MICROCAPSULES WITH MINERAL LAYER - FIRMENICH SA (2023)

MICROCAPSULES WITH MINERAL COATING

technical area

The present invention relates to the field of delivery systems. In particular, the present invention relates to microcapsules comprising a core based on a hydrophobic ingredient, preferably a perfume or flavoring, a shell and a mineral layer on the shell. The subject of the invention is also a process for the production of these microcapsules. Perfumed compositions and consumer products comprising these microcapsules also form part of the invention, in particular perfumed consumer products in the form of fine fragrances, household care or personal care products.

Background of the Invention

One of the problems facing the perfume industry is the relatively rapid loss of the olfactory benefits provided by scented compounds due to their volatility, particularly the "top notes". This problem is usually solved with a delivery system, e.g. Capsules containing a perfume to release the fragrance in a controlled manner.

In order to be successfully used in consumer products, fragrance delivery systems must meet several criteria. The first requirement concerns stability in an aggressive environment. Indeed, delivery systems can suffer from stability problems, particularly when incorporated into surfactant-based products such as detergents, where such systems tend to deteriorate and lose effectiveness in odor retention capacity. It is also difficult to achieve good stability and good dispersion of the capsules as a whole. The dispersion factor is very important because the aggregation of the capsule increases the tendency of the product containing the capsule to phase separate, which is a real disadvantage. On the other hand, perfume delivery systems must also function during the consumer's actual use of the final product, particularly in terms of olfactory performance, since the perfume must be released on demand. Another problem faced by the perfumery industry, for example, is to provide delivery systems that deposit well on the substrate for the treatment of the end product, such as textiles, skin, hair or other surfaces, in such a way that they may remain on the substrate as well after a rinsing step. In order to solve this specific problem, the use of cationic capsules has been described in the prior art. It is also known that cationic capsules disperse better in various applications.

For example, WO 01/41915 describes a process for producing capsules containing cationic fillers. Such a method is presumably applicable to a wide variety of microcapsules, in particular polyurethane-polyurea microcapsules are mentioned. After formation, the capsules are placed in a favorable environment for treatment with cationic polymers. The treatment with cationic polymers is carried out after purification of the basic suspension of the capsule in order to eliminate the anionic or neutral polymers that were not incorporated into the capsule wall during its formation and other free electrically charged compounds that intervene. the encapsulation process. In particular, capsules are diluted, isolated and then resuspended in water or even washed to further remove anionic compounds. After the cleaning step, the capsules are shaken vigorously and the cationic polymers are added. In addition to many other suitable polymers, partially quaternized copolymers of polyvinylpyrrolidones are mentioned for this purpose. The process described involves several steps subsequent to the formation of the capsule, which is why this process takes a long time and is not economically viable.

US 2006/0216509 also describes a method for producing positively charged polyurea capsules. In this process, polyamines are added during wall formation so that the capsules carry latent charges depending on the pH of the medium. Once formed, the capsules are then cationized by acid action or alkylation to promote permanent positive charges. Therefore, the cationic compounds react with the capsule wall and chemically modify it.

WO2009/153695 discloses a simplified process for the production of polyurea microcapsules carrying permanent positive charges based on the use of a special stabilizer and showing good deposition on a substrate.

In addition to improved deposition, it would also be interesting to have a coating that survives the wide pH ranges of various consumer applications.

Notwithstanding the above disclosures, there is still a need to improve the ability of hydrophobic ingredient delivery systems (e.g., perfumes) to deposit on and adhere to a substrate for rinse-off and rinse-off applications, while remaining related to the release work and stability of hydrophobic components.

The microcapsules of the invention solve this problem since they show an improvement in terms of deposition properties compared to what has been known up to now. In addition, the mineral coating has proven to be stable in various types of consumer products.

Summary of the Invention

The present invention provides microcapsules with good performance in various consumer products. In particular, the growth of a specific mineral layer on a terminally charged surface of the microcapsule ensures better deposition on different substrates. In addition, the mineral layer has been shown to be stable in consumer products with different pH values.

Therefore, a first object of the invention is a mineralized core-shell microcapsule comprising: a) a core, preferably an oil-based core, comprising a hydrophobic ingredient, preferably a perfume; b) a shell with a terminal charged functional surface; and c) a mineral layer on the terminally charged functional surface, characterized in that the mineral layer comprises at least one salt selected from the group consisting of barium salt, strontium salt, magnesium salt and mixtures thereof.

Another subject of the invention is a mineralized core-shell microcapsule suspension comprising at least one microcapsule as defined above.

A second object of the invention is a process for preparing a suspension of mineralized core-shell microcapsules as defined above, comprising the steps:

(i) producing a core-shell microcapsule suspension comprising microcapsules having a terminally charged functional surface;

(ii) adsorption of at least one mineral precursor onto the loaded surface;

(iii) Applying suitable conditions to induce crystal growth of the mineral on the loaded surface to form a mineral layer, wherein the mineral precursor is adsorbed on the loaded surface by using the core-shell microcapsule suspension obtained in step (i) for at least incubating for a period of time a mineral precursor solution, wherein the mineral precursor solution is selected from the group consisting of barium brine, strontium brine, magnesium brine, phosphate-based brine, phosphate-based brine, sulfate, carbonate-based brine, and mixtures thereof.

A third object of the invention is a perfumed composition comprising the microcapsules defined above, in which the oil-based core comprises a perfume.

A fourth subject of the invention is a consumer product (perfumed consumer product or flavored consumer product) comprising microcapsules. Brief description of the figures

The figure shows a scanning electron micrograph of mineralized microcapsules (Al capsules) according to the invention.

1b shows a scanning electron micrograph of mineralized microcapsules according to the invention (capsules A2).

2 shows a scanning electron micrograph of mineralized microcapsules according to the invention (capsules B).

Figure 3 shows a scanning electron micrograph of mineralized microcapsules according to the invention (capsules C).

Figure 4 shows a scanning electron micrograph of control soft microcapsules (Capsules X).

Figure 5 shows the percentage of microcapsule deposition of mineralized microcapsules according to the invention (A1 capsules) compared to soft control capsules (X capsules) on the hair of a model surfactant mixture.

Figure 6 shows the percentage of microcapsule deposition of mineralized microcapsules according to the invention (capsules B) compared to soft control capsules (capsules X) on hair of a model surfactant mixture.

Figure 7 shows the percent deposition of microcapsules of mineralized microcapsules according to the invention (A1-capsules) compared to soft control capsules (X-capsules) on fabric softener-based cotton towel samples.

Figure 8 shows the percent deposition of microcapsules of mineralized microcapsules according to the invention (A1 capsules) compared to soft control capsules (X capsules) on detergent-based cotton towel samples.

Figure 9 shows the stability of the mineral shell of the inventive mineralized microcapsule (Al capsules) after incubation in a low pH fabric softener base for one month at 37°C.

Detailed description of the invention

Unless otherwise indicated, percentages (%) are percentages by weight of a composition.

The definition

A "core-shell microcapsule" or the like is intended herein to mean a capsule having a micron-sized particle size distribution (e.g. mean diameter (d(v,0.5))) between about 1 and 3000 microns, preferably between 1 and 500 microns) and comprises a solid outer shell based on an oligomer or polymer shell and a continuous inner phase surrounded by the outer shell. For the avoidance of doubt, coacervates are considered core-shell microcapsules in the present invention.

By "microcapsule suspension" is meant microcapsule(s) dispersed in a liquid. According to one embodiment, the suspension is an aqueous suspension, ie the microcapsule(s) is/are dispersed in an aqueous phase.

By "mineralized core-shell microcapsule" is meant a microcapsule having a mineralized surface induced by the growth of crystalline or amorphous inorganic solid inorganic material.

By "charged emulsifier" is meant a compound that has emulsifying properties and that is negatively charged and/or positively charged. The charged emulsifier can be a charged biopolymer.

By "charged biopolymer" is meant a biopolymer that is negatively charged (anionic biopolymer) and/or positively charged (cationic or protonated biopolymer) and/or zwitterionic. As non-limiting examples one can cite gum arabic, pectin, sericin, sodium caseinate and amphiphilic proteins such as soy protein, rice protein, whey protein, protein albumin, casein, sodium caseinate, gelatin, albumin, bovine whey, hydrolyzed soy protein. B. hydrolyzed sericin, pseudocollagen, silk protein, sericin powder, gelatin and mixtures thereof as anionic biopolymers.

By "biopolymers" is meant biomacromolecules produced by living organisms. Biopolymers are characterized by molecular weight distributions ranging from 1,000 (1,000) to 1,000,000,000 (1,000 million) daltons. These macromolecules can be carbohydrates (sugar based) or proteins (amino acid based) or a combination of both (gummies) and can be linear or branched. The biopolymers according to the invention can also be chemically modified.

According to one embodiment, the biopolymers are amphiphilic or anionic, that is, they are negatively charged in water with a pH greater than 9.

In the context of the invention, a "mineral layer" consists of a stable inorganic crystalline phase or amorphous phase that grows perpendicular to the terminally charged surface of the shell to produce a preferentially rough, spiky, wrinkled, lamellar, ribbed or other layer .highly textured . mineral appearance.

By "mineral precursor" is meant a mineral precursor necessary for the growth of the desired crystalline phase. The mineral precursor is preferably a water-soluble mineral salt containing the ions necessary for the growth of the desired solid crystalline phase. The term "incubate" is used in the context of the present invention to describe the process of immersing the microcapsules in the precursor solution and allowing time for it to interact with the microcapsules.

By "polyurea-based" wall or shell, it is meant that the polymer comprises urea linkages created by an amino-functional crosslinking agent or by hydrolysis of isocyanate groups to create amino groups that can further react with isocyanate groups during interfacial polymerization.

By "polyurethane-based" wall or shell it is meant that the polymer comprises urethane linkages generated by the reaction of a polyol with isocyanate groups during interfacial polymerization.

By "polyamide-based microcapsules" is meant that the microcapsule shell comprises a polyamide material made from the reaction between an acid chloride and at least one amino compound. The term "polyamide-based microcapsules" can also encompass a shell made from a composite comprising a polyamide material and another material, for example a polymer (such as a protein).

For the sake of clarity, the term "dispersion" in the present invention is understood to mean a system in which particles are dispersed in a continuous phase of different composition and specifically includes a suspension or an emulsion.

MICROCÁPSULAS CORE-SHELL

Therefore a first object of the invention is a mineralized core-shell microcapsule comprising: a) a core, preferably an oil-based core, comprising a hydrophobic material, preferably a perfume; b) a shell with a terminal charged functional surface; and c) a mineral layer on the terminally charged functional surface, characterized in that the mineral layer comprises at least one salt selected from the group consisting of barium salt, strontium salt, magnesium salt and mixtures thereof.

In one embodiment, the mineral layer does not include a calcium salt.

hydrophobes Material

The hydrophobic material of the present invention can be an "inert" material such as solvents or drugs. The core is preferably an oil based core. When the hydrophobic material is an active ingredient, it is preferably selected from the group consisting of flavors, aromatics, fragrances, perfume ingredients, nutraceuticals, cosmetics, pesticides, biocidal actives, and mixtures thereof.

According to a particular embodiment, the hydrophobic material comprises a mixture of a fragrance with another ingredient selected from the group consisting of nutraceuticals, cosmetics, pesticides and active biocides.

According to one embodiment, the hydrophobic material comprises a phase change material (PCM).

According to a particular embodiment, the hydrophobic material comprises a mixture of biocidal active ingredients with another ingredient selected from the group consisting of perfumes, nutraceuticals, cosmetics, pesticides.

According to a particular embodiment, the hydrophobic material comprises a mixture of pesticides with another ingredient selected from the group consisting of perfumes, nutraceuticals, cosmetics, biocidal active ingredients.

According to a particular embodiment, the hydrophobic material comprises a perfume.

According to a particular embodiment, the hydrophobic material consists of a perfume.

According to a particular embodiment, the hydrophobic material consists of biocidal active substances.

According to a particular embodiment, the hydrophobic material consists of pesticides.

By "perfume" (or also "perfume oil") is meant here an ingredient or composition that is preferably liquid at about 20°C. According to any of the above embodiments, the perfumed oil may be a single perfumed ingredient or a mixture of ingredients in the form of a perfumed composition. By "fragrant ingredient" herein is meant a compound used for the primary purpose of transmitting or modulating an odor. In other words, an ingredient of this type that is to be considered perfumed must be recognized by a person skilled in the art as capable of at least positively or pleasantly transferring or modifying the odor of a composition, and not just having an odor. For the purposes of the present invention, perfume oil also includes a combination of fragrant ingredients with substances that together enhance, enhance or modify the delivery of the fragrant ingredients, such as pre-perfumes, modulators, emulsions or dispersions, and combinations thereof impart an additional benefit that exceeds modifying or transferring an odor, such as prolonged duration, flowering, neutralizing bad odors, antimicrobial activity, microbial stability, pest control.

The nature and nature of the perfumed ingredients contained in the oily phase do not require further description here, which would in any case not be exhaustive, and the person skilled in the art can select them according to his general knowledge and depending on the intended use. Determination . use or application and the desired organoleptic effect. Generally speaking, these perfume ingredients belong to chemical classes as diverse as alcohols, aldehydes, ketones, esters, ethers, acetates, nitriles, terpenoids, heterocyclic nitrogen or sulfur containing compounds and essential oils (e.g. thyme oil) and said perfume adjuvants may be natural or be of synthetic origin. Many of these co-ingredients are already listed in reference texts such as S. Arctander's Perfume and Flavor Chemicals, 1969, Montclair, New Jersey, USA, or later versions, or in other works of a similar nature. , as well as the extensive patent literature in the field of perfumery .

In particular, one can cite fragrant ingredients commonly used in perfume formulations, such as:

Aldehyde ingredients: decanal, dodecanal, 2-methylundecanal, 10-undecenal, octanal, nonal and/or nonnal;

Aromatic herbal ingredients: eucalyptus oil, camphor, eucalyptol, 5-methyltricyclo[6.2.1.0^2,7]Undecan-4-ona, 1-Methoxy-3-hexanothiol, 2-Ethyl-4,4-dimethyl-1,3-oxatiano, 2,2,7/8,9/10-tetramethylespiro[5,5]undec -8 -en-l-ona, Menthol e/o alfa-pineno;

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

- Citrus ingredients: dihydromyrcenol, citral, orange oil, linalyl acetate, citronellyl nitrile, orange terpenes, limonene, l-p-menton-8-yl and/or l,4(8)-p-mentadiene acetate;

Florais Inhaltsstoffe: Methyldihydrojasmonat, Linalool, Citronellol, Phenylethanol, 3-(4-tert-Butylphenyl)-2-methylpropanal, Hexylzimtaldehyd, Benzylacetat, Benzylsalicylat, Tetrahydro-2-isobutyl-4-methyl-4(2H)- Pyranol, Betaionon, Methyl-2-(methylamino)benzoat, (E)-3-Methyl-4-(2,6,6-trimethyl-2-cyclohexen-1-yl)-3-buten-2-on, ( 1E)-1-(2,6,6-Trimethyl-2-cyclohexen-1-yl)-1-penten-3-on, 1-(2,6,6-Trimethyl-1,3-cyclohexadien-1- yl)-2-buten-1-on, (2E)-1-(2,6,6-Trimethyl-2-cyclohexen-1-yl)-2-buten-1-on, (2E)-1 -[ 2,6,6-Trimethyl-3-cyclohexen-1-yl]-2-buten-1-on, (2E)-1-(2,6,6-Trimethyl-1-cyclohexen-1-yl)-2 -Buten-1-on, 3-(3,3/1,1-Dimethyl-5-indanyl)propanal, 2,5-Dimethyl-2-indanmethanol, 2,6,6-Trimethyl-3-cyclohexen- 1- Carboxylat, 3-(4,4-Dimethyl-1-cyclohexen-1-yl)propanal, Hexylsalicylat, 3,7-Dimethyl-1,6-nonadien-3-ol, 3-(4-Isopropylphenyl) -2- Methylpropanal, Verdilacetat, Geraniol, p-Menth-1-en-8-ol, 4-(1,1-Dimethylethyl)-1-cyclohexylacetat, 1,1-Dimethil-2-phenylacetat Ethyl, 4-Cyclo-hexyl-2-methyl-2-butanol, Amylsalicylat, Methyldihydrojasmonat hoch-cis, 3-Methyl-5-phenyl-1-pentanol, Verdilpropionat, Geranylacetat, Tetrahydrolinalool, cis- 7-p-Methanol, Propyl(S)-2-(1,1-dimethylpropoxy)propanoat, 2-Methoxynaphthalin, 2,2,2-Trichlor-1-phenylethylacetat, 4/3-(4- Hydroxy-4- Methylpentyl)-3-cyclo-hexen-1-carbaldehyd, Amylzimtaldehyd, 8-Decen-5-olid, 4-Phenyl-2-butanon, Isononylacetat, 4-(1,1-Dimethylethyl)-1-cyclohexyl, Verdil Isobutyrat und/oder gemischte Isomere von Methyliononen;

Fruchtige Zutaten: Gamma-Undecalacton, 2,2,5-Trimethyl-5-pentylcyclopentanon, 2-Methyl-4-propyl-1,3-oxathian, 4-Decanolide, Ethyl-2-Methylpentanoat, Hexylacetat, 2-Ethylmethylbutanoat , Gamma-Nonalacton, Allylheptanoat, 2-Phenoxyethylisobutyrat, Ethyl-2-methyl-1,3-dioxolan-2-acetat, Diethyl-1,4-cyclohexandicarboxylat, 3-Methylacetat, 2-Ethyl-hexen-1-yl, Diethyl 1-[3,3-Dimethylcyclohexyl][3-ethyl-2-oxiranyl]acetat und/oder 1,4-Cyclohexandicarboxylat;

Green Ingredients: 2-Methyl-3-hexanone (E)-oxime, 2,4-dimethyl-3-cyclohexene-l-carbaldehyde, 2-tert-butyl-1-cyclohexyl acetate, styryl acetate, allyl(2-methylbutoxy) acetate, 4-methyl-3-decen-5-ol, diphenyl ether, (Z)-3-hexen-1-ol and/or 1-(5,5-dimethyl-1-cyclohexen-1-y-1)-4- pentene-1-um;

Moschus Zutaten: 1,4-Dioxa-5,17-Cycloheptadecanedion, (Z)-4-Cyclopentadecen-1-on, 3-Methylcyclopentadecanon, 1-Oxa-12-cyclohexadecen-2-on, 1-Oxa-13-cyclohexadecen -2-on, (9Z)-9-Cycloheptadecen-1-on, 2-{(1S)-1-[(1R)-3,3-Dimethylcyclohexyl]ethoxy}-2-oxoethylpropionat, 3-Methyl-5- Cyclopentadecen-1-on, 4,6,6,7,8,8-Hexamethyl-1,3,4,6,7,8-Hexahydrocyclopenta[g]isochromen,

(1S,rR)-2-[1-(3',3'-Dimethyl-r-cyclohexyl)ethoxy]-2-methylpropylpropanoat, Oxacyclohexadecan-2-on oder (1S,rR)-[1-( 3',3'-Dimethyl-r-cyclohexyl)ethoxycarbonyl]methylpropanoat;

Woody ingredients: 1-[(1RS,6SR)-2,2,6-trimethylcyclohexyl]-3-hexanol, 3,3-dimethyl-5-[(1R)-2,2,3-trimethyl-3-cyclopentene- 1-yl]-4-penten-2-ol, 3,4'-dimethylspiro[oxirane-2,9'-tricyclo[6.2.1.0^2,7]undec[4]ene, (1-ethoxyethoxy)cyclododecane, 2,2,9, 11-tetramethylspiro[5,5]undec-8-en-1-yl acetate, 1-(octahydro-2,3,8, 8 - Tetramethyl-2-naphthalenyl)-l-ethanone, Patchouli Oil, Terpene Fractions of Patchouli Oil, Clearwood^®, (rR,E)-2-Ethyl-4-(2',2',3'-trimethyl-3'-cyclopenten-1'-yl)-2-buten-1-ol, 2-Ethyl-4- (2,2,3-Trimethyl-3-cyclopenten-1-yl)-2-buten-1-ol, Methylcedrylketon, 5-(2,2,3-Trimethyl-3-cyclopentenyl)-3-methylpentan- 2-ol, 1-(2,3,8,8-Tetramethyl-1,2,3,4,6,7,8,8a-octahydronaphthalin-2-yl)ethan-1-on und/oder Isobornylacetat;

Other ingredients (e.g. amber, spice powder or aqueous): dodecahydro-3a,6,6,9a-tetramethyl-naphtho[2,1-b]furan and one of its stereoisomers, heliotropin, anisaldehyde, eugenol, cinnamaldehyde, clove oil, 3-(1,3-Benzodioxol-5-yl)-2-methylpropanal, 7-methyl-2H-1,5-benzodioxepin-3(4H)-one, 2,5,5-trimethyl-1,2,3 ,4,4a,5,6,7-octahydro-2-naphthalenol, 1-phenylvinyl acetate, 6-methyl-7-oxa-1-thia-4-azaspiro[4.4]nonane and/or 3-( 3-isopropyl- 1-phenyl)butanal.

