax greater than 650 nm up to 780 nm limits inclusive.
A fragranced coloured composition may be in any form that is suitable for its application to keratin materials and/or clothing. It may notably be in liquid or solid form, for example in powder form.
The term “ powder ” means a composition in pulverulent form, which is preferably essentially free of dust. In other words, the particle size distribution of the particles is such that the weight content of particles which have a size of less than or equal to 50 pm (content of fines), preferably less than or equal to 10 pm (content of fines) is advantageously less than or equal to 5%, preferably less than 2% and more particularly less than 1% (particle size evaluated using a Retsch AS 200 Digit particle size analyser; oscillation height: 1.25 mm/screening time: 5 minutes). Advantageously, the particle size is between 10 pm and 500 pm. The powder of solid natural material(s) may be screened to obtain particles with upper limit sizes corresponding to the orifices or mesh sizes of the screen particularly between 35 and 80 mesh (US). According to a particular mode of the invention, the size of the particles of the powder of solid natural material(s) is fine. According to the invention, this more particularly means a particle size of less than or equal to 900 pm. Preferentially, the powder is constituted of fine particles between 7 and 700 pm and better still between 100 nm and 500 pm in size. For the purposes of the present invention, the term ‘‘ fragrancing substance ” means any odorous starting material or aroma that is capable of giving off a pleasant odour, in particular as defined in the continuation of the text. For the purposes of the present invention, ‘fragrancing” , “ odorous ” or “ odoriferous ” substances are synonymous.
A composition according to the invention is generally suitable for application to keratin materials, in particular topical application to the skin, and thus generally comprises a physiologically acceptable medium, i.e. a medium that is compatible with the skin.
It is preferably a cosmetically acceptable medium, i.e. a medium which has a pleasant colour, odour and feel and which does not cause any unacceptable discomfort, i.e. stinging, tautness or redness, liable to discourage the user from applying this composition.
For the purposes of the present invention, a “ stabilizer ” is intended to denote a compound that is capable of stabilizing the fragranced composition comprising same, in particular in terms of conservation of its organoleptic properties with respect to external attacking factors, notably to light, or temperature or oxygen differences, in particular the colour and/or the odour of said composition.
A (Cx-Cz)alkyl group represents a linear or branched hydrocarbon-based chain comprising from x to z carbon atoms. For example, a (C1-C6)alkyl group represents a linear or branched hydrocarbon-based chain comprising from 1 to 6 carbon atoms.
A (Cx-Cz)alkenyl group represents a linear or branched hydrocarbon-based chain comprising from x to z carbon atoms, and comprising one or more conjugated or non-conjugated unsaturations, preferably only one unsaturation. For example, a (C2-C10)alkenyl group represents a linear or branched hydrocarbon-based chain comprising from 2 to 10 carbon atoms and comprising one or more unsaturations.
A (Cx-Cz)alkoxy group represents a radical -O-(Cx-Cz)alkyl in which the (Cx-Cz)alkyl group is as defined previously. The term “ cycloalkyl ” means a fused or non-fused, more preferentially fused, saturated or unsaturated, preferably saturated, non-aromatic, monocyclic or polycyclic carbocycle (cyclic hydrocarbon-based group), preferably of between 2 and 5 rings, comprising from 5 to 42 carbon atoms, in particular comprising from 6 to 10 carbon atoms.
The term “aryl” means a monocyclic or fused or non-fused polycyclic carbocycle comprising from 6 to 22 carbon atoms, and in which at least one ring is aromatic; preferentially, the aryl radical is a phenyl, biphenyl, naphthyl, indenyl, anthracenyl or tetrahydronaphthyl, preferably phenyl.
The term “ glycosyl ” group is intended to denote a monovalent radical obtained from a monosaccharide or polysaccharide by replacement of one of the hemiacetal hydroxyl groups of said monosaccharide or polysaccharide with a covalent bond with the compound bearing the group.
For the purposes of the present invention, the term “ natural ” is intended to denote any compound obtained directly from the earth or the soil, or from plants or animals, via, where appropriate, one or more physical processes, for instance milling, refining, distillation, purification or filtration, or else from a biotechnological process, notably obtained from microbiological or cell cultures, for example from fungi or from bacteria. Among the “ natural ” dyes or pigments are compounds that are present in nature and that can be reproduced by chemical (semi)synthesis.
For the purposes of the present invention, the term “of natural origin” is intended to denote any compound obtained from a natural substance which has undergone one or more associated chemical or industrial treatments, giving rise to changes which do not affect the essential qualities of this substance. As non-limiting examples of additional chemical or industrial treatments bringing about modifications which do not affect the essential qualities of a natural compound, mention may be made of those permitted by the controlling bodies, such as Ecocert (Reference system for organic and ecological cosmetic products, January 2003), or defined in recognized handbooks in the field, such as Cosmetics and Toiletries Magazine, 2005, volume 120, 9:10.
According to the invention, a compound is considered to be natural or of natural origin when it is predominantly composed of natural constituents, i.e. when the weight ratio of natural constituents to non-natural constituents which make up the compound is greater than 1. More advantageously, the ester of formula (I) is a “ green ” compound, that is to say that it adheres to at least one of the twelve principles of green chemistry.
The American chemists Paul Anastas and John C. Warner, who were members of the EPA (“ United States Environmental Protection Agency”), proposed twelve principles of green chemistry in 1998 in the publication “ Green chemistry: theory and practice”, Oxford Science, New York, P. T. Anastas et al, (1998). The indicators of green chemistry, such as the E-factor or the economy of atoms, make it possible to measure the various aspects of a chemical process by referring to the principles of green chemistry. The publications Kirk- Othmer, Encyclopedia of Chemical Technology, Green Chemistry, Michael A. Matthews, 2013, volume 12, pages 799 to 818, and Ibid., Green Chemistry, Applications, Albert S. Matlack, pages 1 to 33, illustrate such indicators.
For the purposes of the present invention, the term “ geometrical isomer” is understood to denote any molecule whose constitution is identical to that of formula (I) defined above, but in which the spatial organization of the atoms is different. In particular, they may be conformational stereoisomers, i.e. compounds which differ in their rotation around a single bond, or configurational stereoisomers, in particular enantiomers or diastereoisomers.
The term “ anionic counterion” means an anion or an anionic group derived from an organic or mineral acid salt which counterbalances the cationic charge of the dye; more particularly, the anionic counterion is chosen from: i) halides such as chloride or bromide; ii) nitrates; iii) sulfonates, including C1-C6 alkylsulfonates: Alk-S(O)2O- such as methylsulfonate or mesylate and ethylsulfonate; iv) arylsulfonates: Ar-SO)2O- such as benzenesulfonate and toluenesulfonate or tosylate; v) citrate; vi) succinate; vii) tartrate; viii) lactate; ix) alkyl sulfates: Alk-O-S(O)O- such as methyl sulfate and ethyl sulfate; x) aryl sulfates: Alk-O- S(O)O- such as benzene sulfate and toluene sulfate; xi) alkoxy sulfates: Alk-O-S(O)2O- such as methoxy sulfate and ethoxy sulfate; xii) aryloxy sulfates: Ar-O-S(O)2O-, xiii) phosphates O=P(OH)2-O-, O=P(O )2-OH O=P(O )3, HO-[P(O)(O )]W-P(O)(O )2 with w being an integer; xiv) acetate; xv) triflate; and xvi) borates such as tetrafluoroborate; xvii) disulfate (O=)2S(O-)2 or SO42- and monosulfate HSO4-; the anionic counterion, derived from the organic or mineral acid salt, ensures the electrical neutrality of the molecule.
Moreover, the addition salts that may be used in the context of the invention are notably chosen from addition salts with a cosmetically acceptable base such as the basifying agents as defined below, for instance alkali metal hydroxides such as sodium hydroxide, potassium hydroxide, aqueous ammonia, amines or alkanolamines.
The term “at least one” is equivalent to “ one or more”.
The term “ inclusive ” for a range of concentrations means that the limits of the range are included in the defined interval.
For the purposes of the present invention, the term “ organic or mineral acid or base salt” is intended to denote a salt obtained between an ionic form of an ester of formula (I) and a corresponding counterion. In particular, such a salt is obtained by addition of an organic or mineral acid or base, which is notably cosmetically acceptable, to the ester of formula (I). Examples of mineral bases that may be mentioned include hydroxides or carbonates of alkali metals or alkaline-earth metals, such as sodium, potassium, calcium, ammonium, magnesium, lithium or sodium. Examples of organic bases that may be mentioned include amines or alkanolamines. Examples of acids that may be mentioned include hydrochloric acid, hydrobromic acid, sulfuric acid, alkylsulfonic acids, arylsulfonic acids, citric acid, succinic acid, tartaric acid, lactic acid, alkoxysulfinic acids, aryloxysulfinic acids, phosphoric acid and acetic acid.
For the purposes of the present invention, the term “ solvate ” is intended to denote the form of the ester of formula (I) when it is associated with a solvent. The solvates include conventional solvates formed during the process for the preparation of the ester of formula (I). Examples of solvates are those obtained in the presence of water or of a linear or branched alcohol, in particular ethanol or isopropanol.
The expressions “ between ... and...”, “comprises from ... to...”, “formed from ... to...” and “ranging from... to...” should be understood as being inclusive of the limits, unless otherwise specified.
Other features, variants and advantages of the compositions according to the invention will emerge more clearly on reading the description and the examples that follow.
Detailed description a) Organic acid esters of formula (I) As mentioned previously, a fragranced composition according to the invention comprises at least one organic acid ester of formula (I), or a geometrical isomer thereof, an organic or mineral acid or base salt thereof, or a solvate thereof, in particular hydrates:
[Chem 2]
Figure imgf000015_0001
in which formula (I):
R1, R4 and R5 represent, independently of each other, a hydrogen atom or a hydroxyl group, preferably a hydrogen atom;
R2 represents a hydrogen atom, a hydroxyl group or a (C1-C6)alkoxy group, preferably a (C1- C4)alkoxy group, in particular methoxy;
R3 represents a hydroxyl group or a (C1-C6)alkoxy group, preferably a hydroxyl group; and R6 represents a group chosen from: i) (C1-C6)alkyl, preferably (C1-C4)alkyl, in particular methyl or ethyl, optionally substituted with one or more groups chosen from hydroxyl, amino, carboxyl and/or amido, preferably hydroxyl and/or carboxyl, ii) cycloalkyl, optionally substituted with one or more groups chosen from (C1- C10)alkyl, (C2-C10)alkenyl, hydroxyl, amino, carboxyl and/or amido, preferably hydroxyl and/or carboxyl, and iii) glycosyl.
According to a particular embodiment of the invention, R6 represents a (C1-C6)alkyl group i), as defined above.
According to another particular embodiment of the invention, R6 represents a saturated or unsaturated, preferably saturated, non-aromatic monocyclic cycloalkyl group ii), comprising from 5 to 7 carbon atoms and optionally substituted with one or more (C1-C4)alkyl groups and/or with one or more groups chosen from hydroxyl, amino, carboxyl and/or amido, preferably hydroxyl and/or carboxyl.
In particular, the cycloalkyl group is cyclohexyl, optionally substituted with 1 to 5 hydroxyl and/or carboxyl groups. In particular, the cycloalkyl group is cyclohexyl and is optionally substituted with one or more groups chosen from hydroxyl, amino, carboxyl and/or amido, preferably hydroxyl and/or carboxyl. More particularly, the cycloalkyl group is cyclohexyl, optionally substituted with 1 to 5 hydroxyl and/or carboxyl groups.
According to another particular embodiment of the invention, R6 represents a polycyclic cycloalkyl group ii), preferably comprising between 2 and 5 fused rings, comprising from 12 to 32 carbon atoms and being optionally substituted; in particular, the cycloalkyl is a polycyclic group comprising between 4 and 5 fused rings, said rings being 3-, 5- or 6- membered and containing 16 to 20 carbon atoms, better still 17 or 18 carbon atoms, said cycloalkyl being optionally substituted with one or more linear or branched (C1-C10)alkyl or linear or branched (C1-C10)alkenyl groups.
Preferably, the organic acid ester is of formula (I) in which:
R1, R4 and R5 represent hydrogen atoms;
R2 represents a hydroxyl group or a (C1-C6)alkoxy group, preferably a (C1-C4)alkoxy group, in particular methoxy;
R3 represents a hydroxyl group or a (C1-C6)alkoxy group; and
R6 represents a group chosen from i) (C1-C6)alkyl, preferably (C1-C4)alkyl, and also the geometrical isomers thereof, the organic or mineral acid or base salts thereof, and the solvates thereof such as hydrates.
According to a particularly preferred embodiment, the ester of formula (I) is of formula (I') below:
[Chem 3]
Figure imgf000017_0001
in which formula (I'):
R6 is as defined above; and
R7 represents a hydrogen atom or a C1-C6 alkyl group.
According to one embodiment, the organic acid ester may more particularly be of formula (I') in which R6 represents a (C1-C6)alkyl and preferably (C1-C4)alkyl group, preferably an ethyl group; and R7 is a (C1-C6)alkyl and preferably (C1-C4)alkyl group, preferably a methyl group.
