Classifications

• • B—PERFORMING OPERATIONS; TRANSPORTING
  • B82—NANOTECHNOLOGY
  • B82Y—SPECIFIC USES OR APPLICATIONS OF NANOSTRUCTURES; MEASUREMENT OR ANALYSIS OF NANOSTRUCTURES; MANUFACTURE OR TREATMENT OF NANOSTRUCTURES
  • B82Y5/00—Nanobiotechnology or nanomedicine, e.g. protein engineering or drug delivery
• • 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
  • A61K8/19—Cosmetics or similar toiletry preparations characterised by the composition containing inorganic ingredients
  • A61K8/25—Silicon; Compounds thereof
• • 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
  • A61K8/58—Cosmetics or similar toiletry preparations characterised by the composition containing organic compounds containing atoms other than carbon, hydrogen, halogen, oxygen, nitrogen, sulfur or phosphorus
  • A61K8/585—Organosilicon compounds
• • 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
• • C—CHEMISTRY; METALLURGY
  • C11—ANIMAL OR VEGETABLE OILS, FATS, FATTY SUBSTANCES OR WAXES; FATTY ACIDS THEREFROM; DETERGENTS; CANDLES
  • C11D—DETERGENT COMPOSITIONS; USE OF SINGLE SUBSTANCES AS DETERGENTS; SOAP OR SOAP-MAKING; RESIN SOAPS; RECOVERY OF GLYCEROL
  • C11D3/00—Other compounding ingredients of detergent compositions covered in group C11D1/00
  • C11D3/50—Perfumes
  • C11D3/502—Protected perfumes
  • C11D3/507—Compounds releasing perfumes by thermal or chemical activation
• • A—HUMAN NECESSITIES
  • A61—MEDICAL OR VETERINARY SCIENCE; HYGIENE
  • A61K—PREPARATIONS FOR MEDICAL, DENTAL OR TOILETRY PURPOSES
  • A61K2800/00—Properties of cosmetic compositions or active ingredients thereof or formulation aids used therein and process related aspects
  • A61K2800/40—Chemical, physico-chemical or functional or structural properties of particular ingredients
  • A61K2800/41—Particular ingredients further characterized by their size
  • A61K2800/413—Nanosized, i.e. having sizes below 100 nm
• • A—HUMAN NECESSITIES
  • A61—MEDICAL OR VETERINARY SCIENCE; HYGIENE
  • A61K—PREPARATIONS FOR MEDICAL, DENTAL OR TOILETRY PURPOSES
  • A61K2800/00—Properties of cosmetic compositions or active ingredients thereof or formulation aids used therein and process related aspects
  • A61K2800/40—Chemical, physico-chemical or functional or structural properties of particular ingredients
  • A61K2800/57—Compounds covalently linked to a(n inert) carrier molecule, e.g. conjugates, pro-fragrances

Definitions

• the present invention relates to the field of the chemical delivery systems, and more precisely to the perfumery and pharmaceutical fields.
• the invention concerns a delivery system which comprises a nano particle moiety and a releasing moiety.
• the invention's delivery system is capable of liberating in a controlled manner an active compound belonging to the ⁇ , ⁇ -unsaturated etone, aldehyde or carboxylic ester families.
• the present invention concerns also the use of said delivery system as perfuming ingredient as well as the perfuming compositions or perfumed articles comprising the invention's delivery system.
• Other objects of the invention are pharmaceutical compositions or drugs comprising the invention's delivery system.
• Inorganic materials have been described in the prior art as useful carriers for active ingredients.
• silica has been widely disclosed as carrier for perfumes or perfume precursors, also referred to as "pro-perfumes".
• WO 01/83398 discloses a delivery system consisting of porous silica carrying pro-perfumes.
• the pro-perfumes are either adsorbed in silica pores, or chemically bonded after chemical modification of the pores' surface.
• the size of the silica particles is not specifically cited in this document, it can be deduced from the description of silica pores that the systems are certainly on a micron scale. As a consequence, the particles are not able to form solid suspensions in a liquid.