It is also understood that the ingredients can also be compounds known to release in a controlled manner various types of fragrance compounds, also known as propofumes or profragrances. Non-limiting examples of suitable vapors may include 4-(dodecylthio)-4-(2,6,6-trimethyl-2-cyclohexen-1-yl)-2-butanone, 4-(dodecylthio)-4-(2,6, 6-Trimethyl-1-cyclohexen-1-yl)-2-butanone, 3-(Dodecylthio)-1-(2,6,6-trimethyl-3-cyclohexen-1-yl)-1-butanone, 2 - ( Dodecylthio)octan-4-one, 2-phenylethyloxo(phenyl)acetate, 3,7-dimethylocta-2,6-dien-1-yloxo(phenyl)acetate, (Z)-hex-3-en-1-yloxo( phenyl) acetate, 3,7-dimethyl-2,6-octadien-1-yl hexadecanoate, bis(3,7-dimethylocta-2,6-dien-1-yl) succinate, (2-( (2-methylundec-1 -en-1-yl)oxy)ethyl)benzene, 1-Methoxy-4-(3-methyl-4-phenethoxybut-3-en-1-yl)benzene, (3-methyl-4-phenethoxybut-3-ene -1-yl)benzene, 1-(((Z)-Hex-3-en-1-yl)oxy)-2-methylundec-1-ene, (2-((2-methylundec - 1-en-1 -yl)oxy)ethoxy)benzene, 2-methyl-1-(octan-3-yloxy)undec-1-ene, 1-methoxy-4-(1-phenethoxyprop-1-en-2). - yl)benzene, 1-methyl-4-(1-phenethoxyprop-1-en-2-yl)benzene, 2-(1-phenethoxyprop-1-en-2-yl)naphthalene, (2-phenethoxyvinyl)benzene, 2-(1-((3,7-dimethyloct-6-en-1-yl)oxy)prop-1-en-2-yl)naphthalene, (2-((2-pentylcyclopentylidene)methoxy)ethyl)benzene, 4-allyl-2-methoxy-1-((2-methoxy-2-phenylvinyl)oxy)benzene, (2-((2-heptylcyclopentylidene)methoxy)ethyl)benzene, 1-isopropyl -4-methyl-2-( (2-pentylcyclopentylidene)methoxy)benzene, 2-methoxy-1-((2-pentylcyclopentylidene)methoxy)-4-propylbenzene, 3-methoxy-4-((2-methoxy-2-phenylvinyl)oxy)benzaldehyde, 4- ((2-(hexyloxy)-2-phenylvinyl)oxy)-3-methoxybenzaldehyde or a mixture thereof.

Perfume ingredients can be dissolved in a solvent commonly used in the perfume industry. The solvent is preferably non-alcohol. Examples of such solvents are diethyl phthalate, isopropyl myristate, abalyn^®(rosins available from Eastman), benzyl benzoate, ethyl citrate, triethyl citrate, limonene or other terpenes or isoparaffins. Preferably, the solvent is highly hydrophobic and highly sterically hindered, such as Abalyn^®or benzyl benzoate. Preferably the perfume comprises less than 30% solvent. More preferably the perfume comprises less than 20% and even more preferably less than 10% solvent, all such percentages by weight being defined relative to the total weight of the perfume. More preferably, the perfume is essentially solvent-free.

Preferred perfume ingredients are those with high steric hindrance (bulky materials) and especially those from one of the following groups:

Group 1: Fragrance ingredients comprising a cyclohexane, cyclohexene, cyclohexanone or cyclohexenone ring substituted by at least one linear or branched C1 to C4 alkyl or alkenyl substituent;

Group 2: Fragrance ingredients comprising a cyclopentane, cyclopentene, cyclopentanone or cyclopentenone ring substituted by at least one linear or branched C4 to Cx alkyl or alkenyl substituent;

Group 3: Perfume ingredients comprising a phenyl ring or perfume ingredients comprising a cyclohexane, cyclohexene, cyclohexanone or cyclohexenone ring substituted with at least one linear or branched C5 to Cx alkyl or alkenyl substituent or with at least one phenyl and optionally one or more linear substituents, branched C1 to C3 alkyl or alkenyl substituents or substituents;

Group 4: Perfumes comprising at least two fused or linked C5 and/or Ce rings; Group 5: Perfumes comprising a camphor-like ring structure;

Group 6: Fragrance ingredients comprising at least one C7 to C20 ring structure;

Group 7: Perfumed ingredients with a logP value greater than 3.5 and containing at least one tert-butyl or at least one trichloromethyl substituent;

Examples of ingredients from each of these groups are:

Group 1: 2,4-dimethyl-3-cyclohexene-1-carbaldehyde (origin: Firmenich SA, Geneva, Switzerland), isocyclocitral, menthone, isomentune, 2,2-dimethyl-6-methylene-1-cyclohexanecarboxylic acid methyl ester (origin: Firmenich SA, Geneva, Switzerland), nerone, terpineol, dihydroterpineol, terpenyl acetate, dihydroterpenyl acetate, dipentene, eucalyptol, hexilate, rose oxide, (S)-1,8-p-mentadien-7-ol (origin: Firmenich SA, Geneva, Switzerland) , l-p-menthen-4-ol, (1RS,3RS,4SR)-3-p-menthanyl acetate, (1R,2S,4R)-4,6,6-trimethylbicyclo[3,1,l]heptane-2 -ol, tetrahydro-4-methyl-2-phenyl-2H-pyran (origin: Firmenich SA, Geneva, Switzerland), cyclohexyl acetate, cyclanol acetate, 1,4-1,4-1. cyclohexane (origin: Firmenich SA, Geneva, Switzerland), (3RS,3aRS,6SR,7ASR)-perhydro-3,6-dimethyl-benzo[B]furan-2-one (origin: Firmenich SA, Geneva, Switzerland); ((6R)-Perhydro-3,6-dimethyl-benzo[B]furan-2-one (origin: Firmenich SA, Geneva, Switzerland), 2,4,6-trimethyl-4-phenyl-1,3-dioxane , 2,4,6-trimethoyl-3-cyclohexene-1-carbaldehyde;

Group 2: (E)-3-Methyl-5-(2,2,3-trimethyl-3-cyclopenten-1-yl)-4-penten-2-ol (origin: Givaudan SA, Vernier, Switzerland), ( rR,E)-2-ethyl-4-(2',2',3'-trimethyl-3'-cyclopenten-1'-yl)-2-buten-1-ol (origin: Firmenich SA, Geneva, Switzerland ), (1'R,E)-3,3-dimethyl-5-(2',2',3'-trimethyl-3'-cyclopenten-r-yl)-4-penten-2-ol (origin: Firmenich SA, Geneva, Switzerland), 2-heptylcyclopentanone, methyl cis-3-oxo-2-pentyl-1-cyclopentane acetate (origin: Firmenich SA, Geneva, Switzerland), 2,2,5-trimethyl-5-pentyl - 1-cyclopentanone (origin: Firmenich SA, Geneva, Switzerland), 3,3-dimethyl-5-(2,2,3-trimethyl-3-cyclopenten-1-yl)-4-penten-2-ol (origin: Firmenich SA, Geneva, Switzerland), 3-methyl-5-(2,2,3-trimethyl-3-cyclopenten-1-yl)-2-pentanol (source, Givaudan SA, Vernier, Switzerland);

Group 3: apricots, 1-(5,5-dimethyl-1-cyclohexen-1-yl)-4-penten-1-one (origin: Firmenich SA, Geneva, Switzerland), (rR)-2-[2- (4'-Methyl-3'-cyclohexen-r-yl)propyl]cyclopentanone, alpha-ionone, beta-ionone, damascenone, 1-(5,5-dimethyl-1-cyclohexen-1-yl)-4-mixture - Penten-1-one and 1-(3,3-dimethyl-1-cyclohexen-1-yl)-4-penten-1-one (origin: Firmenich SA, Geneva, Switzerland), 1-(2,6, 6). -Trimethyl-1-cyclohexen-1-yl)-2-buten-1-one (origin: Firmenich SA, Geneva, Switzerland), (1S,1'R)-[1-(3',3'-dimethyl - r-Cyclohexyl)ethoxycarbonyl]methylpropanoate (origin: Firmenich SA, Geneva, Switzerland), 2-tert-butyl-1-cyclohexyl acetate (origin: International Flavors and Fragrances, USA), 1-(2,2,3,6 - Tetramethyl-cyclohexyl)-3-hexanol (origin: Firmenich SA, Geneva, Switzerland), trans-1-(2,2,6-trimethyl-1-cyclohexyl)-3-hexanol (origin: Firmenich SA, Geneva, Switzerland) . ), Switzerland), (E)-3-methyl-4-(2,6,6-trimethyl-2-cyclohexen-1-yl)-3-buten-2-one, terpenyl isobutyrate clohexyl, 4-(l,l -dimethylethyl)-l-cy (origin: Firmenich SA, Geneva, Switzerland), 8-methoxy-1-p-menthene, (1S,1'R)-2-[1-(3',3'-dimethyl- F-cyclohexyl)ethoxy]-2-methylpropylpropanoate (origin: Firmenich SA, Geneva, Switzerland), for tert-butylcyclohexanone, mantenethiol, 1-methyl-4-(4-methyl-3-pentenyl)-3-cyclohexene-1- carbaldehyde, allyl cyclohexyl propionate, cyclohexyl salicylate, 2-methoxy-4-methylphenylmethyl, 2-methoxy-4-methylphenylethyl carbonate, 4-ethyl-2-methoxyphenylmethyl carbonate;

Group 4: methyl cedryl ketone (origin: International Flavors and Fragrances, USA), a mixture of (1RS,2SR,6RS,7RS,8SR)-tricyclo[5.2.1.0²'⁶]dec-3-en-8-yl-2-methylpropanoat und (1RS,2SR,6RS,7RS,8SR)-Tricyclo[5.2.1.0²'⁶]dec-4-en-8-yl-2-methylpropanoate, vetiverol, vetiverone, l-(octahydro-2,3,8,8-tetramethyl-2-naphthalenyl)-l-ethanone (origin: International Flavors and Fragrances, EE UU.), (5RS,9RS,10SR)-2,6,9,10-Tetramethyl-1-oxaspiro[4,5]deca-3,6-diene and the isomer (5RS,9SR,10RS), 6 - Ethyl-2,10,10-trimethyl-1-oxaspiro[4,5]deca-3,6-diene,1,2,3,5,6,7-hexahydro-1,1,2,3,3 -Pentamethyl-4-indenone (origin: International Flavors and Fragrances, USA), a mixture of 3-(3,3-dimethyl-5-indanyl)propanal and 3-(1,1-dimethyl-5-indanyl)propanal ( origin: Firmenich SA, Geneva, Switzerland), 3',4-dimethyl-tricyclo[6.2.1.0(2,7)]undec-4-ene-9-spiro-2'-oxirane (origin: Firmenich SA, Geneva) . , Switzerland), 9/10-ethyldiene-3-oxatriccyclo[6.2.1.0(2,7)]undecane, (perhydro-5,5,8A-trimethyl-2-naphthalenyl acetate (origin: Firmenich SA, Geneva, Switzerland) ; , octalinol, (dodecahydro-3a,6,6,9a-tetramethyl-naphtho[2,1-b]furan, origin: Firmenich SA, Geneva, Switzerland), tricyclo[5.2.1.0(2,6)]dec- 3 -en-8-yl acetate and tricyclo-o[5.2.1.0(2,6)]dec-4-en-8-yl acetate and tricyclo[5.2.1.0(2,6)]dec-3-en-8-ylpropanoate and tricyclo[5.2.1,0(2,6)]dec-4-en-8-yl, (+)-(1S,2S,3S)-2,6,6-trimethylbicyclo[3.1 ]propanoate .1] heptane-3-spiro-2'-cyclohexen-4'-one;

Group 5: camphor, bomeol, isobomil acetate, 8-isopropyl-6-methyl-bicyclo[2.2.2]oct-5-ene-2-carbaldehyde, pinene, camphene, 8-methoxyedrane, (8-methoxy-2, 6 , 6,8-Tetramethyl-tricyl[5.3.1.0(1,5)]undecane (origin: Firmenich SA, Geneva, Switzerland), cedrene, cedrenol, cedrol, 9-ethylidene-3-oxatricyl[6.2.1.0] mixture ( 2, 7)] undecan-4-one and 10-ethylidene-3-oxatricyclo[6.2.1.0^2,7]undecan-4-one (origin: Firmenich SA, Geneva, Switzerland), 3-methoxy-7,7-dimethyl-10-methylene-bicyclo[4.3.1]decane (origin: Firmenich SA, Geneva, Switzerland);

Group 6: (trimethyl-13-oxabicyclo-[10.1.0]-trideca-4,8-diene (origin: Firmenich SA, Geneva, Switzerland), 9-hexadecene-16-olide (origin: Firmenich SA, Geneva, Switzerland ). ) ), pentadecenolides (origin: Firmenich SA, Geneva, Switzerland), 3-methyl-(4/5)-cyclopentadecenone, (origin: Firmenich SA, Geneva, Switzerland), 3-methylcyclopentadecanone (origin: Firmenich SA, Geneva , Switzerland). ), pentadecanolide (origin: Firmenich SA, Geneva, Switzerland), cyclopentadecanone (origin: Firmenich SA, Geneva, Switzerland), 1-ethoxyethoxy)cyclododecane (origin: Firmenich SA, Geneva, Switzerland), 1,4-dioxacycloheptadecane-5, 17-dione, 4,8-cyclododecadien-1-one;

Group 7: (+-)-2-methyl-3-[4-(2-methyl-2-propanyl)phenyl]propanal (origin: Givaudan SA, Vernier, Switzerland), 2,2,2-trichloro-1- phenylethyl acetate. Preferably the perfume comprises at least 30%, preferably at least 50%, more preferably at least 60% ingredients selected from groups 1 to 7 as defined above. More preferably, the perfume comprises at least 30%, preferably at least 50% of the components of groups 3 to 7 as defined above. More preferably, the perfume comprises at least 30%, preferably at least 50% of the components of group 3, 4, 6 or 7 as defined above.

According to another preferred embodiment, the perfume comprises at least 30%, preferably at least 50%, more preferably at least 60% ingredients with a logP greater than 3, preferably greater than 3.5 and even more preferably greater than 3.75.

According to a particular embodiment, the perfume used according to the invention contains less than 10% by weight of primary alcohols, less than 15% by weight of secondary alcohols and less than 20% by weight of tertiary alcohols. Advantageously, the perfume used in the invention does not contain primary alcohols and contains less than 15% secondary and tertiary alcohols.

According to one embodiment, the oil phase (or oil core) comprises:

25-100% by weight, preferably 25-98%, of a perfume oil comprising at least 15% by weight of high-impact perfume raw materials with log T < -4, and

0-75% by weight, preferably 2-75%, of a density balancing material having a density greater than 1.07 g/cm³.

By "high impact perfume raw materials" is meant perfume raw materials with a LogT < -4. The odor threshold concentration of a chemical compound is determined in part by its shape, polarity, partial charges, and molecular weight. For convenience, the odor threshold concentration is given as the logarithm of the threshold concentration, ie Log [Threshold] ("LogT").

By "density balancing material" is meant a material having a density greater than 1.07 g/cm³and preferably with little or no odor.

The density of a component is defined as the ratio of its mass to its volume (g/cm³).

There are several methods available for determining the density of a component.

For example, reference may be made to the ISO 298:1998 method for measuring the d20 density of essential oils.

According to one finding, the density balancing material is selected from the group consisting of benzyl salicylate, benzyl benzoate, cyclohexyl salicylate, benzyl phenyl acetate, phenylethyl phenoxyacetate, triacetin, methyl and ethyl salicylate, benzyl cinnamate, and mixtures thereof. According to a particular embodiment, the density balancing material is selected from the group consisting of benzyl salicylate, benzyl benzoate, cyclohexyl salicylate, and mixtures thereof.