According to this embodiment, ethyl ferulate is preferred.
According to one embodiment, the organic acid ester may more particularly be of formula (I') in which R6 represents a saturated monocyclic cycloalkyl group comprising from 5 to 7 carbon atoms, optionally substituted with one or more groups, preferably between 1 and 4 groups, chosen from hydroxyl and/or carboxyl; and R7 is a hydrogen atom.
According to this embodiment, chlorogenic acid is preferred.
According to one embodiment, the organic acid ester may more particularly be of formula (I') in which R6 represents a polycyclic group comprising between 3 and 5 saturated fused rings, comprising between 16 and 20 carbon atoms, substituted with at least one, preferably at least two, (C1-C4)alkyl groups, preferably ethyl, and with at least one, preferably one, branched (C8-C10)alkenyl or (C8-C10)alkyl group, and R7 is a (C1-C6)alkyl and preferably (C1-C4)alkyl group, preferably a methyl group.
According to another embodiment, oryzanol, and in particular Gamma-oryzanol, is particularly preferred.
The compounds of formulae (I) and (I') in accordance with the invention are preferably chosen from natural compounds or compounds of natural origin. They are preferably “green” compounds. As particular examples of esters of formula (I) or (I'), mention may be made of methyl ferulate, ethyl ferulate, chlorogenic acid, isopropyl ferulate or ferulic acid esters of sterols, such as oryzanol, notably gamma-oryzanol.
The compounds of formulae (I) and (I') may be obtained via any method known to those skilled in the art.
For example, the ferulic acid esters may be obtained by esterification of ferulic acid, which is itself obtained, for example, by biosynthesis via methoxylation of caffeic acid using the enzyme caffeic acid-0 -methyl transferase , or by extraction from a plant extract, in particular wheat bran, for example using concentrated bases such as sodium hydroxide and potassium hydroxide.
Gamma-Oryzanol may be obtained by extraction using an organic solvent, notably from rice bran.
The compounds of formula (I) or (I') defined above may optionally be introduced into a fragranced composition according to the invention in the form of a plant extract. For example, Gamma-oryzanol may be used in the form of a rice bran extract. Chlorogenic acid may be used in the form of an extract of green coffee, blackcurrant, sunflower, artichoke, honeysuckle, plum, apple, potato, sweet potato, blueberry, arnica or damask rose.
A certain number of compounds of formula (I) or (I') are also commercially available, for instance Gamma-oryzanol available under the trade name Oryzanol® from the company Tsuno Rice Fine Chemicals, Gamma Oryzanol® from the company Ikeda or Oryzanolgamma V® from the company Ichimaru Pharcos, ethyl ferulate under the reference Ethyl Ferulate, Natural or COS by the company Gfn Selco, also available from Sigma-Aldrich, and chlorogenic acid under the reference Eucommia Leaves Extract Chlorogenic Acid 98% by the company Guilin Layn Natural Ingredients.
Preferably, a composition according to the invention comprises an organic acid ester chosen from ethyl ferulate, oryzanol and in particular Gamma-oryzanol, chlorogenic acid, and mixtures thereof.
A fragranced composition according to the invention may comprise from 0.01% to 5.0% by weight, in particular from 0.03% to 2.0% by weight, preferably from 0.05% to 1.0% by weight and more preferentially from 0.1% to 0.8% by weight of organic acid ester(s) of formula (I), relative to the total weight of said composition. As mentioned above, the ester of formula (I) may be used in the form of a plant extract also known as a “ crude raw material ”, comprising one or more compounds of formula (I) as defined previously. Thus, a fragranced composition according to the invention may comprise, for example, from 2.0% to 20% by weight of plant extract containing at least one organic acid ester of formula (I), relative to the total weight of said composition. b) Water-soluble anthocyani(di)n dye which is natural or of natural origin
As mentioned previously, a fragranced composition according to the invention comprises at least one water-soluble dye that is natural or of natural origin, chosen from anthocyani(di)ns and derivatives thereof.
For the purposes of the invention, the term “ water-soluble dye ” denotes any natural or synthetic, generally organic dye, which is soluble in an aqueous phase or in water-miscible solvents. In particular, a dye is water-soluble when its solubility in water, measured at 25 °C, is at least equal to 0.01 g/L.
The term “ anthocyani(di)ns and derivatives ” refers to any natural dye belonging to the flavonoid family in the broad sense, comprising a phenyl benzopyrylium cation. More precisely, the anthocyanidins, also known as “anthocyanidols”, cover “anthocyanidins”, i.e. compounds comprising a phenyl benzopyrylium cation (II) as defined below including a hydroxyl group on the carbon atom in position 3 of ring C (corresponding to the radical R3 of formulae (IIA) and (lie)) and “anthocyanins” comprising an -O-Sugar group on the carbon atom in position 3 of ring C (corresponding to the radical R3 of formulae (IIA), (HB), (He) and (IID)).
The term anthocyani(di)n “ derivatives ” is more specifically intended to denote heterosides derived from the condensation of a sugar or “saccharide” with the anthocyani(di)n molecule (non-carbohydrate molecule referred to as an “aglycone”), optionally bearing one or more acyl groups, and/or cosmetically acceptable salts thereof. In particular, the heteroside derivatives of the anthocyani(di)ns are also known as anthocyans, anthocyanosides or anthocyanins.
The term “ acyl ” means that at least one hydroxyl group of a sugar undergoes the condensation (esterification) of a hydroxyl group with a carboxyl group of another molecule (i.e. of a carboxylic acid notably of formula (I) or (I') as defined previously) to form an ester bond. The anthocyani(di)n natural dyes of the invention comprise in their chemical structures a phenyl benzopyrylium cation (II), notably 2-phenylchromenylium or 2- phenylbenzopyrilyum or 3-phenylchromenylium, preferably 2-phenylchromenylium having the following formula, and also the optical isomers thereof, the geometrical isomers thereof, the tautomers thereof, the organic or mineral acid or base salts thereof, and the solvates thereof such as hydrates:
[Chem 4]
Figure imgf000020_0001
in which formula (II):
- ring A comprises at least one hydroxyl or -O-Sugar group, particularly two hydroxyl groups or one hydroxyl group and one -O-Sugar group, preferably located on the carbon atoms in position 5 and/or 7;
- ring B is connected to ring C on carbon atoms 2, 3 or 4, particularly on the carbon atoms in position 2 or 3, preferably on carbon atom 2; ring B comprises at least one hydroxyl group, particularly at least two hydroxyl groups, or at least one hydroxyl group and at least one (Ci- C6)alkoxy group; and
- ring C preferably comprises, in position 3, a hydroxyl or -O-Sugar group.
The term “O-Sugar” means a monosaccharide radical or a polysaccharide radical consisting of 2 to 5 saccharide units, in particular from 2 to 3 and preferably 2 saccharide units connected to the rest of the molecule via an oxygen atom. Structurally, the anthocyani(di)ns are substituted glycoside salts and acyl glycosides of 2-phenylbenzopyrylium.
According to one embodiment of the invention, the anthocyani(di)ns are of formula (IIA) below, and also the optical or geometrical isomers thereof, the tautomers thereof, the organic or mineral acid or base salts thereof, and the solvates thereof such as hydrates:
[Chem 5]
Figure imgf000021_0001
in which formula (IIA):
- R3 represents a hydrogen atom or hydroxyl (OH), or -O-Sugar, preferably hydroxyl or -O- Sugar; “O-Sugar” denoting a monosaccharide radical or a polysaccharide radical consisting of 2 to 5 saccharide units, in particular from 2 to 3 and preferably 2 saccharide units connected to the rest of the molecule via an oxygen atom; in particular, Sugar is as defined below, notably glucoside;
- R5 and R7, which may be identical or different, represent a hydrogen atom or a (C1-C6)alkyl, (C1-C6)alkoxy or hydroxyl group, preferably a hydroxyl group; - R6 represents a hydrogen atom or a (C1-C6)alkyl, (C1-C6)alkoxy, (di)(C1-C6)(alkyl)amino, hydroxyl or -O-Sugar group, preferably hydrogen;
- R’3 represents a hydrogen atom or a (C1-C6)alkyl, (C1-C6)alkoxy such as methoxy, hydroxyl or -O-Sugar group; preferably a hydrogen atom or a (Ci-COalkoxy such as methoxy, or hydroxyl group; - R’4 represents a hydrogen atom or a (C1-C6)alkyl, (C1-C6)alkoxy, hydroxyl or -O-Sugar group, preferably a hydroxyl group;
- R’5 represents a hydrogen atom or a (C1-C6)alkyl, (C1-C6)alkoxy such as methoxy, hydroxyl or -O-Sugar group; preferably a hydrogen atom or a (Ci-COalkoxy such as methoxy, or hydroxyl group, more preferentially a hydrogen atom; and - Q" represents an anionic counterion.
According to a preferred embodiment, the sugar is attached to the oxygen atom of the -O- Sugar via carbon atom Ci of the 3- or 4-membered monosaccharide of the following -Sugar radical:
[Chem 6]
Figure imgf000022_0001
Ra representing a hydrogen atom, a (C1-C4)alkyl group such as methyl or a (poly)hydroxy(C1-C4)alkyl group such as hydroxymethyl or 1,2-dihydroxy ethyl, the hydroxyl group(s) of the (poly)hydroxy(C1-C4)alkyl group being substituted with A as defined below; it being understood that the radical Ra is in position C5 if the sugar unit is in pyranose form or in position C4 if it is in furanose form;
Re represents a hydrogen atom or a group -CH2-O-A, preferably hydrogen;
A representing a (C1-C6)alkyl group or a group Rd-C(O)-, and Rd representing a group from among: i) (C1-C4)alkyl optionally substituted with one or more hydroxyl and/or carboxyl groups, ii) aryl optionally substituted with one or more hydroxyl and/or (C1-C4)alkoxy groups such as methoxy, iii) aryl(C2-C4)alkenyl optionally substituted with one or more hydroxyl and/or (C1-C4)alkoxy groups such as methoxy; in particular, A represents Rd-C(O)- with Rd representing ii) an aryl group optionally substituted with one or more hydroxyl groups, such as hydroxyphenyl (4-hydroxyphenyl) or iii) an aryl(C2-C4)alkenyl group, notably styryl, the phenyl group of which is optionally substituted with one or more groups chosen from hydroxyl and/or (C1-C4)alkoxy such as methoxy; and n is equal to 0 or 1; preferably, n is equal to 1 and m is equal to 1, 2, 3 or 4.
Preferably Rd represents a group of formula (I”):
[Chem 7]
Figure imgf000022_0002
in which formula (I”):
R1 to R5 are as defined in formula (I); preferably, Rd represents a caffeyl or 3, 4-dihydroxy styryl, ferulyl or 3-methoxy-4- hydroxystyryl, sinapyl or 3,5-dimethoxy-4-hydroxystyryl, 4-coumaryl or 4-hydroxystyryl group.
In particular, the “Sugar” radical represents a monosaccharide which may be acylated; more particularly, said sugar is chosen from pentoses such as ribose, arabinose, xylose, lyxose, ribulose or xylulose; hexoses such as allose, altrose, galactose, glucose, gulose, idose, mannose, talose, fructose, psicose, sorbose, arabinose or tagatose, and deoxyhexoses, such as fucose or rhamnose. These monosaccharides may be of D or L configuration, preferentially of D configuration.
According to a particular embodiment, said “Sugar” radical represents a group which may be acylated chosen from glucose, rhamnose, xylose, galactose, arabinose and fructose, preferentially D-glucose, D-rhamnose, L-rhamnose, D-xylose, D-galactose, arabinose and fructose, and more preferentially D-glucose.
According to a preferred embodiment, the dye comprises at least one -O-Sugar group in which the “Sugar” radical represents a monosaccharide which may be acylated chosen from pentoses such as ribose, arabinose, xylose, lyxose, ribulose or xylulose; hexoses such as allose, altrose, galactose, glucose, gulose, idose, mannose, tallose, fructose, psicose, sorbose, arabinose or tagatose; and deoxyhexoses such as fucose or rhamnose; the monosaccharide may be of D or L configuration, preferentially of D configuration; more particularly, said “Sugar” radical represents a group which may be acylated chosen from glucose, rhamnose and xylose, preferentially D-glucose, D-rhamnose and D-xylose, and more preferentially D- glucose.