• the disclosed delivery systems when used in application such as in a cleaning or detergent product, due to their size, the disclosed delivery systems present the risk of leaving residues on the treated surfaces, for instance a fabric in the case of a detergent. Finally, these systems also present stability problems, as the pro-perfumes adsorbed within the pores of the inorganic material are susceptible to diffuse in the environment during a prolonged storage. To the best of our knowledge, systems based on other inorganic materials do not solve these problems.
• the present invention now provides a solution to the above-mentioned problems, thanks to a delivery system which is on a nanosize scale and which comprises an inorganic nano particle moiety covalently bonded to at least one organic releasing moiety.
• the nano-size of the particles allows using the delivery systems of the invention in the form of solid dispersions in a liquid.
• Systems on a nanosize scale have been described in the prior art. i particular WO 02/50230 or yet DE 19841147 disclose "nano" systems. However the latter documents are based on the use of organic carriers, i.e. polymers or oligomers dissolved in one phase. These carriers are therefore dispersed in water so as to form nanoemulsions.
• a nanoemulsion is a liquid system which is, by virtue of its nature, susceptible of being destabilized easily when used in an application, for instance in the presence of a surfactant system.
• coalescence, and ripening may be cited as examples of such destabilization phenomena and they consequently alter the nanometric distribution of the emulsion system.
• the present invention provides a solution to said problem with the use of an inorganic carrier such as SiO 2 , which is modified in its surface so as to be covalently bonded with organic moiety such as pro-perfumes.
• an inorganic carrier such as SiO 2
• organic moiety such as pro-perfumes.
• the inorganic nature of the carrier allows to prepare solid dispersions which are much more stable than emulsion-type systems and which present, as a consequence, a stable nanometric distribution.
• a delivery system comprising a nano particle moiety covalently bonded to at least one ⁇ -oxy, ⁇ -thio or ⁇ -amino carbonyl moiety is a valuable perfuming or therapeutical ingredient capable of liberating in a controlled manner an active compound.
• active compound we mean here a compound capable of bringing a benefit into the surrounding environment into which is it released by the invention's delivery system. Said benefit could be related to an olfactif effect, e.g. an odor, or to a therapeutical effect. Therefore, said "active compound” can be an active perfuming ingredient or an active therapeutical ingredient.
• said active compound is an active ⁇ , ⁇ -unsaturated ketone, aldehyde or carboxylic ester, preferably an active ⁇ , ⁇ -unsarurated ketone or aldehyde.
• said active compound is a perfuming ingredient.
• perfuming ingredient it is meant here a compound, which is of current use in the perfumery industry, i.e. a compound which is used as active ingredient in perfuming preparations or compositions in order to impart a hedonic effect.
• said active compound is a therapeutical ingredient.
• therapeutic ingredient it is meant here a compound, which is of current use in the pharmaceutical industry, i.e. a compound which is incorporated into a pharmaceutical preparation, as active ingredient, to treat a disease or pain.
• an ingredient, to be considered as being a therapeutical one must be recognized by a person skilled in the art of pharmacy as being able to provide a positive effect to the health of a patient.
• the delivery system of the invention comprises a nano particle moiety.
• Said moiety constitutes the inorganic part of the invention's delivery system and is a mono or multi radical, depending on the number of releasing moieties bonded to it.
• Said moiety is derived from an inorganic nano particle.
• nano particle we mean here a particle having a mean particle size comprised between 2 run and 500 nm, measured with the Microtrac Ultrafine Particle Analyser (UP A). Preferably the size is comprised between 15 nm and 50 nm.
• the inorganic nario particle, from which the nano particle moiety can be derived can be made from inorganic materials such as amorphous or crystalline metal oxides, hydroxides, oxo-hydroxides or mixtures thereof.
• Suitable examples of such metals are elements of the I, II, HI or IV main group, e.g. Al, Si, hi, Sn, Ca, Ba or Sr, or yet the transition elements, e.g. Ti, Zr, Fe, Ag or Zn.
• Particularly suitable nano particle moieties are those derived from a nano particle made from oxides or hydroxides of Ti, Si, Zr, Al, Fe or mixtures thereof.