The threshold odor concentration of a fragrance compound is determined using a gas chromatograph ("GC"). In particular, the gas chromatograph is calibrated to determine the exact volume of perfume oil ingredient injected through the syringe, the exact split ratio, and the hydrocarbon response using a hydrocarbon standard of known concentration and chain length distribution. The air flow rate is accurately measured and, assuming the duration of a human inhalation is 12 seconds, the sample volume is calculated. Because the exact concentration in the detector is known at any given time, the inhaled mass per volume and hence the concentration of the odorant compound is known. To determine the threshold concentration, the solutions with the calculated concentration are sent back to the detection port. A panel member smells the GC effluent and determines the retention time when the odor is noticed. The average of all panellists determines the odor threshold concentration of the fragrance compound. The determination of the odor threshold is described in more detail in C. Vuilleumier et al., Multidimensional Visualization of Perceptual and Physical Data Leading to a Creative Approach in Fragrance Development, Perfume & Flavorist, vol. 33, September 2008, pages 54-61.

The nature of high potency perfume raw materials with Log T <-4 and density balancing material with a density greater than 1.07 g/cm³They are described in document WO2018115250, the content of which is incorporated by reference.

According to one modality, the highly effective perfume raw materials with a log T < -4 are selected from the group consisting of (+-)-1-methoxy-3-hexanethiol, 4-(4-hydroxy-1-phenyl)-2-butanone, 2 -Methoxy-4-(l-propenyl)-1-phenylacetate, pyrazobutyl, 3-propylphenol, l-(3-methyl-1-benzofuran-2-yl)ethanone, 2-(3-phenylpropyl))pyridine, 1- (3,3/5,5-dimethyl-1-cyclohexen-1-yl)-4-penten-1-one, 1-(5,5-dimethyl-1-cyclohexen-1-yl)-4-penten- 1-one, a mixture comprising (3RS,3aRS,6SR,7ASR)-peridro-3,6-dimethyl-benzo[b]furan-2-one and (3SR,3aRS,6SR,7ASR). ) - Perhydro-3,6-dimethyl-benzo[b]furan-2-one, (+-)-1-(5-ethyl-5-methyl-1-cyclohexen-1-yl)-4-penten-1 -um, (1'S,3'R)-1-methyl-2-[(r,2',2'-trimethylbicyclo[3.1.0]hex-3'-yl)methyl]cyclopropyl}methanol, (+-) - 3-mercaptohexyl acetate, (2E)-1-(2,6,6-trimethyl-1,3-cyclohexadien-1-yl)-2-buten-1-one, H-methyl-2h - 1,5-benzodioxepin -3(4H)-one, (2E,6Z)-2,6-nonadien-1-ol, (4Z)-4-dodecenal, (+-)-4-hydroxy-2,5-dimethyl-3( 2H )-furanone, methyl 2,4-dihydroxy-3,6-dimethylbenzoate, 3-methylindole, (+-)-peridro-4alpha,8abeta-dimethyl-4a-naphthalenol, patchoulol, 2-methoxy-4-(l -propenyl)phenol, mixture contains (+-)-5,6-dihydro-4-methyl-2-phenyl-2H-pyran and tetrahydro-4-methylene-2-phenyl-2H-pyran, a mixture comprising 4-methylene -2-phenyltetrahydro-2H-pyran and (+-)-4-methyl-2-phenyl-3,6-dihydro-2H-pyran, 4-hydroxy-3-methoxybenzaldehyde, nonylene aldehyde, 2-methoxy-4- propylphenol, 3-methyl-5-phenyl-2-pentenenitrile, l - (spiro[4.5]dec-6/7-en-7-yl)-4-penten-l-one(, 2-methoxynaphthalene, (-) -(3aR,5AS,9AS,9BR)-3a,6, 6,9a-Tetramethyldodecahydronaphtho[2,l-b]furan, 5-nonanolide, (3aR,5AS,9AS,9BR)-3a,6,6,9a-Tetramethyldodecahydronaphtho[2,l-b]furan, 7-Isopropyl-2H,4H- 1,5-benzodioxepin-3-one, coumarin, 4-methylphenyl isobutyrate, (2E)-1-(2,6,6-trimethyl-1,3-cyclohexadien-1-yl)-2-buten-1-one, beta, 2,2,3-tetramethyl-delta-methylene-3-cyclopentene-1-butanol, delta-damascone ((2E)-l-[(lRS,2SR)-2,6,6-trimethyl-3-cyclohex en -1-yl]-2-buten-1-one), (+-)-3,6-dihydro-4,6-dimethyl-2-phenyl-2h-pyran, anisaldehyde, paracresol, 3-ethoxy- 4-Hydroxybenzaldehyde, Methyl 2-aminobenzoate, Ethylmethylphenylglycidate, Gamma-Octalactone, 3-Ethyl, (-)-(2E)-2-Ethyl-4 -[(lR)-2,2,3-Trimethyl-3-cyclopentene -1-yl]-2-buten-1-phenyl-2-propenoat-ol, paracresyl acetate, dodecalactone, tricyclone, (+)-(3R ,5Z)-3-methyl-5-cyclopentadecen-1-one, undecalactone, (1R,4R)-8-mercapto-3-p-menthanone, (3S,3AS,6R,7AR)-3,6-dimethyl] hexahydro-1-benzofuran-2(3H)-one, beta-ionone, ( +-)-6-pentyltetrahydro-2H-pyran-2-one, (3E,5Z)-1,3,5-undecatriene, 10-undecenal , (9 E)-9-undecenal, (9Z)-9-undecenal, (Z)-4-decenal, ethyl(+-)-2-methylpentanoate, 1,2-diallyldisulfane, 2-tridecenonitrile, 3-tridecenonitrile, (+ - )-2-ethyl-4,4-dimethyl-1,3-oxathiane, (+)-(3R,5Z)-3-methyl-5-cyclopentadecen-1-one, 3-(4-tert-butylphenyl)propanal , (cyclohexyloxy)allyl acetate, methyl naphthyl ketone, (+-)-(4E)-3-methyl-4-cyclopentadecene-

1-ona, (+-)-5E3-metil-5-ciclopentadecen-1-ona, 3-hexenoato de cyclopropylmetilo, (4E)-4-metil-5-(4-metilfenil)-4-pentanal, (+- )-1-(5-Propyl-1,3-benzodioxol-2-yl)ethanon, 4-Methyl-2-pentylpyridin, (+-)-(E)-3-Methyl-4-(2,6,6). - Trimetil-2-ciclohexen-l-yl)-3-buten-2-on, (3aRS,5aSR,9aSR,9bRS)-3a,6,6,9a-tetrametildodecahidronafto[2,l-b]furano,

(2S,5R)-5-Methyl-2-(2-propanyl)cyclohexanonoxim, 6-Hexyltetrahydro-2H-pyran-2-on, (+-)-3-(3-Isopropyl-1-phenyl)butanal, Methyl-2-(3-oxo-2-pentylcyclopentyl)acetat, 1-(2,6,6-Trimethyl-1-cyclohex-2-enyl)pent-1-en-3-on, Indol, 7-Propyl-2H ,4H-1,5-Benzodioxepin-3-on, Ethylpraline, (4-Methylphenoxy)acetaldehyd, Ethyltricyclo[5.2.1.0.^2,6]decan-2-carboxylat, (+)-(rS,2S,E)-3,3-Dimethyl-5-(2',2',3'-trimethyl-3'-cyclopenten-r-yl)-4 -penten-

2-ol, (4E)-3,3-Dimethyl-5-[(1R)-2,2,3-trimethyl-3-cyclopenten-1-yl]-4-penten-2-ol, 8-Isopropyl- 6-Metil-biciclo[2.2.2]oct-5-eno-2-carbaldeído, Metilnoniacetaldeído, 2-Metilpropanoato de 4-formil-2-methoxyfenilo, (E)-4-decenal, (+-)-2-etil - 4-(2,2,3-Trimethyl-

3-Cyclopenten-1-yl)-2-buten-1-ol, (1R,5R)-4,7,7-Trimethyl-6-thiabicyclo[3.2.1]oct-3-en, (1R,4R, 5R)-4,7,7-Trimethyl-6-thiabicyclo[3.2.1]octan, (-)-(3R)-3,7-Dimethyl-1,6-octadien-3-ol, (E)-3 -Phenyl-2-propenitril, 4-Methoxybenzylacetat, (E)-3-Methyl-5-(2,2,3-trimethyl-3-cyclopenten-1-yl)-4-penten-2-ol, Allyl ( 2/3-Methylbutoxy, (+-)-(2E)-1 -(2,6,6-Trimethyl-2-cyclohexen-1-yl)-2-buten-1-on, (IE)- 1 - ( 2,6,6-Trimethyl-1-cyclohexen-1-yl)-1-penten-3-on und seine Mischungen.

According to one embodiment, perfume raw materials with a log T <−4 are selected from the group consisting of aldehydes, ketones, alcohols, phenols, lactone esters, ethers, epoxides, nitriles and mixtures thereof.

According to one embodiment, the perfume raw materials with a log T < -4 comprise at least one compound selected from the group consisting of alcohols, phenols, lactone esters, ethers, epoxides, nitriles and mixtures thereof, preferably in an amount between 20 and 100% 70% by weight. % based on the total weight of the perfume raw materials with a log T < -4.

According to one embodiment, the Log T<-4 perfume raw materials comprise between 20 and 70% by weight of aldehydes, ketones and mixtures thereof, based on the total weight of the Log T<-4 perfume raw materials. logT <-4.

The remaining perfume raw materials contained in the oil-based core can therefore have a Log T > -4.

According to one embodiment, perfume raw materials with a Log T > -4 are selected from the group consisting of ethyl 2-methylbutyrate, (E)-3-phenyl-2-propenyl acetate, (+-)-6/8-sec-butylquinoline, ( +-)-3-(1,3-Benzodioxol-5-yl)-2-methylpropanal, verdyl propionate, 1-(octahydro-2,3,8,8-tetramethyl-2-naphthalenyl)-1 -ethanone, methyl- 2-((1RS,2RS)-3-oxo-2-pentylcyclopentyl)acetate, (+-)-(E)-4-methyl-3-decen-5-ol, 2,4-dimethyl-3-cyclohexene- 1-carbaldehyde, 1,3,3-trimethyl-2-oxabicyclo[2.2.2]octane, tetrahydro-4-methyl-2-(2-methyl-1-propenyl)-2H-pyran, dodecanal, 1-oxa- 12/13-cyclohexadecen-2-one, (+-)-3-(4-isopropylphenyl)-2-methylpropanal, CII-aldehyde, (+-)-2,6-dimethylallyl-7-octen-2-ol, 3-cyclohexylpropanoate, (Z)-3-hexenyl acetate, 5-methyl-2-(2-propanyl)cyclohexanone, allyl heptanoate, 2-(2-methyl-2-propanyl)cyclohexyl, 1,1-dimethyl-2-phenylethylbutyrate, geranyl acetate, neryl acetate, (+-)-1-phenylethyl acetate, 1,1-dimethyl-2-phenylethyl acetate, 3-methyl-2-butenylacetate ethyl, 3-oxobutane ethyl-(2Z)-3-hydrox γ-2-butenoate, 8-p-methanol, 8-p-menthanyl acetate, 1-p-menthanyl, 3-methyl-3-cyclohexen-1-yl)-2-propanyl (+ -)-2-(4- acetate), (+-)-2-methylbutylbutanoate, 2-{(1S)oxoethyl-1-[(1R)-3,3-dimethylcyclohexyl|ethoxy}-2-propionate, 3,5,6-trimethyl-3- cyclohexene-1-carbaldehyde, 2,4,6-trimethyl-3-cyclohexene-1-carbaldehyde, 2-cyclohexylethyl acetate, octanal, ethyl butanoate, (+-)-(3E)-4 -(2,6,6-trimethyl- 1/2-cyclohexen-1-yl)-3-buten-2-one, 1-[(1RS,6SR)-2,2,6-trimethylcyclohexyl 1]-3-hexanol, 1,3,3-trimethyl- 1-2-oxabicyclo[2.2.2]octane, 1,3,3-trimethyl-2-oxabicyclo[2.2.2]octane, ethyl hexanoate, undecanal, decanal, 2-phenylethyl acetate , (1S,2S,4S)-1, 7,7-trimethylbicyclo[2.2.1]heptan-2-ol, (1S,2R,4S)-1,7,7-trimethylbicyclo[2.2.1]heptan-2-ol), (+-)-3, 7-dimethyl-3-octanol, 1-methyl-4-(2-propanylidene)cyclohexene, (+)-(R)-4-(2-methoxypropan-2-yl)-1-methylcyclohexyl-1-ene, verdyl acetate , (3R)-1-[(1R,6S)-2,2,6-trimethylcyclohexyl]-3-hexanol, (3S)-1-[(1R,6S )-2,2,6-trimethylcyclohexyl]- 3-hexanol, (3R)-1-[(1S,6S)-2,2, 6-Trimethylcyclohexyl]-3-hexanol, (+)-(1S,rR)-2-[1-(3'-dimethyl-r-cyclohexyl)ethoxy]-2-methylpropyl',3-propanoate and mixtures thereof.

According to one embodiment, the perfume formulation comprises

0 to 60% by weight of a hydrophobic solvent (based on the total weight of the perfume formulation),

40 to 100% by weight of a perfume oil (based on the total weight of the perfume formulation), the perfume oil having at least two, preferably all of the following properties: or at least 35%, preferably at least at least 40%, preferably at least 50%, more preferably at least 60% fragrance ingredients with a log P greater than 3, preferably greater than 3.5, or at least 20%, preferably at least 25%, preferably at least 30%, more preferably at least 40% bulk materials from groups 1 to 6, preferably 3 to 6 as defined above and or at least 15%, preferably at least 20%, more preferably at least 25%, even more preferably at least at least 30% high impact perfume materials with a Log T < -4 as defined above, optionally other hydrophobic active ingredients.

According to a particular embodiment, the perfume contains from 0 to 60% by weight of a hydrophobic solvent.

According to a particular embodiment, the hydrophobic solvent is a density-compensating material, preferably selected from the group consisting of benzyl salicylate, benzyl benzoate, cyclohexyl salicylate, benzyl phenyl acetate, phenylethyl phenyl acetate, triacetin, ethyl citrate, methyl and ethyl salicylate, benzyl cinnamate, and mixtures thereof.

In a particular embodiment, the hydrophobic solvent has Hansen solubility parameters compatible with the encapsulated perfume oil.

The term "Hansen's solubility parameter" means a solubility parameter approach proposed by Charles Hansen, used to predict polymer solubility and developed on the basis of the fact that the total vaporization energy of a liquid consists of several individual parts. To calculate the "weighted Hansen solubility parameter" the effects of dispersion (atomic) forces, permanent (molecular) dipole-dipole forces and (molecular) hydrogen bonding (electron exchange) must be combined. The "weighted Hansen solubility parameter" is calculated as (5D²+RD²+dH²)⁰⁵, where dϋ is the Hansen scattering value (hereinafter also referred to as atomic scattering), dR is the Hansen polarizability value (hereinafter also referred to as the dipole moment), and dH is the Hansen hydrogen bond ("h-bond") (hereinafter also referred to as called hydrogen bonds). For a more detailed description of the parameters and values, see Charles Hansen, The Three Dimensional Solubility Parameter and Solvent Diffusion Coefficient, Danish Technical Press (Copenhagen, 1967).

The Euclidean difference in solubility parameter between a fragrance and a solvent is

Calculate what dϋ solvent, dPsoivent, and oHsoivcm are the Hansen dispersion value, Hansen polarizability value, and Hansen h-bonding values ​​of the solvent, respectively; and DD_FR_awarded, dP_Fragrance, and SH_Fragranceare the Hansen dispersion value, the Hansen polarizability value and the Hansen h-bonding values ​​of the fragrance, respectively.

In a particular embodiment, the perfume oil and the hydrophobic solvent have at least two Hansen solubility parameters selected from a first group consisting of: an atomic dispersive power (dϋ) from 12 to 20, a dipole moment (dR) from 1 to 8, and hydrogen bonding (dH) from 2.5 to 11.

In a particular embodiment, the perfume oil and the hydrophobic solvent have at least two Hansen solubility parameters selected from a second group consisting of: an atomic dispersive power (6D) of 12 to 20, preferably 14 to 20, a dipole moment (dR) of 1 to 8, preferably 1 to 7, and a hydrogen bonding (dH) of 2.5 to 11, preferably 4 to 11.

In a particular embodiment, at least 90% of the perfume oil, preferably at least 95% of the perfume oil, more preferably at least 98% of the perfume oil, has at least two Hansen solubility parameters selected from a first group consisting of: an atomic dispersibility (dϋ) from 12 to 20 , a dipole moment (dR) from 1 to 8 and a hydrogen bond (dH) from 2.5 to 11.

In a particular embodiment, the perfume oil and the hydrophobic solvent have at least two Hansen solubility parameters selected from a second group consisting of: an atomic dispersive power (6D) of 12 to 20, preferably 14 to 20, a dipole moment (dR) of 1 to 8, preferably 1 to 7, and a hydrogen bond (5H) of 2.5 to 11, preferably 4 to

11

According to one embodiment, the perfume formulation comprises a fragrance modulator (which can be used in addition to the hydrophobic solvent, if present, or as a substitute for the hydrophobic solvent if a hydrophobic solvent is not present).

The scent modulator is preferably defined as a scent with i. a vapor pressure of less than 0.0008 torr at 22°C; ii. a clogP of 3.5 and greater, preferably 4.0 and greater, and most preferably 4.5 iii. at least two Hansen solubility parameters selected from a first group consisting of: an atomic dispersive power of 12 to 20, a dipole moment of 1 to 7, and a hydrogen bonding of 2.5 to 11, iv. at least two Hansen solubility parameters selected from a second group consisting of: an atomic dispersibility of 14 to 20, a dipole moment of 1 to 8, and a hydrogen bonding of 4 to 11 when in solution with a compound that with a vapor pressure in the range of 0, 0.08 to 0.08 torr at 22°C.

