WO2021023670A1 - Compounds for providing a long-lasting mint odor - Google Patents

Abstract

The present invention relates to the field of perfumery. More particularly, it relates to a linear random co-polymer that is able to generate 2-methyl-5-(1-propen-2-yl)-2- cyclohexen-1-one and thus to provide a long-lasting or substantive mint odor to the environment. Moreover, the present invention relates to a method of imparting a long- lasting mint odor to surfaces, such as hard surfaces, fabric, skin or hair. Furthermore, the present invention relates to the use of said compounds in perfumery, as well as the perfuming or malodor compositions or perfumed articles comprising the invention's compounds.

Description

COMPOUNDS FOR PROVIDING A LONG-LASTING MINT ODOR

Technical field

The present invention relates to the field of perfumery. More particularly, it relates to a linear random co-polymer that is able to generate 2-methyl-5-(l-propen-2-yl)-2- cyclohexen-l-one and thus to provide a long-lasting or substantive mint odor to the environment. Moreover, the present invention relates to a method of imparting a long- lasting mint odor to surfaces, such as hard surfaces, fabric, skin or hair. Furthermore, the present invention relates to the use of said compounds in perfumery, as well as the perfuming or malodor compositions or perfumed articles comprising the invention’s compounds.

Background of the Invention

Consumers often correlate the efficiency of perfumed articles with the long- lastingness or substantivity of perfume perception. Perfumes are composed of a multitude of different volatile compounds, which are applied to a surface from which they evaporate to be smelled. The perfume is applied to surfaces, such as hard surfaces, fabric, skin or hair, via a perfume composition or a perfumed consumer article, as for example fine fragrances or diverse washing and cleaning agents. Due to the high volatility of the fragrances, which constitute perfumes, the odor emitted from the perfumed surface can only be perceived over a limited amount of time. In particular, the so-called top-notes of a perfume evaporate quite rapidly. They are the most volatile compounds of the composition and represent the freshness of a perfume. Top-notes typically comprise, among others, citrus, flowery, mint, green and fruity notes, and especially the minty notes are well- appreciated by the consumers such as the one imparted by 2-methyl-5-(l-propen-

2-yl)-2-cyclohexen-l-one (l,8-p-menthadien-6-one, carvone). However, the compound is quite volatile, and its odor imparted to surfaces, such as hard surfaces, fabric, skin or hair, only lasts for a relatively short period of time.

Consumers seek for fragrances that are stable in the targeted application and at the same time long-lasting or substantive to be smelled for several hours or even days after application. In particular, long-lasting minty notes are desirable. Therefore, it is the goal of the present invention to provide a system that is able to deliver a long-lasting or substantive minty odor to the environment. Furthermore, another objective of the present invention is to find a method of imparting a long-lasting minty odor to surfaces, such as hard surfaces, fabric, skin or hair, via the application of perfuming compositions or perfumed articles.

Description of the invention

We have now found that some specific compounds derived from carvone can advantageously be employed to bring a long-lasting or substantive mint odor from a given surface into the environment, and thus to be useful as ingredients for perfuming compositions or perfumed articles.

The present invention’s polymers can be used as perfuming or malodor counteracting ingredients.

A first object of the present invention concerns a linear random polysiloxane co- polymer, capable of releasing in a controlled manner an odoriferous a,b-unsaturated ketone, and comprising or consisting of a) at least one repeating unit of formula

wherein the double hatched lines indicate the bonding to another repeating unit b) at least one repeating unit of formula

wherein the double hatched lines have the same meaning as described for formula (I); and c) optionally, at least one repeating unit of formula

wherein the double hatched lines have the same meaning as described for formula (I).

By the term “linear”, it is meant the normal meaning in the art, i.e. the polymer consists of one main chain by contrast to a branched polymer. In other words, the co polymer of the invention can also be characterized by being not cross-linked, and in particular by the siloxane skeleton not being cross-linked.

By the term “co-polymer”, it is meant the normal meaning in the art; i.e. the polymer is made from different monomers. In other words, a co-polymer comprises different repeating units by contrast to a homo-polymer comprising only one type of repeating unit.

The term “random” designates a co-polymer wherein the different repeating units are organized in a random way.

The term “polysiloxane” has the normal meaning in the art and designates a polymer comprising (-Si-O)- groups as repeating units. The polysiloxane is also known as silicone.

According to any embodiment of the invention, the invention’s co-polymer may be characterized by a weight average molecular weight (M_w) comprised in the range between 370 Da and 50000 Da, particularly between 500 Da and 20000 or 30000 Da, more particularly between 1000 Da and 10000 Da, more particularly between 1500 Da and 5000 Da or even 4500 Da.

According to any embodiment of the invention, the invention’s co-polymers may be characterized by a viscosity V comprised in the range between 0.3 (Pa s) and 100 (Pa s), particularly between 0.5 (Pa s) and 60 (Pa s), more particularly between 1.0 (Pa s) and 20 or 30 (Pa s).

In particular one may mention the combination of any one of the above weight average molecular weight (M_w) ranges with any one of the above viscosity ranges.

According to any embodiment of the invention, the invention’s co-polymers may be characterized by a combination of M_w and V ranges, such as that the polymers can also be characterized by a ratio [1000*V/M_W] comprised in the range between 0.3 (Pa s)/Da and 10 (Pa s)/Da, or comprised in the range between 0.3 (Pa s)/Da and 6 (Pa s)/Da.

According to any embodiment of the invention, the co-polymer comprises repeating units (I) and (II), and siloxane repeating units other than units (I) and (II). In particular said co-polymer may comprise essentially (i.e. more than 90%, 95% or even 100% molar percent) siloxane repeating units. Polymers comprising 100% molar percent of siloxane repeating units are preferred.

Furthermore, it is also useful to mention that in said invention’s co-polymers the total amount of the repeating unit (I), relative to the total amount of repeating units and without accounting the terminal groups, (hereinafter (I)/(Tot) and expressed in molar percent) can be comprised between 5% and 100%, and in particular between 30% and 100%, or even between 45% and 95% or 100%.

According to any embodiment of the invention, the co-polymer of the invention can also be characterized by a molar ratio of the repeating units (I)/[(II)+(III)] comprised between 99/1 and 20/80, or comprised between 90/10 and 40/60, or even between 85/15 and 45/55.

According to any embodiment of the invention, a particular type of co-polymers of the invention is the one obtainable by a process comprising the following steps:

I) reacting together, at a temperature comprised between 20°C and 95°C, preferably between 60°C and 95 °C:

- a monomer of formula

wherein R¹ represents a C1-3 alkyl group, in particular a methyl or an ethyl group; - monomers of formulae (ii) and optionally of formula (iii)

(ii) (iii) SH wherein R¹ has the same meaning as indicated above;

- optionally a monomer of formulae (iv), (v), or (vi)

wherein R¹ has the same meaning as indicated above;

- and between 0.5 and 1.1 equimolar amounts of water with respect to the O-R¹ groups; and

- optionally, but preferably, an amount of a base; II) optionally, evaporating the alcohol R'-OH obtained after polymerization.

According to any embodiment of the invention, alternatively a particular type of co-polymers of the invention is the ones obtainable by a process comprising the following steps: I) reacting together, at a temperature comprised between 20°C and 95°C, preferably between 60°C and 95 °C:

- a monomer of formula

wherein R¹ has the same meaning as indicated above and A represents a hydrogen atom or an alkali metal atom;

- monomers of formulae (ii) and

wherein R¹ has the same meaning as indicated above; - optionally a monomer of formulae (iv), (v), or (vi) wherein R¹ has the same meaning as indicated above;

- and between 0.5 and 1.1 equimolar amounts of water with respect to the O-R¹ groups; and - optionally, but preferably, an amount of a base;

II) reacting the co-polymers obtained in the previous step with 2-methyl-5-(prop-l-en-2- yl)cyclohex-2-en-l-one; and

III) optionally, after step I) or II), evaporating the alcohol R'-OH obtained after polymerization. According to any embodiment of the invention, the amount of water used in the above process can be comprised between 0.7 and 1.0 equimolar amounts with respect to the O-R¹ groups.

For the sake of clarity, by the expression “an amount of a base” or the similar, it is here meant that the reaction is performed at an alkaline pH, in general comprised above 10, or 12 or even 14, and that the base can be any base and in particular a hydroxide, such as NaOH or KOH, or triethanolamine.

The monomers of formulae (iv), (v), and (vi) are meant to be end-chain units.

According to any embodiment of the invention, said polymer has terminal groups, which can be of various nature, depending on the manner of the preparation of the polymer. In particular, said terminal groups are siloxane groups of formula:

-(0)_x-Si(0R²)a((CH₂)3-B)b(CH3)c (IV) wherein x is 0 when the terminal groups is linked to an oxygen atom of the repeating unit and x is 1 when the terminal group is linked to a silicon atom of the repeating unit; a and b are, independently of each other, 0 or 1 and c is either 1, 2 or 3 and (a + b + c) = 3, and in particular b can be 0; each B represents independently from each other

wherein the wavy line indicates the location of the bond between Ct and B, or a SH group; each R² represents independently from each other a hydrogen atom or a R¹ group as defined above.

According to any embodiment of the invention, said terminal group is a Si(CH₃)₂0H, Si(CH₃)₂0R¹ or Si(CH3)3 group. In particular said terminal group is a Si(CH₃)₂OH or Si(CH )₂OR¹.

Said monomer (i) can be obtained by [1,4] -addition of an appropriate compound of formula (i’) (wherein A represents a hydrogen atom or an alkali metal atom) to 2- methyl-5-(prop-l-en-2-yl)cyclohex-2-en-l-one.

The other monomers are either commercially available or can be obtained following standard procedures well known by a person skilled in the art.

In particular according to any embodiment of the invention, said polymer is linear and comprises only siloxane units of types (II), (III) and (IV), and of formula (I).

According to any embodiment of the invention, the co-polymer of the invention is a linear co-polymer wherein the molar ratio of the repeating units (I)/[(II)+(III)] is comprised between 85/15 and 45/55, and said co-polymer having

- a weight average molecular weight (M_w) comprised in the range between 1000 Da and 5000 Da;

- terminal groups of formula:

-(0)x-Si(0R²)a(CH₃)c (IV’) wherein x is 0 when the terminal groups is linked to an oxygen atom of the repeating unit and x is 1 when the terminal group is linked to a silicon atom of the repeating unit; a is either 0 or 1 and c is either 2 or 3 and (a + c) = 3; each R² represents independently from each other a hydrogen atom or a R¹ group as defined above; and optionally a viscosity V comprised in the range between 1.0 (Pa s) and 60 (Pa s).

Owing to their particular chemical structure, the invention’s co-polymers are capable of releasing, via a decomposition reaction, a residue and 2-methyl-5-(l-propen-2- yl)-2-cyclohexen-l-one (l,8-p-menthadien-6-one, also denominated as carvone). Carvone exists in the form of two enantiomers, namely (R)-(-)-2-methyl-5-(l-propen-2-yl)-2- cyclohexen-l-one (L-carvone or carvone laevo) and (S)-(+)-2-methyl-5-(l-propen-2-yl)- 2-cyclohexen-l-one (D-carvone or carvone dextro). The two enantiomers have been reported to have slightly different mint odor tonalities. Nevertheless, according to the invention, both enantiomers are expected to have a similar effect in view of the preparation of the co-polymer and the release efficiency. According to the invention, carvone can either be used as a racemate or as a mixture enriched in either one of the two enantiomers. Preferably, a mixture enriched in carvone laevo is used.