According to one embodiment of the invention, the -O-Sugar radical represents a monosaccharide radical chosen from -O-S1 to -O-S5:
[Chem 8]
Figure imgf000024_0001
-O-S1 to -O-S5 in which one or more hydroxyl groups may be replaced with a group Rd- C(O)-O-, with Rd as defined previously, preferably (C1-C4)alkyl optionally substituted with a carboxyl group, such as methyl or styryl, the phenyl group of which is optionally substituted with one or more groups chosen from hydroxyl and/or (C1-C4)alkoxy such as methoxy, preferably a replacement of the hydroxyl, notably of the hydroxyl in the position of carbon C6 of -O-S1 and C5 of -O-S5; more particularly, the -O-Sugar radical represents - O-S1, -O-S4 or -O-S5, particularly -O-S1 or -O-S4, and preferentially -O-Sugar represents: [Chem 9]
Figure imgf000024_0002
O-glucoside O-galactoside O-arabinoside preferably chosen from O-galactoside and O-glucoside, it being understood that for -O-glucoside, -O-galactoside and -O-arabinoside, a hydroxyl group may be replaced with a group -Rd-C(O)-O-, with Rd as defined previously, preferably (C1-C4 )alkyl optionally substituted with a carboxyl group, such as methyl or styryl, the phenyl group of which is optionally substituted with one or more groups chosen from hydroxyl and/or (C1-C4)alkoxy such as methoxy, preferably the replacement of the hydroxyl, notably of the hydroxyl in the position of carbon C6 of -O-glucoside and -O-galactoside. According to another embodiment, the -O-Sugar radical represents a polysaccharide radical constituted of 2 to 5 saccharide units, in particular 2 to 3, and preferably 2 saccharide units, linked together via an oxygen atom (oxy) by 1 → 4 bonding, i.e. Ci of one saccharide unit → C4 of the other saccharide unit, or by 1 → 3 bonding, i.e. Ci of one saccharide unit → C3 of the other saccharide unit, or by 1 → 6 bonding, i.e. Ci of one saccharide unit → C6 of the other saccharide unit, of which each saccharide unit is constituted of a heterocycle comprising 4 or 5 carbon atoms; more preferentially, -Sugar represents -Sugar’ of the following formula:
[Chem 10]
Figure imgf000025_0001
in which formula -Sugar’ :
- p and q are independently equal to 0, 1, 2, 3 or 4 with p + q being equal to 1, 2, 3 or 4, particularly equal to 1, 2 or 3; preferentially, p + q is equal to 1 or 2; preferably, p is equal to 0 and q is equal to 1 or else q is equal to 0 and p is equal to 1 ;
- Ra, which may be identical or different, are as defined previously for the monosaccharide -Sugar,
- Re, which may be identical or different, are as defined previously for the monosaccharide -Sugar,
- A, which may be identical or different, are as defined previously for the monosaccharide - Sugar,
- m, which may be identical or different, are as defined previously for the monosaccharide - Sugar,
- n, which may be identical or different, are as defined previously for the monosaccharide - Sugar, it being understood that the two sugar units between the brackets q and p may be inverted, i.e. they may represent the following sequence: [Chem 11]
Figure imgf000026_0001
According to this embodiment, the -Sugar” radical represents a disaccharide which may be acylated, chosen from: lactose, diglucoside or gentiobiose (6-0-β-D-glucosyl-D-glucose), maltulose, palatinose, lactulose, amygdalose, turanose, cellobiose, isomaltose, rutinose (6- O-α-L-rhamnosyl-D-glucose), sophorose (2-O-β-D-xylosyl-D-glucose), sambubiose (2-0- b-D-xylosyl-D-glucose), maltose, xylosylrutinose and glycosylrutinose; and particularly chosen from mtinose, sophorose, diglugoside or gentiobiose, sambubiose, xylosylrutinose and glycosylmtinose, more particularly chosen from mtinoside and diglucoside; said disaccharide radical being linked to the rest of the molecule via a bond between carbon atom C1 of the sugar or of one of the sugars and this bond possibly being a or b anomeric.
More particularly, -O-Sugar” represents a monosaccharide radical chosen from -O-S6 to -O-
S10: [Chem 12]
Figure imgf000027_0001
in which formulae -O-S8 and -O-S9:
- R8 represents a hydrogen atom, Rd-C(O)- with Rd representing an aryl group optionally substituted with one or more hydroxyl groups such as hydroxyphenyl (4-hydroxyphenyl) or aryl(C2-C4)alkenyl, notably styryl, the phenyl group of which is optionally substituted with one or more groups chosen from hydroxyl and/or (Ci-C4)alkoxy such as methoxy; in particular, Rd represents a group of formula (I”) as defined previously, more particularly caffeyl or 3,4-dihydroxystyryl, ferulyl or 3-methoxy-4-hydroxystyryl, sinapyl or 3,5- dimethoxy-4-hydroxystyryl, 4-coumaryl or 4-hydroxystyryl, more preferentially Rd-C(O)- a caffeoyl (3,4-dihydroxystyrylcarbonyl), feruloyl, 4-coumaroyl or sinapoyl group;
- R9 and Rio, which may be identical or different, preferably different, represent a hydrogen atom, Rd-C(O)- with Rd representing a group from among: ii) aryl optionally substituted with one or more hydroxyl groups such as hydroxyphenyl (4-hydroxyphenyl) or iii) aryl(C2- C4)alkenyl, notably styryl, the phenyl group of which is optionally substituted with one or more groups chosen from hydroxyl and/or (C1-C4)alkoxy ; in particular, Rd represents a group of formula (II”) as defined previously, more particularly methoxy (3,4-dihydroxystyryl or 3- methoxy-4-hydroxystyryl, sinapyl), more preferentially Rd-C(O)- represents a 4- hydroxyphenyl (p-hydroxyphenyl), caffeoyl or feruloyl (3-methoxy-4- hydroxystyrylcarbonyl) group, and Rio represents a hydrogen atom or an -O group.
More particularly, -O-Sugar” represents a group chosen from:
[Chem 13]
Figure imgf000029_0001
with R8 and R9 as defined previously, and more particularly defined in Table 1 below: [Table 1]
Figure imgf000030_0001
and more preferentially Cy3 and Pn3; with “O-Sugar” as defined previously, preferably chosen from S1, S4, Sugar’ and Sugar”. Notably, R3 represents a group -O-Sugar -O-S1 or -O-S4, preferably -O-S1 such as glucoside, R5 represents a disaccharide -O-Sugar”, particularly -O-S6 to -O-S8, more particularly -O- S6’ to -O-S8’. The compounds comprising acylated or non-acylated Pg, Cy, Dp, Pn, Pt, Mv are found in natural extracts of plants, notably of red cabbage.
According to one embodiment of the invention, the anthocyani(di)ns of formula (II) as defined previously are chosen from those of formula (IIB) below, and also the optical or geometrical isomers thereof, the tautomers thereof, the organic or mineral acid or base salts thereof, and the solvates thereof such as hydrates:
[Chem 14]
Figure imgf000031_0001
in which formula (IIB): R3’ represents a hydroxyl group or a (C1-C4)alkoxy group such as methoxy; and R8, R9 and Rio and Q- are as defined previously.
More particularly, the compounds of formula (IIB) are:
[Table 2]
Figure imgf000032_0001
Compounds 1 to 10 are found in natural extracts of plants, notably of violet sweet potato. Compounds 11 to 22 are found in natural extracts, notably of red radish.
According to one embodiment of the invention, the anthocyani(di)ns of formula (II) as defined previously are chosen from those of formula (lie) below, and also the optical or geometrical isomers thereof, the tautomers thereof, the organic or mineral acid or base salts thereof, and the solvates thereof such as hydrates:
[Chem 15]
Figure imgf000033_0001
in which formula (lie):
R3’ represents a hydroxyl group or a (C1-C4)alkoxy group such as methoxy, preferably a hydroxyl group; and R3 is as defined previously, and preferably represents a hydroxyl or -O-Sugar group as defined previously, preferably -O-S1 and more particularly -O-glucoside, and R7 represents a hydroxyl group or an -O-Sugar group as defined previously, preferably -O-S8, more particularly -O-S8’ with R8 preferably representing a group Rd-C(O)- with Rd representing a (C1-C4)alkyl group optionally substituted with a carboxyl and/or hydroxyl group such as acetyl [CH3-C(O)-], oxalyl [HO-C(O)-C(O)-], malonyl [HO-C(O)-CH2-C(O)-] and succinyl [HO-C(O)-CH2-CH2-C(O)-], malyl [HO-C(O)-CH(OH)-CH2-C(O)- or HO-C(O)-CH2- CH(OH)-C(O)-]; more preferentially, R8 represents a malonyl group and Q" is as defined previously.
Compounds (lie) are found in natural extracts of plants, notably of red onion. According to one embodiment of the invention, the anthocyani(di)ns of formula (II) as defined previously are chosen from those of formula (IID) below, and also the optical or geometrical isomers thereof, the tautomers thereof, the organic or mineral acid or base salts thereof, and the solvates thereof such as hydrates:
[Chem 16]
Figure imgf000034_0001
in which formula (IID):
R3’ represents a hydrogen atom or a hydroxyl group or (C1-C4)alkoxy group such as methoxy; R8 and Q- are as defined previously; preferably, R8 represents a group chosen from sinapoyl, feruloyl and 4-coumaroyl.
More particularly, the compounds of formula (IID) are chosen from:
[Table 3]
Figure imgf000034_0002
Compounds (IID), notably 23 to 29, are found in natural extracts of plants, notably in black and purple carrots.
The various anthocyani(di)n compounds of the invention differ notably in the number and position of the hydroxyl and/or (C1-C4)alkoxy groups, notably methoxy groups, attached to their position 3, 5, 6, 7, 3’, 4’ and/or 5’. The colour of the anthocyani(di)ns of the invention ranges from yellow, orange or red to purple or even blue.
For example, pelargonidol has an orange-red colour, cyanidol a red colour, peonidol a pink colour, delphinidol a blue-violet colour, petunidol a violet colour and malvidol a mauve colour (see, for example, Critical Reviews in Analytical Chemistry, J. M. Bueno et ah, “Analysis and Antioxidant Capacity of Anthocyanin Pigments. Part II: Chemical Structure, Color, and Intake of Anthocyanins” 42: 126-151, (2012)).
These dyes may notably be characterized by the following CAS numbers: 134-01-1, 134- 04-3, 528-53-0, 528-28-5, 643-84-5, 1429-30-7, 11029-12-2, etc., and defined by the “CTFA - International Color Handbook” , Third Edition, CTFA, pages 856-857.
They are responsible for the natural colour of leaves, petals and fruit, and are more precisely located in the vacuoles of the cells.
Preferably, the natural anthocyani(di)ns of the invention are derived from extracts of plants or plant parts. For the purposes of the invention, said extracts will be assimilated in their entirety as compound b).
The anthocyanidin dye(s) of the invention are present in the form of extracts from plants, notably chosen from extracts of blueberry, blackberry, loganberry, black grape, blood orange, a<jai berry, chokeberry, aubergine, cranberry, purple potato, purple sweet potato, plum, sloe, cornflower (wild lowbush blueberry, not to be confused with cornflower), mallow, red grape (and red wine), strawberry, raspberry and black raspberry, banana, cranberry, red radish, potato, apple (notably the skin or peel), elderberry, peach, pear, fig, cherry, onion, notably red onion, redcurrant, red cabbage, rhubarb, blackcurrant, violet (purple) carrot, passionfruit, stringbean, pomegranate, grape, black rice, black bean, blue and purple maize, blue and purple maize grain, and blue and purple maize leaves. They give their colour both to autumn leaves and to red fruit.
These natural dyestuffs may be used in a form dissolved in an aqueous phase.
As formulations of anthocyani(di)n dyes that are suitable for use in the invention, mention may be made notably of anthocyani(di)n emulsions containing from 5% to 40% by weight or even from 25% to 35% by weight of anthocyani(di)ns, and in the presence or absence of surfactant, preferably without surfactants. According to a particular embodiment, the water-soluble dyes that are natural or of natural origin, that are suitable for use in the invention, are derived from extracts of bacteria, fungi, algae or plants, used in their entirety or partially.
They are preferentially derived from extracts of plants or plant parts such as the fruit, including citrus fruit, vegetables, trees and shrubs. Mixtures of these extracts may also be used.
Thus, the water-soluble dye(s) that are natural or of natural origin may be introduced into a fragranced composition according to the invention in the form of a natural extract.
Such extracts may be obtained by extraction of various plant parts, for instance the root, the wood, the bark, the leaf, the flower, the fruit, the seed, the pod or the peel.
Among the extracts of plants, mention may be made of extracts of cornflower, of mallow flower, of rose petals, of hibiscus or of black rice envelope.
Among the extracts of fruit, mention may be made of extracts of blueberry, of blackberry, of plum, of cherry, of blood orange or of black grape. [Table 4]
Figure imgf000036_0001
Among the extracts of vegetables, mention may be made of extracts of red radish, of red cabbage, of aubergine, of purple sweet potato or of purple potato, of red onion, of purple maize and of black or violet (purple) carrot, preferably of purple sweet potato. Preferentially, the extracts of vegetables are chosen from extracts of red radish, of red cabbage, of purple sweet potato or of purple potato, of red onion and of black or violet (purple) carrot, preferably of purple sweet potato.
Use may also be made of mixtures of plant extracts. All the enantiomers, diastereoisomers and geometrical isomers of the dyes defined above may be suitable for use as water-soluble dye that is natural or of natural origin, and also the racemic mixtures.
The water-soluble anthocyanin dye(s) b) that are natural or of natural origin, in particular obtained from natural extract(s), which is suitable for use in the invention may be in any form enabling its dissolution in the fragranced composition, in particular in aqueous, alcoholic or aqueous -alcoholic medium. It may notably be in powder or liquid form, preferably in powder form.