Preferably, as examples, the following ingredients can be listed as modulators, but the list is not limited to the following materials: C12 alcohol, oxacyclohexadec-12/13-en-2-one, 3-[(2',2', 3 '-Trimethyl-3'-cyclopenten-r-yl)methoxy]-2-butanol, cyclohexadecanone, (Z)-4-cyclopentadecen-1-one, cyclopentadecanone, (8Z)-oxacycloheptadec-8-en-2-one, 2-[5-(Tetrahydro-5-methyl-5-vinyl-2-furyl)-tetrahydro-5-methyl-2-furyl]-2-propanol, sooraldehyde, 1,5,8-trimethyl-13-oxabicyclo[ 10.1.0]trideca-4,8-diene, (+-)-4,6,6,7,8,8-hexamethyl-1,3,4,6,7,8-hexahydrocyclopenta[g]isochromen , ( +)-(1S,2S,3S,5R)-2,6,6-Trimethyl-1-spyro Ib i c y c 1 o [3.1.1 ]heptane-3,1'-cyclohexane]-2'-ene -4' -one, oxacyclohexadecan-2-one, 2-{(1S)-1-[(1R)-3,3-dimethylcyclohexyl]ethoxy}-2-oxoethylpropionate, (+)-(4R,4aS,6R) - 4, 4a-dimethyl-6-(1-propen-2-yl)-4,4a,5,6,7,8-hexahydro-2(3H)-naphthalenone, amylcinnamaldehyde, hexylcinnamaldehyde, hexylsalicylate, (1E)- 1-( 2,6,6-trimethyl-1-cyclohexen-1-yl) -1,6-heptadiene 3-one, (9Z)-9-cycloheptadecen-1-one.

According to a particular embodiment, the hydrophobic material is free of active ingredients (such as perfume). According to this particular embodiment, it comprises, consists preferably of hydrophobic solvents, preferably selected from the group consisting of isopropyl myristate, triglycerides (e.g. Neobee® MCT oil, vegetable oils), D-limonene, silicone oil, mineral oil and mixtures thereof with optionally hydrophilic ones Solvents preferably selected from the group consisting of 1,4-butanediol, benzyl alcohol, triethyl citrate, triacetin, benzyl acetate, ethyl acetate, propylene glycol (1,2-propanediol), 1,3-propanediol, dipropylene glycol, glycerol B. glycol ethers and mixtures thereof.

The term “biocide” refers to a chemical capable of killing, reducing or preventing the growth and/or accumulation of living organisms (e.g. microorganisms). Biocides are widely used in medicine, agriculture, forestry and industry, where they prevent, for example, contamination of water, agricultural products including seeds and pipelines. A biocide can be a pesticide, including a fungicide, herbicide, insecticide, algicide, molluscicide, acaricide, and rodenticide; and/or an antimicrobial agent such as a germicidal, antibiotic, antibacterial, antiviral, antifungal, antiprotozoal and/or antiparasitic agent.

As used herein, a "pest control agent" means a substance that serves to repel or attract, reduce, inhibit, or enhance the growth, development, or activity of pests. Pests refer to any living organism, whether animal, plant or fungus, that is invasive or irritating to plants or animals, Pests include insects, especially arthropods, mites, spiders, fungi, weeds, bacteria and other microorganisms.

According to a particular embodiment, the hydrophobic material is free of active ingredients (such as perfume). According to this particular embodiment, it comprises, consists preferably of hydrophobic solvents, preferably selected from the group consisting of isopropyl myristate, triglycerides (e.g. Neobee® MCT oil, vegetable oils), D-limonene, silicone oil, mineral oil and mixtures thereof with optionally hydrophilic ones Solvents preferably selected from the group consisting of 1,4-butanediol, benzyl alcohol, triethyl citrate, triacetin, benzyl acetate, ethyl acetate, propylene glycol (1,2-propanediol), 1,3-propanediol, dipropylene glycol, glycerol B. glycol ethers and mixtures thereof.

By "flavor oil" is meant herein a flavor ingredient or mixture of flavor ingredients, solvents or adjuvants commonly used to prepare a flavor formulation, i. H. a specific mixture of ingredients intended to be added to an edible composition. or chewable product to impart, improve or modify its organoleptic properties, in particular its aroma and/or taste. The flavoring components are well known to a person skilled in the art and their nature does not justify a detailed description here, which would in any case not be exhaustive, since the flavoring specialist can choose them based on his general knowledge and according to the intended use and the organoleptic effect to be obtained. Many of these flavoring substances are listed in reference texts such as the book by S. Arctander, Perfume and Flavor Chemicals, 1969, Montclair, N.J., USA, or more recent versions thereof, or in other works of a similar nature, such as the Manual of Fenaroli of Flavor Ingredients, 1975, CRC Press or Synthetic Food Adjuncts, 1947 by M.B. Jacobs, van Nostrand Co., Inc. Solvents and adjuvants currently used to prepare a flavor formulation are also well known in the art.

In a particular embodiment, the aroma is a mint aroma. In a more specific embodiment, mint is selected from the group consisting of peppermint and spearmint.

In another embodiment, the aroma is a coolant or mixtures thereof.

In another embodiment, the flavor is a menthol flavor.

Flavors derived from or based on fruit in which citric acid is the predominant natural acid include, but are not limited to, citrus (e.g., lemon, lime), lime, strawberry, orange, and pineapple. In one embodiment, the flavored food is lemon, lime, or orange juice extracted directly from the fruit. Other flavoring embodiments include the juice or liquid extracted from oranges, lemons, grapefruits, limes, citrons, clementines, mandarins, tangerines, and other citrus fruits, or a variation or hybrid thereof. In a particular embodiment, the flavoring comprises a liquid extracted from orange, lemon, grapefruit, lime, citron, clementine, tangerine, tangerine, any other citrus fruit or variation or hybrid thereof, pomegranate, kiwi, watermelon, apple, banana, blueberry or is distilled , melon, ginger, peppers, cucumber, passion fruit, mango, pear, tomato and strawberry.

In a particular embodiment the aroma comprises a composition comprising limonene, in a particular embodiment the composition is a citrus also comprising limonene.

In another particular embodiment, the flavor comprises a flavor selected from the group consisting of strawberry, orange, lemon, tropical, berry and pineapple.

The term "flavor" includes not only flavors that impart or modify the odor of food, but also ingredients that impart or modify taste. The latter do not necessarily have a taste or smell of their own, but are capable of modifying the taste of other ingredients, e.g. B. Ingredients that increase saltiness, those that increase sweetness, ingredients that increase flavor, bitterness, etc.

Alternatively, suitable sweetening components can be incorporated into the particles herein. In a particular embodiment, a sweetener component is selected from the group consisting of sugar (for example but not limited to sucrose), a stevia component (such as but not limited to stevioside or rebaudioside A), sodium cyclamate, aspartame B. sucralose, sodium saccharin and acesulfame K or mixtures thereof.

According to one embodiment, the hydrophobic material represents between 10 and 95% by weight based on the total weight of the oily phase. According to another embodiment, the hydrophobic material represents between 10 and 80% by weight based on the total weight of the oily phase. According to another embodiment, the hydrophobic material represents between 10 and 60% by weight based on the total weight of the oily phase. According to another embodiment, the hydrophobic material represents between 15 and 45% by weight based on the total weight of the oily phase.

According to one embodiment, the core of the microcapsule is liquid.

According to another embodiment, the core of the microcapsule is solid.

According to one embodiment, the mineral layer forms a spiny surface covered with small lamellar peaks, grooves or protrusions perpendicular to the terminal charged functional surface (typically between 100 and 600 nm long and with an aspect ratio greater than 1).

Indeed, the surface of the mineral layer may have a rough, spiky, pointed, rough, orthorhombic, studded, cubic, dendritic, or textured appearance with rough, heterogeneous crystalline features on the surface.

According to a particular embodiment, the mineral layer has an arithmetic mean roughness (R_A) greater than 15 nm, preferably greater than 50 nm and/or average peak-to-valley height (R_z) greater than 50 nm, preferably greater than 100 nm.

The instrument used in the present invention for evaluating surface properties and determining surface roughness parameters R_Aand R.S_zis a Keyence VK-X series confocal laser scanning microscope profilometer with a violet band laser. A Bruker Dimension ICON Atomic Force Microscope (AFM) was also used to evaluate the surface properties.

Roughness parameters are well known to those skilled in the art and can be defined as follows.

The arithmetic mean roughness (R_A) is the mean deviation of the surface height from the mean height of the roughness profile. The mean peak-to-valley height (R_z) is the average maximum localized roughness or average height difference from peak to valley per unit length analyzed.

Good separation can be achieved with the microcapsules according to the invention, in particular due to this specific spiky or rough surface which can adhere to target substrates.

Bark type/formation

According to one embodiment, the coating is a polymer coating.

According to another embodiment, the cover does not include a polymeric material. According to one embodiment, the shell comprises hydrogel. According to another embodiment, the shell is hydrogel (i.e., coacervate).

In one embodiment, the polymer shell is formed by interfacial polymerization or by precipitation in the presence of a charged emulsifier.

One of the essential features of the present invention is that the shell, preferably a polymeric shell, has an end-loaded functional surface covered by a mineral layer. Various ways can be used to impart this charged surface to the polymer shell. The terminally charged functional surface can be anionic or cationic.

According to a particular embodiment, the terminal charged functional surface is a terminal anionic functional surface.

Emulsifier = anionic emulsifier

According to a first embodiment, the loaded emulsifier is an anionic emulsifier and forms an anionic surface after the end of the interfacial polymerization.

The anionic emulsifiers can be amphiphilic materials, colloidal stabilizers, or biopolymers.

In one embodiment, the anionic emulsifier is selected from the group consisting of polyvinyl alcohol, polyvinylpyrrolidone, acacia, casein, sodium caseinate, soy protein, rice protein, whey protein, egg white albumin, gelatin, bovine whey, hydrolyzed soy. Protein, hydrolyzed sericin, pseudocollagen, silk protein, sericin powder, sugar beet pectin, gelatin and mixtures thereof.

In one embodiment, gum arabic is preferred.

According to one embodiment, whey proteins and/or sodium caseinate are preferred.

According to a particular embodiment, the anionic surface (formed by the anionic emulsifier) ​​is the terminal anionic functional surface directly covered by the mineral layer.

However, in order to improve the connection of the mineral layer to the anionic surface, a polyelectrolyte structure made of an oppositely charged polyelectrolyte layer can be provided between the anionic surface and the mineral layer.

Thus, according to a particular embodiment, the microcapsule comprises a polyelectrolyte structure on the anionic surface, the polyelectrolyte structure comprising at least one layer of cationic polyelectrolyte and at least one layer of anionic polyelectrolyte, the top layer being a layer of anionic polyelectrolyte. final layer. functional surface of the shell. According to this embodiment, the first layer of the polyelectrolyte framework is a layer of cationic polyelectrolyte arranged on the anionic surface (formed by the anionic emulsifier), and the last layer of the polyelectrolyte framework is a layer of anionic polyelectrolyte to form the functional surface. Termination anion in which the mineral layer is covered.

The number of layers of the polyelectrolyte skeleton is not particularly limited.

According to a particular embodiment, the polyelectrolyte framework consists of two pairs of oppositely charged polyelectrolyte layers.

This means that according to this modality, the microcapsule of the invention comprises the following successive layers in the polymer shell, a first layer of cationic polyelectrolyte on the anionic surface (formed by the anionic emulsifier), a first layer of negative polyelectrolyte, a second cationic polyelectrolyte-polyelectrolyte layer , a second negative polyelectrolyte layer (forming the final anionic functional surface) and a mineral layer.

Emulsifier = cationic emulsifier According to a second embodiment

- the charged emulsifier is a cationic emulsifier forming a cationic surface, and

- the microcapsule comprises at least one layer of anionic polyelectrolyte on the cationic surface.

According to one embodiment, the cationic emulsifier is obtained by mixing a weakly anionic emulsifier (like PVOH) with a highly charged polyquat or cationic polymer (like Salcare® SC-60 from BASF).

As non-limiting examples of cationic emulsifiers, one can cite, for example, cationically functionalized polyvinyl alcohol (e.g. cationic Kuraray C-506) or chitosan at a suitable pH (typically at a slightly acidic pH (pH around 6.5)).

According to a particular embodiment, the anionic surface (formed by the anionic polyelectrolyte layer) is the terminal anionic functional surface directly covered by the mineral layer.

According to another embodiment, at least one layer of cationic polyelectrolyte and at least a second layer of anionic polyelectrolyte are sequentially deposited on the layer of anionic polyelectrolyte.

However, this embodiment is not limited to a single pair of opposing polyelectrolyte layers, but includes 2, 3, 4 or even more pairs of opposing polyelectrolyte layers, provided that the last polyelectrolyte layer is a polyelectrolyte layer. anionic polyelectrolyte to form the anionic termination layer. functional interface. According to one embodiment, the cationic polyelectrolyte layer is selected from the group consisting of poly(allylamine hydrochloride), poly-L-lysine and chitosan.

According to another embodiment, the anionic polyelectrolyte layer is selected from the group consisting of poly(sodium 4-styrene sulfonate) (PSS), polyacrylic acid, polyethyleneimine, humic acid, carrageenan, acacia and mixtures thereof.

According to a particular embodiment, the anionic polyelectrolyte layer is PSS.

The nature of the polymeric shell of the microcapsules of the invention can vary. As non-limiting examples, the polymer shell may comprise a material selected from the group consisting of polyurea, polyurethane, polyamide, polyhydroxyalkanoates, polyacrylate, polyesters, polyaminoesters, polyepoxides, polysiloxane, polycarbonate, polysulfonamide, urea-formaldehyde, melamine-formaldehyde Resin, melamine-formaldehyde consists of resin crosslinked with polyisocyanate or aromatic polyols, melamine-urea resin, melamine-glyoxal resin, gelatin/gum arabic shell wall and mixtures thereof.

According to one embodiment, the microcapsule comprises a composite shell comprising a first material and a second material, where the first material and the second material are different, the first material is a coacervate, the second material is a polymeric material. In a particular embodiment, the weight ratio of the first material to the second material is between 50:50 and 99.9:0.1. In a particular embodiment, the coacervate comprises a first polyelectrolyte, preferably selected from proteins (such as gelatin), polypeptides or polysaccharides (such as chitosan), particularly preferably gelatin, and a second polyelectrolyte, preferably alginate salts, cellulose derivatives, guar gum. pectin salts. carrageenan, polyacrylic and methacrylic acid or xanthan gum, or even plant gums such as acacia (gum acacia), more preferably acacia. The first coacervate material can be chemically hardened using a suitable crosslinking agent such as glutaraldehyde, glyoxal, formaldehyde, tannic acid or genipin, or it can be enzymatically hardened using an enzyme such as transglutaminase. The second polymeric material can be selected from the group consisting of polyurea, polyurethane, polyamide, polyester, polyacrylate, polysiloxane, polycarbonate, polysulfonamide, polymers of urea and formaldehyde, melamine and formaldehyde, melamine and urea, or melamine and glyoxal, and mixtures thereof. itself, preferably polyurea and/or polyurethane. The second material is preferably present in an amount of less than 3%, preferably less than 1% by weight based on the total weight of the microcapsule suspension.

As non-limiting examples, the shell of the microcapsules can be based on aminoplast, polyurea or polyurethane. The shell of the microcapsules can also be hybrid, i. H. organic-inorganic, such as a hybrid shell composed of at least two types of inorganic particles bonded together, or even a shell resulting from the hydrolysis and condensation reaction of a polyalkoxysilane macrocomposite monomer.

According to one aspect, the shell of the microcapsules comprises an aminoplast copolymer such as melamine-formaldehyde or urea-formaldehyde or melamine-formaldehyde or glyoxal-melamine.

According to a further aspect, the shell of the microcapsules consists, for example, of polyurea, but is not limited to isocyanate-based monomers and amine-containing crosslinkers, such as guanidine carbonate and/or guanazole. Certain polyurea microcapsules comprise a polyurea wall which is the product of the polymerization reaction between at least one polyisocyanate having at least two isocyanate functions and at least one reagent selected from the group consisting of an amine (e.g. a water-soluble guanidine salt, water and guanidine) ; a colloidal stabilizer or emulsifier; and an encapsulated perfume. However, the use of an amine can be dispensed with. In a particular aspect, the colloidal stabilizer comprises an aqueous solution of between 0.1% and 0.4% polyvinyl alcohol, between 0.6% and 1% of a cationic copolymer of vinylpyrrolidone and a quaternized vinylimidazole (all percentages are defined by weight, based on the total weight of the colloidal stabilizer). In another aspect, the emulsifier is an anionic or amphiphilic biopolymer, which in one aspect may be selected from the group consisting of gum arabic, soy protein, gelatin, sodium caseinate, and mixtures thereof.

According to another embodiment, the wall material of the microcapsule can comprise any suitable resin and in particular comprise melamine, glyoxal, polyurea, polyurethane, polyamide, polyester and so on. 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, dimethylol methylated urea, urea resorcinol and mixtures thereof. Materials suitable for manufacture may be obtained from one or more of the following companies: Solutia Inc. (St. Louis, Missouri, USA), Cytec Industries (West Paterson, NJ, USA), Sigma-Aldrich (St. Louis, Missouri, UNITED STATES).

According to another embodiment, the microcapsules are monoshell aminoplast core-shell microcapsules obtainable by a process comprising the steps of:

1) blending a fragrance oil with at least one polyisocyanate having at least two isocyanate functional groups to form an oil phase; 2) dispersing or dissolving an aminoplast resin and optionally a stabilizer in water to form an aqueous phase;

3) preparing an oil-in-water dispersion in which the average droplet size is between 1 and 100 microns by mixing the oil phase and the aqueous phase;

4) performing a curing step to form the wall of the microcapsule; It is

5) optionally drying the final dispersion to obtain the dry core-shell microcapsule. According to one embodiment, the microcapsules are formaldehyde-free capsules. A typical process for preparing an aminoplast-formaldehyde-free suspension of microcapsules comprises the steps

1) Preparation of an oligomeric composition comprising the reaction product or obtained by the co-reaction: a. a polyamine component in the form of melamine or a mixture of melamine and at least one C1-C4 compound comprising two NH2 functions; B. an aldehyde component in the form of a mixture of glyoxal, a C4-62,2-dialkoxyethanal and optionally a glyoxalate, the mixture having a glyoxal/C4-62,2-dialkoxyethanal molar ratio of between 1/1 and 10/1; and C. a protonic acid catalyst;

2) preparing an oil-in-water dispersion in which the droplet size is between 1 and 600 microns and comprising: a. an oil; B. an aqueous medium: c. at least one oligomeric composition as obtained in step 1; D. at least one crosslinking agent selected from: i. aromatic or aliphatic C4-C12 diisocyanates or triisocyanates and their biurets, triurets, trimers, trimethylolpropane adducts and mixtures thereof; and/or ii. a di- or tri-oxirane compound of the formula:

A-(Oxiran-2-ylmethyl)_NorteWo_Norte2 or 3 and 1 represents a C2 group optionally comprising 2 to 6 nitrogen and/or oxygen atoms; My. optionally a C₁-C₄compounds comprising two N¾ functional groups;

3) heating the dispersion; It is

4) dispersion cooling. In another particular embodiment, the microcapsule comprises an oil-based core comprising a hydrophobic material, preferably perfume, optionally an inner shell of polymerized polyfunctional monomer; a biopolymer shell comprising a protein, wherein at least one protein is crosslinked. According to a particular embodiment, the protein is selected from the group consisting of milk proteins, caseinate salts such as sodium caseinate or calcium caseinate, casein, whey protein, hydrolyzed proteins, gelatin, gluten, pea, soy protein, silk protein and mixtures. preferably sodium caseinate, more preferably sodium caseinate

According to a particular embodiment, the protein comprises sodium caseinate and a globular protein, preferably selected from the group consisting of whey protein, beta-lactoglobulin, ovalbumin, bovine serum albumin, vegetable proteins and mixtures thereof.