An example of the above-mentioned decomposition reaction is illustrated in the following scheme, wherein only one repeating unit is shown:

(co-polymeric residue) and the decomposition reaction, which leads to the release of the odoriferous molecules, is believed to be influenced by the presence of oxygen, pH changes or by heat, but may also be triggered by other types of mechanisms.

In one embodiment, the invention’s co-polymer is encapsulated. The invention’s co-polymer can be encapsulated in a microcapsule. In one embodiment, invention’s co-polymer is encapsulated in a core-shell microcapsule wherein the invention’s co-polymer is contained in the core surrounded by the shell. The shell of the microcapsule protects the invention’s co-polymer from the environment. The shell is made of material which is able to release the invention’s co-polymer. In one embodiment, the shell is made of material which is able to release the invention’s co-polymer upon breakage of the shell and/or by diffusion through the shell. A person skilled in the art is well aware of processes to prepare said microcapsules.

The nature of the polymeric shell from the microcapsules of the invention can vary. As non-limiting examples, the shell can be aminoplast-based, polyamide-based, polyester-based, polyurea-based or polyurethane-based. According to an embodiment, the shell is a biopolymer-based shell comprising a protein.

The shell can also be a hybrid, namely organic-inorganic such as a hybrid shell composed of at least two types of inorganic particles that are cross-linked, or yet a shell resulting from the hydrolysis and condensation reaction of a polyalkoxysilane macro- monomeric composition.

According to an embodiment, the shell comprises an aminoplast co-polymer, such as melamine-formaldehyde or urea-formaldehyde or cross-linked melamine formaldehyde or melamine glyoxal.

According to another embodiment, the microcapsules have a polymeric shell resulting from complex coacervation wherein the shell is possibly cross-linked.

According to another embodiment the shell is polyurea-based made from, for example but not limited to isocyanate-based monomers and amine-containing crosslinkers such as guanidine carbonate and/or guanazole. Preferred polyurea microcapsules comprise a polyurea wall which is the reaction product of the polymerization between at least one polyisocyanate comprising at least two isocyanate functional groups and at least one reactant selected from the group consisting of an amine (for example a water soluble guanidine salt and guanidine); a colloidal stabilizer or emulsifier; and an encapsulated perfume. However, the use of an amine is optional.

According to a particular embodiment, the colloidal stabilizer includes an aqueous solution of between 0.1% and 0.4% of polyvinyl alcohol, between 0.6% and 1% of a cationic co-polymer of vinylpyrrolidone and of a quatemized vinylimidazole (all percentages being defined by weight relative to the total weight of the colloidal stabilizer). According to another embodiment, the emulsifier is an anionic or amphiphilic biopolymer preferably chosen from the group consisting of gum Arabic, soy protein, gelatin, sodium caseinate and/or mixtures thereof. The preparation of an aqueous dispersion/slurry of core-shell microcapsules is well known by a skilled person in the art. In one aspect, said microcapsule wall material may comprise any suitable resin and especially including melamine, glyoxal, polyurea, polyurethane, polyamide, polyester, etc. Suitable resins include the reaction product of an aldehyde and an amine, suitable aldehydes include, formaldehyde and glyoxal. Suitable amines include melamine, urea, benzoguanamine, glycoluril, and mixtures thereof. Suitable melamines include, methylol melamine, methylated methylol melamine, imino melamine and mixtures thereof. Suitable ureas include, dimethylol urea, methylated dimethylol urea, urea-resorcinol, and mixtures thereof. Suitable materials for making may be obtained from one or more of the following companies Solutia Inc. (St Louis, Missouri U.S.A.), Cytec Industries (West Paterson, New Jersey U.S.A.), Sigma- Aldrich (St. Louis, Missouri U.S.A.).

According to a particular embodiment, the core-shell microcapsule is a formaldehyde-free capsule. A typical process for the preparation of aminoplast formaldehyde-free microcapsules slurry comprises the steps of 1) preparing an oligomeric composition comprising the reaction product of, or obtainable by reacting together a) a polyamine component in the form of melamine or of a mixture of melamine and at least one C1-C4 compound comprising two NH2 functional groups; b) an aldehyde component in the form of a mixture of glyoxal, a C4-6 2,2-dialkoxy- ethanal and optionally a glyoxalate, said mixture having a molar ratio glyoxal/C4-6 2,2-dialkoxy-ethanal comprised between 1/1 and 10/1; and c) a protic acid catalyst;

2) preparing an oil-in-water dispersion, wherein the droplet size is comprised between 1 and 600 pm, and comprising: i. an oil; ii. a water medium iii. at least an oligomeric composition as obtained in step 1; iv. at least a cross-linker selected amongst

A) C4-C12 aromatic or aliphatic di- or tri-isocyanates and their biurets, triurets, trimers, trimethylol propane-adduct and mixtures thereof; and/or

B) a di- or tri-oxiran compound of formula Q-(oxiran-2-ylmethyl)n wherein n stands for 2 or 3 and Q represents a C2-C6 group optionally comprising from 2 to 6 nitrogen and/or oxygen atoms; v. optionally a C₁-C₄ compound comprising two NH₂ functional groups;

3) Heating said dispersion; 4) Cooling said dispersion.

This process is described in more details in WO 2013/068255, the content of which is included by reference.

According to another embodiment, the shell of the microcapsule is polyurea-or polyurethane-based. Examples of processes for the preparation of polyurea and polyureathane-based microcapsule slurry are for instance described in WO 2007/004166, EP 2300146, EP 2579976 the contents of which are also included by reference. Typically a process for the preparation of polyurea or polyurethane-based microcapsule slurries include the following steps: a) Dissolving at least one polyisocyanate having at least two isocyanate groups in an oil to form an oil phase; b) Preparing an aqueous solution of an emulsifier or colloidal stabilizer to form a water phase; c) Adding the oil phase to the water phase to form an oil-in-water dispersion, wherein the mean droplet size is comprised between 1 and 500 pm, preferably between 5 and 50 pm; d) Applying conditions sufficient to induce interfacial polymerisation and form microcapsules in the form of a slurry.

In an alternative embodiment, the capsule may be a granule wherein the hydrophobic ingredient; i.e. the invention’s polymer, is dispersed or adsorbed in a matrix or a carrier being a water soluble material. According to any embodiment, the water soluble matrix or carrier is a monomeric, oligomeric or polymeric carrier material, or a mixture of two or more of these. An oligomeric carrier is a carrier wherein 2-10 monomeric units are linked by covalent bonds. For example, if the oligomeric carrier is a carbohydrate, the oligomeric carrier may be sucrose, lactose, raffinose, maltose, trehalose, or a fructo-oligosaccharide.

Examples of monomeric carrier materials are glucose, fructose, mannose, galactose, arabinose, fucose, sorbitol, mannitol.

Polymeric carriers have more than 10 monomeric units that are linked by covalent bonds. The carrier may be a polymeric carrier material. Non-limiting examples of polymeric carrier materials include urea, polyvinyl acetates, polyvinyl alcohol, dextrins, maltodextrins, glucose syrups, natural or modified starch, polysaccharides, carbohydrates, chitosan, gum Arabic, polyethylene glycol (PEG), polyvinyl pyrrolidone, acrylamides, acrylates, methacrylates, polyacrylic acid and related structures, maleic anhydride co- polymers, amine-functional polymers, polyvinyl benzyl chloride, vinyl ethers, styrenes, polystyrenesulfonates, vinyl acids, ethylene glycol-propylene glycol block co-polymers, vegetable gums, gum acacia, pectins, xanthanes, alginates, carragenans, cellulose or cellulose derivatives, such as carboxymethyl methylcellulose, methylcellulose, ethylcellulose, propylcellulose or hydroxyethyl cellulose, polyols/sugar alcohols such as sorbitol, maltitol, xylitol, erythritol, and isomalt, PVP, citric acid or any water soluble solid acid, fatty alcohols or fatty acids and mixtures thereof.

According to a particular embodiment, the water soluble polymer comprises maltodextrin having a Dextrose Equivalent (DE) comprised between 3 and 20, preferably between 10 and 18. According to an embodiment, the water soluble polymer comprises Maltodextrin

18DE and/or Maltodextrin 10DE.

According to a particular embodiment, the water soluble polymer comprises Maltodextrin 10DE.

According to an embodiment, the carrier is an inorganic material chosen in the group consisting of sodium chloride, sodium sulfate, sodium acetate, zeolite, sodium carbonate, sodium bicarbonate, clay, talc, calcium carbonate, magnesium sulfate, gypsum, calcium sulfate, magnesium oxide, zinc oxide, titanium dioxide, calcium chloride, potassium chloride, magnesium chloride, zinc chloride.

According to a particular embodiment, the solid carrier is sodium chloride and/or urea. According to a particular embodiment, the solid carrier is sodium chloride.

According to a particular embodiment, the solid carrier is a mixture of clay and PEG, preferably the mixture comprises 0-30% of clay and 20-80% of PEG, preferably between 1-30% of clay and 20-80% of PEG, based on the total weight of the carrier. According to a particular embodiment, the solid carrier is a mixture of sodium acetate and PEG, preferably the mixture comprises 0-80% of sodium acetate and 0-50% of PEG, preferably 1-80% of sodium acetate and 1-50% of PEG.

PEG has preferably a molecular weight greater than 1000 g/mol, preferably between 1000 and 8000 g/mol.

As mentioned above, the invention concerns the use of the above-described co- polymers as perfuming ingredients. In other words, it concerns a method to confer, enhance, improve or modify the odor properties of a perfuming composition or of a perfumed article or of a surface, which method comprises adding to said composition or article an effective amount of at least one co-polymer according to the invention. By “use of an invention’s co-polymer” it has to be understood here also the use of any composition containing said co-polymer and which can be advantageously employed in perfumery industry as active ingredients.

Said 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 comprising: i) as perfuming ingredient, at least one invention’s co-polymer 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. By “perfumery carrier” it is meant 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 or a solid.

As 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. A detailed description of the nature and type of solvents commonly used in perfumery cannot be exhaustive. However, one can cite as non-limiting examples, solvents such as butylene or propylene glycol, glycerol, dipropyleneglycol and its monoether, 1,2,3- propanetriyl triacetate, dimethyl glutarate, dimethyl adipate, l,3-diacetyloxypropan-2-yl acetate, diethyl phthalate, isopropyl myristate, benzyl benzoate, benzyl alcohol, 2-(2- ethoxyethoxy)-l-ethano, tri-ethyl citrate or mixtures thereof, which are the most commonly used. For the compositions which comprise both a perfumery carrier and a perfumery base, other suitable perfumery carriers than those previously specified, 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), or hydrogenated castor oils such as those known under the trademark Cremophor^® RH 40 (origin: BASF).

Solid carrier is meant to designate a material to which the perfuming composition or some element of the perfuming composition can be chemically or physically bound. In general such solid carriers are employed either to stabilize the composition, or to control the rate of evaporation of the compositions or of some ingredients. Solid carriers are of current use in the art and a person skilled in the art knows how to reach the desired effect. However by way of non-limiting examples of solid carriers, one may cite absorbing gums or polymers or inorganic materials, such as porous polymers, cyclodextrins, wood based materials, organic or inorganic gels, clays, gypsum talc or zeolites.