• the nano particles moieties made from oxides or hydroxides of Si are especially suitable for the purpose of the invention, whereas for a pharmaceutical application, it is preferable to use Si or Fe based nano particle moieties.
• the nano particle, from which the nano particle moiety is derived has X-ray diffraction characteristics, measured with a Siemens D500 X-ray diffractometer with Cu-K ⁇ radiation and scintillation counter, in the 2 ⁇ range between 15° and 85°. Said 2 ⁇ range indicates that the spherical nano particles made of silica are mainly amorphous. Density can also be used to characterise the nano particles.
• a nano particle made from silica may have a density comprised between 2 and 2.4 g/cm 3 , preferably between 2.2 and 2.3 g/cm 3
• a nano particle made from titanium oxide may have a density ranging from 3.8 to 4.3 g/cm 3 , preferably from 3.8 to 3.9 g/cm 3
• the nano particle made from alumina may have a density ranging from 3.8 to 4.2 g/cm 3
• a nano particle made from iron oxide may have a density comprised between 5.0 and 6.0 g/cm 3 .
• the specific surface area as measured by He-gas pycnometer AccuPyc 1330 from Micromeritics, is comprised between approximately 20 and 200 m 2 /g, preferably between 40 and 60 m 2 /g.
• the surface charge of the particle is negative and the Zeta potential, measured with Malvern Zetasizer 2000, does not reveal no-charge point in the range from pH 2 to pH 11.
• This inorganic nano particle moiety is covalently bonded by means of n (Si-O)- bondsto at least one releasing moiety of formula (P-X) m -R-Si(OR 5 ) 3-n (O ⁇ ) n (I) wherein the arrow indicates the location of the bond between said releasing moiety and the nano particle moiety, n representing an integer comprised between 1 to 3, and wherein a) P represents a group derived from a active perfume ingredient and which is represented by formula (H)
• R 1 represents a hydrogen atom, a to Ce alkoxyl radical or a d to C 15 linear or branched or cyclic alkyl, alkenyl or alkadienyl group, optionally substituted by one to four Ci to C 4 alkyl groups
• R 2 , R 3 and R 4 represent a hydrogen atom, a C 6-8 aromatic ring or a Ci to C1 5 linear, cyclic or branched alkyl, alkenyl or alkadienyl group, optionally substituted by one to four Ci to C 4 alkyl groups; two, or three, of said R 1 to R 4 being optionally bonded together to form a saturated or unsaturated ring having 6 to 20 carbon atoms and including the carbon atom to which said R 1 , R 2 , R 3 or R 4 groups are bonded, this ring being optionally substituted by one to four Ci to C linear or branched alkyl or alken
• R 10 represents a hydrogen atom or a hydroxy group
• R 11 represents a hydrogen atom or a C ⁇ CH, CH 3 CO or HOCH 2 CO group
• X represents a functional group selected from the group consisting of the formulae i) to vi): ⁇ ) iii)
• R represents a linear, branched or cyclic multivalent group (with a m+1 valence) derived from a -C 15 alkyl or alkylaryl group, said group optionally containing one or two functional groups selected from the group consisting of oxygen and sulfur atoms, CO, COO, CONR 6 , COS and N ⁇ R 6 ) a , R 6 being defined as above and a representing 0 or 1, d) R 5 represents a linear or branched Ci to C alkyl group; and e) m represents 1, 2 or 3.
• P in formula (I) is a group derived from an active perfuming ⁇ , ⁇ -unsaturated ketone, aldehyde or carboxyhc ester having from 8 to 20 carbon atoms, or more preferably between 11 and 15 carbon atoms.
• P is a group derived from a therapeutical ⁇ , ⁇ -unsaturated steroid having from 19 to 26 carbon atoms, or more preferably between 19 and 21 carbon atoms.
• the invention's delivery system will preferably comprise a releasing moiety (I) wherein P is a group selected from the group consisting of the formulae (P-l) to (P-12)
• P is a group of formula (P-13) or (P-14) (P-13) (P-14)
• the X group is preferably selected from the group consisting of formulae i), ii) and iii), as defined above, R 6 representing a hydrogen atom or a methyl or ethyl group. More preferably, X represents a group of formula ii) or iii), as defined above, R 6 representing a hydrogen atom or a methyl or ethyl group.