A certain number of dyes chosen from anthocyani(di)ns and derivatives thereof are commercially available, for instance the anthocyanin powder from red cabbage sold under the name 600008 Vitiva DD from the company Vitiva, from black radish D 600549 from the company Vitiva, and from black carrot (Black Carrot Powder EV-9 Blue sold by Secna). For obvious reasons, the amount of water-soluble anthocyani(di)n dye(s) that are natural or of natural origin present in a composition according to the invention is able to vary significantly with regard to the hue or the chromatic intensity sought by its presence. According to the invention, the natural anthocyani(di)n dye(s), and/or the natural extract(s), used as ingredient b) the composition according to the invention preferably represent from 0.0001% to 20% by weight relative to the total weight of the composition(s) containing the anthocyani(di)n dye(s) or the extract(s).
As regards the pure anthocyani(di)n dye(s) b), the content in the fragrancing composition containing same preferably ranges from 0.0001% to 5% by weight, preferably from 0.001% to 3.0% by weight, more preferentially from 0.01% to 1.0% by weight and even more preferentially from 0.1% to 0.5% by weight of anthocyani(di)n dye(s) relative to the total weight of said composition.
Thus, the content in the fragranced composition of the anthocyani(di)n dye(s) b) in the form of extract(s) particularly ranges from 0.01% to 20% by weight, more particularly from 0.1% to 10% by weight, preferably from 0.2% to 8.0% by weight, more preferentially from 0.3% to 3.0% by weight, even more preferentially from 0.4% to 2.0% by weight and better still from 0.5% to 1% by weight of extract(s) b) in said composition.
According to a particular embodiment of the invention, the total amount of water-soluble dye(s) that are natural or of natural origin chosen from anthocyani(di)ns and derivatives thereof contained in the composition ranges from 1 to 300 ppm (parts per million) and more particularly from 1 to 200 ppm.
Advantageously, a content of water-soluble dye(s) that are natural or of natural origin of the type such as anthocyani(di)n or anthocyani(di)n derivative of less than or equal to 300 ppm in the fragranced coloured composition makes it possible to prevent the formation of marks during its application, in particular on clothing, irrespective of the dyestuff used.
As mentioned above, the water-soluble dye(s) that are natural or of natural origin chosen from anthocyani(di)ns and derivatives thereof may be introduced into the fragranced composition of the invention in the form of a natural extract.
Thus, a fragranced composition according to the invention may comprise from 0.05% to 15% by weight of natural extract comprising a water-soluble dye that is natural or of natural origin chosen from anthocyani(di)ns and derivatives thereof, relative to the total weight of said composition.
Preferably, a composition according to the invention comprises one or more anthocyani(di)n dye(s) in a content ranging from 0.0001% to 20% by weight relative to the total weight of the composition containing the anthocyani(di)n dye(s) or the extracts containing same, preferably:
- when the anthocyani(di)n dye(s) are pure b), the content in the fragrancing composition ranges from 0.0001% to 5% by weight, preferably from 0.001% to 3.0% by weight, more preferentially from 0.01% to 1.0% by weight and even more preferentially from 0.1% to 0.5% by weight of anthocyani(di)n dye(s) relative to the total weight of said composition;
- when the anthocyani(di)n dye(s) are b) in the form of extract(s), the content of extract(s) b) in the composition ranges from 0.01% to 20% by weight, particularly from 0.1% to 10% by weight, more particularly from 0.2% to 8.0% by weight, for example from 0.3% to 3.0% by weight, notably from 0.4% to 2.0% by weight and better still from 0.5% to 1% by weight of extract(s) b) in said composition. c) Fragrancing substance
As mentioned previously, a fragranced composition according to the invention comprises at least one fragrancing substance.
Perfumes are compositions notably containing the starting materials described in S. Arctander, Perfume and Flavor Chemicals ( Montclair , N.J., 1969), in S. Arctander, Perfume and Flavor Materials of Natural Origin ( Elizabeth , N.J., 1960 ) and in Flavor and Fragrance Materials - 1991, Allured Publishing Co., Wheaton, III.
A fragranced composition according to the invention preferably comprises at least one fragrancing substance chosen from essential oils, perfumes and aromas of synthetic or natural origin, and mixtures thereof.
They may be natural products, such as essential oils, absolutes, resinoids, resins, concretes, and/or synthetic products, such as terpene or sesquiterpene hydrocarbons, alcohols, phenols, aldehydes, ketones, ethers, acids, esters, nitriles or peroxides, which may be saturated or unsaturated, and aliphatic or cyclic.
According to the definition given in the international standard ISO 9235 and adopted by the Commission of the European Pharmacopoeia, an essential oil is an odorous product, generally of complex composition, obtained from a botanicahy defined plant starting material, either by steam distillation, or by dry distillation, or by an appropriate mechanical process without heating (cold pressing). The essential oil is generally separated from the aqueous phase via a physical process which does not result in any significant change in the composition.
The choice of the method for obtaining essential oils depends mainly on the starting material: its original state and its characteristics, its intrinsic nature. The “ essential oil/plant starting material” yield may be extremely variable depending on the plant: 15 ppm to more than 20%. This choice determines the characteristics of the essential oil, in particular viscosity, colour, solubility, volatility, and richness or poorness in certain constituents.
Steam entrainment corresponds to vaporization, in the presence of steam, of a sparingly water-miscible substance. The raw material is placed in contact with boiling water or steam in an alambic. The steam entrains the essential oil vapour, which is condensed in the condenser and recovered as a liquid phase in a Florentine vase (or essence jar), where the essential oil is separated from the water by settling. The aqueous distillate that remains after the steam distillation, once the separation of the essential oil has been performed, is known as the “ aromatic water” or “ hydrolate ” or “distilled floral water”.
Production by dry distillation consists in obtaining the essential oil by distillation of woods, barks or roots, without addition of water or steam, in a closed chamber designed so that the liquid is recovered at the bottom. Cade oil is the best known example of a product obtained in this way. The method of production by cold pressing applies only to citrus fruits (Citrus spp.) via mechanical processes at room temperature. The principle of the method is as follows: the zests are tom into pieces and the contents of the secretory sacs that have been broken are recovered by a physical process. The conventional process consists in exerting an abrasive action on the entire surface of the fruit under a stream of water. After removal of the solid waste, the essential oil is separated from the aqueous phase by centrifugation. The majority of industrial installations allow simultaneous or sequential recovery of the fruit juices and of the essential oil.
Essential oils are generally volatile and liquid at room temperature, which distinguishes them from “set” oils. They are more or less coloured and their density is generally less than that of water. They have a high refractive index and most of them deflect polarized light. They are liposoluble and soluble in the usual organic solvents, distillable with steam, and very sparingly soluble in water.
Among the essential oils that may be used according to the invention, mention may be made of those obtained from plants belonging to the following botanical families: Abietaceae or Pinaceae, for example conifers; Amaryllidaceae; Anacardiaceae; Anonaceae, for example ylang ylang; Apiaceae, for example Umbelliferae, in particular dill, angelica, coriander, sea fennel, carrot or parsley; Araceae; Aristolochiaceae; Asteraceae, for example yarrow, artemisia, camomile, helichrysum; Betulaceae; Brassicaceae; Burseraceae, for example frankincense; Caryophyllaceae; Canellaceae; Cesalpiniaceae, for example copaifera (copaiba balsam); Chenopodaceae; Cistaceae, for example rock rose; Cyperaceae; Dipterocarpaceae; Ericaceae, for example gaultheria (wintergreen); Euphorbiaceae; Fabaceae; Geraniaceae, for example geranium; Guttiferae; Hamamelidaceae; Hemandiaceae; Hypericaceae, for example St- John’s wort; Iridaceae; Juglandaceae; Lamiaceae, for example thyme, oregano, monarda, savory, basil, marjorams, mints, patchouli, lavenders, sages, catnip, rosemary, hyssop, balm, rosemary; Lauraceae, for example ravensara, sweet bay, rosewood, cinnamon, litsea; Liliaceae, for example garlic; Magnoliaceae, for example magnolia; Malvaceae; Meliaceae; Monimiaceae; Moraceae, for example hemp or hop; Myricaceae; Myristicaceae, for example nutmeg; Myrtaceae, for example eucalyptus, tea tree, paperbark tree, cajuput, backhousia, clove, myrtle; Oleaceae; Piperaceae, for example pepper; Pittosporaceae; Poaceae, for example citronella grass, lemongrass, vetiver; Polygonaceae; Renonculaceae; Rosaceae, for example roses; Rubiaceae; Rutaceae: all citrus plants; Salicaceae; Santalaceae, for example sandalwood; Saxifragaceae; Schisandraceae; Styracaceae, for example benzoin; Thymelaceae, for example agarwood; Tilliaceae; Valerianaceae, for example valerian, spikenard; Verbenaceae, for example lantana, verbena; Violaceae; Zingiberaceae, for example galangal, turmeric, cardamom, ginger; Zygophyllaceae.
Mention may also be made of the essential oils extracted from flowers (lily, lavender, rose, jasmine, ylang ylang, neroli), from stems and leaves (patchouli, geranium, petitgrain), from fruit (coriander, aniseed, cumin, juniper), from fruit peel (bergamot, lemon, orange), from roots (angelica, celery, cardamom, iris, sweet flag, ginger), from wood (pinewood, sandalwood, gaiac wood, rose of cedar, camphor), from grasses and gramineae (tarragon, rosemary, basil, lemongrass, sage, thyme), from needles and branches (spruce, fir, pine, dwarf pine) and from resins and balms (galbanum, elemi, benzoin, myrrh, olibanum, opopanax).
Examples of fragrancing substances are notably: geraniol, geranyl acetate, famesol, bomeol, bomyl acetate, linolool, linalyl acetate, linalyl propionate, linalyl butyrate, tetrahydrolinolool, citronellol, citronellyl acetate, citronellyl formate, citronellyl propionate, dihydromyrcenol, dihydromyrcenyl acetate, tetrahydromyrcenol, terpineol, terpinyl acetate, nopol, nopyl acetate, nerol, neryl acetate, 2-phenylethanol, 2-phenylethyl acetate, benzyl alcohol, benzyl acetate, benzyl salicylate, styrallyl acetate, benzyl benzoate, amyl salicylate, dimethylbenzylcarbinol, trichloromethylphenylcarbinyl acetate, p-tert-butylcyclohexyl acetate, isononyl acetate, vetiveryl acetate, vetiverol, a-hexylcinnamaldehyde, 2-methyl-3- (p-tert-butylphenyl)propanal, 2-methyl-3-(p-isopropylphenyl)propanal, 3-(p-tert- butylphenyl)propanal, 2,4-dimethylcyclohex-3-enylcarboxaldehyde, tricyclodecenyl acetate, tricyclodecenyl propionate, 4-(4-hydroxy-4-methylpentyl)-3- cyclohexenecarboxaldehyde, 4-(4-methyl-3-pentenyl)-3-cyclohexenecarboxaldehyde, 4- acetoxy-3-pentyltetrahydropyran, 3-carboxymethyl-2-pentylcyclopentane, 2-n-4- heptylcyclopentanone, 3-methyl-2-pentyl-2-cyclopentenone, menthone, carvone, tagetone, geranylacetone, n-decanal, n-dodecanal, 9-decen-l-ol, phenoxy ethyl isobutyrate, phenylacetaldehyde dimethyl acetal, phenylacetaldehyde diethyl acetal, geranonitrile, citronellonitrile, cedryl acetate, 3-isocamphylcyclohexanol, cedryl methyl ether, isolongifolanone, aubepinonitrile, aubepine, heliotropin, coumarin, eugenol, vanillin, diphenyl ether, citral, citronellal, hydroxycitronellal, damascone, ionones, methylionones, isomethylionones, solanone, irones, cis-3-hexenol and esters thereof, musk-indans, musk- tetralins, musk-isochromans, macrocyclic ketones, musk-macrolactones, aliphatic musks and ethylene brassylate, and mixtures thereof.
A fragranced composition according to the invention preferably comprises a fragrancing substance chosen from essential oils, perfumes and aromas of synthetic or natural origin, and mixtures thereof.
According to a preferred embodiment of the invention, a mixture of different fragrancing substances that generate in common a note that is pleasant to the user is used.
Thus, according to a preferred embodiment, the fragranced composition comprises at least 1% by weight of a mixture of fragrancing substances, in particular of at least two different fragrancing substances, relative to the total weight of the composition, and preferably at least three different fragrancing substances.
The fragrancing substances will preferably be chosen such that they produce notes (head, heart and base) in the following families: citrine, aromatic, floral notes, in particular pink flowers and white flowers, spicy, woody, gourmand, chypre, fougere, leathery, musk.
For obvious reasons, the amount of fragrancing substance(s) present in a composition according to the invention is able to vary significantly with regard to the odour or the odour intensity sought by its presence.
By way of illustration, a fragranced composition according to the invention may comprise from 0.0001% to 10% by weight, particularly from 0.001% to 8.0% by weight, more particularly from 0.01% to 5.0% by weight and preferentially from 0.1% to 1.0% by weight of fragrancing substance(s), relative to the total weight of said composition.
As mentioned above, the fragrancing substances may be introduced into a fragranced composition in accordance with the invention in the form of a perfume concentrate.
