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WO2025153393A1 - Microcapsules et procédé de préparation de microcapsules - Google Patents

Microcapsules et procédé de préparation de microcapsules

Info

Publication number
WO2025153393A1
WO2025153393A1 PCT/EP2025/050463 EP2025050463W WO2025153393A1 WO 2025153393 A1 WO2025153393 A1 WO 2025153393A1 EP 2025050463 W EP2025050463 W EP 2025050463W WO 2025153393 A1 WO2025153393 A1 WO 2025153393A1
Authority
WO
WIPO (PCT)
Prior art keywords
nucleophile
microcapsules
derivatives
origin
shell
Prior art date
Legal status (The legal status is an assumption and is not a legal conclusion. Google has not performed a legal analysis and makes no representation as to the accuracy of the status listed.)
Pending
Application number
PCT/EP2025/050463
Other languages
English (en)
Inventor
Laura ETCHENAUSIA
Damien Berthier
Yongtao WU
Jia-jun SHEN
Lahoussine Ouali
Jessica AUGUGLIARO
Shi-Wen Gao
Current Assignee (The listed assignees may be inaccurate. Google has not performed a legal analysis and makes no representation or warranty as to the accuracy of the list.)
Firmenich SA
Original Assignee
Firmenich SA
Priority date (The priority date is an assumption and is not a legal conclusion. Google has not performed a legal analysis and makes no representation as to the accuracy of the date listed.)
Filing date
Publication date
Application filed by Firmenich SA filed Critical Firmenich SA
Publication of WO2025153393A1 publication Critical patent/WO2025153393A1/fr
Pending legal-status Critical Current
Anticipated expiration legal-status Critical

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Classifications

    • B—PERFORMING OPERATIONS; TRANSPORTING
    • B01—PHYSICAL OR CHEMICAL PROCESSES OR APPARATUS IN GENERAL
    • B01J—CHEMICAL OR PHYSICAL PROCESSES, e.g. CATALYSIS OR COLLOID CHEMISTRY; THEIR RELEVANT APPARATUS
    • B01J13/00—Colloid chemistry, e.g. the production of colloidal materials or their solutions, not otherwise provided for; Making microcapsules or microballoons
    • B01J13/02—Making microcapsules or microballoons
    • B01J13/06—Making microcapsules or microballoons by phase separation
    • B01J13/14—Polymerisation; cross-linking
    • B01J13/16—Interfacial polymerisation
    • A—HUMAN NECESSITIES
    • A01—AGRICULTURE; FORESTRY; ANIMAL HUSBANDRY; HUNTING; TRAPPING; FISHING
    • A01N—PRESERVATION OF BODIES OF HUMANS OR ANIMALS OR PLANTS OR PARTS THEREOF; BIOCIDES, e.g. AS DISINFECTANTS, AS PESTICIDES OR AS HERBICIDES; PEST REPELLANTS OR ATTRACTANTS; PLANT GROWTH REGULATORS
    • A01N25/00—Biocides, pest repellants or attractants, or plant growth regulators, characterised by their forms, or by their non-active ingredients or by their methods of application, e.g. seed treatment or sequential application; Substances for reducing the noxious effect of the active ingredients to organisms other than pests
    • A01N25/26—Biocides, pest repellants or attractants, or plant growth regulators, characterised by their forms, or by their non-active ingredients or by their methods of application, e.g. seed treatment or sequential application; Substances for reducing the noxious effect of the active ingredients to organisms other than pests in coated particulate form
    • A01N25/28—Microcapsules or nanocapsules
    • A—HUMAN NECESSITIES
    • A61—MEDICAL OR VETERINARY SCIENCE; HYGIENE
    • A61K—PREPARATIONS FOR MEDICAL, DENTAL OR TOILETRY PURPOSES
    • A61K8/00—Cosmetics or similar toiletry preparations
    • A61K8/02—Cosmetics or similar toiletry preparations characterised by special physical form
    • A61K8/11—Encapsulated compositions
    • A—HUMAN NECESSITIES
    • A61—MEDICAL OR VETERINARY SCIENCE; HYGIENE
    • A61K—PREPARATIONS FOR MEDICAL, DENTAL OR TOILETRY PURPOSES
    • A61K8/00—Cosmetics or similar toiletry preparations
    • A61K8/18—Cosmetics or similar toiletry preparations characterised by the composition
    • A61K8/72—Cosmetics or similar toiletry preparations characterised by the composition containing organic macromolecular compounds
    • A61K8/73—Polysaccharides
    • A—HUMAN NECESSITIES
    • A61—MEDICAL OR VETERINARY SCIENCE; HYGIENE
    • A61Q—SPECIFIC USE OF COSMETICS OR SIMILAR TOILETRY PREPARATIONS
    • A61Q19/00—Preparations for care of the skin
    • C—CHEMISTRY; METALLURGY
    • C11—ANIMAL OR VEGETABLE OILS, FATS, FATTY SUBSTANCES OR WAXES; FATTY ACIDS THEREFROM; DETERGENTS; CANDLES
    • C11D—DETERGENT COMPOSITIONS; USE OF SINGLE SUBSTANCES AS DETERGENTS; SOAP OR SOAP-MAKING; RESIN SOAPS; RECOVERY OF GLYCEROL
    • C11D17/00—Detergent materials or soaps characterised by their shape or physical properties
    • C11D17/0039—Coated compositions or coated components in the compositions, (micro)capsules
    • C—CHEMISTRY; METALLURGY
    • C11—ANIMAL OR VEGETABLE OILS, FATS, FATTY SUBSTANCES OR WAXES; FATTY ACIDS THEREFROM; DETERGENTS; CANDLES
    • C11D—DETERGENT COMPOSITIONS; USE OF SINGLE SUBSTANCES AS DETERGENTS; SOAP OR SOAP-MAKING; RESIN SOAPS; RECOVERY OF GLYCEROL
    • C11D3/00—Other compounding ingredients of detergent compositions covered in group C11D1/00
    • C11D3/50—Perfumes
    • C11D3/502—Protected perfumes
    • C11D3/505—Protected perfumes encapsulated or adsorbed on a carrier, e.g. zeolite or clay
    • D—TEXTILES; PAPER
    • D06—TREATMENT OF TEXTILES OR THE LIKE; LAUNDERING; FLEXIBLE MATERIALS NOT OTHERWISE PROVIDED FOR
    • D06M—TREATMENT, NOT PROVIDED FOR ELSEWHERE IN CLASS D06, OF FIBRES, THREADS, YARNS, FABRICS, FEATHERS OR FIBROUS GOODS MADE FROM SUCH MATERIALS
    • D06M23/00—Treatment of fibres, threads, yarns, fabrics or fibrous goods made from such materials, characterised by the process
    • D06M23/12—Processes in which the treating agent is incorporated in microcapsules
    • A—HUMAN NECESSITIES
    • A61—MEDICAL OR VETERINARY SCIENCE; HYGIENE
    • A61K—PREPARATIONS FOR MEDICAL, DENTAL OR TOILETRY PURPOSES
    • A61K2800/00—Properties of cosmetic compositions or active ingredients thereof or formulation aids used therein and process related aspects
    • A61K2800/40—Chemical, physico-chemical or functional or structural properties of particular ingredients
    • A61K2800/41—Particular ingredients further characterized by their size
    • A61K2800/412—Microsized, i.e. having sizes between 0.1 and 100 microns

Definitions

  • Polyurea and polyurethane-based microcapsule slurry are widely used for example in perfumery industry for instance as they provide a long lasting pleasant olfactory effect after their applications on different substrates. Those microcapsules have been widely disclosed in the prior art.