• R represents a linear, branched or cyclic divalent or trivalent group derived from a C 2 -C 9 alkyl group, said group optionally containing one or two functional groups selected from the group consisting of oxygen and sulfur atoms, COO, CONR 6 , and N(R 6 ) a , R 6 being defined as above and a representing 0 or 1, R 5 represents a methyl, ethyl or propyl group, and m is 1 or 2.
• R represents a linear, branched or cyclic divalent group derived from a C 2 -C 6 alkyl group optionally containing one functional groups selected from the group consisting of oxygen and sulfur atoms, COO, and N(R 6 ) a , R 6 being defined as above and a being 1, R 5 represents a methyl, ethyl or propyl group, and m is 1.
• the invention's delivery system is one wherein P is a radical of formula (P-l) or (P-7), as defined above; X represents a functional group of formula ii) or iii), R 6 representing a hydrogen atom; R represents a linear or branched divalent group derived from a C 2 -C 6 alkyl group; R 5 represents a methyl, ethyl or propyl group; and m is 1, and n represents 1, 2 or 3.
• a further particularly appreciated delivery system is one wherein P is a group of formula (P-2) as defined above, X represents a functional group of formula ii), R represents a linear or branched divalent group derived from a C 2 -C 6 alkyl group, R 5 represents a methyl, ethyl or propyl group, m is 1, and n represents an integer comprised between 1 to 3.
• P is a group of formula (P-2) as defined above
• X represents a functional group of formula ii)
• R represents a linear or branched divalent group derived from a C 2 -C 6 alkyl group
• R 5 represents a methyl, ethyl or propyl group
• m represents 1, and n represents an integer comprised between 1 to 3.
• each of the various P may be identical or different, as well as each of the X, R, R 5 or R 6 groups.
• the delivery system according to the invention may be synthesized using conventional methods. Indeed, the delivery system
• the reaction being carried out in a solvent having a dielectric constant ⁇ comprised between 3 and 81, at a temperature comprised between 20° and 70°C.
• said reaction can be carried out in the presence of a weak acid or base.
• the invention's delivery system is also obtainable by a process comprising the reaction between a nano particle together with at least one molar equivalent of a compound of formula
• Y is a XH or COOR functional group or represents a C 5 -C carboxyhc anhydride, and X, m, R, R 5 and R 6 have the same meaning as indicated above; to obtain a derivatized nano particle, which is subsequently reacted with a compound of formula (IN) or (TV') as defined below, under reactions conditions similar to those susceptible of leading to a Michael addition, i.e. conditions which are for instance used in the preparation of compounds (UP) and which are described further below.
• the first method of preparation is preferred.
• the invention delivery system comprises at least one releasing moiety, and in the preparation of said delivery system a nano particle is reacted with at least one molar equivalent of the compound of formula (III) or (LU').
• at least one it is meant here an amount comprised between 1 and y, y representing ideally the maximum number of releasing moieties or molar equivalent which can be covalently bonded to said nano particle.
• y representing ideally the maximum number of releasing moieties or molar equivalent which can be covalently bonded to said nano particle.
• the maximum number of releasing moieties, which can be attached to the nano particle will depend on the surface of the nano particle used and on the volume of said releasing moieties.
• Suitable solvents for the synthesis of the invention's delivery system are water, linear, branched or cyclic mono-, di-, hi-, oligo- and polyalcohols with a monomer chain length of Ci to C 15 , preferably from Ci to C 5 , or C ⁇ to C 8 ketones, esters, ethers, carbon acids or yet mixtures thereof.
• solvents selected from the group consisting of water, ethanol, metlianol, n-propanol, iso-propanol, n-decanol, dimethyl-ether, methyl-ethyl-ether, glycerol, dipropyl-glycol, 1,2-ethandiol, polyvinylalcohol.
• organic or inorganic acid or base it is possible to use an organic or inorganic acid or base.
• acids like hydrochloric acid, acetic acid, citric acid and bases like ammonia, sodium hydroxide, potassium hydroxide, tetramethyl ammonium hydroxide for the synthesis of the invention's delivery system.