As other non-limiting examples of solid carriers, one may cite encapsulating materials. Examples of such materials may comprise wall-forming and plasticizing materials, such as mono, di- or trisaccharides, natural or modified starches, hydrocolloids, cellulose derivatives, polyvinyl acetates, polyvinyl alcohols, proteins or pectins, or yet the materials cited in reference texts such as H. Scherz, Hydrokolloide: Stabilisatoren, Dickungs- und Geliermittel in Lebensmitteln, Band 2 der Schriftenreihe Lebensmittelchemie, Lebensmittelqualitat, Behr's Verlag GmbH & Co., Hamburg, 1996. The encapsulation is a well-known process to a person skilled in the art, and may be performed, for instance, by using techniques such as spray-drying, agglomeration or yet extrusion; or consists of a coating encapsulation, including coacervation and complex coacervation techniques.

As non-limiting examples of solid carriers, one may cite in particular the core shell capsules with resins of aminoplast, polyamide, polyester, polyurea or polyurethane type or a mixture thereof (all of said resins are well known to a person skilled in the art) using techniques like phase separation processes induced by polymerization, interfacial polymerization, coacervation or altogether (all of said techniques have been described in the prior art), optionally in the presence of a polymeric stabilizer or of a cationic co polymer.

Resins may be produced by the polycondensation of an aldehyde (e.g. formaldehyde, 2,2-dimethoxyethanal, glyoxal, glyoxylic acid or glycolaldehyde and mixtures thereof) with an amine such as urea, benzoguanamine, glycoluryl, melamine, methylol melamine, methylated methylol melamine, guanazole and the like, as well as mixtures thereof. Alternatively one may use preformed resins alkylolated polyamines such as those commercially available under the trademark Urac^® (origin: Cytec Technology Corp.), Cymel^® (origin: Cytec Technology Corp.), Urecoll^® or Luracoll^® (origin: BASF).

Others resins are those produced by the polycondensation of a polyol, like glycerol, and a polyisocyanate, like a trimer of hexamethylene diisocyanate, a trimer of isophorone diisocyanate or xylylene diisocyanate or a Biuret of hexamethylene diisocyanate or a trimer of xylylene diisocyanate with trimethylolpropane (known under the tradename of Takenate^®, origin: Mitsui Chemicals), among which a trimer of xylylene diisocyanate with trimethylolpropane and a Biuret of hexamethylene diisocyanate.

Some of the seminal literature related to the encapsulation of perfumes by polycondensation of amino resins, namely melamine based resins with aldehydes includes represented by articles such as those published by K. Dietrich et al. Acta Polymerica, 1989, vol. 40, pages 243, 325 and 683, as well as 1990, vol. 41, page 91. Such articles already describe the various parameters affecting the preparation of such core-shell microcapsules following prior art methods that are also further detailed and exemplified in the patent literature. US 4’396’670, to the Wiggins Teape Group Limited is a pertinent early example of the latter. Since then, many other authors have enriched the literature in this field and it would be impossible to cover all published developments here, but the general knowledge in encapsulation technology is very significant. More recent publications of pertinence, which disclose suitable uses of such microcapsules, are represented for example by the article of K. Bruyninckx and M. Dusselier, ACS Sustainable Chemistry & Engineering, 2019, vol. 7, pages 8041-8054. By “perfumery base” what is meant here is a composition comprising at least one perfuming co-ingredient.

The nature and type of the 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 his general knowledge and according to the intended use or application and the desired organoleptic effect. In general terms, these perfuming co-ingredients belong to chemical classes as varied as alcohols, lactones, aldehydes, ketones, esters, ethers, acetates, nitriles, terpenoids, nitrogenous or sulphurous heterocyclic compounds and essential oils, and said perfuming co-ingredients can be of natural or synthetic origin. In particular one may cite perfuming co-ingredients which are commonly used in perfume formulations, such as:

- Aldehydic ingredients: decanal, dodecanal, 2-methyl-undecanal, 10-undecenal, octanal and/or nonenal;

- Aromatic -herbal ingredients: eucalyptus oil, camphor, eucalyptol, menthol and/or alpha-pinene;

- Balsamic ingredients: coumarin, ethyl vanillin and/or vanillin;

- Citrus ingredients: dihydromyrcenol, citral, orange oil, linalyl acetate, citronellyl nitrile, orange terpenes, limonene, l-p-menthen-8-yl acetate and/or l,4(8)-p- menthadiene; - Floral ingredients: methyl dihydrojasmonate, linalool, citronellol, phenylethanol, 3-(4- tert-butylphenyl)-2-methylpropanal, hexylcinnamic aldehyde, benzyl acetate, benzyl salicylate, tetrahydro-2-isobutyl-4-methyl-4(2H)-pyranol, beta ionone, methyl 2- (methylamino)benzoate, (E)-3-methyl-4-(2,6,6-trimethyl-2-cyclohexen-l-yl)-3-buten- 2-one, hexyl salicylate, 3,7-dimethyl-l,6-nonadien-3-ol, 3-(4-isopropylphenyl)-2- methylpropanal, verdyl acetate, geraniol, p-menth-l-en-8-ol, 4-(l,l-dimethylethyl)-l- cyclohexyle acetate, l,l-dimethyl-2-phenylethyl acetate, 4-cyclohexyl-2-methyl-2- butanol, amyl salicylate , high cis methyl dihydrojasmonate, 3 -methyl-5 -phenyl- 1- pentanol, verdyl proprionate, geranyl acetate, tetrahydro linalool, cis-7-P-menthanol, propyl (S)-2-(l,l-dimethylpropoxy)propanoate, 2-methoxynaphthalene, 2,2,2- trichloro- 1-phenylethyl acetate, 4/3-(4-hydroxy-4-methylpentyl)-3-cyclohexene- 1- carbaldehyde, amylcinnamic aldehyde, 4-phenyl-2-butanone, isononyle acetate, 4-(l,l- dimethylethyl)-l -cyclohexyl acetate, verdyl isobutyrate and/or mixture of methylionone isomers;

- Fruity ingredients: gamma-undecalactone, 4-decanolide, ethyl 2-methyl-pentanoate, hexyl acetate, ethyl 2-methylbutanoate, gamma-nonalactone, allyl heptanoate, 2- phenoxyethyl isobutyrate, ethyl 2-methyl- l,3-dioxolane-2-acetate and/or diethyl 1,4- cyclohexane dicarboxylate;

- Green ingredients: 2,4-dimethyl-3-cyclohexene-l-carbaldehyde, 2-tert-butyl-l- cyclohexyl acetate, styrallyl acetate, allyl (2-methylbutoxy)acetate, 4-methyl-3-decen- 5-ol, diphenyl ether, (Z)-3-hexen-l-ol and/or l-(5, 5-dimethyl- l-cyclohexen-l-yl)-4- penten-l-one;

- Musk ingredients: l,4-dioxa-5,17-cycloheptadecanedione, pentadecenolide, 3-methyl-

5-cyclopentadecen-l-one, 1,3, 4,6,7, 8-hexahydro-4, 6, 6,7,8, 8-hexamethyl-cyclopenta-g- 2-benzopyrane, ( 1 S , l'R)-2- [ 1 -(3 ',3 '-dimethyl- 1 '-cyclohexyl)ethoxy ] -2-methylpropyl propanoate, pentadecanolide and/or (lS,rR)-[l-(3',3'-dimethyl-r- cyclohexyl)ethoxycarbonyl]methyl propanoate;

- Woody ingredients: l-(octahydro-2,3,8,8-tetramethyl-2-naphtalenyl)-l-ethanone, patchouli oil, terpenes fractions of patchouli oil, (rR,E)-2-ethyl-4-(2',2',3'-trimethyl-3'- cyclopenten-l'-yl)-2-buten-l-ol, 2-ethyl-4-(2,2,3-trimethyl-3-cyclopenten-l-yl)-2- buten-l-ol, methyl cedryl ketone, 5-(2,2,3-trimethyl-3-cyclopentenyl)-3-methylpentan- 2-ol, l-(2,3,8,8-tetramethyl-l,2,3,4,6,7,8,8a-octahydronaphthalen-2-yl)ethan-l-one and/or isobomyl acetate; - Other ingredients (e.g. amber, powdery spicy or watery): dodecahydro-3a,6,6,9a- tetramethyl-naphtho[2,l-b]furan and any of its stereoisomers, heliotropin, anisic aldehyde, eugenol, cinnamic aldehyde, clove oil, 3-(l,3-benzodioxol-5-yl)-2- methylpropanal and/or 3-(3-isopropyl-l-phenyl)butanal. A perfumery base according to the invention may not be limited to the above mentioned perfuming co-ingredients, and many other of these co-ingredients are in any case listed in reference texts such as the book by S. Arctander, Perfume and Flavor Chemicals, 1969, Montclair, New Jersey, USA, or its more recent versions, or in other works of a similar nature, as well as in the abundant patent literature in the field of perfumery. It is also understood that said co-ingredients may also be compounds known to release in a controlled manner various types of perfuming compounds.

According to any embodiments, the invention’s composition comprises, as a co ingredients releasing in a controlled manner various types of perfuming compounds, compounds selected from the group consisting of 4-(dodecylthio)-4-(2,6,6-trimethyl-2- cyclohexen-l-yl)-2-butanone, 4-(dodecylthio)-4-(2, 6, 6-trimethyl- 1-cyclohexen-l -yl)-2- butanone, trans-3-(dodecylthio)-l-(2,6,6-trimethyl-3-cyclohexen-l-yl)-l-butanone and a mixture thereof. According to any embodiment, the weight ratio between the invention’s co-polymer and trans-3-(dodecylthio)-l-(2,6,6-trimethyl-3-cyclohexen-l-yl)-l-butanone may be comprised between 1:0.05 and 1:10; preferably between 1:0.1 and 1:5; even more preferably, between 1:0.3 and 1:3.5. According to any embodiment, the weight ratio between the invention’s co-polymer and a mixture comprising 4-(dodecylthio)-4-(2,6,6- trimethyl-2-cyclohexen- l-yl)-2-butanone and 4-(dodecylthio)-4-(2, 6, 6-trimethyl- 1- cyclohexen-l-yl)-2-butanone may be comprised between 1:0.05 and 1:5; preferably between 1:0.1 and 1:3; even more preferably, between 1:0.3 and 1:2. By “perfumery adjuvant”, it is meant here an ingredient capable of imparting additional added benefit such as a color, a particular light resistance, chemical stability, etc. A detailed description of the nature and type of adjuvant commonly used in perfuming composition cannot be exhaustive, but it has to be mentioned that said ingredients are well known to a person skilled in the art. One may cite as specific non- limiting examples the following: viscosity agents (e.g. surfactants, thickeners, gelling and/or rheology modifiers), stabilizing agents (e.g. preservatives, antioxidant, heat/light and or buffers or chelating agents, such as BHT), coloring agents (e.g. dyes and/or pigments), preservatives (e.g. antibacterial or antimicrobial or antifungal or anti irritant agents), abrasives, skin cooling agents, fixatives, insect repellants, ointments, vitamins and mixtures thereof. It is understood that a person skilled in the art is perfectly able to design optimal formulations for the desired effect by admixing the above mentioned components of a perfuming composition, simply by applying the standard knowledge of the art as well as by trial and error methodologies.

Other suitable co-ingredients optionally used in combination with the co-polymers according to the present invention comprise tertiary amines, in particular those with high water solubility, such as triethanolamine, methyldiethanolamine, dimethylethanolamine, alkyldiethanolamines and ethoxylated alkyldiethanolamines.

Another suitable co-ingredients optionally used in combination with the polymers according to the present invention comprise zinc ricinoleate, laureth-3, tetrahydroxypropyl ethylnediamine, propylene glycol or a mixture thereof.