  • the present invention relates to a core-shell microcapsule comprising:
  • a shell comprising the reaction product between at least a nucleophile and at least one oxidized saccharide and its derivatives.
  • Another object of the invention is a core-shell microcapsule slurry comprising at least one microcapsule, the microcapsule comprising:
  • Another object of the invention is a process for preparing a core-shell microcapsule slurry comprising the steps of: a) Dispersing an oil phase comprising a hydrophobic material into a continuous phase C1 to obtain a two-phases dispersion, b) Optionally, dispersing the two-phases dispersion into a continuous phase C2 to obtain a multiple dispersion, c) curing the dispersion obtained in step a) or b) to form microcapsules in the form of a slurry, wherein an oxidized saccharide and its derivatives is added in step a) and/or b) and/or c), or wherein a saccharide and its derivatives, and an oxidant is added in step a) and/or b) and/or c), and wherein a nucleophile is added in step a) and/or step b) and/or c).
  • the present invention also relates to perfumed consumer products and flavoured edible products comprising the micro
  • active ingredient it is meant a single compound or a combination of ingredients.
  • perfume or flavour oil it is meant a single perfuming or flavouring compound or a mixture of several perfuming or flavouring compounds.
  • consumer product or “end-product” it is meant a manufactured product ready to be distributed, sold and used by a consumer.
  • dispersion in the present invention it is meant a system in which particles are dispersed in a continuous phase of a different composition and it specifically includes a suspension or an emulsion.
  • a “microcapsule”, or the similar, in the present invention it is meant that coreshell microcapsules have a particle size distribution in the micron range (e.g. a mean diameter (d(v, 0.5)) comprised preferably between about 1 and 3000 microns, more preferably between 1 and 500 microns) and comprise an external solid polymeric shell and an internal continuous oil phase enclosed by the external shell.
  • the shell consists of an external solid polymeric shell.
  • the shell is not a coating. In other words, a coating is considered as an additional layer on the shell.
  • Coacervates microcapsules are excluded from the present invention. In other words, microcapsule according to the invention is not a coacervate microcapsule.
  • microcapsule slurry it is meant microcapsule(s) that is (are) dispersed in a liquid.
  • the slurry is an aqueous slurry, i.e. the microcapsule(s) is (are) dispersed in an aqueous phase.
  • Disposing phase and “continuous phase” can be used indifferently in the present invention.
  • the present invention relates to a core-shell microcapsule comprising: - a core comprising a hydrophobic material, and
  • a shell comprising the reaction product between at least a nucleophile and at least one oxidized saccharide and its derivatives.
  • the core is an oil-based core.
  • the hydrophobic material is a hydrophobic active ingredient.
  • the hydrophobic material comprises a phase change material (PCM).
  • PCM phase change material
  • the hydrophobic material comprises a perfume.
  • the hydrophobic material consists of a perfume.
  • perfume an ingredient or a composition that is a liquid at about 20°C.
  • said perfume oil can be a perfuming ingredient alone or a mixture of ingredients in the form of a perfuming composition.
  • a perfuming ingredient it is meant here a compound, which is used for the primary purpose of conferring or modulating an odor.
  • such an ingredient, to be considered as being a perfuming one must be recognized by a person skilled in the art as being able to at least impart or modify in a positive or pleasant way the odor of a composition, and not just as having an odor.
  • perfume oil also includes a combination of perfuming ingredients with substances which together improve, enhance or modify the delivery of the perfuming ingredients, such as perfume precursors, modulators, emulsions or dispersions, as well as combinations which impart an additional benefit beyond that of modifying or imparting an odor, such as long-lastingness, blooming, malodor counteraction, antimicrobial effect, microbial stability, pest control.
  • perfuming ingredients such as perfume precursors, modulators, emulsions or dispersions, as well as combinations which impart an additional benefit beyond that of modifying or imparting an odor, such as long-lastingness, blooming, malodor counteraction, antimicrobial effect, microbial stability, pest control.
  • perfuming ingredients present in the oil phase do not warrant a more detailed description here, which in any case would not be exhaustive, the skilled person being able to select them on the basis of its general knowledge and according to intended use or application and the desired organoleptic effect.