• the compounds of formula (HI) can be prepared using conventional methods, as illustrated herein below and in the examples.
• the compounds (in) wherein X represents a sulfur atom, an oxygen atom or a NR 6 group are obtainable by the [l,4]-addition reaction, optionally in the presence of a base, between a thiol, alcohol or respectively an a ine, of general formula (H-X) m -R-Si(OR 5 ) 3 such as one of formula HSRSi(OR 5 ) 3 , HORSi(OR 5 ) 3 or HNR 6 RSi(OR 5 ) , and the active enone to be released by the invention's delivery systems, for instance an odoriferous ⁇ , ⁇ -unsaturated ketone, aldehyde or carboxyhc ester of formula (IN)
• R, R 1 , R 2 , R 3 , R 4 , R 5 and R 6 have the meaning indicated above and the configuration of the carbon-carbon double bond can be of the E or Z type.
• the compounds of formula (HP) wherein X is a functional group of formula v) or vi) are obtainable, using standard methods, by oxidation of the corresponding system in which X is a sulfur atom.
• the compounds of formula (IH) wherein X represents a carboxyhc functional group can be obtained more advantageously by the reaction between an appropriate compound of formula (HI'), such as ClCORSi(OR 5 ) 3 or EtOCORSi(OR 5 ) 3 , and a compound of formula (IN'), which is the aldol derivative of the odoriferous compound of formula (IV),
• an appropriate compound of formula (HI') such as ClCORSi(OR 5 ) 3 or EtOCORSi(OR 5 ) 3
• a compound of formula (IN') which is the aldol derivative of the odoriferous compound of formula (IV)
• a particular example can be for instance the following:
• aldol derivatives of formula (TV) of the latter compounds are also useful in the synthesis of the invention compounds.
• the preferred are: ⁇ -damascone, (-)-alpha-damascone, ⁇ -damascone, ⁇ -damascone, ⁇ -damascone, trans ⁇ -damascone, ⁇ -ionone, ⁇ -ionone, ⁇ -damascenone, l-(5,5-dimethyl-l-cyclohexen-l- yl)-4-penten-l-one, l-(2,2,3,6-tetramethyl-l-cyclohexyl)-2-buten-l-one, 4-(2,2,3,6- tetramethyl-l-cyclohexyl)-3-buten-2-one or its trans isomer, l(6),8-P-menthadien-2-
• the delivery system of the invention is composed of two main moieties, namely a nano particle moiety and a releasing moiety.
• the latter moiety comprises a release part P-X and a linker part R-Si(OR 5 ) 3-n (O ⁇ ) n .
• the invention's delivery systems are capable of releasing, via a decomposition reaction, a residue and an active enone of formula (IV).
• An example of said decomposition reaction is illustrated in the following scheme:
• X, R, R 1 , R 2 , R 3 and R 4 have the meaning indicated above and NP stand for nano particle moiety.
• the nature of X plays an important role in the release kinetics of the active molecule.
• the second part of the releasing moiety of the delivery system of the invention is the linker R-Si(OR 5 ) 3- ⁇ (O ⁇ ) n -
• said linker part can have also an influence in the releasing properties of the invention's delivery system. Indeed, a shrewd choice of the chemical nature of said fragment, e.g.
• the second moiety of the invention's delivery system is the nano particle moiety. If the invention's delivery system is intended to release a perfuming ingredient, according to a preferred embodiment of the invention, said moiety plays an important role in the effective deposition of the pro-perfume onto a surface and in surface substantivity of the invention's delivery system on the surface treated during an application, especially on fabrics and hair. Moreover it plays a capital role as regards the stability of the product into which the invention's delivery system may be incorporated, avoiding the problems of the above mentioned prior art pro-perfume systems, wherein the pro-perfume was at least partially adsorbed onto silica pores.
• the decomposition reaction which leads to the release of the active enone, is beheved to be influenced by pH changes or heat, but may be triggered by other types of mechanisms.
• the delivery system of the invention can be a useful ingredient for the perfuming of various products or surfaces
• the invention concerns also the use of a invention's delivery system as perfuming ingredients.