A particular aspect of the invention’s perfumery compositions concerns the ones further comprising (in addition to the above mentioned compositions) at least one compound selected amongst the isothiazolones of formula

wherein

R³ represents a hydrogen atom, an alkali metal atom, in particular Na or K, a phenyl or benzyl group possibly substituted with one or two halogen atoms and/or one or two methyl, trifluoromethyl, methoxy or amino groups, an amine group, or a Ci-Cs unsaturated, linear, branched or cyclic hydrocarbon group possibly substituted with one or two nitrogen, oxygen or halogen atoms; and

R⁴ and R⁵ represent, separately and independently of each other, a hydrogen atom, a halogen atom, preferably chlorine, a C1-C4 linear or branched alkyl group, an amino group or a benzylamino group; or, alternatively, R⁴ and R⁵ are taken together to represent a phenyl or pyridine ring, possibly substituted with one to four C1-C4 linear or branched alkyl or alkenyl groups and/or one to two halogen atoms, preferably chlorine atoms.

According to a particular embodiment of the invention said compound of formula (V) is one wherein R⁴ and R⁵ represent, separately and independently of each other, a hydrogen atom, a chlorine atom or a methyl group or, alternatively, R⁴ and R⁵ are taken together to represent a phenyl ring, and R³ represents a hydrogen atom or a methyl group.

According to a particular embodiment of the invention, said compound of formula (V) is selected from the group of isothiazolones consisting of l,2-benzisothiazol-3(2 /)- one, 4- or 5-chloro-2-methylisothiazol-3(2 )-one or 2-methylisothiazol-3(2 )-one, or more preferably 5-chloro-2-methylisothiazol-3(2 )-one or l,2-benzisothiazol-3(2 )-one, and most preferably l,2-benzisothiazol-3(2 )-one.

An invention’s composition consisting of at least one co-polymer and at least one perfumery carrier represents a particular embodiment of the invention as well as a perfuming composition comprising at least one polymer, at least one perfumery carrier, at least one perfumery base, and optionally at least one perfumery adjuvant.

According to a particular embodiment, the compositions mentioned above, comprise more than one of the invention’s co-polymer and enable the perfumer to prepare accords or perfumes possessing the odor tonality of various compounds of the invention, creating thus new building block for creation purposes. Furthermore, an invention’s co-polymer, or a perfuming composition comprising it, is a useful perfuming ingredient, which can be advantageously used in all the fields of modern perfumery, such as fine perfumery or functional perfumery. Indeed, the invention’s compounds may be advantageously employed in fine or functional perfumery to achieve a more controlled deposition, and consequent release, of odoriferous compounds. For example, the co-polymers according to the invention, owing to a good substantivity, a low volatility and a well-controlled release of odoriferous molecules, can be incorporated in any application requiring the effect of rapid or prolonged liberation 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. Consequently, a perfumed consumer product comprising, as a perfuming ingredient, at least one invention’s co-polymer as defined above, is also an object of the present invention.

The invention’s compound can be added as such or as part of an invention’s perfuming composition. For the sake of clarity, “perfumed consumer product” is meant to designate a consumer product which delivers at least a pleasant perfuming effect to the surface or space to which it is applied (e.g. skin, hair, textile, or home surface). In other words, a perfumed consumer product according to the invention is a perfumed consumer product which comprises a functional formulation, as well as optionally additional benefit agents, corresponding to the desired consumer product, and an olfactive effective amount of at least one invention’s compound. For the sake of clarity, said perfumed consumer product is a non-edible product.

The nature and type of the constituents of the perfumed 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 his general knowledge and according to the nature and the desired effect of said product.

Non-limiting examples of suitable perfumed consumer product include a perfume, such as a fine perfume, a splash or eau de parfum, a cologne or a shave or after-shave lotion; a fabric care product, such as a liquid or solid detergent, a fabric softener, a liquid or solid scent booster, a fabric refresher, an ironing water, a paper, a bleach, a carpet cleaner, a curtain-care product; a body-care product, such as a hair care product (e.g. a shampoo, a coloring preparation or a hair spray, a color-care product, a hair shaping product, a dental care product), a disinfectant, an intimate care product; a cosmetic preparation (e.g. a skin cream or lotion, a vanishing cream or a deodorant or antiperspirant (e.g. a spray or roll on), a hair remover, a tanning or sun or after sun product, a nail product, a skin cleansing, a makeup); or a skin-care product (e.g. a soap, a shower or bath mousse, oil or gel, or a hygiene product or a foot/hand care products); an air care product, such as an air freshener or a “ready to use” powdered air freshener which can be used in the home space (rooms, refrigerators, cupboards, shoes or car) and/or in a public space (halls, hotels, malls, etc..); or a home care product, such as a mold remover, a furnisher care product, a wipe, a dish detergent or a hard-surface (e.g. a floor, bath, sanitary or a window-cleaning) detergent; a leather care product; a car care product, such as a polish, a wax or a plastic cleaner.

According to anyone of the invention’s embodiments, said perfumed consumer product is a perfume, fabric detergent, scent booster, all-purpose cleaner or a softener base.

According to anyone of the invention’s embodiments, said perfumed consumer product is a rinse-off product (i,e, a product which requires an rinsing step), such as a shampoo, a rinse-off conditioner or a liquid or powder detergent.

As mentioned above, the co-polymers according to the invention, can impart a fragrance and freshness to a treated surface which will last well beyond the rinsing and/or drying processes.

Typical examples of fabric detergents or softener compositions into which the compounds of the invention can be incorporated are described in WO 97/34986, in WO 2012/113746 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. 71: Powdered Detergents, Marcel Dekker, New York (1988); Proceedings of the World Conference on Detergents (4th, 1998, Montreux, Switzerland), AOCS print.

The consumer product may be in the form of a fabric softener comprising: between 85 and 99.95 % by weight of a fabric softener active base; preferably chosen in the group consisting of dialkyl quaternary ammonium salts, dialkyl ester quaternary ammonium salts, Hamburg esterquat, triethanolamine quat, silicones and mixtures thereof. between 0.0001 to 2 %, preferably between 0.001 to 1%, more preferably between 0.01 and 0.5 % by weight of the invention’s co-polymer.

The consumer product may be in the form of a liquid detergent comprising: between 85 and 99.95 % by weight of a liquid detergent active base; preferably chosen in the group consisting of anionic surfactants such as alkylbenzenesulfonate (ABS), secondary alkyl sulfonate (SAS), primary alcohol sulfate (PAS), lauryl ether sulfate (LES), methyl ester sulfonate (MES) and nonionic surfactant such as alkyl amines, alkanolamide, fatty alcohol poly(ethylene glycol) ether, fatty alcohol ethoxylate (FAE), ethylene oxide (EO) and propylene oxide (PO) co-polymers, amine oxydes, alkyl polyglucosides, alkyl polyglucosamides, and mixtures thereof between 0.0001 to 2 %, preferably between 0.001 to 1%, more preferably between 0.01 and 0.5 % by weight of the invention’s co-polymer.

The consumer product may be in the form of a solid detergent comprising: - between 85 and 99.95 % by weight of a solid detergent active base; preferably chosen in the group consisting of anionic surfactants such as alkylbenzenesulfonate (ABS), secondary alkyl sulfonate (SAS), primary alcohol sulfate (PAS), lauryl ether sulfate (LES), methyl ester sulfonate (MES) and nonionic surfactant such as alkyl amines, alkanolamide, fatty alcohol poly(ethylene glycol) ether, fatty alcohol ethoxylate (FAE), ethylene oxide (EO) and propylene oxide (PO) co-polymers, amine oxydes, alkyl polyglucosides, alkyl polyglucosamides, and mixtures thereof between 0.0001 to 2 %, preferably between 0.001 to 1%, more preferably between 0.01 and 0.5 % by weight of the invention’s co-polymer. The consumer product may be in the form of a shampoo or a shower gel comprising: between 85 and 99.95 % by weight of a shampoo active base; preferably chosen in the group consisting of sodium alkylether sulfate, ammonium alkylether sulfates, alkylamphoacetate, cocamidopropyl betaine, cocamide MEA, alkylglucosides and aminoacid based surfactants - between 0.0001 to 2 %, preferably between 0.001 to 1%, more preferably between

0.01 and 0.5 % by weight of the invention’s co-polymer. The consumer product may be in the form of an oxidative hair coloring composition comprising: between 85 and 99.9 % by weight of a oxidative hair coloring base; comprising an oxidizing phase comprising an oxidizing agent and an alkaline phase comprising an alkakine agent, a dye precursor and a coupling compound; wherein said dye precursor and said coupling compound form an oxidative hair dye in the presence of the oxidizing agent. between 0.0001 to 2 %, preferably between 0.001 to 1%, more preferably between 0.01 and 0.5 % by weight of the invention’s co-polymer. Some of the above-mentioned perfumed consumer products may represent an aggressive medium for the invention’s compound, so that it may be necessary to protect the latter from premature decomposition, for example by encapsulation.

The proportions in which the compounds according to the invention can be incorporated into the various aforementioned products or compositions vary within a wide range of values. These values are dependent on the nature of the product to be perfumed and on the desired olfactory effect as well as the nature of the co-ingredients in a given composition when the compounds according to the invention are mixed with perfuming co-ingredients, solvents or additives commonly used in the art.

For example, in the case of perfuming compositions, typical concentrations are in the order of 0.001% to 30% by weight, or even more, of the invention’s compound based on the weight of the composition into which they are incorporated. In the case of perfumed consumer product, typical concentrations are in the order of 0.0001 % to 2 % by weight, or even more, of the compounds of the invention based on the weight of the consumer product into which they are incorporated, preferably, in the order of 0.01 % to 1 % by weight, preferably, in the order of 0.01 % to 0.5 % by weight, even more preferably, in the order of 0.01 % to 0.2 % of the compounds of the invention based on the weight of the consumer product into which they are incorporated.

A further object of the present invention is a method to confer, enhance, improve or modify the odor properties of a surface, which method comprises depositing on said surface, or washing said surface with, an effective amount of at least one polymer according to the invention. Said surface can be any one, and one can cite as non-limiting examples, textiles, hard surfaces, hair and skin, and in particularly synthetic fibers, such as polyesters, and hair.

Another object of the present invention relates to a method for the perfuming of a surface or to a method for intensifying or prolonging the diffusion effect of the characteristic fragrance of an odoriferous ingredient on a surface, characterized in that said surface is treated in the presence of an invention’s compound. Suitable surfaces are, in particular, textiles, hard surfaces, hair and skin.

Examples 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 NMR spectral data were recorded in CDCb (if not stated otherwise) on a Bruker DPX 400 spectrometer with 400 MHz for ¹ H and 100 MHz for ¹³C, the chemical displacements d are indicated in ppm with respect to the TMS as standard, the coupling constants J are expressed in Hz.