  • these perfuming ingredients belong to chemical classes as varied as alcohols, aldehydes, ketones, esters, ethers, acetates, nitriles, terpenoids, nitrogenous or sulfurous heterocyclic compounds and essential oils (for example Thyme oil), and said perfuming co-ingredients can be of natural or synthetic origin. Many of these co-ingredients are in any case listed in reference texts such as the book by S. Arctander, Perfume and Flavor Chemicals, 1969, Montclair, New Jersey, USA, or its more recent versions, or in other works of a similar nature, as well as in the abundant patent literature in the field of perfumery.
  • perfuming ingredients which are commonly used in perfume formulations, such as:
  • ingredients may also be compounds known to release in a controlled manner various types of perfuming compounds also known as properfume or profragrance.
  • suitable properfumes 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- phenylethyl oxo(phenyl)acetate, 3,7-dimethylocta-2,6-dien-1-yl oxo(phenyl)acetate, (Z)-hex-3-en-1-y
  • Group 2 perfuming ingredients comprising a cyclopentane, cyclopentene, cyclopentanone or cyclopentenone ring substituted with at least one linear or branched C4 to Cs alkyl or alkenyl substituent;
  • Group 5 perfuming ingredients comprising a camphor-like ring structure
  • Group 6 perfuming ingredients comprising at least one C7 to C20 ring structure
  • Group 7 perfuming ingredients having a logP value above 3.5 and comprising at least one tert-butyl or at least one trichloromethyl substitutent;
  • Group 1 2,4-dimethyl-3-cyclohexene-1-carbaldehyde (origin: Firmenich SA, Geneva, Switzerland), isocyclocitral, menthone, isomenthone, methyl 2,2- dimethyl-6-methylene-1 -cyclohexanecarboxylate (origin: Firmenich SA, Geneva, Switzerland), nerone, terpineol, dihydroterpineol, terpenyl acetate, dihydroterpenyl acetate, dipentene, eucalyptol, hexylate, rose oxide, (S)-1 ,8-p- menthadiene-7-ol (origin: Firmenich SA, Geneva, Switzerland), 1-p-menthene-4- ol, (1 RS,3RS,4SR)-3-p-mentanyl acetate, (1 R,2S,4R)-4,6,6-trimethyl- bicyclo[3,1 ,1]heptan-2-ol,
  • Group 3 damascenes, 1-(5,5-dimethyl-1-cyclohexen-1-yl)-4-penten-1-one (origin: Firmenich SA, Geneva, Switzerland), (1'R)-2-[2-(4'-methyl-3'-cyclohexen-1 '- yl)propyl]cyclopentanone, alpha-ionone, beta-ionone, damascenone, mixture of 1- (5,5-dimethyl-1-cyclohexen-1-yl)-4-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), (1 S, 1 ' R)-[ 1 -(3',3'-Dimethyl-1 '-cyclohexyl)ethoxy
  • the perfume comprises at least 30%, preferably at least 50%, more preferably at least 60% of ingredients selected from Groups 1 to 7, as defined above. More preferably said perfume comprises at least 30%, preferably at least 50% of ingredients from Groups 3 to 7, as defined above. Most preferably said perfume comprises at least 30%, preferably at least 50% of ingredients from Groups 3, 4, 6 or 7, as defined above.
  • the perfume comprises at least 30%, preferably at least 50%, more preferably at least 60% of ingredients having a logP above 3, preferably above 3.5 and even more preferably above 3.75.
  • the shell comprises a polyfunctional monomer.
  • the polyfunctional monomer is preferably chosen in the group consisting of acyl chloride, polyaldehyde polyanhydride, polyepoxide, acrylate monomers, polyalkoxysilane, and mixtures thereof.
  • the shell of the microcapsule does not comprise an acrylate or a reaction product thereof.
  • the shell material is a biodegradable material.
  • the shell has a biodegradability of at least 40%, preferably at least 45%, 50%, 60%, 65%, 70%, 75%, 80%, 85%, 90%, 95% or 98%, within 60 days according to OECD301 F.
  • 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% within 60 days according to OECD301 F.
  • the core-shell microcapsule including all components, such as the core, shell and optionally coating may have a biodegradability of at least 40 %, preferably at least 60 %, preferably at least 65%, 70%, 75%, 80%, 85%, 90%, 95% or 98% within 60 days according to OECD301 F.
  • the oil core preferably perfume oil
  • OECD301 F is a standard test method on the biodegradability from the Organization of Economic Co-operation and Development. A typical method for extracting the shell for measuring the biodegradability is disclosed in Gasparini and all in Molecules 2020, 25,718.
  • the microcapsule comprises an outer coating, wherein the outer coating comprises a coating material selected from the group consisting of a non-ionic polymer (such as non-ionic polysaccharide), anionic polymer (such as polysaccharide), a cationic polymer, a polysuccinimide derivative (as described for instance in WO2021185724) and mixtures thereof to form an outer coating to the microcapsule.
  • a non-ionic polymer such as non-ionic polysaccharide
  • anionic polymer such as polysaccharide
  • a cationic polymer such as sodium quaternary ammonide
  • a polysuccinimide derivative as described for instance in WO2021185724
  • the microcapsule does not comprise an outer coating.
  • a coating is considered as an additional layer on the shell.
  • the shell of the microcapsule is not a coating.
  • Non-ionic polysaccharide polymers are well known to a person skilled in the art and are described for instance in WO2012/007438 page 29, lines 1 to 25 and in WO2013/026657 page 2, lines 12 to 19 and page 4, lines 3 to 12.
  • Preferred non-ionic polysaccharides are selected from the group consisting of locust bean gum, xyloglucan, guar gum, hydroxypropyl guar, hydroxypropyl cellulose and hydroxypropyl methyl cellulose.
  • Cationic polymers are well known to a person skilled in the art.
  • Preferred cationic polymers have cationic charge densities of at least 0.5 meq/g, more preferably at least about 1 .5 meq/g, but also preferably less than about 7 meq/g, more preferably less than about 6.2 meq/g.
  • the cationic charge density of the cationic polymers may be determined by the Kjeldahl method as described in the US Pharmacopoeia under chemical tests for Nitrogen determination.