The protein is preferably a mixture of sodium caseinate and whey protein.

According to a particular embodiment, the biopolymer shell comprises a crosslinked protein selected from the group consisting of sodium caseinate and/or whey protein.

According to a particular embodiment, the suspension of microcapsules comprises at least one microcapsule consisting of: an oily core containing the hydrophobic material, preferably perfume; an inner shell of a polymerized polyfunctional monomer; preferably a polyisocyanate having at least two isocyanate functional groups, a biopolymer shell comprising a protein, wherein at least one protein is crosslinked; preferably wherein the protein comprises a mixture comprising sodium caseinate and a globular protein, preferably whey protein. optionally at least one outer mineral layer.

According to one embodiment, the sodium caseinate and/or the whey protein(s) is/are a crosslinked protein(s).

The weight ratio between sodium caseinate and whey protein is preferably between 0.01 and 100, preferably between 0.1 and 10, most preferably between 0.2 and 5.

In another particular embodiment, the microcapsule is a polyamide microcapsule with a polyamide core comprising: an oil-based core comprising a hydrophobic material, preferably perfume, and a polyamide shell comprising or obtainable from: • an acilate chloride,

• a first amino compound, and

• a second amino compound.

According to a particular embodiment, the microcapsules comprise: an oil-based core comprising a hydrophobic material, preferably perfume, and a polyamide shell comprising or obtainable from:

• an acid chloride, preferably in an amount between 5 and 98%, preferably between 20 and 98%, more preferably between 30 and 85% w/w.

• a first amino compound, preferably in an amount between 1% and 50% w/w, preferably between 7 and 40% w/w;

• a second amino compound, preferably in an amount between 1% and 50% w/w, preferably between 2 and 25% w/w.

• a stabilizer, preferably a biopolymer, preferably in an amount between 0 and 90%, preferably between 0.1 and 75%, more preferably between 1 and 70%.

According to a particular embodiment, the microcapsules comprise: an oil-based core comprising a hydrophobic material, preferably perfume, and a polyamide shell comprising or obtainable from:

• an acyl chloride,

• a first amino compound which is an amino acid, preferably selected from the group consisting of L-lysine, L-arginine, L-histidine, L-tryptophan and/or mixtures thereof.

• a second amino compound selected from the group consisting of ethylenediamine, diethylenetriamine, cystamine and/or a mixture thereof, and

• a biopolymer selected from the group consisting of casein, sodium caseinate, bovine serum albumin, whey protein and/or a mixture thereof.

The acyl chloride as defined above may have the following formula (I) wherein n is an integer ranging from 1 to 8, preferably from 1 to 6, more preferably from 1 to 4, and wherein X is a valent (n+1) C1 is to C45 hydrocarbyl group optionally comprising at least one group selected from (i) to (xi), wherein R is a hydrogen atom or an alkyl group such as a methyl or ethyl group, preferably a hydrogen atom.

By hydrocarbon group is meant that the group consists of hydrogen and carbon atoms and may be in the form of an aliphatic hydrocarbon, i. H. a linear or branched saturated hydrocarbon (e.g. an alkyl group), a straight or branched unsaturated hydrocarbon (e.g. an alkenyl or alkynyl group), a saturated cyclic hydrocarbon (e.g. cycloalkyl) or an unsaturated cyclic hydrocarbon (e.g. cycloalkenyl or cycloalkynyl), or it may be in the form of an aromatic hydrocarbon, ie. h aryl group, or it can also be present, for example, as a mixture of such groups. a specific group may include a linear alkyl, a branched alkenyl (e.g. having one or more carbon-carbon double bonds), a (poly)cycloalkyl and an aryl moiety unless a specific limitation to a single type is mentioned. Likewise, in all embodiments of the invention, whenever a group is mentioned as having more than one type of topology (e.g. linear, cyclic or branched) and/or as being saturated or unsaturated (e.g. alkyl, aromatic or alkenyl). also means a group which may include units having any of the topologies mentioned or which are saturated or unsaturated as explained above. Likewise, in all embodiments of the invention when a group is mentioned in the form of a type of saturation or unsaturation (e.g. alkyl), it is to be understood that this group can be in any type of topology (e.g. linear, cyclic or branched) or more have residues with different topologies.

It will be understood that by the term "...a hydrocarbyl group optionally comprising..." is meant that the hydrocarbyl group optionally comprises heteroatoms to form ether, thioether, amine, nitrile or carboxylic acid groups and derivatives ( including e.g. esters, acids, amides) These groups can replace a hydrogen atom of the hydrocarbyl group and thus bond laterally to the hydrocarbyl, or replace a carbon atom (if chemically possible) of the hydrocarbyl group and thus insert into the hydrocarbyl chain or ring.

According to a particular embodiment, the acyl chloride is selected from the group consisting of benzene-1,3,5-tricarbonyltrichloride (trimesoyl trichloride), benzene-1,2,4-tricarbonyltrichloride, benzene-1,2,4,5-tetracarbonyltetrachloride, 1, 3-cyclohexane, 5-tricarbonyl trichloride, isomaltaliole dichloride, diglycolyl dichloride, terephthaloyl chloride, fumaryl dichloride, adipoyl chloride, succinic dichloride, 1-propane, 2,3-tricarbonyl trichloride, 1,2-cyclohexane, 4,5-tetracarbonyltetrachloride, 2,2'-disulfanediyldisuccinyl dichloride, 2 -(2-Chloro-2-oxo-ethyl)sulfanylbutanedioyl dichloride, (4-Chloro-4-oxobutanoyl)-L-glutamoyl, (S)- 4-((1,5-Dichloro-1,5-dioxopentane-2- yl)amino)-4-oxobutanoic acid, 2,2-bis[(4-chloro-4-oxobutanoyl)oxymethyl]butyl 4-chloro-4-oxobutanoate, [2-[2,2-bis[( 4-Chloro-4-oxobutanoyl)oxymethyl]butoxymethyl]-2-[(4-chloro-4-oxobutanoyl)oxymethyl]butyl 4-chloro-4-oxobutanoate], 2,2-bis[ (2-chlorocarbonylbenzoyl)oxymethylorocarbonyl]butyl 2-chlorobenzoate, [2-[2,2-bis[(2-chlorocarbonylbenzoyl)oxyme ethyl]butoxymethyl]-2-[(2-chlorocarbonylbenzoyl)oxymethyl]butyl] 2-chlorocarbonylbenzoate, 4-(2,4,5-trichlorocarbonylbenzoyl)oxybutyl 2,4,5-trichlorocarbonyl-benzoate, propane-1,2, 3-triyltris(4-chloro-4-oxobutanoate), propane-1,2-diylbis(4-chloro-4-oxobutanoate) and mixtures thereof.

According to a further aspect, the shell of the microcapsules is based on polyurea or polyurethane. Examples of processes for preparing a suspension of microcapsules based on polyurea and polyurethane are given, for example, in international patent application publication no. WO2007/004166, European patent application publication no. EP 2300146 and European patent application publication no. EP25799. Normally a process for preparing a suspension of polyurea or polyurethane based microcapsules comprises 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 an aqueous phase; c) addition of the oil phase to the aqueous phase to form an oil-in-water dispersion, the mean droplet size being between 1 and 500 μm, preferably between 5 and 50 μm; and d) applying conditions sufficient to induce interfacial polymerization and form microcapsules in suspension form.

In a particular embodiment, the covering material is a biodegradable material.

In a particular embodiment, the shell has a biodegradability of at least 60%, preferably at least 65%, 70%, 75%, 80%, 85%, 90%, 95% or 98% in 60 days. according to OECD301F .

In a particular embodiment, the core-shell microcapsule has a biodegradability of at least 40%, preferably at least 60%, preferably at least 65%, 70%, 75%, 80%, 85%, 90%, 95%. % or 98%. % in 60 days according to OECD301F.

Therefore, it is understood that the core-shell microcapsule including all components such as the core, the shell and optionally the shell can have a biodegradability of at least 40%, preferably at least 60%, preferably at least 65%, 70%. , 75%. , 80%, 85%, 90%, 95% or 98% in 60 days according to OECD301F.

In a particular embodiment, the oil core, preferably perfume oil, has a biodegradability of at least 40%, preferably at least 60%, preferably at least 65%, 70%, 75%, 80%, 85%, 90%. , 95% or 98% in 60 days according to OECD301F.

OECD301F is an Organization for Economic Co-operation and Development standard test method for biodegradability.

A typical procedure for removing the shell to measure biodegradability is given by Gasparini et al. described in Molecules 2020, 25718.

Cap Mineral

According to the invention, the microcapsule has a mineral layer on the terminally charged functional surface. According to one embodiment, the functional termination surface is anionic and can be obtained using an anionic emulsifier optionally having a polyelectrolyte structure as defined above or using a cationic emulsifier having at least one layer of anionic polyelectrolyte.

According to the invention, the mineral layer comprises at least one salt selected from the group consisting of barium salt, strontium salt, magnesium salt and mixtures thereof.

According to one embodiment, the mineral layer comprises a salt selected from the group consisting of barium sulfate, strontium sulfate, strontium carbonate, strontium phosphate, and mixtures thereof.

According to one embodiment, the mineral layer does not comprise any material selected from the group consisting of iron oxides, iron oxyhydroxide, titanium oxides, zinc oxides, calcium carbonates, calcium phosphates and mixtures thereof.

According to one embodiment, the mineral layer does not include silicon oxides.

Another object of the invention is a powder of core-shell microcapsules obtained by drying the suspension of core-shell microcapsules as defined above.

Another subject of the invention is a solid particle comprising: a carrier material, preferably a polymeric carrier material selected from the group consisting of polyvinyl acetate, polyvinyl alcohol, dextrins, natural or modified starch, plant gums, pectins, xanthans, alginates, carrageenan, cellulose derivatives and mixtures thereof, and Microcapsules as defined above retained in the carrier material and optionally free perfume retained in the carrier material.

The solid particle as defined above and the microcapsule powder can be used interchangeably in the present invention.

optional components

If the microcapsules are in the form of a suspension, the microcapsule suspension may contain auxiliary ingredients selected from the group consisting of thickeners/rheology modifiers, antimicrobial agents, opacifying agents, mica particles, salt, pH stabilizers/buffering ingredients, preferably in a specific amount between 0 and 15% by weight. % based on the total weight of the suspension.

According to another embodiment, the suspension of microcapsules of the invention comprises additional free perfume (i.e. not encapsulated), preferably in an amount between 5 and 50% by weight based on the total weight of the suspension. Process for preparing a mineralized core-shell microcapsule suspension

Another object of the present invention is a method for preparing a suspension of mineralized core and shell microcapsules as defined above, comprising the steps:

(i) producing a core-shell microcapsule suspension comprising microcapsules having a terminally charged functional surface;

(ii) adsorption of at least one mineral precursor onto the loaded surface;

(iii) Applying suitable conditions to induce crystal growth of the mineral on the loaded surface to form a mineral layer, wherein the mineral precursor is adsorbed on the loaded surface by using the core-shell microcapsule suspension obtained in step (i) for at least incubating for a period of time a mineral precursor solution, wherein the mineral precursor solution is selected from the group consisting of barium brine, strontium brine, magnesium brine, phosphate-based brine, phosphate-based brine, sulfate, carbonate-based brine, and mixtures thereof.

According to a particular embodiment, the mineral precursor is selected from the group consisting of barium nitrate, barium chloride, barium bromide, barium iodide, barium chlorate, barium hydroxide, strontium nitrate, strontium chloride, strontium iodide, strontium chlorate, sodium sulfate, potassium sulfate, sodium carbonate, potassium carbonate, ammonium carbonate, sodium phosphate, potassium phosphate, ammonium phosphate, and mixtures of that.

The sodium phosphate used in the present invention may be monobasic (NaH₂P0₄), dibasic (Na2HP04) or tribasic (NasPC).

The potassium phosphate used in the present invention may be monobasic (KH₂AFTER₄), dibásico (K₂HP0₄) or tribasic (K₃AFTER₄).

The ammonium phosphate used in the present invention may be monobasic ((NH₄)H₂P0₄), dibasic ((MH^HPC ) or tribasic ((NH4)3P04_).

According to one embodiment, the mineral precursor is selected from the group consisting of barium nitrate, barium chloride, barium bromide, barium iodide, barium chlorate, barium hydroxide, strontium nitrate, strontium chloride, barium iodide, strontium chlorate, sodium sulfate, potassium sulfate, sodium carbonate, potassium carbonate, ammonium carbonate, sodium phosphate (monobasic) (NaH₂P0₄), sodium phosphate (dibasic) (Na₂HP0₄), sodium phosphate (tribasic): Na₃Computer>₄, Potassium phosphate (monobasic): KH₂AFTER₄, Potassium phosphate (dibasic) (K₂HPO₄), potassium phosphate (tribasic) (K₃AFTER₄), Ammoniumphosphat (monobasisch) ((NtL thPC^), Ammoniumphosphat (dibasisch) ((NtL^kHPC^), Ammoniumphosphat (tribasisch) ((NPL^bPC₎and their mixtures.

According to one embodiment, step ii) consists in the adsorption of two mineral precursors onto the loaded surface.

The water soluble carbonate based salt can be selected from the group consisting of sodium, potassium and ammonium based carbonates.

Step (i) Production of a core-shell microcapsule suspension, comprising microcapsules with a terminally charged functional surface

According to one embodiment, the polymer shell is formed by interfacial polymerization in the presence of a charged emulsifier.

One of the essential features of the present invention is that the polymer shell has an end-loaded functional surface on which a mineral precursor is adsorbed in step (ii). Various ways can be used to impart this charged surface to the polymer shell.

According to a particular embodiment, the terminal charged functional surface is a terminal anionic functional surface.

Emulsifier = anionic emulsifier

According to a first embodiment, the loaded emulsifier is an anionic emulsifier and forms an anionic surface after the end of the interfacial polymerization.

The anionic emulsifiers can be amphiphilic materials, colloidal stabilizers, or biopolymers.

In one embodiment, the anionic emulsifier is selected from the group consisting of polyvinyl alcohol, polyvinylpyrrolidone, acacia, casein, sodium caseinate, soy protein, rice protein, whey protein, egg white albumin, gelatin, bovine whey, hydrolyzed soy. Protein, hydrolyzed sericin, pseudocollagen, silk protein, sericin powder, gelatin and mixtures thereof.

In one embodiment, gum arabic is preferred.

According to one embodiment, sodium caseinate and/or whey protein are preferred. According to a particular embodiment, the anionic surface (formed by the anionic emulsifier) ​​is the terminal anionic functional surface on which a mineral precursor is adsorbed in step (ii).

However, in order to improve the binding of the mineral precursor to the anionic surface, step (i) may include an additional step consisting of the addition of a polyelectrolyte framework consisting of an oppositely charged polyelectrolyte layer once the microcapsules have been formed.

Thus, according to a particular embodiment, the polyelectrolyte structure comprises at least one cationic polyelectrolyte layer and at least one anionic polyelectrolyte layer, the terminal layer being an anionic polyelectrolyte layer to form the terminal anionic functional surface of the shell.

According to this embodiment, the first layer of the polyelectrolyte framework is a layer of cationic polyelectrolyte arranged on the anionic surface (formed by the anionic emulsifier), and the last layer of the polyelectrolyte framework is a layer of anionic polyelectrolyte to form the functional surface. Terminating anion to which a mineral precursor is adsorbed in step (ii).

The number of layers of the polyelectrolyte skeleton is not particularly limited.

According to a particular embodiment, the polyelectrolyte framework consists of two pairs of oppositely charged polyelectrolyte layers.

This means that according to this modality, at the end of step (i), the microcapsule of the invention comprises the following successive layers in the polymer shell, a first layer of cationic polyelectrolyte on the anionic surface (formed by the anionic emulsifier), a first negative polyelectrolyte layer, a second cationic polyelectrolyte layer, a second negative polyelectrolyte layer (forming the terminal anionic functional surface).

Emulsifier = cationic emulsifier

According to a second embodiment, the loaded emulsifier is a cationic emulsifier which forms a cationic surface when the interfacial polymerisation is complete and in step (i) further comprises a step of applying at least one layer of anionic polyelectrolyte to the cationic surface. form the core-shell microcapsule with a terminal anionic functional surface.

According to one embodiment, the cationic emulsifier is obtained by mixing a weakly anionic emulsifier (like PVOH) with a highly charged cationic or polyquaternium polymer (like Salcare® SC-60 from BASF). As non-limiting examples of cationic emulsifiers, one can cite, for example, cationically functionalized polyvinyl alcohol (e.g. cationic Kuraray C-506) or chitosan at a suitable pH (typically at a slightly acidic pH (pH around 6.5)).

According to a particular embodiment, the anionic surface (formed by the anionic polyelectrolyte layer) is the terminal anionic functional surface on which a mineral precursor is adsorbed in step (ii).

According to another embodiment, at least one layer of cationic polyelectrolyte and at least a second layer of anionic polyelectrolyte are sequentially deposited on the layer of anionic polyelectrolyte.

However, this embodiment is not limited to a single pair of opposing polyelectrolyte layers, but includes 2, 3, 4 or even more pairs of opposing polyelectrolyte layers, provided that the last polyelectrolyte layer is a polyelectrolyte layer. anionic polyelectrolyte to form the anionic termination layer. functional interface.

According to one embodiment, the cationic polyelectrolyte layer is selected from the group consisting of poly(allylamine hydrochloride), poly-L-lysine and chitosan.

According to another embodiment, the anionic polyelectrolyte layer is selected from the group consisting of poly(sodium 4-styrene sulfonate) (PSS), polyacrylic acid, polyethyleneimine, humic acid, carrageenan, acacia and mixtures thereof.