Commercially available reagents and solvents were used without further purification, if not stated otherwise. Size exclusion chromatography (SEC) analyses were carried out at room temperature (ca. 22°C) on a Viscotek GPC max VE 2001 GPC Solvent Sample Module connected to a Viscotek UV detector 2500, a Viscotek VE3580 RI detector and a Viscotek-270-Dual-Detector viscometer. Samples were eluted from Waters Styragel HR 4E and HP 5 (7.8 x 300 mm) columns at a flow rate of 1.0 mL min ¹ with tetrahydrofuran (THF, HPLC-grade). Universal calibrations were performed using commercial poly(styrene) standards. The polymer standard (ca. 40 mg) was accurately weighed and dissolved in THF (10 mL); then these solutions (100 mE) were injected for the calibration. For the molecular weights of the polymers determined by SEC, M_w stands for “weight average molecular weight” and M_n stands for “number average molecular weight”. Viscosity measurements were performed on a Bohlin C-VOR 150 rheometer equipped with 4/40 cone/plate geometry (diameter 40 mm, angle 4°) at 25°C and a shear rate from 1/s to 100/s rpm. Example 1

Preparation of co-polymers according to the invention:

In a 50 mL round-bottomed flask, (3-mercaptopropyl)(methyl)dimethoxysilane (25 mmol), dimethyl)diethoxysilane (5 mmol), and (trimethyl)ethoxysilane (15 mmol) were dissolved altogether in water (75 mmol) and sodium hydroxide (1.3 wt% with respect to the amount of water) to give an emulsion. The reaction mixture was stirred at room temperature for 3 h. Ethanol, methanol and possible residual water were removed by evaporation under reduced pressure. 2-methyl-5-(prop-l-en-2-yl)cyclohex-2-en-l-one (25 mmol) and 2,3,4,6,7,8,9,10-octahydropyrimido[l,2-a]azepine (DBU, 1.25 mmol) were added and the reaction mixture was stirred at room temperature for 3 h to give a viscous oil. This oil was diluted in ethyl acetate (10 mL) and washed with aq. NaCl (5 M, 2 x 10 mL). The aqueous layer was back-extracted with ethyl acetate (1 x 10 mL). The organic layers were combined and dried with MgSCE, filtered and dried under vacuum at 50°C overnight to give a viscous liquid.

The co-polymer obtained had a weight average molecular weight (M_w) of 2100 Da (as determined by SEC), and the amount of repeating units of formula (I) in the final co polymer was 83 mol%.

^-NMR: 4.78 (m, 1.9H), 2.89 (m, 0.7H), 2.57 (m, 4H), 2.32 (m, 2H), 2.20 (m, 0.7H), 1.99 (m, 0.5H), 1.82 (m, 1H), 1.75 (m, 3H), 1.62 (m, 2H), 1.23 (m, 3H), 0.63 (m, 2H),

0.09 (m, 6H) ppm;

¹³C-NMR: d 209.8 (s), 147.1 (s), 146.7 (s), 146.4 (s), 144.6 (d), 111.1 (t), 110.5 (t), 110.3 (t), 110.2 (t), 50.2 (d), 50.1 (d), 48.8 (d), 46.4 (t), 46.0 (t), 44.4 (d), 43.3 (t), 43.2 (t), 41.7 (t), 40.7 (d), 40.2 (d), 39.6 (t), 36.0 (t), 35.6 (t), 34.3 (t), 34.2 (t), 34.0 (t), 32.8 (t), 32.0 (t), 31.2 (t), 27.9 (t), 23.8 (t), 23.6 (t), 23.4 (t), 21.5 (d), 21.1 (q), 20.9 (q), 20.5 (q), 20.3 (q),

17.3 (t), 16.5 (t), 15.7 (q), 14.2 (q), 12.6 (q), 1.9 (q), 1.3 (q), -0.3 (q), -1.0 (q) ppm.

Example 2 Preparation of a perfuming composition

A perfume was prepared by admixing the following ingredients: Ingredients weight % ethyl 2-methylbutanoate 0.18%

3-methyl-2-buten-l-yl acetate 0.15% ethyl 2-methylpentanoate 0.38% hexyl acetate 2.09% l-methoxy-4-methylbenzene 0.28%

1-isopropyl-4-methylbenzene 0.39% l,3,3-trimethyl-2-oxabicyclo[2.2.2]octane 0.49% limonene 0.72%

2.6-dimethyl-7-octen-2-ol 5.16% methyl benzoate 0.29%

2-phenylethanol 3.12%

3.7-dimethyl-3-octanol 2.13%

(2RS,4SR/4RS)-4-methyl-2-(2-methyl-l-propen-l-yl)tetrahydro-2H-pyran 0.30% benzyl acetate 2.17% l-(4-methylphenyl)ethanone 0.12%

1-phenylethyl acetate 0.38% alpha-terpineol 0.44% methyl 2,6,6-trimethyl-2-cyclohexene-l-carboxylate 0.60%

3.7-dimethyl-6-octen-l-ol 3.40%

4-methoxybenzaldehyde 1.33%

3.7 -dimethyl-2, 6-octadien- 1 -ol 1.31%

(e)-4-methyl-3-decen-5-ol 0.57%

1 -methoxy-4- [( 1 E)- 1 -propen- 1 -yl]benzene 0.15%

(lR,2R)-l,7,7-trimethyl-bicyclo[2.2.1]hept-2-yl acetate 4.45%

(lRS,2RS/2SR)-2-(2-methyl-2-propanyl)cyclohexyl acetate 2.15% benzo[d] [1 ,3]dioxole-5-carbaldehyde 1.14%

4-(2-methyl-2-propanyl)cyclohexyl acetate 1.14%

2-methoxy-4-(2 -propen- l-yl)phenol 0.63% 3,7-dimethyl-6-octenyl acetate 0.48%

2-methylundecanal 0.33%

(2E)- 1 - [( IRS ,2SR)-2,6,6-trimethyl-3-cyclohexen- 1 -yl]-2-buten- 1 -one 0.47%

I,G-oxy dibenzene 0.65%

2-chromenone 3.35% dodecanal 0.67% tricyclo[5.2.1.0^2,6]dec-3/4-en-8-yl acetate 4.65% allyl 3-cyclohexylpropanoate 0.76%

3-ethoxy-4-hydroxybenzaldehyde 0.48%

2-methoxynaphthalene 2.68%

3-(4-isopropylphenyl)-2-methylpropanal 1.11%

(2Z)-2-phenyl-2-hexenenitrile 0.95%

2,5-dimethyl-2-indanmethanol 0.42%

(3E)-3-methyl-4-(2,6,6-trimethyl-2-cyclohexen-l-yl)-3-buten-2-one and

(IE)- 1 -(2,6,6-trimethyl-2-cyclohexen- 1 -yl)- 1 -penten-3-one 3.31%

(2S/R,4E)-3,3-dimethyl-5-[(lS)-2,2,3-trimethyl-3-cyclopenten-l-yl]-4- penten-2-ol 0.67% tricyclo[5.2.1.0(2,6)]dec-3/4-en-8-yl propanoate 1.91%

(E)-3-methyl-4-(2,6,6-trimethyl-2-cyclohexen-l-yl)-3-buten-2-one 1.48%

2/3-methylbutyl salicylate 2.24%

3-(l,3-benzodioxol-5-yl)-2-methylpropanal 0.31%

5-heptyldihydro-2(3H)-furanone 3.60% methyl 2-((lRS,2RS)-3-oxo-2-pentylcyclopentyl)acetate 1.82% patchouli oil 2.69% l-(2,3,8,8-tetramethyl-l,3,4,5,6,7-hexahydronaphthalen-2-yl)ethanone 12.78%

(lS,l'R)-2-[l -(3 ',3 '-dimethyl- 1 '-cyclohexyl)ethoxy ] -2-methylpropyl propanoate 0.38%

(2E)-2-benzylideneoctanal 12.48%

1 -oxa- 12/13 -cyclohexadecen-2-one 1.08% benzyl 2-hydroxybenzoate 2.29% 2-phenylethyl phenylacetate 0.29%

100

Example 3

Preparation of a perfuming composition A perfume was prepared by admixing the following ingredients:

Ingredients weight % ethyl 2-methylbutanoate 0.16% dipropylene glycol 4.98% hexyl acetate 0.37% limonene 1.67%

2.6-dimethyl-7-octen-2-ol 0.94%

2-phenylethanol 2.15%

3.7-dimethyl- 1 ,6-octadien-3 -ol 0.73%

(2RS,4SR/4RS)-4-methyl-2-(2-methyl-l-propen-l-yl)tetrahydro-2H-pyran 0.30% ethyl 2-methyl- 1 ,3-dioxolane-2-acetate 0.32% benzyl acetate 2.46% allyl heptanoate 0.38% alpha-terpineol 0.88%

3.7-dimethyl-6-octen- 1 -ol 0.55% 4-methoxybenzaldehyde 1.00% (E)-4-methyl-3-decen-5-ol 0.37% [cis/trans-4-(2-propanyl)cyclohexyl]methanol 0.47% 1 -methoxy-4- [( 1 E)- 1 -propen- 1 -yl]benzene 0.15% (lRS,2RS/2SR)-2-(2-methyl-2-propanyl)cyclohexyl acetate 1.95% 1 , l-dimethyl-2-phenylethyl acetate 0.95% tricyclo[5.2.1.0^2,~]dec-3/4-en-8-yl acetate 3.34% allyl 3-cyclohexylpropanoate 0.26%

3-(4-isopropylphenyl)-2-methylpropanal 8.18%

(3E)-3-methyl-4-(2,6,6-trimethyl-2-cyclohexen-l-yl)-3-buten-2-one and 1.13% (IE)- 1 -(2,6,6-trimethyl-2-cyclohexen- 1 -yl)- 1 -penten-3-one

2-phenoxyethyl 2-methylpropanoate 5.38% tricyclo[5.2.1.0(2,6)]dec-3/4-en-8-yl propanoate 2.32%

5-heptyldihydro-2(3H)-furanone 2.30%

2/3-methylbutyl salicylate 1.42%

(3Z)-3-hexen-l-yl salicylate 0.31% l-(2,3,8,8-tetramethyl-l,3,4,5,6,7-hexahydronaphthalen-2-yl)ethanone 16.03% hexyl 2-hydroxybenzoate 5.04%

(2E)-2-benzylideneoctanal 21.21%

(-)-(3aR,5aS,9aS,9bR)-3a,6,6,9a-tetramethyldodecahydronaphtho[2,l- b]furan 0.27%

1 -oxa- 12/13 -cyclohexadecen-2-one 4.78% oxacyclohexadecan-2-one 3.82% benzyl 2-hydroxybenzoate 3.01%

3-(dodecylthio)-l-(2,6,6-trimethyl-3-cyclohexen-l-yl)-l-butanone 0.41%

100

Example 4

Preparation of a liquid detergent comprising the invention’s co-polymer

Table 1: Composition of the liquid detergent formulation

1) Hostapur SAS 60; Origin: Clariant

2) Edenor K 12-18; Origin: Cognis

3) Genapol LA 070; Origin: Clariant

4) Aculyn 88; Origin: Dow Chemical

The liquid detergent was prepared by adding 0.3 to 0.8% by weight, relative to the total weight of the liquid detergent, of perfuming composition of Example 2, 0.15% by weight, relative to the total weight of the liquid detergent, of the invention’s co-polymer of Example 1 and 0.5% by weight, relative to the total weight of the liquid detergent, of trans-3-(dodecylthio)-l-(2,6,6-trimethyl-3-cyclohexen-l-yl)-l-butanone into the unperfumed liquid detergent formulation of Table 1 under gentle shaking.

Example 5 Preparation of a solid detergent comprising the invention’s co-polymer

The chassis of the model powder detergent bases comprised sodium sulfate, sodium carbonate, sodium dodecylbenzensulfonate, sodium silicate, zeolite, C 12-15 pareth-7, bentonite, perborate, TAED, citric acid, sodium acrylic acid/MA co-polymer, sodium carbonate peroxide, tetrasodium etidronate, sodium chloride, sodium bicarbonate, cellulose gum, disodium anilinomorpholinotriazinylaminostilbenesulfonate, phenylpropyl dimethicone, enzyme, dye.