  • the preferred cationic polymers are chosen from those that contain units comprising primary, secondary, tertiary and/or quaternary amine groups that can either form part of the main polymer chain or can be borne by a side substituent directly connected thereto.
  • Salcare®SC60 cationic copolymer of acrylamidopropyltrimonium chloride and acrylamide, origin: BASF
  • Luviquat® such as the PQ 11 N, FC 550 or Style (polyquaternium-11 to 68 or quaternized copolymers of vinylpyrrolidone origin: BASF), or also the Jaguar® (C13S or C17, origin Rhodia).
  • Another object of the invention is a solid particle comprising:
  • the process comprises the steps of: a) Dispersing an oil phase comprising a hydrophobic material into a continuous phase to obtain a two-phases dispersion, b) curing the dispersion obtained in step a) or b) to form microcapsules in the form of a slurry, wherein an oxidized saccharide and its derivatives is added in step a) and/or in step b) or wherein a saccharide and its derivatives, and an oxidant is added in step a) and/or b), and wherein a nucleophile is added in step a) and/or step b).
  • the oxidized saccharide and its derivatives is preferably used in an amount comprised between 0.05% and 50%, preferably between 0.1 % and 10% based on the multiple emulsion.
  • the continuous phase C1 is a water phase.
  • surfactant it meant a substance with a polar and a non-polar group that is added to the liquid to reduce the liquid surface tension.
  • the stabilizer is chosen in the group consisting of inorganic particles, polymeric emulsifier such as polysaccharides, proteins, glycoproteins, and mixtures thereof.
  • the polymeric emulsifier is chosen in the group consisting of gum Arabic, modified starch, polyvinyl alcohol, polyvinylpyrolidone (PVP), carboxymethylcellulose (CMC), anionic polysaccharides, acrylamide copolymer, protein such as soy protein, rice protein, whey protein, white egg albumin, sodium caseinate, gelatin, bovine serum albumin, hydrolyzed soy protein, hydrolyzed sericin, pseudocollagen, silk protein, sericin powder, potato protein, chickpea protein, pea protein, algae protein, faba bean protein, barley protein, oat protein, wheat gluten protein, lupin protein, and mixtures thereof.
  • protein such as soy protein, rice protein, whey protein, white egg albumin, sodium caseinate, gelatin, bovine serum albumin, hydrolyzed soy protein, hydrolyzed sericin, pseudocollagen, silk protein, sericin powder, potato protein, chickpea protein, pea protein, algae protein, faba
  • Potato proteins are typically extracted from potato tuber (Solanum tuberosum). According to an embodiment, the potato protein is a native potato protein and preferably patatin.
  • the protein used in this invention may be native, partially or completely denaturated by any suitable method.
  • Denaturation is a process which modify the conformational structure of a protein by unfolding, i.e. , it involves the disruption and possible destruction of both the secondary and tertiary structures of the protein. Indeed, denaturation implicates the breaking of many of the weak linkages, or bonds (e.g., hydrogen bonds), within a protein molecule that are responsible for the highly ordered structure of the protein in its native state. Denaturation is reversible (the proteins can regain their native state when the denaturating influence is removed) or irreversible.
  • Denaturation can be brought about in various ways. Proteins can be denatured by exposure to temperature, radiation or mechanical stress including shear, changes in pH (treatment with a base or an acid), treatment with oxidizing or reducing agents, inorganic salt, certain organic solvents, chaotropic agents (i.e, compounds having a positive chaotropic value - kJ Kg -1 mole on the Hallsworth Scale - such as guanidine salts - e.g., guanidine carbonate, guanidine hydrochloride -, urea, calcium chloride, n- butanol, ethanol, lithium perchlorate, lithium acetate, magnesium chloride, phenol, 2- propanol, sodium dodecyl sulfate, thiourea).
  • chaotropic agents i.e, compounds having a positive chaotropic value - kJ Kg -1 mole on the Hallsworth Scale - such as guanidine salts - e.
  • the protein used in this invention can also be derivatized or modified (e.g., derivatized or chemically modified).
  • the protein can be modified by covalently attaching sugars, lipids, peptides or chemical groups such as phosphates or methyl.
  • a base is added in the continuous phase C1.
  • the base is chosen in the group consisting of guanidine carbonate, sodium carbonate, potassium carbonate, sodium hydroxide, potassium hydroxide, and mixtures thereof.
  • the base When used, the base is typically used in an amount comprised between 0.1 and 10%, preferably between 3 and 7% by weight based on the total weight of the continuous phase C1.
  • the nucleophile can be added in an amount comprised between 0.5 and 10%, preferably between 1 and 4% by weight based on the total weight of the two-phases dispersion.
  • step b) or c) the dispersion obtained respectively in step a) or b) is cured to form microcapsules in the form of a slurry.
  • the microcapsules of the invention can be used in combination with a second type of microcapsules.
  • Another object of the invention is a microcapsule delivery system comprising:
  • microcapsules of the present invention as a first type of microcapsule
  • the microcapsule delivery system is in the form of a slurry.
  • the wall of the second type of microcapsules can vary.
  • the polymer shell of the second type of microcapsules comprises a material selected from the group consisting of polyurea, polyurethane, polyamide, polyhydroxyalkanoates, polyacrylate, polyesters, polyaminoesters, polyepoxides, organosilicon, polycarbonate, polysulfonamide, urea formaldehyde, melamine formaldehyde resin, melamine formaldehyde resin cross-linked with polyisocyanate or aromatic polyols, melamine urea resin, melamine glyoxal resin, gelatin/ gum arabic shell wall, and mixtures thereof.
  • the second type of microcapsule can comprise an oil-based core comprising a hydrophobic active, preferably perfume, and a composite shell comprising a first material and a second material, wherein the first material and the second material are different, the first material is a coacervate, the second material is a polymeric material.
  • the weight ratio between the first material and the second material is comprised between 50:50 and 99.9:0.1.