According to a particular embodiment, the anionic polyelectrolyte layer is PSS.

The preparation of an aqueous suspension of core-shell microcapsules is well known to those skilled in the art and has been described above.

According to one embodiment, the microcapsules are rinsed before step (ii) to remove excess emulsifier. For example, the microcapsules can be rinsed by centrifugation and, after removing the supernatant, resuspended in water.

Step (ii) and Step (iii) - mineralization and crystal growth

Without wishing to be limited by theory, it is believed that the charged termination surface provides functional anchoring sites and a high local density of charge groups and nucleation sites on the surface of the microcapsule, resulting in enhanced adsorption of the microcapsules. Mineral precursor species followed by crystalline initiation. Growth process by the in situ addition of a precipitating species.

The mineral precursors are adsorbed onto the surface of the microcapsules by incubating the loaded capsules in at least one solution containing an oppositely charged mineral precursor, with sufficient agitation and time to completely coat the surfaces of the capsules. Excess precursor can be removed from the solution to avoid the formation of free crystalline material in the solution, and the crystal growth process is initiated by the in situ addition of a precipitant species.

One skilled in the art is able to select the appropriate conditions for the crystal growth process (e.g., precursor selection, reaction conditions, solution concentrations, incubation times, agitation speeds, temperatures, and pH conditions).

Typically: mineralization occurs at room temperature, precursor incubation occurs between 24 and 72 hours, the type of precipitation species depends on the type of precursor.

According to the invention, the mineral precursor solution is selected from the group consisting of a barium salt solution (containing barium ions as precursor), strontium salt solution (containing strontium ions as precursor), magnesium (containing magnesium ions as precursor) B. phosphate-based salt solution (comprising phosphate ions as precursor), sulfate-based salt solution (comprising sulfate ions as precursors), carbonate-based brine (comprising carbonate ions as precursors), and mixtures thereof.

The water-soluble barium-based salt can be selected from the group consisting of barium nitrate, barium chloride, barium bromide, barium iodide, barium chlorate, barium hydroxide, and mixtures thereof.

The water-soluble strontium-based salt can be selected from the group consisting of strontium nitrate, strontium chloride, strontium iodide, strontium chlorate, and mixtures thereof.

The water-soluble magnesium-based salt can be selected from the group consisting of magnesium nitrate, magnesium chloride, magnesium sulfate, magnesium iodide, magnesium bromide, magnesium chlorate, and mixtures thereof.

The water-soluble phosphate-based salt can be selected from the group consisting of sodium phosphate (monobasic) (Na^PC), sodium phosphate (dibasic) (Na^PC).₂HP0₄), Sodium phosphate (tribasic): NasPC, Potassium phosphate (monobasic): KH2PO4, Potassium phosphate (dibasic) (K2HPO4), Potassium phosphate (tribasic) (K3PO4), Ammonium phosphate (monobasic) ((NH₄)H₂P0₄), ammonium phosphate (dibasic) ((NH₄)₂HP0₄), Ammonium phosphate (tribasic) ((N¾)3Rq4₎and their mixtures.

The water soluble carbonate based salt can be selected from the group consisting of sodium, potassium and ammonium based carbonates. According to one embodiment, the mineral precursor does not include silicon oxides.

According to one embodiment, the mineral precursor solution is not a ferrous sulfate solution, a ferric chloride solution, a calcium-based saline solution, a titanium-based precursor solution, a zinc-based precursor solution, and mixtures thereof.

It will be appreciated that the charge on the mineral precursor used in step (ii) of the process is driven by the charge on the finished surface of the microcapsules.

According to a further embodiment, the microcapsules are successively introduced into at least two solutions each containing at least one precursor. Preferably the first solution comprises a water soluble barium salt comprising a barium precursor and the second solution comprises a water soluble sulfate salt comprising a sulfate precursor. The order of addition may change depending on the selection and load of the underlying completion layer.

According to a further embodiment, the microcapsules are successively introduced into at least two solutions each containing at least one precursor. Preferably the first solution comprises a water soluble strontium salt comprising a strontium precursor and the second solution comprises a water soluble phosphate salt comprising a phosphate precursor. The order of addition may change depending on the selection and load of the underlying completion layer.

According to a particular embodiment, the process for preparing the suspension of microcapsules comprises the following steps: a) dissolving at least one polyisocyanate having at least two isocyanate groups in an oil containing a hydrophobic material to form an oily phase; b) preparing an aqueous solution of a charged emulsifier to form an aqueous phase, wherein the charged emulsifier is an anionic emulsifier or a cationic emulsifier; c) adding the oil phase to the aqueous phase to form an oil-in-water dispersion; d) application of appropriate conditions to induce interfacial polymerization to form suspension-form core/shell microcapsules in which:

- the shell has an anionic surface when the emulsifier used in step b) is an anionic emulsifier; any

- the shell has a cationic surface when the emulsifier used in step b) is a cationic emulsifier; e) applying at least one layer of anionic polyelectrolyte to the cationic surface when the emulsifier is a cationic emulsifier to form an anionic surface; f) optional dilution or removal of excess emulsifier; g) adsorption of a mineral precursor onto the anionic surface as defined above; h) application of suitable conditions to induce crystal growth of the mineral on the anionic surface; and i) optionally drying the suspension.

According to this embodiment the method comprises preparing an oil phase by dissolving a polyisocyanate having at least two isocyanate groups in an oil comprising a hydrophobic material as defined above.

According to a preferred embodiment of the invention, an amount of between 10 and 60%, more preferably between 20 and 50% of oil is used in the process according to the invention, these percentages being defined by weight relative to the total weight. of the oil. Obtained suspension of microcapsules.

Suitable polyisocyanates used according to the invention include aromatic polyisocyanates, aliphatic polyisocyanates and mixtures thereof. The polyisocyanate comprises at least 2, preferably at least 3, but may comprise up to 6 or even as little as 4 isocyanate functional groups. According to a particular embodiment, a triisocyanate (3 isocyanate functions) is used.

According to one embodiment, the polyisocyanate is an aromatic polyisocyanate.

The term "aromatic polyisocyanate" is intended to encompass any polyisocyanate that includes an aromatic moiety. Preferably it comprises a phenyl, tolyl, xylyl, naphthyl or diphenyl moiety, more preferably a tolyl or xylyl moiety. Preferred aromatic polyisocyanates are biurets, polyisocyanurates and trimethylolpropane adducts of diisocyanates, most preferably comprising one of the specific aromatic moieties mentioned above. More preferably, the aromatic polyisocyanate is a toluene diisocyanate polyisocyanurate (commercially available from Bayer under the tradename Desmodur^®RC), a trimethylolpropane adduct of toluene diisocyanate (commercially available from Bayer under the tradename Desmodur^®L75), a trimethylolpropane adduct of xylylene diisocyanate (commercially available from Mitsui Chemicals under the tradename Takenate^®D-110N). In a more preferred embodiment, the aromatic polyisocyanate is a trimethylolpropane adduct of xylylene diisocyanate.

According to another embodiment, the polyisocyanate is an aliphatic polyisocyanate. The term "aliphatic polyisocyanate" is defined as a polyisocyanate that does not contain an aromatic moiety. Preferred aliphatic polyisocyanates are hexamethylene diisocyanate trimer, isophorone diisocyanate trimer, trimethylolpropane hexamethylene diisocyanate adduct (available from Mitsui Chemicals) or hexamethylene diisocyanate biuret (commercially available from Bayer under the tradename Desmodur^®N 100), among which a hexamethylene diisocyanate biuret is even more preferred.

According to another embodiment, the at least one polyisocyanate is in the form of a mixture of at least one aliphatic polyisocyanate and at least one aromatic polyisocyanate, both of which contain at least two or three isocyanate functions, such as a mixture of a hexamethylene biuret diisocyanate, a trimethylolpropane adduct of xylylene diisocyanate, a mixture of a hexamethylene diisocyanate biuret with a toluene diisocyanate polyisocyanurate and a mixture of a hexamethylene diisocyanate biuret with a trimethylolpropane diisocyanate adduct. More preferably it is a mixture of a hexamethylene diisocyanate biuret with a trimethylolpropane xylylene diisocyanate adduct. When used as a mixture, the molar ratio between aliphatic polyisocyanate and aromatic polyisocyanate is preferably in the range of 80:20 to 10:90.

The at least one polyisocyanate used in the process of the present invention is present in amounts comprising from 1% to 15%, preferably from 2% to 8% and more preferably from 2% to 6% by weight of the oil phase.

The at least one polyisocyanate is dissolved in an oil which, in a particular embodiment, contains a fragrance or flavoring. The oil may contain another oil-soluble beneficial agent encapsulated along with the fragrance and flavor to provide an additional benefit in addition to the flavor or flavor. As non-limiting examples are ingredients such as cosmetic, skin care, anti-odor, bactericide, fungicide, pharmaceutical or agrochemical ingredients, a diagnostic agent and/or a repellent or insect attractant, and mixtures thereof.

According to one embodiment, the method of the present invention comprises using an anionic or amphiphilic biopolymer in the preparation of the aqueous phase. The materials defined above include, in particular, proteins and polysaccharides. The biopolymer is preferably included in an amount ranging from 0.1% to 5.0% by weight of the microcapsule suspension, preferably from 0.5% to 2% by weight of the microcapsule suspension.

The above ranges also apply when the process involves the use of a charged emulsifier.

According to a first embodiment, the charged emulsifier used in step b) is an anionic emulsifier and forms an anionic surface when step d) is completed.

In one embodiment, the anionic emulsifier is selected from the group consisting of polyvinyl alcohol, polyvinylpyrilidone, acacia, casein, sodium caseinate, soy protein, rice protein, whey protein, protein albumin, gelatin, bovine whey, hydrolyzed soy. Protein, hydrolyzed sericin, pseudocollagen, silk protein, sericin powder, sugar beet pectin, gelatin and mixtures thereof.

According to a particular embodiment, the anionic emulsifier is gum arabic.

According to a second embodiment, a cationic emulsifier is used in step b), which forms a cationic surface after step d).

As non-limiting examples of cationic emulsifiers, mention may be made, for example, of cationically modified polyvinyl alcohol (eg cationically Kuraray's C-506) or chitosan.

According to this embodiment, the method also comprises a step consisting in depositing a layer of anionic polyelectrolyte to provide a negatively charged surface necessary to induce crystal growth of the mineral.

To improve the adsorption of mineral precursors onto the anionic functional cap, the cap can be modified by adsorption on a multilayer polyelectrolyte framework.

Thus, according to one embodiment, the method comprises an additional step after step d) or after step e), consisting in depositing at least one layer of cationic polyelectrolyte and at least one layer of anionic polyelectrolyte, the layer consisting of an anionic polyelectrolyte layer in order to to form the terminal anionic functional surface.

According to this embodiment, the cationic polyelectrolyte layer is located on the anionic surface and the anionic polyelectrolyte layer is the last layer forming the terminal anionic functional surface on which the mineral precursor is adsorbed.

Oppositely charged polyelectrolytes can be deposited sequentially in microcapsules using layer-by-layer polyelectrolyte deposition to provide a multilayer polyelectrolyte framework for mineral precursor adsorption.

According to the invention, the number of layers of the polyelectrolyte structure is not particularly limited.

According to a particular embodiment, the polyelectrolyte framework consists of two pairs of oppositely charged polyelectrolyte layers.

This means that the method according to this modality comprises, after step d) or step e): depositing a layer of cationic polyelectrolyte Cl over the anionic layer; Application of an anionic polyelectrolyte layer A1 to the cationic polyelectrolyte layer

C1, depositing a layer of cationic polyelectrolyte C2 over the layer of anionic polyelectrolyte A1; Depositing a layer of anionic polyelectrolyte A2 over the layer of cationic polyelectrolyte C2, thereby forming the anionically terminated functional surface onto which the mineral precursor is adsorbed.

According to one embodiment, the cationic polyelectrolyte layer is selected from the group consisting of poly(allylamine hydrochloride), poly-L-lysine and chitosan.

According to another embodiment, the anionic polyelectrolyte layer is selected from the group consisting of poly(sodium 4-styrene sulfonate) (PSS), polyacrylic acid, polyethyleneimine, humic acid, carrageenan, acacia and mixtures thereof.

According to a particular embodiment, the anionic polyelectrolyte layer is PSS.

According to a particular embodiment, after step h), the method comprises an additional step consisting in the hydrolysis of the mineral layer. This can be done, for example, by adding caustic soda.

Another subject of the invention is a process for preparing a microcapsule powder, comprising the steps defined above and an additional step iii) which consists in subjecting the suspension obtained in step iii) to spray drying in order to provide the microcapsules as such. that is, in powder form. It is understood that any standard method of carrying out the drying known to those skilled in the art can also be used. In particular, the suspension can be spray-dried, preferably in the presence of a polymeric carrier material such as polyvinyl acetate, polyvinyl alcohol, dextrins, natural or modified starch, plant gums, pectins, xanthans, alginates, carrageenan or cellulose derivatives, in order to provide microcapsules. in powder form.

According to a particular embodiment, the carrier material contains free perfume oil, which can be the same as or different from the perfume in the core of the microcapsules.

However, other drying methods can also be mentioned, such as extrusion, coating, spray granulation, fluidized bed or even room temperature drying using materials (carriers, desiccants) that meet certain criteria, as described in WO2017/134179.

Microcapsule Suspension/Microcapsule Octopus

A suspension of microcapsules or microcapsules obtainable by the process defined above are also subject of the present invention.

Another object of the invention is a microcapsule powder obtained by drying the microcapsule suspension defined above. COMPOSITION OF PERFUME AND CONSUMABLE PRODUCTS

The microcapsules of the present invention can be used in combination with active ingredients. The subject matter of the invention is therefore a composition comprising:

(i) microcapsules or suspensions of microcapsules as defined above;

(ii) an active, preferably selected from the group consisting of a cosmetic ingredient, skin care ingredient, perfume ingredient, flavoring ingredient, anti-odor ingredient, bactericidal ingredient, fungicidal ingredient, pharmaceutical or agrochemical ingredient, disinfectant, insect repellent or attractant, and mixtures thereof.

perfumed consumer goods

The capsules of the invention show good stability in a challenging environment.

Another object of the present invention is a perfume composition comprising:

(i) microcapsules or suspensions of microcapsules as defined above, wherein the oil comprises a perfume;

(ii) at least one ingredient selected from the group consisting of a perfumery carrier, a perfumery co-ingredient, and mixtures thereof;

(iii) optionally at least one perfumery adjuvant.

As liquid perfumery vehicles, one can cite, as non-limiting examples, an emulsifying system, that is to say a solvent-surfactant system, or a solvent commonly used in perfumery. A detailed description of the nature and nature of the solvents commonly used in perfumery cannot be exhaustive. However, solvents such as dipropylene glycol, diethyl phthalate, isopropyl myristate, benzyl benzoate, 2-(2-ethoxyethoxy)-1-ethanol or ethyl citrate, which are most commonly used, can be cited as non-limiting examples. For compositions comprising a perfumery carrier and a perfumery additive, suitable perfumery carriers other than those indicated above may also include ethanol, water/ethanol mixtures, limonene or other terpenes, isoparaffins such as those known under the trademark Isopar° (origin: Exxon Chemical). , be. or glycol ethers and glycol esters known by the trade mark Dowanol⁰(Source: Dow Chemical Company). By "perfumery co-ingredient" is meant herein a compound used in a perfumed preparation or composition to impart a hedonic effect and which is not a microcapsule as defined above. In other words, such a co-ingredient to be considered perfumed must be recognized by a person skilled in the art as at least capable of imparting or modifying the odor of a composition in a positive or pleasant way, and not in the same way as an odor .

The type and nature of the perfumed co-ingredients contained in the perfumed composition do not justify a more detailed description here, which would in any case not be conclusive, since the person skilled in the art can select them according to his general knowledge and depending on the use or application expected and the desired organoleptic effect. Broadly speaking, these fragrance co-ingredients belong to chemical classes as diverse as alcohols, lactones, aldehydes, ketones, esters, ethers, acetates, nitriles, terpenoids, nitrogen- or sulfur-containing heterocyclic compounds, and essential oils and so-called co-ingredients of Perfume can be of natural or synthetic origin. Many of these co-ingredients are already listed in reference texts such as S. Arctander's Perfume and Flavor Chemicals, 1969, Montclair, New Jersey, USA, or later versions, or in other works of a similar nature. , as well as the extensive patent literature in the field of perfumery . It is also understood that the co-ingredients can also be compounds known to release various types of fragrant compounds in a controlled manner. The co-ingredients can be selected from the group consisting of 4-(dodecylthio)-4-(2,6,6-trimethyl-2-cyclohexen-1-yl)-2-butanone, 4-(dodecylthio)-4- (2,6,6-Trimethyl-1-cyclohexen-1-yl)-2-butanone, trans-3-(dodecylthio)-1-(2,6,6-trimethyl-3-cyclohexen-1-yl)- 1-butanone, 2-(dodecylthio)octan-4-one, 2-phenylethyloxo(phenyl)acetate, 3,7-dimethylocta-2,6-dien-1-yloxo(phenyl)acetate, (Z)-3 - ene -1-yl-hex-oxo(phenyl)acetate, 3,7-dimethyl-2,6-octadien-1-yl hexadecanoate, bis(3,7-dimethylocta-2,6-dien-1-yl), (2-((2-Methylundec-1-en-1-yl)oxy)ethyl)benzene, 1-Methoxy-4-(3-methyl-4-phenethoxybut-3-en-1-yl)benzene, (3 - Methyl-4-phenethoxybut-3-en-1-yl)benzene, 1-(((Z)-Hex-3-en-1-yl)oxy)-2-methylundec-1-ene, (2-( (2-methylundec-1-en-1-yl)oxy)ethoxy)benzene, 2-methyl-1-(octan-3-yloxy)undec-1-ene, 1-methoxy-4-(1-phenethoxyprop-1 ). -en-2-yl)benzene, 1-methyl-4-(1-phenethoxyprop-1-en-2-yl)benzene, 2-(1-phenethoxyprop-1-en-2-yl)naphthalene, (2- phenethoxyvinyl)benzene, 2-(1-((3,7-dimethyloct-6-en-1-yl)oxy)prop-1-en-2-yl)naphthalene, (2-(( 2-pentylcyclopentylidene)methoxy) ethyl)benzene, 4-allyl-2-methoxy-1-((2-methoxy-2-phenylvinyl)oxy)benzene, (2-((2-heptylcyclopentylidene)methoxy)ethyl)benzene, 1-isopropyl-4-methyl -2-((2-pentylcyclopentylidene)methoxy)benzene, 2-Methoxy-1-((2-pentylcyclopentylidene)methoxy)-4-propylbenzene, 3-Methoxy-4-((2-methoxy-2-phenylvinyl)oxy) benzaldehyde, 4-((2-(hexyloxy)-2-phenylvinyl)oxy)-3-methoxybenzaldehyde or a mixture thereof.