The model powder detergent bases used have the typical range as reported in Table 2. Table 2: Typical composition of a powder detergent

The solid detergent was prepared by adding 0.3 to 0.6% by weight, relative to the total weight of the liquid detergent, of perfuming composition of Example 3, 0.15% by weight, relative to the total weight of the solid detergent, of the invention’s co-polymer of Example 1, 0.5% by weight, relative to the total weight of the solid detergent, of trans-3- (dodecylthio)-l-(2,6,6-trimethyl-3-cyclohexen-l-yl)-l-butanone and 0.3% by weight, relative to the total weight of the solid detergent, of a mixture comprising 4- (dodecylthio)-4-(2,6,6-trimethyl-2-cyclohexen- l-yl)-2-butanone and 4-(dodecylthio)-4- (2,6,6-trimethyl- l-cyclohexen-l-yl)-2-butanone into the unperfumed solid detergent formulation of Table 2 under gentle shaking.

Example 6 Preparation of a bleach-free solid detergent comprising the invention’s co-polymer

Bleach-free powder formulation is composed of sodium sulfate, sodium carbonate, sodium dodecylbenzensulfonate, sodium silicate, zeolite, C 12-15 pareth-7, bentonite, citric acid, sodium acrylic acid/MA co-polymer, sodium carbonate peroxide, tetrasodium etidronate, sodium chloride, sodium bicarbonate, cellulose gum, disodium anilinomorpholinotriazinylaminostilbenesulfonate, phenylpropyl dimethicone, enzyme, dye.

The model powder detergent bases used have the typical range as reported in Table 3. Table 3: Typical composition of powder detergent

The bleach-free solid detergent was prepared by adding 0.3 to 0.6% by weight, relative to the total weight of the bleach-free solid detergent, of perfuming composition of Example 3, 0.15% by weight, relative to the total weight of the bleach-free solid detergent, of the invention’s co-polymer of Example 1, 0.3% by weight, relative to the total weight of the bleach-free solid detergent, of trans-3-(dodecylthio)-l-(2,6,6-trimethyl-3-cyclohexen-l- yl)-l-butanone and 0.15% by weight, relative to the total weight of the bleach-free solid detergent, of a mixture comprising 4-(dodecylthio)-4-(2,6,6-trimethyl-2-cyclohexen-l- yl)-2-butanone and 4-(dodecylthio)-4-(2,6,6-trimethyl-l-cyclohexen-l-yl)-2-butanone into the unperfumed bleach-free solid detergent formulation of Table 3 under gentle shaking. Example 7

Preparation of a fabric softener comprising the invention’s co-polymer

Table 4: Composition of the softener formulation

1) Stepantex VL90 A Diester Quat; Origin: Stepan

2) Proxel GXL; Origin: Arch

The softener was prepared by weighting methyl bis [ethyl (tallowate)]-2- hydroxy ethyl ammonium methyl sulfate which was heated at 65 °C. Then water and 1,2- benzisothiazolin-3-one were placed in the reactor and were heated at 65 °C under stirring. To the above mixture was added methyl bis [ethyl (tallowate)]-2- hydroxy ethyl ammonium methyl sulfate. The mixture was stirred for 15 min and CaCh was added. Then 0.5 to 2% by weight, relative to the total weight of the softener, of the perfuming composition of Example 2 or 3, 0.15 % by weight, relative to the total weight of the softener, of the invention’s co-polymer of Example 1 and optionally 0.05 % by weight, relative to the total weight of the softener, of 3-(dodecylthio)-l-(2,6,6-trimethyl-3- cyclohexen-l-yl)-l-butanone and/or 0.05% by weight, relative to the total weight of the softener, of 4-(dodecylthio)-4-(2,6,6-trimethyl-2-cyclohexen-l-yl)-2-butanone and 4- (dodecylthio)-4-(2,6,6-trimethyl-l-cyclohexen-l-yl)-2-butanone were added. The mixture was stirred for 15 min and cooled to room temperature under stirring (viscosity measure: result 35 +/- 5 mPa s. (shear rate 106 s ¹)).

Example 8

Preparation of an all-purpose cleaner comprising the invention’s co-polymer

Table 5: Composition of the all-purpose cleaner

1) Neodol 91-8 ®; trademark and origin: Shell Chemical

2) Biosoft D-40®; trademark and origin: Stepan Company

3) Stepanate SCS®; trademark and origin: Stepan Company

4) Kathon CG®; trademark and origin: Dow Chemical Company

The all-purpose cleaner was prepared by adding 0.15% by weight, relative to the total weight of the all-purpose cleaner, of the invention’s co-polymer of Example 1 into the unperfumed all-purpose cleaner formulation of Table 5 under gentle shaking. Example 9

Preparation of a urea-based granulated base comprising the invention’s co-polymer Table 6: Composition of the urea-based granulated base

1) DETE-2624 Alkaline lipase for detergent, powder form, from Creative Enzyme

To the urea beads, 10.85% of the perfuming composition of Example 2 and 0.15% of the invention’s co-polymer of Example 1 were added and the mixture was tumble-mixed. Then Bentonite was added to the perfumed urea beads and the mixture was tumble- mixed.

Example 10

Preparation of a granulated PEG base comprising the invention’s co-polymer

Table 7: Composition of the granulated PEG base

1) DETE-2624 Alkaline lipase for detergent, powder form, from Creative Enzyme

To the PEG base, 26% of dextrose were added and the mixture was melted at 80°C. Then 10.85% of the perfuming composition of Example 3 and 0.15% of the invention’s co- polymer of Example 1 were added. The mixture was then pelletized while cooling, by pouring a thin film of the molten mixture onto a flat surface and cutting it in smaller pieces after solidification.

Example 11

Preparation of low-aqueous liquid detergent format in single chamber pods comprising the invention’s co-polymer

The model liquid base used was a low water liquid detergent composed of C 12-15 pareth 7, MEA-hydrogenated cocoate, MEA-dodecylbenzene sulfonate, propylene glycol, glycerine water, polyvinyl alcohol, polypropylene terephthalate polyoxyoethylene terephthalate, sorbitol, sodium diethyenetriamin pentamethylene phosphonate, MEA- sulfate, potassium sulfite, ethynolamine, peptide salt, glycol, subtilisin, disodium distyrybiphenyl disulfonate, talc, amylase, sodium chloride, denatonium benzoate, disubstitued alaninamide, dye, mannanase. This composition contains 5-15% of anionic surfactants, nonionic surfactants, soap and less than 5% of enzymes mix, optical brighteners, perfume, phosphonate. The pH of the base should be above > 7.

A 27 g single chamber liquid base detergent formulation was prepared according to the formulation above. To this formulation was added 0.8 to 1.5% by weight, relative to the total weight of the liquid detergent, of perfuming composition of Example 2, 0.15% by weight, relative to the total weight of the liquid detergent, of the invention’s co-polymer of Example 1 and 0.5% by weight, relative to the total weight of the liquid detergent, of trans-3-(dodecylthio)-l-(2,6,6-trimethyl-3-cyclohexen-l-yl)-l-butanone. This formulation was introduced into a polyvinylalcohol pouch. Example 12

Preparation of low-aqueous liquid detergent format in dual chamber pods comprising the invention’s co-polymer

A dual chamber liquid base detergent formulation was prepared according to the formulation reported in Example 11. To this formulation was added 2 to 3.5% by weight, relative to the total weight of the liquid detergent, of perfuming composition of Example 3, 0.15% by weight, relative to the total weight of the solid detergent, of the invention’s co-polymer of Example 1 and 0.3% by weight, relative to the total weight of the liquid detergent, of a mixture comprising 4-(dodecylthio)-4-(2,6,6-trimethyl-2-cyclohexen-l- yl)-2-butanone and 4-(dodecylthio)-4-(2,6,6-trimethyl-l-cyclohexen-l-yl)-2-butanone. These formulations are introduced into a dual-polyvinylalcohol pouch.

Example 13 Preparation of a transparent isotropic shampoo comprising the invention’s co-polymer

Table 8: Composition of the transparent isotropic shampoo formulation

1) Ucare Polymer JR-400, Origin: Noveon

2) Origin: Schweizerhall

3) Glydant, Origin: Lonza

4) Texapon NSO IS, Origin: Cognis

5) Tego Betain F 50, Origin: Evonik

6) Amphotensid GB 2009, Origin: Zschimmer &

Schwarz

7) Monomuls 90 L-12, Origin: Gruenau

8) Nipagin Monosodium, Origin: NIPA

The shampoo was prepared by dispersing Polyquaternium-10 in water. The remaining ingredients of Phase A were mixed separately by addition of one after the other while mixing well after each adjunction. This pre-mix was added to the Polyquaternium-10 dispersion and mixed for another 5 min. Then, the premixed Phase B and the premixed Phase C were added (Monomuls 90L-12 was heated to melt in Texapon NSO IS) while agitating. Phase D and Phase E were added while agitating. The pH was adjusted with citric acid solution to 5.5 - 6.0 leading to an unperfumed shampoo formula.

The perfumed shampoo was prepared by adding 0.1 to 0.8% by weight, relative to the total weight of the shampoo, of the perfuming composition of Example 2 and 0.15 % by weight, relative to the total weight of the shower gel, of the invention’s co-polymer of Example 1 into the unperfumed shampoo formulation of Table 8 under gentle shaking. Example 14

Preparation of a structured shower gel comprising the invention’s co-polymer Table 9: Composition of the structured shower gel formulation

1) EDETA B POWDER; trademark and origin: BASF

2) CARBOPOL AQUA SF-1 POLYMER; trademark and origin: NOVEON

3) ZETESOL AO 328 U; trademark and origin: ZSCHIMMER & SCHWARZ

4) TEGO-BETAIN F 50; trademark and origin: GOLDSCHMIDT 5) KATHON CG; trademark and origin: ROHM & HASS

The shower gel was prepared by adding 0.1 to 1.5% by weight, relative to the total weight of the shower gel, of the perfuming composition of Example 3 and 0.15 % by weight, relative to the total weight of the shower gel, of the invention’s co-polymer of Example 1 into the unperfumed shower gel formulation of Table 9 under gentle shaking.

Example 15

Preparation of a transparent shower gel comprising the invention’s co-polymer

Table 10: Composition of the transparent shower gel formulation

1) EDETA B POWDER; trademark and origin: BASF

2) ZETESOL AO 328 U; trademark and origin: ZSCHIMMER & SCHWARZ

3) TEGO-BETAIN F 50; trademark and origin: GOLDSCHMIDT

4) MERQUAT 550; trademark and origin: LUBRIZOL The transparent shower gel was prepared by adding 0.1 to 1.5% by weight, relative to the total weight of the shower gel, of the perfuming composition of Example 3 and 0.15 % y weight, relative to the total weight of the shower gel, of the invention’s co-polymer of Example 1 into the unperfumed shower gel formulation of Table 10 under gentle shaking. Example 16

Preparation of a milky shower gel comprising the invention’s co-polymer

Table 11: Composition of the milky shower gel formulation

1) EDETA B POWDER; trademark and origin: BASF

2) Texapon NSO IS; trademark and origin: COGNIS

3) MERQUAT 550; trademark and origin: LUBRIZOL

4) DEHYTON AB-30; trademark and origin: COGNIS 5) GLUCAMATE LT; trademark and origin: LUBRIZOL

6) EUPERLAN PK 3000 AM; trademark and origin: COGNIS

7) CREMOPHOR RH 40; trademark and origin: BASF

The milky shower gel was prepared by adding 0.1 to 1.5% by weight, relative to the total weight of the shower gel, of the perfuming composition of Example 2 and 0.15 % by weight, relative to the total weight of the shower gel, of the invention’s co-polymer of Example 1 into the unperfumed shower gel formulation of Table 11 under gentle shaking.