  • the coacervate first material can be hardened chemically using a suitable cross-linker such as glutaraldehyde, glyoxal, formaldehyde, tannic acid or genipin or can be hardened enzymatically using an enzyme such as transglutaminase.
  • the second polymeric material can be selected from the group consisting of polyurea, polyurethane, polyamide, polyester, polyacrylate, organosilicon, polycarbonate, polysulfonamide, polymers of urea and formaldehyde, melamine and formaldehyde, melamine and urea, or melamine and glyoxal and mixtures thereof, preferably polyurea and/or polyurethane.
  • the second material is preferably present in an amount less than 3 wt.%, preferably less than 1 wt.% based on the total weight of the second type of microcapsule slurry.
  • the shell of the second type of microcapsules is polyurea-based made from, for example but not limited to isocyanate-based monomers and amine-containing crosslinkers such as guanidine carbonate and/or guanazole.
  • Certain polyurea microcapsules comprise a polyurea wall which is the reaction product of the polymerisation between at least one polyisocyanate comprising at least two isocyanate functional groups and at least one reactant selected from the group consisting of an amine (for example a water-soluble guanidine salt and guanidine); a colloidal stabilizer or emulsifier; and an encapsulated perfume.
  • an amine for example a water-soluble guanidine salt and guanidine
  • colloidal stabilizer or emulsifier for example a colloidal stabilizer or emulsifier
  • an encapsulated perfume for example a water-soluble guanidine salt and guanidine
  • an amine for example a water-soluble guanidine salt and
  • the second type of microcapsules is a formaldehyde- free capsule.
  • a typical process for the preparation of aminoplast formaldehyde-free microcapsules slurry comprises the steps of
  • an oil-in-water dispersion wherein the droplet size is comprised between 1 and 600 microns, and comprising: a. an oil; b. a water medium: c. at least an oligomeric composition as obtained in step 1 ; d. at least a cross-linker selected amongst: i. C4-C12 aromatic or aliphatic di- or tri-isocyanates and their biurets, triurets, trimmers, trimethylol propane-adduct and mixtures thereof; and/or ii. a di- or tri-oxiran compounds of formula:
  • the second type of microcapsule comprises
  • an oil-based core comprising a hydrophobic active, preferably perfume
  • the protein is chosen in the group consisting of milk proteins, caseinate salts such as sodium caseinate or calcium caseinate, casein, whey protein, hydrolyzed proteins, gelatins, gluten, pea protein, soy protein, silk protein and mixtures thereof, preferably sodium caseinate, most preferably sodium caseinate
  • the protein comprises sodium caseinate and a globular protein, preferably chosen in the group consisting of whey protein, betalactoglobulin, ovalbumine, bovine serum albumin, vegetable proteins, and mixtures thereof.
  • the protein is preferably a mixture of sodium caseinate and whey protein.
  • the biopolymer shell comprises a crosslinked protein chosen in the group consisting of sodium caseinate and/or whey protein.
  • the second type of microcapsules slurry comprises at least one microcapsule made of:
  • an oil-based core comprising the hydrophobic active, preferably perfume
  • an inner shell made of a polymerized polyfunctional monomer; preferably a polyisocyanate having at least two isocyanate functional groups
  • biopolymer shell comprising a protein, wherein at least one protein is crosslinked; wherein the protein contains preferably a mixture comprising sodium caseinate and a globular protein, preferably whey protein,
  • sodium caseinate and/or whey protein is (are) cross-linked protein(s).
  • the weight ratio between sodium caseinate and whey protein is preferably comprised between 0.01 and 100, preferably between 0.1 and 10, more preferably between 0.2 and 5.
  • the second type of microcapsules is a polyamide core-shell polyamide microcapsule comprising:
  • an oil-based core comprising a hydrophobic active, preferably perfume, and
  • polyamide shell comprising or being obtainable from:
  • an oil-based core comprising a hydrophobic active, preferably perfume, and
  • polyamide shell comprising or being obtainable from:
  • an acyl chloride preferably in an amount comprised 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 comprised between 1 % and 50% w/w, preferably between 7 and 40% w/w;
  • a second amino compound preferably in an amount comprised between 1 % and 50% w/w, preferably between 2 and 25% w/w
  • the second type of microcapsules comprises:
  • an oil-based core comprising a hydrophobic active, preferably perfume, and
  • polyamide shell comprising or being obtainable from:
  • a first amino-compound being an amino-acid, preferably chosen in the group consisting of L-Lysine, L-Arginine, L-Histidine, L- Tryptophane and/or mixtures thereof.
  • a second amino-compound preferably chosen in the group consisting of ethylene diamine, diethylene triamine, cystamine and/or mixtures thereof, and
  • a biopolymer preferably chosen in the group consisting of potato protein, chickpea protein, pea protein, algae protein, faba bean protein, barley protein, oat protein, wheat gluten protein, lupin protein, soy protein, rice protein, whey protein, white egg albumin, casein, sodium caseinate, gelatin (preferably fish gelatin), bovine serum albumin, hydrolyzed soy protein, hydrolyzed sericin, pseudocollagen, silk protein, sericin powder, gelatin and mixtures thereof,
  • a carbohydrate preferably selected from the group consisting of anionic salt of alginic acid, preferably alginic acid sodium salt, pectin, lignin, anionic modified starch, carboxymethylcellulose, carrageenan and mixtures thereof.
  • the shell of the second type of microcapsules is polyurea-or polyurethane-based.
  • processes for the preparation of polyurea and polyurethane-based microcapsule slurry are for instance described in International Patent Application Publication No. W02007/004166, European Patent Application Publication No. EP 2300146, and European Patent Application Publication No. EP25799.
  • a process for the preparation of polyurea or polyurethane-based microcapsule slurry include the following steps: a) Dissolving at least one polyisocyanate having at least two isocyanate groups in an oil to form an oil phase; b) Preparing an aqueous solution of an emulsifier or colloidal stabilizer to form a dispersing phase; c) Adding the oil phase to the dispersing phase to form an oil-in-water dispersion, wherein the mean droplet size is comprised between 1 and 500 pm, preferably between 5 and 50 pm; and d) Applying conditions sufficient to induce interfacial polymerisation and form microcapsules in the form of a slurry.