The perfume concentrate may be a concrete or an absolute, preferably an absolute.
Thus, a fragranced composition according to the invention particularly comprises from 1.0% to 50% by weight of perfume concentrate, more particularly from 2.0% to 40% by weight, preferentially from 5.0% to 30% by weight and more preferentially from 10% to 20% by weight, for example 15% by weight, relative to the total weight of the composition.
Composition A fragranced composition according to the invention is preferably a cosmetic composition, i.e. a composition that is cosmetically acceptable so as to be applied to keratin materials, notably human keratin materials, without impairing them.
It may be in any presentation form conventionally used for topical application, and notably in the form of an aqueous, alcoholic or aqueous -alcoholic solution or suspension, an oily solution or a solution or dispersion of the lotion or serum type, an emulsion of liquid or semiliquid consistency of the milk type, obtained by dispersing a fatty phase in an aqueous phase (O/W) or, conversely, (W/O), a suspension or emulsion of soft consistency of (O/W) or (W/O) cream type, or an aqueous or anhydrous gel, an ointment, or any other cosmetic form. Preferably, a fragranced composition according to the invention is in the form of a cosmetic cream, milk or gel.
According to a preferred embodiment, a fragranced composition according to the invention is of oil-in- water type, and is preferably in the form of an oil-in-water emulsion.
According to one embodiment, a fragranced composition according to the invention is an alcoholic composition, i.e. a composition comprising at least one alcohol as solvent(s), or an aqueous-alcoholic composition, i.e. a composition comprising a mixture of water and of alcohol as solvents.
Preferably, the composition comprises as solvent(s) (bio)ethanol, pentylene glycol, or a mixture of these compounds optionally in the presence of water.
According to this embodiment, a fragranced composition according to the invention may comprise a mixture of water and alcohol (notably (bio)ethanol) in an alcohol/water mass ratio of less than or equal to 25/75, preferably less than or equal to 20/80, in particular less than 15/85, notably ranging from 15/85 to 25/75, for example ranging from 15/85 to 20/80. More particularly according to this embodiment, a fragranced composition according to the invention may comprise a mixture of water, alcohol (notably (bio)ethanol) and perfume concentrate (water/alcohol (notably (bio)ethanol)/perfume concentrate) in a mass ratio ranging from 40/55/5 notably for after-shave lotions to 25/70/5 for colognes and up to 5/65/30 for eaux de parfums and perfumes.
Alcohols
As mentioned previously, a fragranced composition according to the invention may be an alcoholic or aqueous-alcoholic composition. Preferably, the composition according to the invention is aqueous-alcoholic.
The alcohols that are most particularly suitable for use in the invention are chosen from i) monoalcohols containing from 2 to 6 carbon atoms such as ethanol and isopropanol, and ii) glycols containing from 2 to 8 carbon atoms such as ethylene glycol, propylene glycol, 1 ,3- butylene glycol and dipropylene glycol.
Preferably, the alcohols are of natural origin. In particular, mention may be made of bioethanol.
In particular, a fragranced composition according to the invention comprises as solvent(s) water, (bio)ethanol, pentylene glycol, or a mixture of at least two of these compounds.
A fragranced composition according to the invention may comprise a content of alcohols, notably of (bio)ethanol, ranging from 0.5% to 99.5% by weight, particularly from 5% to 97% by weight, more particularly from 15% to 95% by weight, better still from 25% to 93%, preferably from 40% to 92% by weight, more preferentially from 50% to 90% by weight, even more preferentially from 60% to 88% by weight and better still from 70% to 85% by weight, relative to the total weight of the composition. More preferentially, the amount of alcohol, notably of (bio)ethanol, is less than 75% as pure alcohol.
Advantageously, a fragranced composition according to the invention may comprise a content of alcohols, notably of (bio)ethanol, of less than or equal to 20% by weight, preferably less than 15% by weight, in particular ranging from 0.1% to 20% by weight, more particularly from 0.5% to 15%, for example from 0.5% to 10% by weight, relative to the total weight of the composition.
As mentioned previously, a fragranced composition according to the invention may be an aqueous composition, i.e. a composition comprising water as solvent(s), or an aqueous- alcoholic composition, i.e. a composition comprising a mixture of water and of alcohol as solvents.
A fragranced composition according to the invention may comprise, besides water, at least one water-soluble solvent different from the alcohols defined above.
In the present invention, the term “ water-soluble solvent ” denotes a compound that is liquid at room temperature and water-miscible (miscibility with water of greater than 50% by weight at a temperature ranging from 20°C to 25°C and atmospheric pressure). The water-soluble solvents that may be used in the composition of the invention may also be volatile. Among the water-soluble solvents that may be used in the composition in accordance with the invention, mention may be made notably of C3 and C4 ketones and C2- C4 aldehydes.
Alternatively, a fragranced composition according to the invention may be anhydrous, i.e. it comprises less than 2% by weight of water, preferably less than 1% by weight of water, preferentially less than 0.5% by weight of water, or even is totally free of water.
Polyols
A fragranced composition according to the invention may also comprise at least one C2-C32 polyol. For the purposes of the present invention, the term “ polyol ” should be understood as meaning any organic molecule including at least three free hydroxyl (-OH) groups. Preferably, a polyol in accordance with the present invention is present in liquid form at room temperature. A polyol that is suitable for use in the invention may be a compound of linear, branched or cyclic, saturated or unsaturated alkyl type, bearing on the alkyl chain at least three -OH functions and in particular at least four -OH functions.
The polyols that are advantageously suitable for formulating a composition according to the present invention are those notably containing from 2 to 32 carbon atoms and preferably 3 to 16 carbon atoms.
Preferably, the polyol may be chosen, for example, from pentaerythritol, trimethylolpropane, glycerol, polyglycerols, in particular glycerol oligomers, preferably diglycerol, and mixtures thereof.
Fatty substance
A fragranced composition according to the invention may comprise one or more fatty substances that are liquid at room temperature and/or a fatty substance that is solid at room temperature such as waxes, pasty fatty substances, gums and mixtures thereof. For the purposes of the invention, the term “room temperature” means a temperature equal to 25 °C. Preferably, the fatty substances that are suitable for use in the present invention are liquid at room temperature and at atmospheric pressure.
The oils may be polar or non-polar, of different chemical nature, alone or as a mixture.
In particular, polar oils that may be mentioned include: hydrocarbon-based plant oils with a high content of triglycerides consisting of fatty acid esters of glycerol, for example like wheat germ oil, com oil, sunflower oil, shea oil, castor oil and sweet almond oil; synthetic esters and ethers; saturated C12 to C26 fatty alcohols; and mixtures thereof.
Moreover, the non-polar oils may be chosen in particular from silicone oils such as volatile or non-volatile, linear or cyclic polydimethylsiloxanes, which are liquid at room temperature (20°C ± 5°C) and atmospheric pressure, and linear or branched hydrocarbons of synthetic or mineral origin.
Examples of solid fatty substances that may be mentioned include waxes, notably hydrocarbon-based waxes or silicone waxes, of natural or synthetic origin, insofar as they are compatible with the other components of the composition, and insofar as they do not impair the properties, notably the olfactory and colour properties, of the fragranced composition.
Preferably, the fatty substances are plant oils. Plant oils that may be mentioned include sunflower oil, virgin olive oil or refined sesame oil.
Surfactants
A fragranced composition according to the invention may also comprise one or more anionic, cationic, nonionic, zwitterionic or amphoteric surfactants.
Nonionic surfactants that may be mentioned most particularly include fatty acid esters of sugars, notably those chosen from the group comprising esters or mixtures of esters of C8- C22 fatty acid and of sucrose, of maltose, of glucose or of fructose, and esters or mixtures of esters of C14-C22 fatty acid and of methylglucose. Examples of esters or mixtures of esters of fatty acid and of sucrose, maltose, glucose or fructose that may be mentioned include sucrose monostearate, sucrose distearate and sucrose tristearate, and mixtures thereof, and an example of esters or mixtures of esters of fatty acid and of methylglucose that may be mentioned is methylglucose polyglyceryl-3 distearate, sold by the company Goldschmidt under the name Tego-Care 450.
In addition, the fragranced composition according to the invention may comprise one or more co-emulsifiers. This or these co-emulsifiers may be chosen, for example, from C16-C22 fatty alcohols or esters of C3-C6 polyols with C14-C22 fatty acids, and mixtures thereof. Examples of co-emulsifiers that may be mentioned include cetyl alcohol, stearyl alcohol, cetearyl alcohol (mixture of cetyl alcohol and of stearyl alcohol), glyceryl stearate, and mixtures thereof, and preferably cetyl alcohol.
A fragranced composition may comprise from 0.01% to 10% by weight, more particularly from 0.1% to 5% by weight and preferentially from 1% to 3% by weight of surfactant(s) relative to the total weight of the fragranced composition.
Preserving agents
A fragranced composition according to the invention may also comprise at least one preserving agent.
The term “ preservative ” or “ preserving agent” means any cosmetically or pharmaceutically acceptable compound which can prevent microbial growth (or the growth of microorganisms) which may take place in cosmetic or pharmaceutical compositions, from the moment of their preparation, while they are in storage and up to the time of their conventional use by consumers. Preserving agents that may notably be mentioned include the preserving agents described in Cosmetics, Kirk-Othmer Encyclopedia of Chemical Technology. John Wiley & Sons, Inc., Martin M. Rieger; 5.2 preservatives & table 3, 04/12/2000, https://doi.org/10.1002/0471238961.0315191318090507.a01. According to a particular embodiment, the preserving agent(s) are chosen from organic preserving agents bearing an aromatic group.
A fragranced composition according to the invention may also comprise at least one preserving agent, notably chosen from i) benzene -based carboxylic acids optionally substituted on the phenyl group with one or more groups chosen from hydroxyl, (Ci- Cio)alkyl and (Ci-Cio)alkylcarbonyl, and also the base salts thereof, notably of alkali metals and alkaline-earth metals, ii) hydroxybenzoic acid esters optionally substituted on the phenyl group with one or more groups chosen from (Ci-Cio)alkyl such as parabens, notably methylparaben and ethylparaben and propylparaben, and iii) aromatic alcohols. Preferably, the preserving agent(s) other than a) are chosen from i) and in particular benzoic acid [CAS No. 65-85-0] and also the base salts thereof, notably of alkali metals and alkaline-earth metals; and also salicylic acid optionally substituted with a (Ci-Cx)alkylcarbonyl group, preferably salicylic acid. The preserving agent(s) are notably chosen from aryl(C1- C6)alkanols and aryloxy(C1-C6)alkanols, such as phenylethanol, parabens, such as propylparaben, methylparaben, butylparaben, ethylparaben and isobutylparaben, benzyl alcohol and/or chlorophenesin.
Alkaline agents
A fragranced composition according to the invention may also comprise at least one organic or mineral alkaline agent, for example an amine, in particular a (C2-C6)alkanolamine, in particular 2-amino-2-methyl-l -propanol, or a mineral alkaline agent, for instance alkali metal or alkaline-earth metal hydroxides, such as sodium hydroxide.
Chelating agents
According to a particular embodiment of the invention, the composition comprises one or more chelating agents.
The term “chelating agent” means a ligand or chelating agent which makes it possible to form a metal complex with a chelated cation or metal atom. Generally, the chelating agent is electron-donating and the chelated species is electron-deficient. A “chelate” differs from a simple “complex” in that the metal cation is attached to the chelating ligand or chelating agent via at least two coordination bonds. The metal is thus “gripped” between the chemical functions of the ligand. The number of metal-ligand bonds of a ligand molecule defines the “denticity”: such coordinates or ligands are referred to as being bidentate, tridentate or tetradentate. The central atom is bonded to the neighbouring atoms via at least two bonds, forming a ring structure, a chelate ring. The chelate rings that are the most stable are 5- and 6-membered chelate rings. By means of this effect, chelates are more stable complexes than the complexes of monodentate ligands including the same chemical functions.
In particular, chelating agents are chosen from aminocarboxylic acids, for example ethylenediaminetetraacetic acid (EDTA), aminotriacetic acid, diethylenetriaminepentaacetic acid, and the salts thereof, in particular the alkaline salts, for instance disodium EDTA or dipotassium EDTA, aminopolycarboxylic acids, for instance ethylenediaminedisuccinic acid (EDDS), and salts thereof, in particular alkaline salts, or alternatively one or more phosphate-based chelating agents such as alkali metal metaphosphates such as sodium metaphosphate, alkali metal hexametaphosphates such as sodium hexametaphosphate, tetra- alkaline pyrophosphates such as tetrapotassium pyrophosphate, acids containing phosphorus, such as phytic acid, and salts thereof, in particular alkali metal or alkaline-earth metal salts, such as ethylenediaminetetramethylenephosphonic acid salts, alkali metal phytates such as sodium phytate or potassium phytate, and mixtures thereof, preferably chosen from EDTA as defined previously and alkali metal phytates such as sodium phytate.
Metal salts
According to a particular embodiment of the invention, the composition of the invention comprises one or more metal salts, metal complexes, metal oxides, metal oxoanions, and the hydrates and supported forms thereof.