By “perfume adjuvant” we mean here an ingredient that can confer an additional benefit, e.g. a specific color, light fastness, chemical stability, etc. A detailed description of the nature and type of adjuvants commonly used in perfume bases cannot be exhaustive. but it should be mentioned that these components are well known to a person skilled in the art.

Preferably, the perfume composition according to the invention comprises between 0.01% and 30% by weight of microcapsules as defined above.

The microcapsules according to the invention can be used advantageously in many areas of application and can be used in consumer products. The microcapsules can be used in liquid form for liquid consumer products and in powder form for powdered consumer products.

According to a particular embodiment, the consumable as defined above is liquid and comprises: a) from 2 to 65% by weight, based on the total weight of the consumable, of at least one surfactant; b) water or a water-miscible hydrophilic organic solvent; and c) a suspension of microcapsules or microcapsules as defined above, d) optionally unencapsulated perfume.

According to a particular embodiment, the consumable as defined above is in powder form and comprises: a) from 2% to 65% by weight, based on the total weight of the consumable, of at least one surfactant; b) a microcapsule powder as defined above. c) optionally other perfume powders than the microcapsules defined above.

In the case of microcapsules containing a core based on perfume oil, the products according to the invention can be used in particular in perfumed consumer products such as fine or "functional" perfumery products. Functional perfumery specifically includes personal care products, including hair care, personal cleansing, skin care, hygiene care, as well as home care products, including personal care, clothing, skin care, surface and air care. Accordingly, a further object of the present invention is a perfumed consumer product comprising as perfumed ingredient the microcapsules defined above or a perfumed composition as defined above. The perfume element of the consumer product can be a combination of perfume microcapsules as defined above and free or unencapsulated perfume, as well as other types of perfume microcapsules than those described herein.

In particular a liquid consumer product comprising: a) 2 to 65% by weight, based on the total weight of the consumer product, of at least one surfactant; b) water or a water-miscible hydrophilic organic solvent; and c) a perfumed composition as defined above is a further object of the invention.

Also comprising a powdered consumer product

(a) from 2% to 65% by weight, based on the total weight of the consumable product, of at least one surfactant; It is

(b) a perfume composition as defined above forming part of the invention.

Thus, the microcapsules of the invention may be incorporated into a scented consumer product as such or as part of a scented composition of the invention.

For the sake of clarity, it should be noted that "scented consumer product" means a consumer product that is expected to exert a fragrant effect on the surface to which it is applied (e.g. skin, hair, textiles) in addition to various benefits , paper). or household surfaces) or in the air (ambient, deodorant, etc.). In other words, a perfumed consumer product according to the invention is a manufactured product comprising a functional formulation, also called "base", together with beneficial agents including an effective amount of microcapsules according to the invention.

The nature and nature of the other components of the perfumed consumer product do not justify a detailed description here, which would in any case not be exhaustive, since the person skilled in the art can select them according to his general knowledge and according to the type and effect desired by this product. The base formulations of consumer products into which the microcapsules of the invention can be incorporated can be found in the abundant literature relating to these products. These formulations do not justify a detailed description here, which in any case would not be exhaustive. A person skilled in the art of formulating such consumer products is well able to select the appropriate components given his general knowledge and the available literature.

Non-limiting examples of suitable perfumed consumer products could be perfume, such as fine perfume, cologne, aftershave, body gel; a textile care product such as a liquid or solid detergent, single-dose tablets (single-compartment or multi-compartment tablets), fabric softener, drying cloth, fabric freshener, ironing water or bleach; a personal care product, such as a hair care product (e.g., a shampoo, conditioner, coloring preparation, or hairspray), a cosmetic preparation (e.g., an ephemeral cream, body lotion, or deodorant or antiperspirant), or a skin care product (e.g., B. perfumed). soap, bath or bath mousse, liquid soap, oil or gel, bath salts or hygiene products); an air care product such as a "ready to use" air freshener or air freshener powder; or household cleaners such as all-purpose cleaners, liquid or powder dishwashing detergents or tablets, bathroom cleaners or multi-surface cleaners such as sprays and wipes for treating/refreshing textiles or hard surfaces (floors, tiles, stone floors, etc.); a hygiene product such as sanitary napkins, diapers, toilet paper.

A further object of the invention is a consumer product comprising: an active personal care base and - microcapsules or a suspension of microcapsules as defined above or the perfumed composition as defined above, the consumer product being presented in the form of a composition for personal use Attention.

The personal care active bases into which the microcapsules of the invention may be incorporated may be found in the abundant literature relating to these products. These formulations do not justify a detailed description here, which in any case would not be exhaustive. A person skilled in the art of formulating such consumer products is well able to select the appropriate components given his general knowledge and the available literature.

The personal care composition is preferably selected from the group consisting of a hair care product (e.g. a shampoo, hair conditioner, coloring preparation or hair spray), a cosmetic preparation (for decongestant cream, body lotion or deodorant or antiperspirant) or skin care product (e.g scented soap, bubble bath/shower, liquid soap, oil or gel, bath salts or personal hygiene product);

A further object of the invention is a consumer product comprising: - an active base for household or textile care and microcapsules or a suspension of microcapsules as defined above or the perfumed composition as defined above, wherein the consumer product is in the form of a household care objects or a Composition for treating fabrics.

Active bases for household or fabric care into which the microcapsules of the invention can be incorporated can be found in the abundant literature on these products. These formulations do not justify a detailed description here, which in any case would not be exhaustive. A person skilled in the art of formulating such consumer products is well able to select the appropriate components given his general knowledge and the available literature. Preferably the consumable product comprises from 0.1% to 15%, more preferably between 0.2% and 5% by weight of the microcapsules of the present invention, these weight percentages being defined relative to the total weight of the consumable product. Obviously, the above concentrations can be adjusted according to the desired beneficial effect of each product. An object of the invention is a consumer product, preferably a household or fabric care product, comprising the microcapsules or suspension of microcapsules as defined above, wherein the consumer product has a pH of less than 7.

An object of the invention is a consumer product, preferably a household or fabric care product, comprising the microcapsules or the suspension of microcapsules as defined above, wherein the consumer product has a pH equal to or greater than 7.

For the liquid consumer product mentioned below, by "active base" is meant that the active base comprises active materials (generally including surfactants) and water.

For the solid consumer products mentioned below, by "active base" is meant that the active base includes active materials (typically comprising surfactants) and adjuvants (such as bleaches, buffering agents, builders, separating or suspending polymers) soil; granulated enzymatic particles, corrosion inhibitors, defoamers, antifoams, colorants, fillers and mixtures thereof).

softener

An object of the invention is a consumer product in the form of a fabric softening composition comprising: an active fabric softening base; preferably comprising at least one active ingredient selected from the group consisting of dialkyl quaternary ammonium salts, dialkyl quaternary ammonium ester salts (esterquats), Hamburger Esterquat (HEQ), TEAQ (quaternary triethanolamine), silicones and mixtures thereof, preferably using the base active ingredient an amount between 85 and 99.95% by weight, based on the total weight of the composition, of a suspension of microcapsules or microcapsules as defined above, preferably in an amount of between 0.05 and 15% by weight, more preferably between 0.1 and 5% by weight % by weight based on the total weight of the composition, optionally free perfume oil.

liquid detergent

An object of the invention is a consumer product in the form of a liquid detergent composition comprising: a liquid detergent-active base; preferably comprising at least one active material selected from the group consisting of anionic surfactant such as alkyl benzene sulfonate (ABS), secondary alkyl sulfonate (SAS), primary alcohol sulfate (PAS), lauryl ether sulfate (LES), methyl ester sulfonate (MES) and nonionic surfactants such as alkylamines, alkanolamides, Fatty alcohol polyethylene glycol ether, fatty alcohol ethoxylate (FAE), copolymers of ethylene oxide (EO) and propylene oxide (PO), amine oxides, alkyl polyglycosides, alkyl polyglucosamides, the active ingredient using the base preferably in an amount between 85 and 99.95% by weight, based on the total weight of the composition, a suspension of microcapsules or microcapsules as defined above, preferably in an amount of between 0.05 and 15% by weight, more preferably between 0.1 and 5% by weight, based on the total weight of the composition, optionally free perfume oil .

solid detergent

An object of the invention is a consumer product in the form of a solid detergent composition comprising: a solid detergent-active base; preferably comprising at least one active material selected from the group consisting of anionic surfactant such as alkyl benzene sulfonate (ABS), secondary alkyl sulfonate (SAS), primary alcohol sulfate (PAS), lauryl ether sulfate (LES), methyl ester sulfonate (MES) and nonionic surfactants such as alkylamines, alkanolamides, Fatty alcohol polyethylene glycol ether, fatty alcohol ethoxylate (FAE), copolymers of ethylene oxide (EO) and propylene oxide (PO), amine oxides, alkyl polyglycosides, alkyl polyglucosamides, the active ingredient Use of the base preferably in an amount between 85 and 99.95% by weight, based on the total weight of the Composition, a microcapsule powder or a microcapsule suspension as defined above, preferably in an amount between 0.05 to 15% by weight, more preferably 0.1 to 5% by weight, based on the total weight of the composition, optionally free perfume oil.

Shampoo/Duschgel

An object of the invention is a consumer product in the form of a shampoo or shower gel composition comprising: an active shampoo or shower gel base; preferably comprising at least one active material selected from the group consisting of sodium alkyl ether sulphate, ammonium alkyl ether sulphates, alkyl amphoacetate, cocamidopropyl betaine, cocamide MEA, alkyl glycosides and amino acid based surfactants and mixtures thereof, preferably wherein the active base is used in an amount between 85 and 99.95 wt. -%, based on the total weight of the composition, of a suspension of microcapsules or microcapsules as defined above, preferably in an amount of between 0.05 and 15% by weight, more preferably between 0.05 and 15% and 5% by weight %, based on the total weight of the composition, optionally free perfume oil.

Rinse out the conditioner

One aspect of the invention is a consumer product in the form of a rinse conditioning composition comprising: a rinse conditioning base active; which preferably contains at least one active substance selected from the group consisting of cetyltrimonium chloride, stearyltrimonium chloride, benzalkonium chloride, behentrimonium chloride and mixtures thereof, the active base preferably being used in an amount between 85 and 99.95% by weight, based on the total weight of the Composition, a suspension of microcapsules or microcapsules as defined above, preferably in an amount between 0.05 and 15% by weight, more preferably between 0.1 and 5% by weight, based on the total weight of the composition, optionally free of fragrance oil.

solid fragrance booster

The invention provides a consumer product in the form of a solid flavor-enhancing composition comprising: a solid carrier, preferably selected from the group consisting of urea, sodium chloride, sodium sulfate, sodium acetate, zeolite, carbonate, sodium bicarbonate, clay, talc, calcium carbonate, magnesium sulfate, gypsum, Calcium sulphate, magnesium oxide, zinc oxide, titanium dioxide, calcium chloride, potassium chloride, magnesium chloride, zinc chloride, saccharides such as sucrose, mono-, di- and polysaccharides and derivatives such as starch, cellulose, methyl cellulose, ethyl cellulose, propyl cellulose, sugar polyols/alcohols such as sorbitol, maltitol, Xylitol, erythritol and isomalt, PEG, PVP, citric acid or any water-soluble solid acid, fatty alcohol or acid and mixtures thereof, a suspension of microcapsules or microcapsules as defined above in powder form, preferably in an amount between 0.05 to 15% by weight -%, more preferably between 0.1 and 5% by weight to the total weight of the composition, optionally free perfume oil.

liquid aroma enhancer

An object of the invention is a consumer product in the form of a flavor-enhancing liquid composition comprising: an aqueous phase, a surfactant system consisting essentially of one or more nonionic surfactants, wherein the surfactant system has an average HLB value between 10 and 14, preferably selected from the group consisting of ethoxylated aliphatic alcohols, POE/PPG (polyoxyethylene and polyoxypropylene) ethers, mono- and polyglyceryl esters, sucrose ester compounds, polyoxyethylene hydroxy esters, alkyl polyglucosides, amine oxides, and combinations two alike; a binder selected from the group consisting of alcohol, salts and esters of carboxylic acids, salts and esters of hydroxycarboxylic acids, fatty acids, salts of fatty acids, glycerol fatty acids, surfactant having an HLB value of less than 10, and mixtures thereof, and a suspension microcapsule or microcapsules as defined above, in the form of a suspension, preferably in an amount of between 0.05 and 15% by weight, more preferably between 0.1 and 5% by weight, based on the total weight of the composition, optionally oil-free perfume

dyed hair

The subject of the invention is a consumable product in the form of an oxidizing composition for hair coloring, comprising: an oxidizing phase comprising an oxidizing agent and an alkaline phase comprising an alkaline agent, a dye precursor and a coupling compound; wherein the dye precursor and the coupling compound in the presence of the oxidizing agent, preferably in an amount between 85 and 99.95% by weight, based on the total weight of the composition, microcapsules or suspension of microcapsules as defined above, form an oxidizing hair dye, preferably in an amount of between 0.05 and 15% by weight, more preferably between 0.1 and 5% by weight, based on the total weight of the composition, of optionally free perfume oil

fragrance composition

According to a particular embodiment, the consumer product is presented in the form of a perfume composition comprising:

0.1 to 30%, preferably 0.1 to 20% microcapsules or suspension of microcapsules as defined above,

0 to 40%, preferably 3-40% perfume, and

20-90% by weight, preferably 40-90% by weight ethanol based on the total weight of the perfume composition.

flavored consumer goods

The end products are in particular food, pet food or animal feed.

Since the particles according to the invention have a hydrophobic coating, they are particularly advantageous for rehydratable dry foods such as instant drinks (PSD, chocolate, coffee), confectionery such as chewing gum, instant noodles or bouillon cubes. The particles according to the invention are particularly advantageous for food products with a relatively high water activity, such as ready meals, meat analogs, microwaveable foods, pasta boxes.

The particles of the invention can be used in vegetarian meat analogs or meat substitutes, veggie burgers, sausages, patties, chicken nugget imitations..., meat products (e.g. processed meat, poultry, veal, pork, ham, fresh sausage or raw meat). become ). Meat preparations, seasoned or marinated fresh meat or cured meat products, reformed meat) or meat products using a combination of animal and vegetable proteins in varying proportions, often co-extruded or blended between textured vegetable proteins and animal proteins.

Meat within the meaning of the present invention includes red meat such as beef, pork, mutton, lamb, venison and poultry such as chicken, turkey, goose and duck. Preferably, the food of the present invention is selected beef, poultry and pork.

However, the particles according to the invention can also be of particular interest in the following product examples:

• Baked goods (e.g. bread, dry biscuits, cakes, other baked goods), • Non-alcoholic beverages (e.g. carbonated soft drinks, mineral water, sports/energy drinks, juices, vegetable juices, prepared vegetable juices),

• Alcoholic beverages (e.g. beer and malt beverages, spirits),

• Instant beverages (e.g. instant vegetable beverages, instant beverages, instant coffee and tea),

• Grain products (eg, breakfast cereals, pre-cooked prepared rice products, rice flour products, corn and sorghum products, raw or pre-cooked macaroni and pasta products),

• Dairy products (e.g. cream cheese, soft cheese, hard cheese, milk drinks, whey, butter, products with partially or fully hydrolyzed milk proteins, fermented milk products, condensed milk and the like),

• Dairy products (e.g. fruit or flavored yoghurt, ice cream, fruit sundae)

• Confectionery (e.g. chewing gum, hard and soft candies)

• Chocolate and composite toppings

• Products based on fat and oil or their emulsions (e.g. mayonnaise, spreads, margarines, fats, tartar sauce, seasonings, spice preparations),

• Seasoned, marinated or processed fish products (e.g. fish sausage, surimi),

• Eggs or egg products (dried egg, egg white, egg yolk, cream),

• Desserts (e.g. jams and puddings)

• Products made from soy protein or other soy fractions (e.g. soy milk and derivatives, preparations with soy lecithin, fermented products such as tofu or tempeh or products made from them, soy sauces),

• Vegetable preparations (e.g. ketchup, sauces, processed and reconstituted vegetables, dehydrated vegetables, frozen vegetables, pre-cooked vegetables, pickled vegetables, vegetable concentrates or paste, cooked vegetables, potato preparations),

• Vegetarian meat substitutes, veggie burgers

• Spices or spice preparations (e.g. mustard preparations, horseradish preparations), spice mixtures and in particular seasonings, the z. B. find use in the snack area.

• Snack items (e.g. baked or fried potato chips or potato dough products, bread dough products, corn, rice or peanut extrudates),

• Meat products (e.g. processed meat, poultry, beef, pork, ham, fresh sausage or raw meat preparations, seasoned or marinated fresh or cured meat, health meat), • Ready meals (e.g. instant noodles, rice, noodles, pizza, tortillas, wraps) and soups and broths (e.g. broths, salt cubes, dry soups, instant soups, pre-cooked soups, test-tube soups), sauces (instant sauces, dry sauces, ready-made sauces, meat juices, sweet sauces) . The particles according to the invention are preferably used in products selected from the group consisting of baked goods, instant drinks, grain-based products, dairy products, dairy products, fat- and oil-based products or their emulsions, desserts, vegetable preparations. , vegetarian meat substitutes, spices and condiments, snacks, meat products, ready meals, soups and broths and sauces.

According to a particular embodiment, the flavored product is selected from the group consisting of a food or the like based on meat and/or fish, a broth, a salt cube, a powder mixture, a product based on beef or pork, a shellfish , surimi, instant noodles, rice, soups, sauces, ready meals, frozen or chilled pizza, noodles, fried or potato flakes, macaroni, potato/tortilla chips, microwave popcorn, nuts, pretzels, rice cake, rice crackers, fermented milk analog beverage, acidified milk analog beverage, unfermented milk-like drink, cheese or cheese substitute, yoghurt or yoghurt substitute, dietary supplements, food bars, cereals, ice cream, ice cream without milk, confectionery, gum, candies and powdered drinks.

According to one embodiment, the food, animal feed or animal feed contains between 0.01 and 10% by weight, preferably between 0.1 and 5% by weight, of the particles according to the invention.

Typically, the food, pet food or food product further comprises proteins, particularly vegetable proteins or animal proteins, and mixtures thereof.