  • the composition comprises: - a core-shell microcapsule or core-shell microcapsule slurry obtained by the process according to the present invention or as described herein-above;
  • an active ingredient preferably chosen in the group consisting of a cosmetic ingredient, skin caring ingredient, perfume ingredient, flavor ingredient, malodour counteracting ingredient, bactericide ingredient, fungicide ingredient, pharmaceutical or agrochemical ingredient, a sanitizing ingredient, an insect repellent or attractant, and mixtures thereof.
  • present invention relates to a perfuming composition
  • a perfuming composition comprising
  • the perfuming composition according to the invention comprises between 0.1 and 40 %, preferably between 0.1 and 30% by weight of a core-shell microcapsule or core-shell microcapsule slurry obtained by the process according to the present invention or as described herein-above.
  • free perfume it is herein understood a perfume or perfume oil which is comprised in the perfuming composition and not entrapped in the core-shell microcapsule or core-shell microcapsule slurry obtained by the process according to the present invention or as described herein-above.
  • the total amount of the core-shell microcapsule or core-shell microcapsule slurry obtained by the process according to the present invention or as described herein-above is 0.05 to 5 wt.% (based on the total weight of the perfuming composition) and the total amount of the free perfume oil is 0.05 to 5 wt.% (based on the total weight of the perfuming composition).
  • perfuming co-ingredient it is herein understood a compound, which is used in a perfuming preparation or a composition to impart a hedonic effect and which is not a microcapsule as 20 defined above.
  • a co-ingredient to be considered as being a perfuming one, must be recognized by a person skilled in the art as being able to impart or modify in a positive or pleasant way the odor of a composition, and not just as having an odor.
  • Co-ingredients may be chosen in 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-
  • perfumery adjuvant an ingredient capable of imparting additional 5 added benefit such as a color, a particular light resistance, chemical stability, etc.
  • a detailed description of the nature and type of adjuvant commonly used in perfuming bases cannot be exhaustive, but it has to be mentioned that said ingredients are well known to a person skilled in the art.
  • the core-shell microcapsule or core-shell microcapsule slurry obtained by the process according to the present invention or as described herein-above can advantageously be used in many application fields and used in consumer products.
  • the present invention also relates to a perfumed consumer product comprising
  • the consumer products of the invention can in particular be of used in perfumed consumer products such as product belonging to fine fragrance or “functional” perfumery.
  • Functional perfumery includes in particular personal-care products including hair-care, body cleansing, skin care, hygiene-care as well as homecare products including laundry care and air care.
  • liquid consumer product comprising:
  • a powder consumer product comprising - from 2 to 65% by weight, relative to the total weight of the consumer product, of at least one surfactant;
  • a perfumed consumer product it is meant a consumer product which is expected to deliver among different benefits a perfuming effect to the surface to which it is applied (e.g. skin, hair, textile, paper, or home surface) or in the air (air-freshener, deodorizer etc).
  • a perfumed consumer product according to the invention is a manufactured product which comprises a functional formulation also referred to as “base”, together with benefit agents, among which an effective amount of microcapsules according to the invention.
  • Non-limiting examples of suitable perfumed consumer products can be a fine perfume, a splash or eau de perfume, a cologne, a shave or after-shave lotion, a liquid or solid detergent, a mono or multi chamber unidose detergent , a fabric softener, a fabric refresher, liquid or solid scent-boosters (PEG I urea or salts), a dryer sheet, an ironing water, a paper, a bleach, a carpet cleaners, curtain-care products, a shampoo, a coloring preparation, a color care product, a hair shaping product, a dental care product, a disinfectant, an intimate care product, a hair spray, a hair conditioning product, a vanishing cream, a deodorant or antiperspirant, hair remover, tanning or sun product, nail products, skin cleansing, a makeup, a perfumed soap, shower or bath mousse, oil or gel, or a foot/hand care products, a hygiene product, an air freshener, a “ready to use” powdere
  • the perfumed consumer product is preferably selected from the group consisting of personal care composition, home care composition or fabric care composition, most preferably in form of antiperspirants, hair care products, such as shampoo or hair-conditioner, body care products such as a shower gel, oral care products, laundry care products, preferably a detergent or a fabric softener.
  • microcapsules or a microcapsule slurry as defined above orthe perfuming composition as defined above, wherein the consumer product is in the form of a personal care composition.
  • the personal care composition is preferably chosen in the group consisting of a haircare product (e.g. a shampoo, hair conditioner, a coloring preparation or a hair spray), a cosmetic preparation (e.g. a vanishing cream, body lotion or a deodorant or antiperspirant), or a skin-care product (e.g. a perfumed soap, shower or bath mousse, body wash, oil or gel, bath salts, or a hygiene product);
  • a haircare product e.g. a shampoo, hair conditioner, a coloring preparation or a hair spray
  • a cosmetic preparation e.g. a vanishing cream, body lotion or a deodorant or antiperspirant
  • a skin-care product e.g. a perfumed soap, shower or bath mousse, body wash, oil or gel, bath salts, or a hygiene product
  • Another object of the invention is a consumer product comprising:
  • the consumer product is in the form of a home care or a fabric care composition.
  • the consumer product comprises from 0.1 to 15 wt%, more preferably between 0.2 and 5 wt% of the microcapsules of the present invention, these percentages being defined by weight relative to the total weight of the consumer product.
  • concentrations may be adapted according to the benefit effect desired in each product.
  • active base For liquid consumer product mentioned below, by “active base”, it should be understood that the active base includes active materials (typically including surfactants).
  • active base includes active materials (typically including surfactants) and auxiliary agents (such as bleaching agents, buffering agent; builders; soil release or soil suspension polymers; granulated enzyme particles, corrosion inhibitors, antifoaming, sud suppressing agents; dyes, fillers, and mixtures thereof).