Preferably, a composition according to the invention comprises one or more metal salts. More particularly, the metal(s) are of oxidation state I or II, more particularly II, preferably chosen from 1) Cu, 2) Fe, 3) Zn, 4) Mg and 5) Mn.
The term “ metal salt” means a compound other than alloys, i.e. the salt is formed from a metal combined with certain non-metallic elements.
The formation of metal salts derives from oxidative attack. The metal is oxidized to a cationic species and then combines with an anionic species to give a salt. This formation takes place by applying redox principles and the redox reaction (chemical reaction during which an electron transfer takes place in which the atom that captures the electrons is known as the “oxidizing agent”; the atom that yields the electrons is the “reducing agent”); or via chemical exchange reactions between one salt and another salt or an acid, in the presence or absence of atmospheric oxygen. These reactions are known to those skilled in the art.
Preferentially, the salts according to the invention are soluble in water to a proportion of at least 0.0001 g/L.
The metal salts according to the invention may be introduced in solid form into the compositions or may originate from a natural, mineral or spring water that is rich in these ions, or alternatively from seawater (notably the Dead Sea). They may also originate from mineral compounds, such as plant extracts containing same (cf., for example, FR 2814943). The term “ metal complex” or “ coordination compounds” mean systems in which the metal ion, the central atom, is chemically bonded to one or more electron donors (ligands). A ligand comprising various coordinating groups (capable of coordinating with a metal) gives metal compounds corresponding to coordination sphere principles with a given number of electrons (internal complexes or chelates), as described in Ullmann’s Encyclopedia of Industrial Chemistry, “ Metal complex dyes”, 2005, pages 1-42.
More particularly, the term “metal complex” means: i) metallic dyes or “ metal-complex dyes”, which are complexed dyes derived from azo, azomethine, hydrazono or formazan dyes (free, bidentate, tridentate, tetradentate) such as those described in Ullmann’s Encyclopedia of Industrial Chemistry, “Metal complex dyes”, 2005, pages 1-42, which preferentially comprise Cu and Mg; ii) compounds of the “ aza[18]annulene ” type, also known as “(metallo)porphyrins” and “ phthalocyanines ” which contain 4 and 8 nitrogen atoms, respectively, included in the perimeter of the macrocycle, as described in the book “Co/or Chemistry” , H. Zollinger, 3rd Ed., Wiley-VCH, 2003, chapter 5, Aza[18]annulenes, pages 123-160. The metal ion is then at the centre of said macrocycle bonded by coordination with two hydrogen atoms to the nitrogen atoms of pyrroles, the metal also possibly being stabilized with one or more bidentate or non-bidentate ligands, the metal ion preferentially being Mg2+or Cu2+; the metal complex is particularly:
- a “ metalloporphyrin ” formed from a backbone bearing 4 pyrrole groups that are connected at their a, a’ position via 4 methine groups and contain 16 sp2 hybridized atoms, complexing a metal such as Cu or Mg, or
- a “ chlorine ” (corresponding to a porphyrin in which an external C=C double bond of a pyrrole group has been reduced) complexed to a metal, preferentially Mg2+ such as the chlorophyll chromophore: chlorophyllin;
- “phthalocyanines” , which are tetraaza analogues of tetrabenzoporphyrins, such as Monastral Fast Blue B (C.I. Pigment Blue 15); Monastral Fast Blue G (C.I. Pigment Blue 16) (see “ Color Chemistry”, H. Zollinger, 3rd Ed., Wiley-VCH, 2003, chapter 5, Aza[18]annulenes, page 140); the sulfonyl derivatives Sirius Light Turquoise Blue G (C.I. Direct Blue 86, copper phthalocyanine tetrasulfonic acid) and “phthalocyanines” as described in Ullmann’s Encyclopedia of Industrial Chemistry, “Phthalocyanines”, 2005, pages 1-34, which comprise Cu and Si.
The term “ metal oxide(s)” means compounds of general formula AxOy with A representing a metal element, x being greater than or equal to 1 and less than or equal to 4, and y being greater than or equal to 1 and less than or equal to 12. The term “ metal oxoanion(s)” means compounds of general formula ZzAxOy with A representing a metal element, Z representing an alkali metal such as Li, Na or K or a hydrogen atom or an ammonium ion, z being greater than or equal to 1 and less than or equal to 6, x being greater than or equal to 1 and less than or equal to 4, and y being greater than or equal to 1 and less than or equal to 12.
The term “ supported form(s)” means the forms in which the metal derivative b) is impregnated onto a material known as a “support”. The optional supports for these metal derivatives may be chosen from charcoal, silica, alumina, optionally charged polymers comprising counter-anions or counter-cations (counter-cation or counter-anion of the metallic species). By way of example, the polymers may be polyethylene glycol (PEG). According to one embodiment of the invention, the metal salt(s) are chosen from the (poly)hydroxyalkyl(Ci-Ci6)carboxylates of metals of oxidation state II, notably Fe II, Cu II, Zn II, Mg II and Mn II (poly)hydroxyalkyl(Ci-Ci6)carboxylates. In particular, the metal salt(s) are chosen from Cu gluconate, Fe gluconate, Zn gluconate or Mg gluconate, gluconates of metals of oxidation state II such as Fe, Cu, Zn or Mg gluconates, and lactates of metals of oxidation state II such as Fe, Cu, Zn or Mg lactates. Preferably, the metal salts are Fe, Cu, Mg or Zn gluconate, preferably Fe and Cu gluconate.
Aqueous pH buffers
A fragranced composition according to the invention may also comprise at least one aqueous pH buffer, namely at least one compound which makes it possible to maintain a constant pH in aqueous solution.
The aqueous pH buffer(s) that are particularly suitable for use in the invention may be chosen from benzoic acid, maleic acid, fumaric acid, succinic acid and the salts thereof, in particular the alkali metal or alkaline-earth metal salts, for example sodium benzoate.
Related dyestuffs
A fragranced composition according to the invention may also comprise one or more related dyestuffs, different from the water-soluble anthocyani(di)ns that are natural or of natural origin, defined above.
This (or these) dyestuff(s) are preferably chosen from particulate dyestuffs, liposoluble dyes and water-soluble dyes, and mixtures thereof. As water-soluble dyes that are suitable for use in the invention, mention may be made notably of synthetic or natural water-soluble dyes, for instance FDC Red 4, DC Red 6, DC Red 22, DC Red 28, DC Red 30, DC Red 33, DC Orange 4, DC Yellow 5, DC Yellow 6, DC Yellow 8, FDC Green 3, DC Green 5, FDC Blue 1, betanine (beetroot), carmine, copper chlorophyllin, methylene blue, caramel, sandalwood, gardenia, spirulina and riboflavin.
For the purposes of the invention, the term “liposoluble dye ” denotes any natural or synthetic, generally organic dye, which is soluble in an oily phase or in solvents that are miscible with a fatty substance. As liposoluble dyes that are suitable for use in the invention, mention may notably be made of synthetic or natural liposoluble dyes, for instance DC Red 17, DC Red 21, DC Red 27, DC Green 6, DC Yellow 11, DC Violet 2, DC Orange 5, Sudan red, carotenes (b-carotene, lycopene), xanthophylls (capsanthin, capsorubin, lutein), palm oil, Sudan brown, quinoline yellow, annatto and curcumin.
The colouring particulate materials may be pigments, nacres and/or particles with metallic tints.
For the purposes of the present invention, the term “ pigments ” is intended to denote white or coloured, mineral or organic solid particles.
Pigments are naturally insoluble in the liquid hydrophilic and lipophilic phases usually employed in cosmetics. Alternatively, they may be rendered insoluble by formulation in lake form, where appropriate.
More particularly, the pigment has little or no solubility in aqueous -alcoholic media.
The pigments may be white or colored, mineral and/or organic, and coated or uncoated. Among the mineral pigments that may be mentioned are metal oxides, in particular titanium dioxide, optionally surface-treated, zirconium oxide, zinc oxide or cerium oxide, and also iron oxide, titanium oxide or 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 aluminum.
For the purposes of the present invention, the term “ nacres ” denotes coloured particles of any form, which may or may not be iridescent, notably produced by certain molluscs in their shell, or alternatively synthesized, and which have a colour effect via optical interference. The nacres may be chosen from nacreous pigments such as titanium mica coated with an iron oxide, titanium mica coated with bismuth oxychloride, titanium mica coated with chromium oxide, titanium mica coated with an organic dye and also nacreous pigments based on bismuth oxychloride.
The nacres may more particularly have a yellow, pink, red, bronze, orange, brown, gold and/or coppery color or tint.
For the purposes of the present invention, the term “ particles with a metallic tint” means any compound whose nature, size, structure and surface finish allow it to reflect the incident light, notably in a non-iridescent manner.
The particles with a metallic tint that may be used in the invention may be chosen in particular from particles of at least one metal and/or of at least one metal derivative, particles including a single-material or multi-material organic or mineral substrate, at least partially covered with at least one coat with a metallic tint comprising at least one metal and/or at least one metal derivative, and mixtures of said particles. These particles are different from metal ions.
Among the metals that may be present in said particles, mention may be made, for example, of Ag, Au, Cu, Al, Ni, Sn, Mg, Cr, Mo, Ti, Zr, Pt, Va, Rb, W, Zn, Ge, Te and Se, and mixtures or alloys thereof. Ag, Au, Cu, Al, Zn, Ni, Mo and Cr, and mixtures or alloys thereof (for example bronzes and brasses) are preferred metals.
The term “ metal derivatives” denotes compounds derived from metals, notably oxides, fluorides, chlorides and sulfides.
Preferably, the related dyestuffs, if they are present, are natural or of natural origin.
These related dyestuffs may be present in a content ranging from 0.01% to 30% by weight relative to the total weight of the composition and in particular from 0.02% to 20% by weight relative to the total weight of the composition.
Additives
A fragranced composition according to the invention may also comprise any additive usually used in the field of fragrances, for instance emollients or softeners, in particular sweet almond oil, apricot kernel oil, moisturizers, in particular glycerol, calmatives, in particular a-bisabolol, allantoin and Aloe vera vitamins and derivatives thereof, essential fatty acids, insect repellents, propellants, peptizers, fillers, cosolvents, UV-screening agents, stabilizers or preserving agents other than the organic acid esters of formula (I) as defined according to the invention, and mixtures thereof. It is a matter of routine practice for those skilled in the art to adjust the nature and the amount of the additives present in the compositions in accordance with the invention such that the desired cosmetic properties thereof are not thereby affected.
When they are present in the composition of the invention, these additives may be present in an amount ranging from 0.001% to 10% by weight and better still from 0.01% to 5% by weight relative to the total weight of the composition.
Preparation of the composition
A composition according to the invention may be obtained via any method known to those skilled in the art for the formulation of coloured fragranced compositions.
In particular, a fragranced composition according to the invention may be obtained by simple mixing, at room temperature, namely at a temperature ranging from 20°C to 25°C, of the compounds constituting the composition.
According to a particular embodiment, a fragranced composition according to the invention results from mixing between a colouring solution comprising one or more anthocyani(di)n dyes, on the one hand, and a fragranced solution comprising the ester of formula (I), on the other hand.
Said colouring solution thus comprises at least one water-soluble dye that is natural or of natural origin chosen from anthocyani(di)ns and derivatives thereof, in particular as defined above, in a physiologically acceptable medium, in particular in aqueous or aqueous-alcoholic medium.
Said fragranced solution comprises, for its part, at least one fragrancing substance, in particular as defined above, and at least one ester of formula (I) as defined above, in a physiologically acceptable medium, in particular an aqueous -alcoholic medium.
Said fragranced solution may itself result from mixing between an intermediate fragranced solution, comprising at least one fragrancing substance, in particular as defined above, in a physiologically acceptable medium, in particular in aqueous -alcoholic medium, and an ester of formula (I) as defined above, directly or which is in solution in a physiologically acceptable medium, in particular an aqueous -alcoholic medium.
Alternatively, the ester(s) of formula (I) may be introduced, directly or in solution, into a fragranced composition, also comprising at least one fragrancing substance and at least one water-soluble dye that is natural or of natural origin chosen from anthocyani(di)ns and derivatives thereof, in a physiologically acceptable medium.
It is within the competence of a person skilled in the art to adapt the conditions for preparing a fragranced composition according to the invention.
Intended use of the composition
The invention applies not only to fragrancing products but also to cosmetic products for caring for or treating keratin materials, in particular the skin, including the scalp, and the lips, containing an odorous substance.
A composition according to the invention may thus constitute a cosmetic composition for fragrancing, caring for or treating keratin materials, and may notably be in the form of an eau fraiche, eau de toilette, eau de parfum, aftershave lotion, care lotion, or silicone or hydrosilicone care oil. It may also be in the form of a fragranced two-phase lotion (eau de toilette phase/hydrocarbon-based oil and/or silicone oil phase), a body milk or a shampoo. The compositions according to the invention may be packaged in the form of bottles.
A fragrancing composition according to the invention may be diffused by various systems, such as sprays, aerosols or piezoelectric devices.