Advantageously, the vegetable proteins are preferably selected from soy protein, corn, pea, canola, sunflower, sorghum, rice, amaranth, potato, tapioca, arrowroot, chickpea, lupine, canola, wheat, oats, rye, barley and mixtures thereof.

The particles according to the invention are particularly suitable for extruded and/or baked foods, pet foods or food products that contain animal and/or vegetable proteins in particular. These extruded and/or baked foods, pet foods or food products can generally be selected from meat and/or fish based foods or the like and mixtures thereof (in other words meat based foods and/or fish or the like). or fish-based foods). or meat substitutes or fish substitutes and mixtures thereof); Extruded and/or baked meat analogs or extruded and/or baked fish analogs are preferred. Non-limiting examples of extruded and/or baked foods, pet foods, or food products include snack foods or vegetable proteins that are extruded to texturize the protein from which meat analogs (e.g., hamburgers) are made. The powdered composition can be added before extrusion or after extrusion to the non-extruded vegetable protein isolate/concentrate or texturized vegetable protein from which a hamburger or nugget (etc.) is formed.

The invention will now be further described by means of examples. It should be understood that the claimed invention is not intended to be limited in any way by these examples.

EXAMPLES

example 1

Production of capsules based on biopolymers according to the invention.

Protocol 1

Microcapsules A1, B and C were prepared according to the following protocol.

1) Sodium caseinate and/or whey protein are dissolved in deionized water at room temperature.

2) Slowly add calcium chloride (aqueous solution) to the protein solution and stir at room temperature for about 15 min.

3) The emulsifying solution is combined with a perfumed oil (see Table 2) containing a polyisocyanate (Takenate® D-110N) and homogenized (10,000 rpm for 2 minutes).

4) The emulsion is then transferred to a reactor, the pH adjusted to ~6.5 with NaOH and heated to 45°C.

5) Add transglutaminase (aqueous solution) to the reactor and stir at 45°C for 3 h.

6) Adjust pH to ~5.4 with HCl and then heat to 85°C

7) The reactor is stirred at 85°C for 60 min before cooling to RT.

Table 1: Microcapsule Compositions 1) Ramsen Food and Dairy Products LLC

2) Agropur dairy cooperative

3) See Table 2

4) Trimethylolpropane xylene diisocyanate adduct, source: Mitsui Chemicals, Inc., Japan, 75% polyisocyanate/25% ethyl acetate

5) Origin of Activa TI®: Ajinomoto

Protocol 2

A2 microcapsules were made according to the following protocol.

Benzene 1,3,5-tricarbonyl chloride (1.73g) was dissolved in benzyl benzoate (5g). Sodium caseinate (2 g) was dispersed in benzyl benzoate (5 g) and the dispersion stirred at 60°C for 1 hour. Both oil phases were mixed, stirred at room temperature for 10 minutes and then added to perfumed oil A (25 g - see Table 2) at room temperature to form the oil phase. The latter was mixed with a solution of L-lysine (2.53g) in tap water (94.17g). The reaction mixture was stirred with an Ultra Turrax at 24,000 rpm for 30 seconds to prepare an emulsion. Ethylenediamine (0.12g) and diethylenetriamine (0.22g) were dissolved in tap water (5g) and this solution was added dropwise to the emulsion over a five minute period. The reaction mixture was stirred at 60°C for 4 h to give a white dispersion.

Table 2: Composition of perfume oil A

Chemical name Amount (% by weight)

Isopropylmyristat 0,3

Butyrate of (Z)-3-hexen-1-ol 0.6

Delta Damask 1.0

2,4-Dimethyl-3-cyclohexen-1-carbaldehyd 1,0

Habanolide®¹' 3.0

Hedione®²⁾5,0

Hexylzimtaldehyd 12.0

This is Super®³⁾16,0

Verdillacetate 24.0

Lilial®⁴⁾37,0

1) Firmenich brand; Pentadecenolide origin: Firmenich SA, Geneva, Switzerland 2) Trademarks of Firmenich; Methyl cis-3-oxo-2-pentyl-1-cyclopentaneacetate, origin: Firmenich SA, Geneva, Switzerland

3) Registered trademark of IFF; 7-Acetyl-1,2,3,4,5,6,7,8-octahydro-1,1,6,7-tetramethylnaphthalene

4) Registered trademark of Givaudan; 3-(4-tert-butylphenyl)-2-methylpropanal

15 g of the microcapsule suspension (obtained from protocol 1 or protocol 2) are diluted in 135 g of an alkaline buffer solution (pH 9) (for protocol 1) or an acetic acid buffer solution at pH 4 (for protocol 2) and 4.5 ml 0.3 molar barium nitrate solution are added. The mixture is stirred with an anchor stirrer at 250 rpm in a closed reactor until the barium ions have had sufficient time to interact with the anionic surface of the microcapsules.

(i) 4.5 ml of a 0.3 molar sodium sulfate solution is added slowly via a syringe pump over 60 minutes (75 µL/min) to allow nucleation of mineral material on the surface of the capsule after precipitation of barium cations with the subsequent sulfate anions initiate by stirring for another 60 min.

(ii) Equal volumes of 7.5 ml of 0.3 molar barium nitrate and 0.3 molar sodium sulphate solution are added simultaneously slowly via syringe pump over 60 min (125 µl/min each), followed by 1 hour of stirring to induce more mineral precipitation to allow.

(iii) Equal volumes of 30 mL of 0.3 molar barium nitrate and 0.3 molar sodium sulfate solution are added slowly over 120 min (250 µl/min) simultaneously, followed by 60 min stirring to allow more mineral precipitation. This process is repeated twice more in this example to create a robust mineral layer. The additions can be repeated systematically to achieve the desired mineral coating thickness and properties.

Table 3: Mineralization parameters for nucleation and growth of the barium sulfate-based mineral layer (Capsule A1 and Capsule A2)

Parameter Precursor 1 Addition Precursor 2 Addition

Reagenz Ba(N03)2 Na2S04

Meng 8.00 g 4.35 g

Concentration 0.3M 0.3M

Volume 102 ml 102 ml pH 9.0 (de 4.0) 9.0 (de 4.0)

Addition time (hours) 1 1 Temperature (°C) RT (22) RT (22) Mixing speed (rpm) 250 250

example 2

Preparation of biopolymer-based capsules according to the invention (B) Microcapsules B were prepared using Protocol 1 similar to that described in Example 1 with a composition as indicated in Table 1, except that the biomineralization of the capsules was carried out using the precursors listed in Table 4 a strontium phosphate mineral

Table 4: Mineralization parameters for nucleation and growth of the strontium phosphate-based mineral layer (capsule B)

Parameter Precursor 1 Addition Precursor 2 Addition

Reactives Sr(N0)₂Von₂HP0₄

Meng 6.48 g 2.89 g

Concentration 0.3M 0.2M

Volumen 102ml 102ml pH 9,0 9,0

Addition time (hours) 1 1 Temperature (°C) RT (22) RT (22) Mixing speed (rpm) 250 250

Example 3

Production of capsules based on biopolymers according to the invention (C) Microcapsules C were produced using a protocol 1 similar to that described in Example 1 with a composition as indicated in Table 1, except that the biomineralization of the capsules was carried out using the following precursors , listed in Table 5, is a magnesium carbonate mineral.

Table 5: Mineralization parameters for nucleation and growth of the magnesium carbonate-based mineral layer (capsule C) Parameter Precursor 1 Addition Precursor 2 Addition

MgCh in the reagent₂C0

Quantity 2.9 lg 3-24g

Concentration 0.3M 0.3M

Volumen 102ml 102ml pH 9,0 9,0

Addition time (hours) 1 1

Temperature (°C) TA (22) TA (22)

Mixing speed (RPM) 250 250

example 4

Production of control capsules based on biopolymer (X)

Control X microcapsules were prepared using a protocol 1 similar to that described in Example 1 with a composition as indicated in Table 1, except that the control capsules are unmodified (i.e. no mineralization). Example 5

Characterization of capsules and deposition results.

Capsule microscopy:

To image the microcapsules, diluted capsule suspensions were dried on carbon tape, which was adhered to aluminum pieces and then sputter-coated with gold/palladium plasma. The pieces were placed in a scanning electron microscope (JEOL 6010 PLUS LA) for analysis. Images of A1 capsules, A2 capsules, B capsules, and C capsules are shown in Figure la, Figure lb, Figure 2, and Figure 3, respectively, to illustrate the rough, robust, and stable mineralized microcapsules obtained by growing a crystalline mineral shell can be generated in structures of smooth polyurea microcapsules.

In contrast, comparative X microcapsules have a smooth, unmodified surface (Figure 4). Hair Deposition Tests:

The following procedure was used to quantify hair deposition. A 500 mg mini hair swatch was wetted with 40 mL of tap water (37-39°C) and directed onto the holder using a 140 mL syringe. Excess water was gently squeezed out once and 0.1 mL of a surfactant-template mix containing UV marker-loaded microcapsules (Uvinul A Plus) was applied with a 100 µL positive-displacement pipette. The surfactant mixture was dispensed into 10 horizontal and 10 vertical passes. The sample was then rinsed with 100 mL of tap water (37-39°C) and 50 mL was applied to each side of the sample toward the frame. Excess water was gently squeezed out and then the hair sample was clamped into a pre-weighed 20 ml scintillation vial. This process was repeated 2 more times and then the flasks containing the cut hairs were dried in a vacuum oven at 50-60°C (100 torr) for at least 5 hours. After drying, the bottles were weighed again to determine the hair mass in the bottles. Controls were also prepared by placing capsules containing 0.1 ml of the model surfactant blend into an empty vial. 4 mL of 200 proof ethanol was then added to each flask and sonicated for 60 min. After sonication, the samples were filtered through a 0.45 µm PTFE filter and analyzed by HPLC using a UV detector. To determine the percentage of microcapsule deposition from a model surfactant mixture, the amount of Uvinul extracted from hair samples was compared to the amount of Uvinul extracted from control samples. Table 6: Model surfactant blend

1. Acrylamidopropyltrimonium chloride/acrylamide copolymer; Origin BASF Deposition on hair samples was measured using this simplified surfactant mixture model, which is intended to be representative of personal cleansing formulations such as shampoo or shower gel. The results are shown in Figure 5 for Capsule A1 and in Figure 6 for Capsule B. The data presented in Figure 5 shows that the addition of a mineral layer of barium sulfate to an anionic biopolymer stabilized capsule significantly increases deposition in 1.8% hair samples for control X capsules greater than 5.8% for mineralized A1 capsules at standard formulation pH and can reach up to 12% scale percentage at pH 4. The capsules according to the invention increase deposition up to three times better than prior art capsules and benefit from being detectable from pH 4 to pH 7.

The data presented in Figure 6 shows that the addition of a strontium phosphate mineral layer to an anionic biopolymer stabilized capsule significantly increases deposition in hair samples from 2.4% for control X capsules to over 13%. 0.6% for standard level mineralized B capsules. pH of the formulation. Capsules according to the invention increase deposition up to 5.6 times better than prior art capsules with demonstrable benefits from pH 5 to pH 7.

Tissue Deposition Tests:

For the quantitative deposition of microcapsules onto fabric, a 1.0 g cotton towel sample was subjected to a miniature laundering simulation process for rapid detection. A 50 mL centrifuge tube was used as a model wash vessel, and an IKA high-speed (fixed) vortexer was used to simulate the wash action. 30 mL of tap water (room temperature) was added to the centrifuge tube and a positive displacement pipette was used to add 100 µL of laundry care base containing microcapsules loaded with a UV marker. The 1.0 g sample of decontaminated white cotton towel was placed in the centrifuge tube, which was capped and vortexed for 30 seconds to mix the contents well. To test fabric softener deposition, the liquid was poured and the towel sample was gently squeezed, gently rolling a pipette over the surface to expel excess water without squeezing the capsules, and the sample was line dried overnight. For the detergent test, samples were immersed in an additional 30mL of clean tap water and vortexed for an additional 30 seconds to simulate the rinse cycle before draining the water and pipetting the towels to remove excess detergent water and leaving on overnight air dry. . The dried samples were then immersed in 10 mL of ethanol (HPLC grade 200) and sonicated in an ultrasonic bath for 1 hour to rupture the capsules and extract the precipitated oil containing the UV marker Uvinul A+. Simultaneously, 100 µL controls of the fabric softener base containing the capsules were placed in 4 mL ethanol scintillation vials and extracted by sonication to determine the total oil content, which was loaded into the miniature laundry simulators. The UV tracer containing ethanol extracted from the oil was passed through an HPLC (Luna C8 column) with a UV-Vis detector to recalculate the extracted oil content of each sample. The oil content values ​​of the controls were compared to the oil content values ​​found in the fabric samples (taking dilutions into account) to determine the percentage of total oil deposited on the fabric. The results of the quantitative evaluation of the plasticizer deposit are shown in Figure 7. The detergent results are shown in Figure 8.

The data illustrated in Figure 7 shows that the addition of a barium sulfate mineral layer to an anionic biopolymer stabilized capsule significantly increases the deposition of fabric softener base, from 61% for control X capsules to 82% for mineralized Al capsules, which is 31 % is equivalent to. Increase in deposited oil.

The data illustrated in Figure 8 shows that the addition of a barium sulfate mineral layer to an anionic biopolymer stabilized capsule significantly increases tissue deposition of a detergent base from 56% for Control X capsules to 77% for mineralized Al capsules. representing a 37% increase in deposited oil.

Example 6

Stability in a low pH surfactant composition

Figure 9 represents scanning electron micrographs of mineralized microcapsules according to the invention (Al capsules) incubated for one month in the fabric softening composition according to Table 1.

Example 7

fabric softener composition

The microcapsules of the present invention are dispersed in a fabric softening composition to provide a 0.116% concentration of encapsulated fragrance oil.

Table 7: Fabric softener composition

example 8

liquid detergent composition

The microcapsules of the present invention are dispersed in a liquid detergent base to provide a 0.22% concentration of encapsulated fragrance oil.

Table 8: Liquid detergent composition

1) Hostapur® SAS 60; Which: Clariant

2) Edenor® K 12-18; Origin: Cognis

3) Genapol® LA 070; Which: Clariant

4) Aculyn® 88; Origin: Dow Chemical

example 9

Unit dose formulation

A sufficient quantity of the exemplified microcapsules is weighed and mixed into a unit dose formulation to add the equivalent of 0.2% perfume.

The unit dose formulation may be contained in a film of PVOH (polyvinyl alcohol).

Table 9: Composition of the unit dose example 10

Rinse conditioner

The microcapsules of the present invention are dispersed in a rinse conditioning base to provide a 0.5% concentration of encapsulated fragrance oil.

Table 10: Composition of the rinse conditioner 1) Genamin KDM P, Clariant

2) Tylose H10 Y G4, Shin Etsu

3) Laneta O, BASF

4) Arlacel 165-FP-MBAL-PA-(RB), Rind

5) Incroquat Behenyl TMS-50-MBAF-PA-(MH) HA4112, Croda. 6) Brücke SP S20 MBAF-PA(RB), Croda

7) Xiameter DC-Emulsion MEM-0949, Dow Corning 8) Alpha Aesar

Example 11

shampoo composition

The microcapsules of the present invention are weighed and mixed into a shampoo composition to add the equivalent of 0.2% perfume.

Table 11: Shampoo composition

1) Ucare JR-400 Polymer, Noveon

2) Schweizerhall 3) Glydant, Lonza

4) Texapon NSO IS, Cognis

5) Tego Betaine F50, Evonik

6) amphoteric surfactant GB 2009, Zschimmer & Schwarz

7) Monomuls 90 L-12, Grunau

8) Monosodium nipagin, NIPA

Example 12

Antiperspirant Emulsion Roll-on Composition The microcapsules of the present invention are weighed and blended into the antiperspirant emulsion roll-on composition to add the equivalent of 0.2% perfume.

Table 12: Composition of the antiperspirant roll-on emulsion

1) FRY 72; Origin: HERE 2) BRIJ 721; Source: HERE

3) ARLAMOL-E; Origin : UNIQEMA-CRODA

4) LOCRONL; Origin: CLARIAN

Parts A and B are separately heated to 75°C; Part A is added to Part B with stirring and homogenized for 10 minutes. Then the mixture is cooled with stirring; and slowly add part C when the mixture reaches 45°C and part D when the mixture reaches 35°C while stirring. Then the mixture is cooled to room temperature. Example 13

Deodorant spray composition

The microcapsules of the present invention are weighed and blended into an antiperspirant roll-on emulsion composition to add the equivalent of 0.2% perfume.

Table 13: Composition of the deodorant spray

1) Irgasan^®PS300; Trademark and origin: BASF All ingredients according to the order in Table 11 are mixed and dissolved. The aerosol cans are then filled, compressed and the propellant gas added (aerosol fill: 40% active ingredient solution, 60% propane/butane, 2.5 bar).

Example 14 Shower gel composition

The microcapsules of the present invention are weighed and blended into the following composition to add the equivalent of 0.2% perfume. Table 14: Composition of shower gel 6) EDETA B POWDER; Trademark and provenance: BASF

7) CARBOPOL AQUA SF-1 POLYMER; Brand and origin: NOVEON

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

9) TEGO BETAIN F 50; Brand and origin: GOLDSCHMIDT 10) KATHON CG; Trademark and provenance: ROHM & HASS

Example 15

Toothpaste Formulation A sufficient amount of M microcapsule suspension (prepared according to Protocol 1 described in Example 1 except that a menthol flavor is encapsulated) is weighed into the following composition to add the equivalent of 0.2% flavor.

Table 15: Toothpaste formulation 1) Tixosil 73; Brand and origin:

2) Thixosil 43; Brand and origin: Example 16

Formulation of a toothpaste based on dicalcium phosphate

A sufficient amount of M-microcapsule suspension (prepared according to Protocol 1 described in Example 1 except that a menthol flavor is encapsulated) is weighed out and mixed into the following composition to add the equivalent of 0.2% flavor.

Table 16: Toothpaste formulation 1) Aerosil®200; Brand and origin:

Example 17

Alcohol Free Mouthwash Formulation A sufficient amount of M microcapsule suspension (prepared according to Protocol 1 described in Example 1 except that a menthol flavor is encapsulated) is weighed into the following composition to add the equivalent of 0.2% flavor.

Table 17: Mouthwash formulation

Example 18

mouthwash formulation

A sufficient amount of M-microcapsule suspension (prepared according to Protocol 1 described in Example 1 except that a menthol flavor is encapsulated) is weighed out and mixed into the following composition to add the equivalent of 0.2% flavor. Table 18: Mouthwash formulation