  • active materials typically including surfactants
  • auxiliary agents such as bleaching agents, buffering agent; builders; soil release or soil suspension polymers; granulated enzyme particles, corrosion inhibitors, antifoaming, sud suppressing agents; dyes, fillers, and mixtures thereof.
  • the home or fabric care composition is preferably chosen in the group consisting of fabric softener, liquid detergent, powder detergent, liquid scent booster and solid scent booster.
  • microcapsules or a microcapsule slurry as defined above preferably in an amount comprised between 0.05 to 15 wt%, more preferably between 0.1 and 5 wt% by weight based on the total weight of the composition,
  • An object of the invention is a consumer product in the form of a rinse-off conditioner composition
  • a rinse-off conditioner composition comprising:
  • a rinse-off conditioner active base preferably comprising at least one active material chosen in the group consisting of cetyltrimonium chloride, stearyl trimonium chloride, benzalkonium chloride, behentrimonium chloride and mixture thereof, the active base being used preferably in an amount comprised between 85 and 99.95% by weight based on the total weight of the composition,
  • microcapsules or a microcapsule slurry as defined above preferably in an amount comprised between 0.05 to 15 wt%, more preferably between 0.1 and 5 wt% by weight based on the total weight of the composition,
  • An object of the invention is a consumer product in the form of a solid scent booster composition comprising:
  • a solid carrier preferably chosen in the group consisting of urea, sodium chloride, sodium sulphate, sodium acetate, zeolite, sodium carbonate, sodium bicarbonate, clay, talc, calcium carbonate, magnesium sulfate, gypsum, calcium sulfate, magnesium oxide, zinc oxide, titanium dioxide, calcium chloride, potassium chloride, magnesium chloride, zinc chloride, saccharides such as sucrose, mono-, di-, and polysaccharides and derivatives such as starch, cellulose, methyl cellulose, ethyl cellulose, propyl cellulose, polyols/sugar alcohols such as sorbitol, maltitol, xylitol, erythritol, and isomalt, PEG, PVP, citric acid or any water soluble solid acid, fatty alcohols or fatty acids and mixtures thereof,
  • Sucrose oxidation The reaction was performed under inert atmosphere. Sucrose (5 g) was dissolved in water (150 mL). The solution was heated to 70°C under stirring. (Diacetoxyiodo)benzene was added to the mixture (2 portions of 6.2 g each 2 hours). After the last addition, the mixture was stirred for 24 hours at 70°C. The final mixture was then extracted with Ethyl acetate (five times) and the purified oxidized product was recovered as a white powder by freeze-drying of the aqueous phase.
  • An oil phase is prepared by mixing a perfume oil (see table 1), the oxidized sucrose monopalmitate ((OP1) prepared in Example 1), optionally with an inert solvent.
  • the oil phase is emulsified into a water phase containing a colloidal stabilizer using an Ultraturrax probe and the dispersion is introduced in a double jacketed reactor. At least one nucleophile is added in the water phase before and/or after the emulsification step. The dispersion is then heated to the desired temperature and stirred. The final product is a milky dispersion.
  • Microcapsules 2A An oil phase is prepared by mixing perfume oil (28 g) and oxidized sucrose monopalmitate.
  • This oil phase is emulsified into a water phase containing 1 % of PVOH and 1 % of potato protein (nucleophile) (Solanic 200 origin: Avebe, NL) (67 g) using an Ultraturrax probe (1 min, 10000 RPM) and the dispersion is introduced in a double jacketed reactor. The dispersion is then heated to 80°C and stirred for 6 hours at 80°C. The final product is a milky dispersion.
  • Microcapsules according to the invention oxidized polysaccharide and nucleophile added in the oil phase
  • An oil phase is prepared by mixing a perfume oil (see Table 1), the oxidized sucrose monopalmitate ((0P1) prepared in Example 1), a nucleophile and optionally an inert solvent.
  • the oil phase is emulsified into a water phase containing a colloidal stabilizer using an Ultraturrax probe and the dispersion is introduced in a double jacketed reactor.
  • other nucleophiles can be added in the water phase before and/or after the emulsification step.
  • the dispersion is then heated to the desire temperature and stirred.
  • the final product is a milky dispersion.
  • Origin Zhejiang aoxing biotech. 3) Origin: Vetec
  • Microcapsules 4B - A water phase is prepared by mixing water (13.72 g), oxidized saponin (0.28 g).
  • An oil phase is prepared by mixing isophthalaldehyde (0.3 g) in perfume oil (5.7 g), it is emulsified with prepared water phase using an Ultraturrax probe (3 min, 7000 RPM) and the dispersion is introduced in a double jacketed reactor.
  • a solution of chitosan oligosaccharide (0.2 g) in DI water (1 .8 g) was added drop wise in 20 min. It was adjusted to pH 6 ⁇ 7 by 10% NaOH.
  • solution of urea 0.2 g) in DI water (2 g) was added. Then, it was stirred at 50°C for 2 h.
  • the final product is a milky dispersion.
  • An oil phase is prepared by mixing a perfume oil (see Table 1), optionally with an inert solvent.
  • the oil phase is emulsified into water using an Ultraturrax probe and the dispersion is introduced in a double jacketed reactor.
  • other nucleophiles can be added in the water phase before and/or after the emulsification step.
  • the oxidized sucrose (5%) ((OP3) prepared in Example 1) is added after the emulsification step
  • the dispersion is then heated to the desired temperature and stirred.
  • the final product is a milky dispersion.
  • Microcapsules 5A The perfume oil phase is emulsified into a water phase containing canola protein (CanolaPro origin: dsm-firmenich, Switzerland) using an Ultraturrax probe (1 min, 25000 RPM) and the dispersion is introduced in a double jacketed reactor (20% of oil in final dispersion).
  • RNA RNA from yeast, origin: Roche, Germany
  • Oxidized sucrose (5%) ((OP3) prepared in Example 1 ), is then added, and the pH is readjusted using 1 M sodium hydroxide solution.
  • the dispersion is then stirred for 4 hours at RT or 80°C.