Example 17

Preparation of a pearly shampoo comprising the invention’s co-polymer

Table 12: Composition of the pearly isotropic shampoo formulation

2) Jaguar C14 S, Origin: Rhodia

3) Ucare Polymer JR-400, Origin: Noveon

4) Sulfetal LA B-E, Origin: Zschimmer & Schwarz

5) Zetesol LA, Origin: Zschimmer & Schwarz

6) Tego Betain F 50, Origin: Evonik

7) Xiameter MEM- 1691, Origin: Dow Corning

8) Lanette 16, Origin: BASF

9) Comperlan 100, Origin: Cognis

10) Cutina AGS, Origin: Cognis

11) Kathon CG, Origin: Rohm & Haas

12) D-Panthenol, Origin: Roche

The pearly shampoo was prepared by dispersing Tetrasodium EDTA, Guar hydroxypropyltrimonium chloride and Polyquaternium-10 in water. NaOH 10% solution (Phase B) was added once Phase A was homogeneous. Then, the premixed Phase C was added, and the mixture was heated to 75°C. Phase D ingredients were added and mixed until the mixture was homogeneous. The mixture was cooled. At 45°C, Phase E ingredients were added while mixing. The final viscosity was adjusted with 25% NaCl solution and a pH of 5.5-6 was adjusted with 10% NaOH solution.

The perfumed pearly shampoo was prepared by adding 0.1 to 0.8% by weight, relative to the total weight of the shampoo, of the perfuming composition of Example 3 and 0.15 % by weight, relative to the total weight of the shower gel, of the invention’s co-polymer of Example 1 into the unperfumed shampoo formulation of Table 12 under gentle shaking.

Example 18

Preparation of a structured shower gel comprising the invention’s composition

Table 13: Composition of the milky shower gel formulation

6) EDETA B POWDER; trademark and origin: BASF 7) CARBOPOL AQUA SF- 1 POLYMER; trademark and origin: NOVEON

8) ZETESOL AO 328 U; trademark and origin: ZSCHIMMER & SCHWARZ

9) TEGO-BETAIN F 50; trademark and origin: GOLDSCHMIDT

10) KATHON CG; trademark and origin: ROHM & HASS The transparent shower gel was prepared by adding 0.1 to 1.5% by weight, relative to the total weight of the shower gel, of the perfuming composition of Example 2 and 0.15 % by weight, relative to the total weight of the shower gel, of the invention’s co-polymer of Example 1 into the unperfumed shower gel formulation of Table 13 under gentle shaking.

Example 19

Preparation of an antiperspirant spray anhydrous formulation comprising the invention’s co-polymer

Table 14: Composition of the antiperspirant spray anhydrous formulation

1) Dow Corning^® 345 Fluid; trademark and origin: Dow Coming

2) Aerosil^® 200 ; trademark and origin: Evonik

3) Bentone^® 38; trademark and origin: Elementis Specialities

4) Micro Dry Ultrafine; origin: Reheis The antiperspirant spray anhydrous formulation was prepared by using a high speed stirrer. Silica and Quaternium-18-Hectorite were added to the isopropyl miristate and cyclomethicone mixture. Once completely swollen, aluminium chlorohydrate was added portion wise under stirring until the mixture was homogeneous and without lumps. Then 0.85 % of the perfuming composition of Example 2 and 0.15 % of the invention’s co- polymer of Example 1 were added under gentle shaking. Aerosol cans were filled with 25 % of the suspension and with 75 % of propane/butane (2.5 bar). Example 20

Preparation of an antiperspirant spray emulsion formulation comprising the invention’s co-polymer

Table 15: Composition of the antiperspirant spray emulsion formulation

1) Tween 65; trademark and origin: CRODA

2) Dehymuls PGPH; trademark and origin: BASF

3) Abil EM- 90; trademark and origin: BASF 4) Dow Coming 345 fluid; trademark and origin: Dow Coming

5) Crodamol ipis; trademark and origin: CRODA

6) Phenoxy ethanol; trademark and origin: LANXESS

7) Sensiva sc 50; trademark and origin: KRAFT

8) Tegosoft TN; trademark and origin: Evonik 9) Aerosil R 812; trademark and origin: Evonik 10)Nipagin mna; trademark and origin: CLARIANT

11) Locron L; trademark and origin: CLARIANT

The antiperspirant spray emulsion formulation was prepared by weighing the ingredients of Part A and Part B separately. The ingredients of Part A were heated to 60°C and the ingredients of Part B to 55 °C. The ingredients of Part B were poured in small parts under continuous stirring into Part A. The mixture was well stirred until room temperature was reached. Then, the ingredients of Part C were added. The emulsion was mixed and introduced into aerosol cans. The propellant was crimped and added. Aerosol filling: 30% Emulsion, 70% propane / butane (2.5 bar)

Example 21

Preparation of a deodorant spray emulsion formulation comprising the invention’s co- polymer

Table 16: Composition of the deodorant spray formulation

1) Irgasan^® DP 300; trademark and origin: BASF The deodorant spray formulation was prepared by mixing and dissolving all the ingredients according to the sequence of the Table 16. Then 1.35 % of the perfuming composition of Example 2 and 0.15 % of the invention’s co-polymer of Example 1 and 0.05 % of 3-(dodecylthio)-l-(2,6,6-trimethyl-3-cyclohexen-l-yl)-l-butanone and 0.05% of 4-(dodecylthio)-4-(2,6,6-trimethyl-2-cyclohexen-l-yl)-2-butanone and 4-(dodecylthio)- 4-(2,6,6-trimethyl-l-cyclohexen-l-yl)-2-butanone were added under gentle shaking. Then aerosol cans were filled, and the propellant was crimped and added.

Aerosol filling: 40% active solution 60% propane / butane (2.5 bar). Example 22

Preparation of an antiperspirant roll-on emulsion formulation comprising the invention’s co-polymer

Table 17: Composition of the antiperspirant roll-on emulsion formulation

1) BRIJ 72; origin: ICI

2) BRIJ 721; origin: ICI

3) ARLAMOL E; origin: UNIQEMA-CRODA 4) LOCRON L; origin: CLARIANT

The antiperspirant roll-on emulsion formulation was prepared by heating Parts A and B separately to 75°C. Part A was added to Part B under stirring, and the mixture was homogenized for 10 min. Then, the mixture was cooled under stirring; and Part C was slowly added when the mixture reached 45°C and Part D when the mixture reached at 35 °C. Then the mixture was cooled to room temperature.

Example 23 Preparation of an antiperspirant roll-on clear formulation comprising the invention’s co polymer Table 18: Composition of the antiperspirant roll-on clear formulation

1) LOCRON L; origin: CLARIANT

2) EUMULGIN B-l; origin: BASF

3) EUMULGIN B-3; origin: BASF

The antiperspirant roll-on emulsion formulation was prepared by mixing the ingredients of Part B in the vessel, and the ingredients of Part A were added. Then Part C was dissolved in Parts A and B. The Part D was added by using 1 part of Cremophor RH40 for 1 part of perfume while mixing well.

Example 24

Preparation of a deodorant roll-on formulation comprising the invention’s co-polymer Table 19: Composition of the deodorant roll-on formulation

1) Natrosol^® 250 H; trademark and origin: Ashland

2) Irgasan^® DP 300; trademark and origin: BASF

3) Cremophor^® RH 40; trademark and origin: BASF The deodorant roll-on formulation was prepared by preparing Part A by sprinkling little by little the hydroxyethylcellulose into the water whilst rapidly stirring with a turbine. The stirring was continued until the hydroxyethylcellulose had entirely swollen and giving a limpid gel. Then, Part B was poured little by little into Part A whilst continuing stirring until the entire mixture was homogeneous. Part C was added. Then 0.85 % of the perfuming composition of Example 3 and 0.15 % of the invention’s co-polymer of Example 1 and 0.05 % of 3-(dodecylthio)-l-(2,6,6-trimethyl-3-cyclohexen-l-yl)-l- butanone and 0.05% of 4-(dodecylthio)-4-(2,6,6-trimethyl-2-cyclohexen-l-yl)-2-butanone and 4-(dodecylthio)-4-(2,6,6-trimethyl-l-cyclohexen-l-yl)-2-butanone were added under gentle shaking.

Example 25

Preparation of an antiperspirant stick formulation comprising the invention’s composition Table 20: Composition of the antiperspirant stick formulation

1) Dow Corning^® 345 Fluid; trademark and origin: Dow Coming

2) Lanette^® 18; trademark and origin: BASF

3) Tegosoft^® PBE; trademark and origin: Evonik

4) Cutina^® HR; trademark and origin: BASF

5) Summit AZP-908; trademark and origin: Reheis The antiperspirant stick formulation was prepared by weighing all the components of Part A (Table 20), heating to 70-75°C and mixing well. The ingredient of Part B was dispersed in Part A. The mixture was mixed and putted into a tick at 65 °C. Then 0.85 % of the perfuming composition of Example 2 and 0.15 % of the invention’s co-polymer of Example 1 and 0.05 % of 3-(dodecylthio)-l-(2,6,6-trimethyl-3-cyclohexen-l-yl)-l- butanone and 0.05% of 4-(dodecylthio)-4-(2,6,6-trimethyl-2-cyclohexen-l-yl)-2-butanone and 4-(dodecylthio)-4-(2,6,6-trimethyl-l-cyclohexen-l-yl)-2-butanone were added under gentle shaking. Example 26

Preparation of a deodorant stick formulation comprising the invention’s composition

Table 21: Composition of the deodorant stick formulation

1) Edeta^® B Power; trademark and origin: BASF

2) Cremophor^® A25; trademark and origin: BASF

3) Tegosoft^® APM; trademark and origin: Evonik

4) Irgasan^® DP 300; trademark and origin: BASF The deodorant stick formulation was prepared by weighing all the components of Part A (Table 21) and heating to 70-75°C. Ceteareth-25 was added once the other Part A ingredients were mixed and heated. Once the Ceteareth-25 was dissolved, Stearic Acid was added. Part B was prepared by dissolving Triclosan (Table 21) in 1,2-propylene glycol (Table 21). Water which has evaporated was added. Slowly, under mixing, Part B was poured into Part A. To stock, a plastic bag into the bucket was put in to be sealed after cooling. Moulds were filled at about 70°C. Then 0.85 % of the perfuming composition of Example 2 and 0.15 % of the invention’s co-polymer of Example 1 and 0.05 % of 3-(dodecylthio)-l-(2,6,6-trimethyl-3-cyclohexen-l-yl)-l-butanone and 0.05% of 4-(dodecylthio)-4-(2,6,6-trimethyl-2-cyclohexen-l-yl)-2-butanone and 4-(dodecylthio)- 4-(2,6,6-trimethyl-l-cyclohexen-l-yl)-2-butanone were added under gentle shaking.