• a method to confer, enhance, improve or modify the odor properties of a perfuming composition or of a perfumed article which method comprises adding to said composition or article an effective amount of at least an invention's delivery system.
• use of an invention's delivery system it has to be understood here also the use of any composition containing said delivery system and which can be advantageously employed in perfumery industry as active ingredients.
• compositions which in fact can be advantageously employed as perfuming ingredient, are also an object of the present invention. Therefore, another object of the present invention is a perfuming composition
• a perfuming composition comprising: i) as perfuming ingredient, at least an invention's delivery system of formula (I) as defined above, provided that P is a group of formula (IT) as defined above; ii) at least one ingredient selected from the group consisting of a perfumery carrier and a perfumery base; and iii) optionally at least one perfumery adjuvant.
• perfumery carrier we mean here a material which is practically neutral from a perfumery point of view, i.e. that does not significantly alter the organoleptic properties of perfuming ingredients.
• Said carrier may be a liquid.
• liquid carrier one may cite, as non-limiting examples, an emulsifying system, i.e. a solvent and a surfactant system, or a solvent commonly used in perfumery.
• emulsifying system i.e. a solvent and a surfactant system
• a solvent commonly used in perfumery A detailed description of the nature and type of solvents commonly used in perfumery cannot be exhaustive.
• solvents such as dipropyleneglycol, diethyl phthalate, isopropyl myristate, benzyl benzoate, 2-(2- ethoxyethoxy)-l-ethanol or ethyl citrate, which are the most commonly used.
• suitable liquid carrier is water or a water-based medium.
• perfumery base we mean here a composition comprising at least one perfuming co-ingredient.
• Said perfuming co-ingredient is not an invention's delivery system.
• perfuming co-ingredient it is meant here a compound, which is used in perfuming preparation or composition to impart a hedonic effect.
• a co- ingredient to be considered as being a perfuming one, must be recognized by a person skilled in the art as being able to impart or modify in a positive or pleasant way the odor of a composition, and not just as having an odor.
• perfuming co-ingredients present in the base do not warrant a more detailed description here, which in any case would not be exhaustive, the skilled person being able to select them on the basis of its general knowledge and according to intended use or application and the desired organoleptic effect.
• these perfuming co-ingredients belong to chemical classes as varied as alcohols, aldehydes, ketones, esters, ethers, acetates, nitriles, terpene hydrocarbons, nitrogenous or sulphurous heterocyclic compounds and essential oils, and said perfuming co-ingredients can be of natural or synthetic origin. Many of these co-ingredients are in any case listed in reference texts such as the book by S.
• compositions which comprise both a perfumery carrier and a perfumery base can be also ethanol, water/ethanol mixtures, limonene or other terpenes, isoparaffins such as those known under the trademark Isopar ® (origin: Exxon Chemical) or glycol ethers and glycol ether esters such as those known under the trademark Dowanol ® (origin: Dow Chemical Company).
• isoparaffins such as those known under the trademark Isopar ® (origin: Exxon Chemical) or glycol ethers and glycol ether esters such as those known under the trademark Dowanol ® (origin: Dow Chemical Company).
• perfumery adjuvant we mean here an ingredient capable of imparting additional added benefit such as a color, a particular light resistance, chemical stability and etc.
• An invention's composition consisting of at least one compound of formula (I) and at least one perfumery carrier represents a particular embodiment of the invention as well as a perfuming composition comprising at least one compound of formula (I), at least one perfumery carrier, at least one perfumery base, and optionally at least one perfumery adjuvant.
• a particular perfuming composition comprises: i) as perfuming ingredient, at least an invention's delivery system as defined above, provided that P is a group of formula (H) as defined above; ii) water; and iii) optionally at least an anti-floculant ingredient.
• Anti-fioculant ingredients are compound well known per se by a person skilled in the art.
• a suitable anti-floculant ingredient is the high molecular weigh co-polymer known under the name Disperbyk-190 (origin: Byk Chemie).