  • the final product is a milky dispersion.
  • Microcapsules slurry is added to the obtained mixture. Then, the resulting mixture is then mixed gently at 25°C (room temperature).
  • Granulated powder A-E are prepared by spray-drying Emulsion A-E using a Sodeva Spray Dryer (Origin France), with an air inlet temperature set to 215°C and a throughput set to 500 ml per hour. The air outlet temperature is of 105°C. The emulsion before atomization is at ambient temperature.
  • compositions 1-6 Different ringing gel compositions are prepared (compositions 1-6) according to the following protocol.
  • aqueous phase water
  • solvent propylene glycol
  • surfactants are mixed together at room temperature under agitation with magnetic stirrer at 300 rpm for 5 min.
  • the linker is dissolved in the hydrophobic active ingredient (fragrance) at room temperature under agitation with magnetic stirrer at 300 rpm. The resulting mixture is mixed for 5 min.
  • Neodol 91-8 ® trademark and origin : Shell Chemical
  • compositions are prepared.
  • Polyquaternium-10 is dispersed in water.
  • the remaining ingredients of phase A are mixed separately by addition of one after the other while mixing well after each adjunction.
  • this pre-mix is added to the Polyquaternium-10 dispersion and was mixed for 5 min.
  • Phase B and the premixed Phase C (heat to melt Monomuls 90L-12 in Texapon NSO IS) are added.
  • the mixture is mixed well.
  • Phase D and Phase E are added while agitating.
  • the pH was adjusted with citric acid solution till pH: 5.5 - 6.0.
  • a sufficient amount of exemplified microcapsules is weighed and mixed in a shampoo composition to add the equivalent of 0.2% perfume.
  • a premix comprising Guar Hydroxypropyltrimonium Chloride and Polyquaternium-10 are added to water and Tetrasodium EDTA while mixing. When the mixture is homogeneous, NaOH is added. Then, Phase C ingredients are added and the mixture was heat to 75 °C. Phase D ingredients are added and mixed till homogeneous. The heating is stopped and temperature of the mixture is decreased to RT. At 45 °C, ingredients of Phase E while mixing final viscosity is adjusted with 25% NaCI solution and pH of 5.5-6 is adjusted with 10% NaOH solution.
  • a sufficient amount of exemplified microcapsules is weighed and mixed in a rinse-off composition to add the equivalent of 0.2% perfume.
  • Aerosol filling 30% Emulsion: 70% Propane I Butane 2,5 bar
  • Irgasan® DP 300 trademark and origin : BASF
  • Antiperspirant roll-on emulsion composition
  • a sufficient amount of exemplified microcapsules is weighed and mixed in antiperspirant roll-on emulsion composition to add the equivalent of 0.2% perfume.
  • Part A and B are heated separately to 75°C; Part A is added to part B under stirring and the mixture is homogenized for 10 minutes. Then, the mixture is cooled down under stirring; and part C is slowly added when the mixture reached 45°C and part D when the mixture reached at 35 °C while stirring. Then the mixture is cooled down to RT.
  • a sufficient amount of exemplified microcapsules is weighed and mixed in antiperspirant roll-on composition to add the equivalent of 0.2% perfume.
  • Part A is prepared by sprinkling little by little the Hydroxyethylcellulose in the water whilst rapidly stirring with the turbine. Stirring is continued until the Hydroxyethylcellulose is entirely swollen and giving a limpid gel. Then, Part B is poured little by little in Part A whilst continuing stirring until the whole is homogeneous. Part C is added.
  • a sufficient amount of exemplified microcapsules is weighed and mixed in the following composition to add the equivalent of 0.2% perfume.
  • CARBOPOL AQUA SF-1 POLYMER trademark and origin: NOVEON
  • a sufficient amount of exemplified microcapsules is weighed and mixed in the following composition to add the equivalent of 0.2% perfume.
  • Soap bar A sufficient amount of exemplified microcapsules is weighed and mixed in a soap bar formulation a concentration of 7.5% w/w.
  • a sufficient amount of exemplified microcapsules is weighed and mixed into a cosmetic skin cream (see composition below) at a concentration of 5%w/w.

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Abstract

La présente invention concerne des microcapsules cœur-écorce. Un procédé de préparation desdites microcapsules est également un objet de l'invention. L'invention concerne également des compositions parfumantes et des produits de consommation comprenant lesdites microcapsules, en particulier des produits de consommation parfumés sous la forme de produits de soins à domicile ou de soins personnels.
PCT/EP2025/050463 2024-01-17 2025-01-09 Microcapsules et procédé de préparation de microcapsules Pending WO2025153393A1 (fr)

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Citations (4)

* Cited by examiner, † Cited by third party
Publication number Priority date Publication date Assignee Title
US20180305468A1 (en) * 2012-06-28 2018-10-25 Covidien Lp Medical Devices Based On Oxidized Cellulose
CN111820213B (zh) * 2020-07-28 2021-11-19 仲恺农业工程学院 一种生物基缓控释农药液态地膜及其制备方法和应用
US20230060181A1 (en) * 2021-08-12 2023-03-02 Trucapsol Llc Environmentally biodegradable microcapsules
EP4212239A1 (fr) * 2022-01-14 2023-07-19 International Flavors & Fragrances Inc. Microcapsules de prépolymère biodégradables

Patent Citations (4)

* Cited by examiner, † Cited by third party
Publication number Priority date Publication date Assignee Title
US20180305468A1 (en) * 2012-06-28 2018-10-25 Covidien Lp Medical Devices Based On Oxidized Cellulose
CN111820213B (zh) * 2020-07-28 2021-11-19 仲恺农业工程学院 一种生物基缓控释农药液态地膜及其制备方法和应用
US20230060181A1 (en) * 2021-08-12 2023-03-02 Trucapsol Llc Environmentally biodegradable microcapsules
EP4212239A1 (fr) * 2022-01-14 2023-07-19 International Flavors & Fragrances Inc. Microcapsules de prépolymère biodégradables

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