Example 27

Preparation of a deodorant pump formulation without alcohol comprising the invention’s co-polymer

Table 22: Composition of the deodorant pump formulation without alcohol

1) Ceraphyl 41; trademark and origin: ASHLAND

2) DOW CORNING 200 FLUID 0.65cs; trademark and origin: DOW CORNING CORPORATION 3) Ceraphyl 28; trademark and origin: ASHLAND

4) Eutanol G; trademark and origin: BASF

5) Irgasan^® DP 300; trademark and origin: BASF The deodorant pump formulation without alcohol was prepared by mixing all the ingredients of Table 22 according to the sequence indicated in the table. The mixture was slightly heated to dissolve the cetyl lactate. Example 28

Preparation of a deodorant pump formulation with alcohol comprising the invention’s co polymer Table 23: Composition of the deodorant pump formulation with alcohol

1) Softigen 767; trademark and origin: CRODA

2) Cremophor^® RH 40; trademark and origin: BASF

The deodorant pump formulation without alcohol was prepared by mixing the ingredients from Part B. The ingredients of Part A were dissolved according to the sequence indicated in the table and poured into Part B .

Example 29 Preparation of a day cream base O/W emulsion comprising the invention’s co-polymer

Table 24: Composition of the day cream base O/W emulsion

1) Arlacel 985

2) Tefose 2561

3) Biolip P 90

4) Mineral oil 30-40 CPS 5) Petroleum jelly

6) Nipaguard PO 5

7) PNC 400

The day cream base O/W emulsion was prepared by heating Phases A and B separately to 70-75 °C. Phase A was added to Phase B, then vacuum was applied. The mixture was stirred and cooled to 55°C under stirring over 15 min.

The mixture was cooled to room temperature and Phenoxyethanol (AND) PIROCTONE OLAMINE was added when a temperature of 45°C was reached. The mixture was stirred for 5 min before Sodium carbomer and perfuming composition of example 3 and co- polymer of example 1 were added. The mixture was stirred for 3 min. Then the stirring was stopped during 15 min. When the temperature of the mixture reached 30°C, the stirring was switched on for another 15 min until the cream was homogeneous, glossy and without lumps. If necessary the pH was adjusted to 6.70 - 7.20 with Glydant, Phenonip or Nipaguard P05 or the pH was adjusted to 6.30 - 7.00 with Nikkoguard. Example 30

Preparation of a hand dishwash comprising the invention’s co-polymer Table 25: Composition of the hand dishwash

1) Biosoft S-l 18®; trademark and origin: Stepan Company

2) Ninol 40-CO®; trademark and origin: Stepan Company

3) Stepanate SXS®; trademark and origin: Stepan Company

4) Tergitol 15-S-9®; trademark and origin: Dow Chemical Company

The hand dishwash was prepared by mixing water with sodium hydroxide and diethanolamide. LAS was added. After neutralizing the LAS, the remaining ingredients were added. The pH was checked (=7-8) and adjusted if necessary.

Then 0.85 % of the perfuming composition of Example 2 and 0.15 % of the invention’s co-polymer of Example 1 and 0.05 % of 3-(dodecylthio)-l-(2,6,6-trimethyl-3-cyclohexen- l-yl)-l-butanone and 0.05% of 4-(dodecylthio)-4-(2,6,6-trimethyl-2-cyclohexen-l-yl)-2- butanone and 4-(dodecylthio)-4-(2,6,6-trimethyl-l-cyclohexen-l-yl)-2-butanone were added under gentle shaking.

Example 31

Preparation of a rinse-off hair conditioner comprising the invention’s co-polymer Table 26: Composition of the rinse-off hair conditioner

1) Genamin KDMP, Origin: Clariant

2) Tylose H10 Y G4, Origin: Shin Etsu

3) Lanette O, Origin: BASF 4) Arlacel 165, Origin: Croda

5) Incroquat Behenyl TMS-50-PA- (MH), Origin: Croda

6) Brij S20, Origin: Croda

7) Xiameter MEM-949, Origin: Dow Corning

8) Origin: Alfa Aesar

The ingredients of Phase A were mixed until an uniform mixture was obtained. Tylose was allowed to completely dissolve. Then the mixture was heated to 70-75°C. The ingredients of Phase B were combined and melted at 70-75°C. Then ingredients of Phase B were added to Phase A with good agitation and the mixing was continued until that the mixture had a temperature of 60°C. Then, the ingredients of Phase C were added while agitating and keeping mixing until the mixture cooled to 40°C. The pH was adjusted with citric acid solution to 3.5 - 4.0. Then 0.85 % of the perfuming composition of Example 2 and 0.15 % of the invention’s co-polymer of Example 1 and 0.05 % of 3-(dodecylthio)-l- (2,6,6-trimethyl-3-cyclohexen-l-yl)-l-butanone and 0.05% of 4-(dodecylthio)-4-(2,6,6- trimethyl-2-cyclohexen- l-yl)-2-butanone and 4-(dodecylthio)-4-(2, 6, 6-trimethyl- 1- cyclohexen-l-yl)-2-butanone were added under gentle shaking.

Example 32

Preparation of encapsulated perfume A comprising a pro-perfume a. Exemplary perfume (Perfume A)

Perfume A relates to the following composition in Table 27:

Table 27: Composition of perfume A

b. Exemplary fragrance delivery systems

An emulsion of the following composition was spray-dried in a Bi chi spray-drier (origin : Switzerland) to obtain spray-dried starch matrix granules having the following compositions:

Table 28: Composition of the spray-dried granules A & B

Claims

Claims

1. A linear random polysiloxane co-polymer, capable of releasing in a controlled manner an odoriferous a,b-unsaturated ketone, and comprising or consisting of a) at least one repeating unit of formula

wherein the double hatched lines indicate the bonding to another repeating unit b) at least one repeating unit of formula

wherein the double hatched lines indicate the bonding to another repeating unit; and c) optionally, at least one repeating unit of formula

wherein the double hatched lines have the same meaning as described for formula

(I)·

2. The co-polymer according claim 1, wherein said co-polymer is characterized by a weight average molecular weight comprised in the range between 1500 Da and 5000 Da.

3. The co-polymer according to any one of claims 1 to 2, wherein the molar ratio of the repeating units (I)/[(II)+(III)] is comprised between 85/15 and 45/55, and said co-polymer having a weight average molecular weight (M_w) comprised in the range between 1000 Da and 5000 Da; terminal groups of formula: -(0)x-Si(0R²)a(CH )c (IV’) wherein x is 0 when the terminal groups is linked to an oxygen atom of the repeating unit and x is 1 when the terminal group is linked to a silicon atom of the repeating unit; a is either 0 or 1 and c is either 2 or 3 and (a + c) = 3; each R² represents independently from each other a hydrogen atom or a R¹ group; R¹ represents a C1-3 alkyl group; and optionally a viscosity V comprised in the range between 1.0 (Pa s) and 60

(Pas).

4. A perfuming composition comprising: i) as perfuming ingredient, at least one co-polymer according to any one of claims 1 to 3; 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.

5. The perfuming composition according to claim 4, wherein the perfuming composition comprises 4-(dodecylthio)-4-(2,6,6-trimethyl-2-cyclohexen- l-yl)-2- butanone, 4-(dodecylthio)-4-(2, 6, 6-trimethyl- 1 -cyclohexen- 1 -yl)-2-butanone, trans-3 - (dodecylthio)-l-(2,6,6-trimethyl-3-cyclohexen-l-yl)-l-butanone.

6. A perfumed consumer product comprising as perfuming ingredient, at least one co-polymer according to any one of claims 1 to 3 or a perfuming composition as defined in claims 4 to 5.

7. The perfumed consumer product according to claim 6, wherein such perfuming consumer product is a perfume, a fabric care product, a body-care product, an air care product or a home care product.

8. The perfumed consumer product according to any one of claims 6 to 7, wherein it is in the form of a fabric softener comprising: - between 85 and 99.95 % by weight of a fabric softener active base; preferably chosen in the group consisting of dialkyl quaternary ammonium salts, dialkyl ester quaternary ammonium salts, Hamburg esterquat, triethanolamine quat, silicones and mixtures thereof. between 0.0001 to 2 %, preferably between 0.001 to 1%, more preferably between 0.01 and 0.5 % by weight of co-polymer as defined in claims 1 to 4.

9. The perfumed consumer product according to any one of claims 6 to 7, wherein it is in the form of a liquid detergent comprising: between 85 and 99.95 % by weight of a liquid detergent active base; preferably chosen in the group consisting of anionic surfactant such as alkylbenzenesulfonate (ABS), secondary alkyl sulfonate (SAS), primary alcohol sulfate (PAS), lauryl ether sulfate (LES), methyl ester sulfonate (MES) and nonionic surfactant such as alkyl amines, alkanolamide, fatty alcohol poly (ethylene glycol) ether, fatty alcohol ethoxylate (FAE), ethylene oxide (EO) and propylene oxide (PO) co-polymers, amine oxydes, alkyl polyglucosides, alkyl polyglucosamides, and mixtures thereof - between 0.0001 to 2 %, preferably between 0.001 to 1%, more preferably between 0.01 and 0.5 % by weight of co-polymer as defined in claims 1 to 4.

10. The perfumed consumer product according to any one of claims 6 to 7, wherein it is in the form of a solid detergent comprising: - between 85 and 99.95 % by weight of a solid detergent active base; preferably chosen in the group consisting of anionic surfactant such as alkylbenzenesulfonate (ABS), secondary alkyl sulfonate (SAS), primary alcohol sulfate (PAS), lauryl ether sulfate (LES), methyl ester sulfonate (MES) and nonionic surfactant such as alkyl amines, alkanolamide, fatty alcohol poly (ethylene glycol) ether, fatty alcohol ethoxylate (FAE), ethylene oxide (EO) and propylene oxide (PO) co-polymers, amine oxydes, alkyl polyglucosides, alkyl polyglucosamides, and mixtures thereof between 0.0001 to 2 %, preferably between 0.001 to 1%, more preferably between 0.01 and 0.5 % by weight of co-polymer as defined in claims 1 to 4.

11. The perfumed consumer product according to any one of claims 6 to 7, wherein it is in the form of a shampoo or a shower gel comprising: between 85 and 99.95 % by weight of a shampoo active base; preferably chosen in the group consisting of sodium alkylether sulfate, ammonium alkylether sulfates, alkylamphoacetate, cocamidopropyl betaine, cocamide MEA, alkylglucosides and aminoacid based surfactants between 0.0001 to 2 %, preferably between 0.001 to 1%, more preferably between 0.01 and 0.5 % by weight of co-polymer as defined in claims 1 to 4.

12. The consumer product according to any one of claims 6 to 7, wherein it is in the form of an oxidative hair coloring composition comprising: between 85 and 99.9 % by weight of a oxidative hair coloring base; comprising an oxidizing phase comprising an oxidizing agent and an alkaline phase comprising an alkakine agent, a dye precursor and a coupling compound; wherein said dye precursor and said coupling compound form an oxidative hair dye in the presence of the oxidizing agent. between 0.0001 to 2 %, preferably between 0.001 to 1%, more preferably between 0.01 and 0.5 % by weight of co-polymer as defined in claims 1 to 4.

13. A method to confer, enhance, improve or modify the odor properties of a perfuming composition, the air surrounding the perfuming composition, of a surface or of a perfumed article, comprising adding to the composition, the air, or article, or contacting or treating the surface with an effective amount of at least one co-polymer as defined in claims 1 to 3.

14. A method for intensifying or prolonging the diffusion effect of the characteristic fragrance of carvone, on a surface or the air surrounding the perfuming composition, wherein the surface, or the air is treated with at least one co-polymer as defined in claims 1 to 3, or with a composition as defined in claims 4 to 5 or perfumed consumer product as defined in claims 6 to 12, under conditions susceptible of allowing the release of carvone over time.

15. Use as perfuming ingredient of a co-polymer as defined in claims 1 to 3.