They may also be applied in the form of fine particles by means of mechanical pressurization or propellant gas devices. The devices in accordance with the invention are well known to those skilled in the art and comprise pump-bottles or “sprays”, aerosol containers comprising a propellant and aerosol pumps using compressed air as propellant. These devices are notably described in patents US 4 077 441 and US 4 850 517.
The compositions conditioned as aerosols in accordance with the invention generally contain conventional propellants, for instance dimethyl ether, isobutane, n-butane or propane. According to a particular form of the invention, the compositions according to the invention are lotions and preferably have a viscosity ranging from 10 to 120 DU, more preferentially from 30 to 120 DU and even more preferentially from 40 to 80 DU; the viscosity being measured using a Rheomat TVe-05 viscometer, at 25°C, rotation speed 200 rpm, spindle No. 1, 10 minutes.
These low viscosities allow the compositions of the invention to be packaged using mechanical pressurization or propellant gas devices so as to be applied in the form of fine particles (vaporization). A fragranced composition according to the invention may also be in the form of a body milk or in the form of a shampoo.
The invention is illustrated in greater detail by the examples presented below. Unless otherwise indicated, the amounts indicated are expressed as mass percentages.
Examples
Measurement and evaluation methods
The stability of the compositions is evaluated by observation of the change in colour over time, visually and using a spectrocolorimeter (L*, a*, b*) Konica Minolta CM 3600A, and by olfactory evaluation of the change in the notes of the fragranced composition.
In particular, the compositions are poured into 50 mL borosilicate glass bottles and are then observed after storage for 2 months, at atmospheric pressure and under various conditions: a) in an oven, at a temperature of 45°C. Storage of the compositions for two months at 45°C simulates accelerated ageing of the product corresponding to a shelf life of 3 years; b) in natural light and at room temperature, namely between 20°C and 25 °C, and then: b.l) 16 hours in an Atlas brand SunTest CPS+ ageing device, equipped with a xenon lamp, irradiating light source whose spectral distribution is close to that of sunlight, delivering an energy of 765 W/m2, simulating exposure to neon lights in a shop; or b.2) 2 weeks in an oven at a temperature of 45 °C, simulating an extreme condition for the perfume; c) in the refrigerator, at a temperature of 4°C; d) at room temperature, namely between 20°C and 25 °C, protected from light; e) in an oven, at a temperature of 37°C; f) at room temperature, namely between 20°C and 25 °C, in natural light.
The intensity difference DL between a reference composition and a composition tested after storage under the conditions mentioned above may be calculated from the L*a*b values according to the following formula:
[Math 1]
Figure imgf000056_0001
in which Li* is the intensity of the colour of the reference composition and L2* is the intensity of the colour of the composition tested after storage. Example 1
Preparation of the colouring solutions
The colouring solutions C1 to C3 are prepared using the weight proportions detailed in Table 5 below. The values are expressed as weight percentages relative to the total weight of the colouring solution.
[Table 5]
Figure imgf000057_0001
Table 5
Protocol for preparing the dye solutions The colouring compositions are prepared by dissolving the dyes in the appropriate solvent or mixture of solvents.
In particular, for 100 g of colouring solution, the required amount of dye is weighed out in a beaker. The amount of solvents (ethanol, water, propylene glycol and/or pentylene glycol) is then added and the mixture is left stirring by magnetic stirring for 20 minutes.
Example 2
Preparation of the coloured fragranced compositions
Three fragranced compositions PI, P2 and P3 according to the invention and a fragranced composition P4 outside the invention are prepared using the weight proportions as detailed in Table 6 below.
The values are expressed as weight percentages relative to the total weight of the fragranced composition.
[Table 6]
Figure imgf000058_0001
(*) Perfume of the floral woody musk type characterized by:
- its head notes of peach, coriander, plum and green notes,
- its heart notes of peony, lily, freesia, lily of the valley, jasmine, ylang-ylang, rose and coffee, and
- its base notes of tonka bean, musk, vanilla, sandalwood and cedarwood; and/or (**) Perfume of the citrine type characterized by:
- its head notes of lime, citron, mint and eucalyptus, and
- its heart notes of coconut.
Table 6
Protocol for preparing the coloured fragranced compositions
15 g of perfume concentrate are weighed out in a beaker.
95° ethanol is added to the perfume concentrate, and water is then added.
For compositions PI to P3, 0.5 g of Gamma-oryzanol, chlorogenic acid and ethyl ferulate are respectively added and the mixture is then left under magnetic stirring for 10 minutes, so as to obtain a fragranced solution.
0.05 g of the colouring solution is then added using a pipette.
Composition P4 is prepared according to the same protocol, with the exception of the addition of organic acid ester ( without Gamma-oryzanol, chlorogenic acid or ethyl ferulate).
Example 3 Stability tests
The stability of the coloured fragranced compositions is evaluated visually according to the protocol detailed above. The change in colour of the compositions according to the invention (PI, P2 and P3) and outside the invention (P4), for each of the colouring solutions Cl to C3, is observed visually after 16 hours in the SunTest ageing device. The results are detailed in Table 7 below. [Table 7]
Figure imgf000059_0001
Table 7
The study was performed with various perfume concentrates from different olfactory families, similar results being obtained for each perfume concentrate.
Composition P4 outside the invention, not comprising any organic acid ester, becomes colourless after ageing. It is thus seen that despite the presence of ethanol in large amount (predominant amount of ingredient in the composition), the composition according to the invention conserves for a longer time its base colour originating from anthocyani(di)n natural dyes due to the presence of the organic acid ester of formula (I) according to the invention.
In conclusion, the fragranced composition according to the invention is more stable over time and with respect to external attacking factors such as light, than a composition not in accordance with the invention.

Claims

Claims
1. Fragranced composition, notably a cosmetic composition, comprising: a) at least one organic acid ester of formula (I), or a geometrical isomer thereof, organic or mineral acid or base salts thereof, or solvates thereof, in particular hydrates:
Figure imgf000060_0001
in which formula (I):
R1, R4 and R5 represent, independently of each other, a hydrogen atom or a hydroxyl group, preferably a hydrogen atom;
R2 represents a hydrogen atom, a hydroxyl group or a (C1-C6)alkoxy group, in particular a (C1-C4)alkoxy group, and preferably a methoxy;
R3 represents a hydroxyl group or a (C1-C6)alkoxy group, preferably a hydroxyl group; and
R6 represents a group chosen from: i) (C1-C6)alkyl, in particular a (C1-C4)alkyl group, preferably methyl or ethyl, optionally substituted with one or more groups chosen from hydroxyl, amino, carboxyl and/or amido, preferably hydroxyl and/or carboxyl, ii) cycloalkyl, optionally substituted with one or more groups chosen from (Ci-Cio)alkyl, (C2-Cio)alkenyl, hydroxyl, amino, carboxyl and/or amido, preferably hydroxyl and/or carboxyl, and iii) glycosyl, b) at least one water-soluble dye that is natural or of natural origin chosen from anthocyani(di)ns and derivatives thereof; and c) at least one fragrancing substance.
2. Composition according to the preceding claim, said composition being aqueous, alcoholic or aqueous-alcoholic, in particular aqueous or aqueous-alcoholic, preferably comprising a mixture of water and alcohol (notably (bio)ethanol) in an alcohol/water mass ratio ofless than or equal to 25/75, preferably less than or equal to 20/80, in particular less than 15/85, notably ranging from 15/85 to 25/75, for example ranging from 15/85 to 20/80.
3. Composition according to any one of the preceding claims, in which said organic acid ester is of formula (F):
Figure imgf000061_0001
in which formula (F):
R6 represents a group chosen from: i) (C1-C6)alkyl, in particular a (C1-C4)alkyl group, preferably methyl or ethyl, optionally substituted with one or more groups chosen from hydroxyl, amino, carboxyl and/or amido, preferably hydroxyl and/or carboxyl, ii) cycloalkyl, optionally substituted with one or more groups chosen from (Ci-Cio)alkyl, (C2-Cio)alkenyl, hydroxyl, amino, carboxyl and/or amido, preferably hydroxyl and/or carboxyl, and iii) glycosyl; and
R7 represents a hydrogen atom or a (C1-C6)alkyl group; preferably, said organic acid ester of formula (F) is chosen from methyl ferulate, ethyl ferulate, chlorogenic acid, isopropyl ferulate or ferulic acid esters of sterols, such as oryzanol, notably Gamma-oryzanol.
4. Composition according to any one of the preceding claims, in which said organic acid ester is chosen from compounds that are natural or of natural origin.
5. Composition according to any one of the preceding claims, comprising from 0.01% to 5.0% by weight, in particular from 0.03% to 2.0% by weight, preferably from 0.05% to 1.0% by weight and more preferentially from 0.1% to 0.8% by weight of organic acid ester(s) of formula (I), relative to the total weight of said composition.
6. Composition according to any one of the preceding claims, in which said water-soluble dye that is natural or of natural origin is chosen from the compounds of formula (IIA), and also the optical isomers thereof, the geometrical isomers thereof, the tautomers thereof, the organic or mineral acid or base salts thereof, and the solvates thereof such as hydrates:
Figure imgf000062_0001
in which formula (IIA):
- R3 represents a hydrogen atom or hydroxyl (OH), or -O-Sugar, preferably hydroxyl or -O-Sugar; “O-Sugar” denoting a monosaccharide radical or a polysaccharide radical consisting of 2 to 5 saccharide units, in particular from 2 to 3 and preferably 2 saccharide units connected to the rest of the molecule via an oxygen atom;
- R5 and R7, which may be identical or different, represent a hydrogen atom or a (C1-C6)alkyl, (C1-C6)alkoxy or hydroxyl group, preferably a hydroxyl group;
- R6 represents a hydrogen atom or a (C1-C6)alkyl, (C1-C6)alkoxy, (di)(C1- C6)(alkyl)amino, hydroxyl or -O-Sugar group, preferably hydrogen;
- R’3 represents a hydrogen atom or a (C1-C6)alkyl, (C1-C6)alkoxy such as methoxy, hydroxyl or -O-Sugar group; preferably a hydrogen atom or a (C1-C4)alkoxy such as methoxy, or hydroxyl group;
- R’4 represents a hydrogen atom or a (C1-C6)alkyl, (C1-C6)alkoxy, hydroxyl or -O-Sugar group, preferably a hydroxyl group;
- R’5 represents a hydrogen atom or a (C1-C6)alkyl, (C1-C6)alkoxy such as methoxy, hydroxyl or -O-Sugar group; preferably a hydrogen atom or a (C1-C4)alkoxy such as methoxy, or hydroxyl group, more preferentially a hydrogen atom; and
- Q- represents an anionic counterion.
7. Composition according to the preceding claim, in which said dye comprises at least one -O-Sugar group linked to carbon atom C1 of the 3- or 4-membered monosaccharide of the following -Sugar radical:
Figure imgf000063_0001
Ra representing a hydrogen atom, a (C1-C4)alky 1 group such as methyl or a (poly)hydroxy(C1-C4)alkyl group such as hydroxymethyl or 1 ,2-dihydroxyethyl, the hydroxyl group(s) of the (poly)hydroxy(C1-C4)alky 1 group being substituted with A as defined below; it being understood that the radical Ra is in position Cs if the sugar unit is in pyranose form or in position C4 if it is in furanose form;
Re represents a hydrogen atom or a group -CH2-O-A, preferably hydrogen;
A representing a (C1-C6)alkyl group or a group Rd-C(O)-, and Rd representing a group from among: i) (C1-C4)alkyl optionally substituted with one or more hydroxyl and/or carboxyl groups, ii) aryl optionally substituted with one or more hydroxyl and/or (C1- C4)alkoxy groups such as methoxy, iii) aryl(C2-C4)alkenyl optionally substituted with one or more hydroxyl and/or (C1-C4)alkoxy groups such as methoxy; in particular, A represents Rd-C(O)- with Rd representing ii) an aryl group optionally substituted with one or more hydroxyl groups, such as hydroxyphenyl (4-hydroxyphenyl) or iii) an aryl(C2-C4)alkenyl group, notably styryl, the phenyl group of which is optionally substituted with one or more groups chosen from hydroxyl and/or (C1-C4)alkoxy such as methoxy; and n is equal to 0 or 1 ; preferably, n is equal to 1 and m is equal to 1, 2, 3 or 4; preferably, Rd represents a group of formula (I”):
Figure imgf000063_0002
in which formula (I”):
R1 to R5 are as defined in formula (I) of Claim 1 ; preferably, Rd represents a caffeyl or 3 ,4-dihydroxystyryl, ferulyl or 3-methoxy- 4-hydroxystyryl, sinapyl or 3 ,5 -dimethoxy-4-hydroxy styry 1, 4-coumaryl or 4-hydroxystyryl group; in particular, the “ Sugar ’ radical represents a monosaccharide which may be acylated; more particularly, said sugar is chosen from pentoses such as ribose, arabinose, xylose, lyxose, ribulose or xylulose; hexoses such as allose, altrose, galactose, glucose, gulose, idose, mannose, talose, fructose, psicose, sorbose, arabinose or tagatose; and deoxyhexoses, such as fucose or rhamnose; more particularly, said “Sugar” radical represents a group which may be acylated chosen from glucose, rhamnose, xylose, galactose, arabinose and fructose, preferentially D-glucose, D-rhamnose, L-rhamnose, D-xylose, D- galactose, arabinose and fructose, and more preferentially D-glucose.