• an invention's delivery system in any of its above- mentioned forms, is a useful perfuming ingredient which can be advantageously used in all the fields of modern perfumery, such as fine perfumery or functional perfumery, as it enables a controlled release of odoriferous molecules.
• the invention's delivery system may be advantageously employed in fine or functional perfumery to achieve a more controlled deposition and/or release, of an active perfuming ingredient.
• perfuming ingredients present as such in washing or perfuming compositions can have little staying-power on a surface and consequently be often eliminated, for example in the rinsing water or upon drying of said surface.
• the invention's delivery system owing to a good substantivity, a low volatility and a controlled release of odoriferous molecules, can be incorporated in any application requiring the effect of rapid or prolonged release of an odoriferous component as defined hereinabove and furthermore can impart a fragrance and a freshness to a treated surface which will last well beyond the rinsing and/or drying processes.
• Suitable surfaces are, in particular, textiles, hard surfaces, hair and skin.
• one of the major advantages of the invention resides in the fact that the invention's delivery system imparts an intense fragrance to the treated surface, produced by an odoriferous enone, which would not be detected on said surface over a sufficiently long period if the ⁇ , ⁇ -unsaturated carbonyl derivative of formula (IN) had been used as such, i.e. without a precursor. Therefore, another object of the present invention is a perfumed article comprising: i) as perfuming ingredient at least one invention's delivery system as defined above, provided that P is a group of formula (H) as defined above; and ii) a consumer product base; is also an object of the present invention.
• a consumer product base we mean here a consumer product, i.e. a consumable product such as a detergent or a perfume.
• a perfumed article according to the invention comprises the functional formulation, as well as optionally additional benefit agents, corresponding to a consumer product, e.g. a detergent or an air freshener, and an olfactive effective amount of at least one invention's delivery system.
• a consumer product e.g. a detergent or an air freshener
• an olfactive effective amount of at least one invention's delivery system e.g. a detergent or an air freshener
• the nature and type of the constituents of the consumer product do not warrant a more detailed description here, which in any case would not be exhaustive, the skilled person being able to select them on the basis of its general knowledge and according to the nature and the desired effect of said product.
• suitable perfumed articles include solid or liquid detergents and fabric softeners as well as all the other articles of common use in perfumery, namely perfumes, colognes or after-shave lotions, perfumed soaps, shower or bath salts, mousses, oils or gels, hygiene products or hair care products such as shampoos, body-care products, deodorants or antiperspirants, air fresheners and also cosmetic preparations.
• perfumes there are intended applications such as detergent compositions or cleaning products for washing up or for cleaning various surfaces, e.g. intended for textile, dish or hard-surface treatment, whether they are intended for domestic or industrial use.
• Other perfumed articles are fabric refreshers, ironing waters, papers, wipes or bleaches.
• Preferred articles are perfumes, fabric detergents or softener bases.
• Typical examples of fabric detergents or softener compositions into which the compounds of the invention can be incorporated are described in WO 97/34986 or in US patents 4,137,180 and 5,236,615 or EP 799 885.
• Other typical detergent and softening compositions which can be used are described in works such as Ullman's Encyclopedia of Industrial Chemistry, vol. A8, pages 315 - 448 (1987) and vol. A25, pages 747 - 817 (1994); Flick, Advanced Cleaning Product Formulations, Noye Publication, Park Ridge, New Jersey (1989); Showell, in Surfactant Science Series, vol.
• a further object of the present invention concerns the use of a delivery system as defined above, wherein P is derived from an active therapeutical steroid, as a pharmaceutical agent. Furthermore, the present invention concerns also a pharmaceutical composition comprising a delivery system according to the second main embodiment of the invention.
• the invention will now be described in further detail by way of the following examples, wherein the abbreviations have the usual meaning in the art, the temperatures are indicated in degrees centigrade (°C) ; the ]MMR spectral data were recorded in CDC1 3 1 1 ⁇
• component 1 315 g tetraethoxysilane (1.27 mol) are mixed with 782 g ethanol (17 mol) (component 1). Separately, 21.23 g of a 35% w/w aqueous solution of ammonia were diluted with 498 g of water (component 2). Component 2 is mixed under vigorous stirring with component 1.