8. Composition according to either of Claims 6 and 7, in which said dye comprises at least one -O-Sugar group representing a monosaccharide radical chosen from - O-S1 to — O-S5:
Figure imgf000064_0001
in which -O-S1 to -O-S5 one or more hydroxyl groups may be replaced with a group Rd-C(O)-O-, with Rd as defined in Claim 7, preferably (C1-C4)alky 1 optionally substituted with a carboxyl group, such as methyl or styryl, the phenyl group of which is optionally substituted with one or more groups chosen from hydroxyl and/or (C1-C4)alkoxy such as methoxy, preferably a replacement of the hydroxyl, notably of the hydroxyl in the position of carbon C6 of -O-S1 and C5 of -O-S5; more particularly, the -O-Sugar radical represents -O-S1, -O-S4 or -O-S5, particularly -O-S1 or -O-S4, and preferentially -O-Sugar represents:
Figure imgf000065_0001
preferably chosen from O-galactoside and O-glucoside; it being understood that for -O-glucoside, -O-galactoside and -O-arabinoside, a hydroxyl group may be replaced with a group Rd-C(O)-O-, with Rd as defined in Claim 7, preferably (C1-C4)alky 1 optionally substituted with a carboxyl group, such as methyl or styryl, the phenyl group of which is optionally substituted with one or more groups chosen from hydroxyl and/or (C1-C4)alkoxy such as methoxy, preferably the replacement of the hydroxyl, notably of the hydroxyl in the position of carbon C6 of -O-glucoside and -O- galactoside.
9. Composition according to Claim 6, in which said dye comprises at least one
-O-Sugar group representing a polysaccharide radical constituted of 2 to 5 saccharide units, in particular 2 to 3, and preferably 2 saccharide units, linked together via an oxygen atom (oxy) by 1 → 4 bonding, i.e. Ci of one saccharide unit → C4 of the other saccharide unit, or by 1 → 3 bonding, i.e. Ci of one saccharide unit → C3 of the other saccharide unit, or by 1 → 6 bonding, i.e. Ci of one saccharide unit → C6 of the other saccharide unit, of which each saccharide unit is constituted of a heterocycle comprising 4 or 5 carbon atoms; more preferentially, -Sugar represents -Sugar’ of the following formula:
Figure imgf000065_0002
in which formula -Sugar’: - p and q are independently equal to 0, 1, 2, 3 or 4 with p + q being equal to 1, 2, 3 or 4, particularly equal to 1, 2 or 3; preferentially, p + q is equal to 1 or 2; preferably, p is equal to 0 and q is equal to 1 or else q is equal to 0 and p is equal to 1 ;
- Ra, which may be identical or different, are as defined in Claim 7 for the monosaccharide -Sugar,
- Re, which may be identical or different, are as defined in Claim 7 for the monosaccharide -Sugar,
- A, which may be identical or different, are as defined in Claim 7 for the monosaccharide -Sugar,
- m, which may be identical or different, are as defined in Claim 7 for the monosaccharide -Sugar,
- n, which may be identical or different, are as defined in Claim 7 for the monosaccharide -Sugar, it being understood that the two sugar units between the brackets q and p may be inverted, i.e. they may represent the following sequence:
Figure imgf000066_0001
10. Composition according to any one of Claims 6 to 9, in which said dye comprises at least one -O-Sugar group in which the “Sugar” radical represents a disaccharide which may be acylated, chosen from: lactose, diglucoside or gentiobiose (6-O-β-D-glucosyl- D-glucose), maltulose, palatinose, lactulose, amygdalose, turanose, cellobiose, isomaltose, rutinose (6-O-α-L-rhamnosyl-D-glucose), sophorose (2-O-P-D-xylosyl-D-glucose), sambubiose (2-O-β-D-xylosyl-D-glucose), maltose, xylosylrutinose and glycosylrutinose; and particularly chosen from rutinose, sophorose, diglugoside or gentiobiose, sambubiose, xylosylrutinose and glycosylrutinose, more particularly chosen from rutinoside and diglucoside; said disaccharide radical being linked to the rest of the molecule via a bond between carbon atom Ci of the sugar or of one of the sugars and this bond possibly being a or b anomeric.
11. Composition according to any one of Claims 6, 9 or 10, in which said dye comprises at least one -O-Sugar” group representing a monosaccharide radical chosen from
Figure imgf000067_0001
in which formulae -O-S8 and -O-S9:
- R8 represents a hydrogen atom, Rd-C(O)- with Rd representing an aryl group optionally substituted with one or more hydroxyl groups such as hydroxyphenyl (4- hydroxyphenyl) or aryl(C2-C4)alkenyl, notably styryl, the phenyl group of which is optionally substituted with one or more groups chosen from hydroxyl and/or (C1-C4)alkoxy such as methoxy; in particular, Rd represents a group of formula (I”) as defined in Claim 7, more particularly caffeyl or 3 ,4-dihydroxystyryl, ferulyl or 3 -methoxy-4-hydroxy styryl, sinapyl or 3 , 5 -dimethoxy-4-hydroxy styryl, 4-coumaryl or 4-hydroxystyryl, more preferentially Rd-C(O)- a caffeoyl (3 ,4-dihydroxy styrylcarbonyl), feruloyl, 4-coumaroyl or sinapoyl group;
- R9 and R10, which may be identical or different, preferably different, represent a hydrogen atom, Rd-C(O)- with Rd representing a group from among: ii) aryl optionally substituted with one or more hydroxyl groups such as hydroxyphenyl (4-hydroxyphenyl) or iii) aryl(C2-C4)alkenyl, notably styryl, the phenyl group of which is optionally substituted with one or more groups chosen from hydroxyl and/or (C1-C4)alkoxy; in particular, Rd represents a group of formula (I”) as defined in Claim 7, more particularly methoxy (3 ,4- dihydroxystyryl or 3 -methoxy-4-hydroxy styryl, sinapyl), more preferentially Rd-C(O)- represents a 4-hydroxyphenyl (p-hydroxyphenyl), caffeoyl or feruloyl (3-methoxy-4- hydroxystyrylcarbonyl) group, and Rio represents a hydrogen atom or an -O group, more particularly, -O-Sugar” represents a group chosen from:
Figure imgf000069_0001
with R8 and R9 as defined previously.
12. Composition according to any one of Claims 6 to 11, in which said anthocyani(di)n dye is chosen from those of formula (IIB) below, and also the optical isomers thereof, the geometrical isomers thereof, the tautomers thereof, the organic or mineral acid or base salts thereof, and the solvates thereof such as hydrates:
Figure imgf000070_0001
in which formula (IIB):
R 3' represents a hydroxyl group or a (C1-C4)alkoxy group such as methoxy; and R8, R9 and Rio are as defined in Claim 11, and Q- being an anionic counterion; more particularly, the compounds of formula (IIB) are chosen from:
Figure imgf000071_0001
13. Composition according to any one of Claims 6 to 12, in which said anthocyani(di)n dye is chosen from those of formula (lie) below, and also the optical isomers thereof, the geometrical isomers thereof, the tautomers thereof, the organic or mineral acid or base salts thereof, and the solvates thereof such as hydrates:
Figure imgf000072_0001
in which formula (lie):
R3 ' represents a hydroxyl group or a (Ci-C4)alkoxy group such as methoxy, preferably a hydroxyl group; and R3 is as defined in Claim 6, and preferably represents a hydroxyl or -O- Sugar group as defined in Claim 7, preferably -O-S1 and more particularly -O-glucoside, and R7 represents a hydroxyl group or an -O- Sugar group as defined in Claim 7, preferably -O-S8, more particularly -O-S8’ with R8 preferably representing a group Rd-C(O)- with Rd representing a (Ci-C4)alkyl group optionally substituted with a carboxyl and/or hydroxyl group such as acetyl [CH3-C(O)-], oxalyl [HO-C(O)-C(O)-] , malonyl [HO-C(O)-CH2- C(O)-] and succinyl [HO-C(O)-CH2-CH2-C(O)-], malyl [HO-C(O)-CH(OH)-CH2-C(O)- or HO-C(O)-CH2-CH(OH)-C(O)-]; more preferentially, Rg represents a malonyl group and Q" being an anionic counterion.
14. Composition according to any one of Claims 6 to 13, in which said anthocyani(di)n dye is chosen from those of formula (IID) below, and also the optical isomers thereof, the geometrical isomers thereof, the tautomers thereof, the organic or mineral acid or base salts thereof, and the solvates thereof such as hydrates:
Figure imgf000073_0001
in which formula (IID):
R3’ represents a hydrogen atom or a hydroxyl group or (C1-C4)alkoxy group such as methoxy; R8 being as defined in Claim 11, and Q- being an anionic counterion; preferably, R8 represents a group chosen from sinapoyl, feruloyl and 4-coumaroyl; more particularly, the compounds of formula (IID) are chosen from:
Figure imgf000073_0002
15. Composition according to any one of the preceding claims, in which the anthocyani(di)n dye(s) b) are present in the form of extracts of plants, notably chosen from extracts of blueberry, blackberry, loganberry, black grape, blood orange, açai berry, chokeberry, aubergine, cranberry, purple potato, purple sweet potato, plum, sloe, cornflower (wild lowbush blueberry), mallow, red grape (and red wine), strawberry, raspberry and black raspberry, banana, cranberry, red radish, potato, apple (notably the skin or peel), elderberry, peach, pear, fig, cherry, onion, notably red onion, redcurrant, red cabbage, rhubarb, blackcurrant, violet (purple) carrot, passionfruit, stringbean, pomegranate, grape, black rice, black bean, blue and purple maize, blue and purple maize grain, and blue and purple maize leaves; preferably extracts of red radish, of red cabbage, of aubergine, of purple sweet potato or of purple potato, of red onion, of purple maize, and of black or violet (purple) carrot, preferably of purple sweet potato, more preferentially extracts chosen from extracts of red radish, of red cabbage, of purple sweet potato or of purple potato, of red onion and of black or violet (purple) carrot, even more preferentially of purple sweet potato.
16. Composition according to any one of the preceding claims, comprising from 0.0001% to 20% by weight of water-soluble dye(s) that are natural or of natural origin, chosen from anthocyani(di)nes and derivatives thereof, of the total weight of the composition containing the water-soluble dye(s) that are natural or of natural origin or the extract(s) containing them, preferably:
- when the water-soluble dye(s) that are natural or of natural origin chosen from anthocyani(di)ns and derivatives thereof are pure, the content in the fragrancing composition ranges from 0.0001% to 5% by weight, preferably from 0.001% to 3.0% by weight, more preferentially from 0.01% to 1.0% by weight and even more preferentially from 0.1% to 0.5% by weight relative to the total weight of said composition;
- when the water-soluble dye(s) that are natural or of natural origin chosen from anthocyani(di)ns and derivatives thereof are in the form of extract(s), the content of extract(s) in the composition ranges from 0.01% to 20% by weight, particularly from 0.1% to 10% by weight, more particularly from 0.2% to 8.0% by weight, preferentially from 0.3% to 3.0% by weight, more preferentially from 0.4% to 2.0% by weight and better still from 0.5% to 1% by weight of extract(s) in said composition, relative to the total weight of said composition.
17. Composition according to any one of the preceding claims, said fragrancing substance being chosen from essential oils, perfumes and aromas of synthetic or natural origin, and mixtures thereof.
18. Composition according to any one of the preceding claims, comprising from 0.0001% to 10% by weight, in particular from 0.001% to 8.0% by weight, more particularly from 0.01% to 5.0% by weight and preferentially from 0.1% to 1.0% by weight of fragrancing substance(s), relative to the total weight of said composition.
19. Composition according to any one of the preceding claims, comprising one or more metal salts notably chosen from (poly)hydroxyalkyl(C 1 -C 16)carboxylates of metals of oxidation state II, notably Fe II, Cu II, Zn II, Mg II and Mn II (poly)hydroxyalkyl(C 1 - C 16)carboxy lates ; particularly Cu gluconate, Fe gluconate, Zn gluconate or Mg gluconate, gluconates of metals of oxidation state II such as Fe, Cu, Zn or Mg gluconates, lactates of metals of oxidation state II such as Fe, Cu, Zn or Mg lactates; preferably, the metal salts are Fe, Cu, Mg or Zn gluconate, preferably Fe and Cu gluconate.
20. Use of an organic acid ester as defined according to any one of Claims 1 and 3, as a stabilizer in a fragranced composition, notably a cosmetic composition, notably an aqueous-alcoholic composition, also comprising at least one water-soluble dye that is natural or of natural origin, chosen from anthocyani(di)ns and derivatives thereof, and at least one fragrancing substance.
21. Cosmetic process for treating keratin materials, in particular the skin, or clothing, comprising at least one step of applying a fragranced composition as defined according to any of Claims 1 to 19 to said keratin materials and/or said clothing.
PCT/EP2022/067896 2021-06-29 2022-06-29 Fragranced cosmetic composition comprising at least one organic acid ester, an anthocyani(di)n dye and a fragrancing material WO2023275142A1 (en)

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