• the mixture thus obtained is heated up to 70° C for 8 hours. Afterwards, to the mixture thus obtained were added 9.5 g of Polyoxyethylene sorbitan monooleate (Tween 80, origin ICI), and the mixture was heated under stirring in an autoclave for 4 hours at 230° C, while mamtaining the pressure between 30 and 40 bar. To remove the precipitated powder from the solvent decanting and filter pressing has been used. The so prepared SiO 2 powders have been mixed with 12 % w/w, relative to the amount of powder, of the surface modifier Polyoxyethylene sorbitan monooleate (Tween 80), and dipropylene glycol was added.
• Teween 80 Polyoxyethylene sorbitan monooleate
• Mortary mill This is a milling machine form by a round Zirconium container.
• a round Zirconium pistil is set very close (2 ⁇ m) to one side of the pot and is touching the bottom of the container.
• the container turns with 120 rpm while the pistil is pressed to the bottom of the container with a force of 10 N (1kg).
• N 10 N
• the starting nano particle has no Zero cross over at any pH value while the treated one has a Zero cross over at the pH value of 3. This is a certain indication that the pro-perfume has been bound chemically to the particle, otherwise the zeta potential would only slightly be changed in the measured pH range.
• the density of the so modified material changed slightly to 2.27 g/cm 3 , while the surface area decreased to 37.4 m 2 /g.
• the particles did not grow during the modification process and still showed a main primary particle size of 20 to 50 nm.
• the untreated SiO 2 has no Zero cross over at any pH value while the treated one has a Zero cross over at the pH value of 3. This is a certain indication that the pro-perfume has been bound chemically to the particle, otherwise the zeta potential would only slightly be changed in the measured pH range.
• the density and the surface area of this invention's delivery system are similar to those of the one described in example 2.b.i).
• the untreated SiO 2 has no Zero cross over at any pH value while the treated one has a Zero cross over at the pH value of 3. This is a certain indication that the pro-perfume has been bound chemically to the particle, otherwise the zeta potential would only slightly be changed in the measured pH range.
• the density and the surface area of this invention's delivery system are similar to those of the one described in example 2.b.i).
• the untreated SiO 2 has no Zero cross over at any pH value while the treated one has a Zero cross over at the pH value of 3. This is a certain indication that the pro-perfume has been bound chemically to the particle, otherwise the zeta potential would only slightly be changed in the measured pH range.
• the density and the surface area of this invention's delivery system are similar to those of the one described in example 2.b.i).
• a dispersion of a delivery system according to the invention in DIPG c) were added to 85 g of unperfumed market powder detergent "Via” (Lever Faberge AB, Sweden).
• the perfumed detergent was introduced in the powder compartment of a Miele Novotronic W900-79 CH washing machine. No fabric-softener was used. The machine was loaded with 16 terry towels (28x28cm, about 40g each) and approx. 2.3kg of cotton towels (11 towels, sized 45x85cm). This load was washed at 40°C using the normal cycle program and setting the spin drying adjustment to 900 rpm.
• the 16 terry towels were line-dried, in a drying room for 24 hours before being evaluated by a 20 people panel. They were then packed loosely in aluminum foil and further evaluated by a 20 people panel after 1, 4 and 7 days. Each panelist was asked to rate the various terry towels tested on an intensity scale of 1 to 7. 1 : no odor, 2 : weak odor, 3 : slightly weak odor, 4 : medium odor, 5 : slightly strong odor, 6 : strong odor, 7 : very strong odor.
• Table 1 Average value of the intensity rated by panelists over 7 days
• both delivery systems according to the invention are able to impart to a fabric a significantly more intense odor, than the active compound as such. This effect being present over a long period of time.
• Example 4
• a concentrated fabric softener base was prepared by admixing the following ingredients:
• the delivery system according to the invention in the form of a dispersion in DIPG, was added to 36 g of fabric-softener base above. After a vigorous stirring the mixture was poured in the fabric-softener compartment of a Miele Novotronic W900-79 CH washing machine. No detergent is applied.
• Table 2 Average intensity rating of all three evaluations on dry fabric (1, 3 and 7 days after the wash)

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