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WO2018115330A1 - Microcapsules à couche minérale - Google Patents

Microcapsules à couche minérale Download PDF

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Publication number
WO2018115330A1
WO2018115330A1 PCT/EP2017/084178 EP2017084178W WO2018115330A1 WO 2018115330 A1 WO2018115330 A1 WO 2018115330A1 EP 2017084178 W EP2017084178 W EP 2017084178W WO 2018115330 A1 WO2018115330 A1 WO 2018115330A1
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WO
WIPO (PCT)
Prior art keywords
anionic
mineral
microcapsules
layer
capsules
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.)
Ceased
Application number
PCT/EP2017/084178
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English (en)
Inventor
Huda JERRI
Nicholas IMPELLIZZERI
Valery Normand
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
Priority to US16/471,804 priority Critical patent/US11135561B2/en
Priority to MX2019006632A priority patent/MX2019006632A/es
Priority to CN201780079605.6A priority patent/CN110099743B/zh
Priority to EP17818582.3A priority patent/EP3558509B1/fr
Priority to JP2019534264A priority patent/JP7078629B2/ja
Publication of WO2018115330A1 publication Critical patent/WO2018115330A1/fr
Anticipated expiration legal-status Critical
Ceased legal-status Critical Current

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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
    • 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
    • B01J13/20—After-treatment of capsule walls, e.g. hardening
    • B01J13/22—Coating
    • 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

Definitions

  • the present invention relates to the field of delivery systems. More specifically, the present invention relates to microcapsules comprising a hydrophobic active ingredient-based core, preferably a perfume or a flavour, a polymeric shell and a mineral layer onto the polymeric shell. A process for the preparation of said microcapsules is also an object of the invention. Perfuming compositions and consumer products comprising said microcapsules, in particular perfumed consumer products in the form of fine fragrance, home care or personal care products, are also part of the invention.
  • perfume delivery systems In order to be successfully used in consumer products, perfume delivery systems must meet a certain number of criteria.
  • the first requirement concerns stability in aggressive medium. In fact delivery systems may suffer from stability problems, in particular when incorporated into surfactant-based products such as detergents, wherein said systems tend to degrade and lose efficiency in the perfume-retention ability. It is also difficult to have a good stability and a good dispersion of the capsules altogether. The dispersion factor is very important because the aggregation of capsules increases the tendency of the capsule- containing product to phase separate, which represents an real disadvantage.
  • perfume delivery systems must also perform during the actual use of the end-product by the consumer, in particular in terms of odor performance, as the perfume needs to be released when required.
  • WO 01/41915 discloses a process for the preparation of capsules carrying cationic charges. Such a process is allegedly applicable to a large variety of microcapsules, in particular polyurethane-polyurea microcapsules are mentioned.
  • the capsules are placed in a medium which is favourable for the treatment with cationic polymers.
  • the treatment with cationic polymers is carried out after purification of the basic capsule slurry, in order to eliminate anionic or neutral polymers which were not incorporated in the capsule wall during formation thereof, and other free electrically charged compounds involved in the encapsulation process.
  • the capsules are diluted, isolated and then re-suspended in water, or even washed to further eliminate anionic compounds.
  • the capsules are agitated vigorously and the cationic polymers are added.
  • Partially quaternized copolymers of polyvinylpyrrolidones are cited to this purpose, among many other suitable polymers.
  • the described process comprises several steps following the capsule formation, said process being therefore time consuming and not economically profitable.
  • US 2006/0216509 also discloses a process to render polyurea capsules positively- charged. This process involves the addition, during the wall formation, of polyamines, the capsules thus bearing latent charges, depending on the pH of the medium. Once formed, the capsules are subsequently cationized by acid action or alkylation to bear permanent positive charges. The cationic compounds therefore react with the capsule wall, chemically changing the latter.
  • WO2009/153695 discloses a simplified process for the preparation of polyurea microcapsules bearing permanent positive charges based on the use of a specific stabilizer and which present good deposition on a substrate.
  • microcapsules of the invention solve this problem as they proved to show improvement in terms of deposition properties compared to what was known heretofore such as cationic delivery systems.
  • the present invention provides microcapsules with boosted deposition properties.
  • the specific growth of a mineral layer onto a terminating charged surface of the microcapsule is unexpectedly tremendously improving the percentage of deposition of microcapsules on a substrate.
  • a first object of the invention is therefore a mineralized core-shell microcapsule slurry comprising at least one microcapsule having:
  • an oil-based core comprising a hydrophobic active ingredient, preferably a perfume
  • a second object of the invention is a process for preparing a mineralized core-shell microcapsule slurry as defined above comprising the steps of:
  • a third object of the invention is a perfuming composition comprising the microcapsules as defined above, wherein the oil-based core comprises a perfume.
  • a fourth object of the invention is a consumer product comprising the microcapsules or a perfuming composition as defined above.
  • a fifth object of the invention is a method for improving deposition of microcapsules on a surface, which comprises treating said surface with a perfuming composition or a consumer product as defined above.
  • Figure 1 represents scanning electron micrographs of mineralized microcapsules according to the invention (Capsules A, B, and C) compared to smooth, unmineralized control capsules (Capsules X, Y, and Z).
  • Figure 2 represents scanning electron micrographs of the mineralized surface of microcapsules according to the invention (Capsules A) achieved through directed growth of the mineral layer (goethite).
  • Figure 3 represents scanning electron micrographs of the mineralized surface of microcapsules according to the invention (Capsules H) achieved through directed growth of the mineral layer (calcium phosphate).
  • Figure 4 represents the percentage of microcapsule deposition of mineralized microcapsules according to the invention (Capsules A, E, F,G) compared to smooth relevant control capsules (Capsules V, W, Y,Z) onto hair after rinsing from a model surfactant mixture loaded at 0.5wt% equivalent free oil.
  • Figure 5 represents scanning electron micrographs of microcapsules according to the invention (mineralized Capsules A) deposited onto Caucasian, brunette, virgin hair from a model surfactant mixture after rinsing.
  • Figure 6 represents the percentage of microcapsule deposition of mineralized microcapsules according to the invention (Capsules A, B, C and D) compared to smooth control capsules (Capsules W and X) onto a lg cotton fabric swatch from a model detergent base after subjecting swatch to a miniaturized laundry cycle simulation.
  • Figure 7 represents the percentage of microcapsule deposition of mineralized capsules according to the invention (Capsules A, B, C and D) compared to smooth control capsules (Capsules W and X) onto a lg cotton fabric swatch from a model fabric softener base after subjecting swatch to a miniaturized laundry cycle simulation.
  • Figure 8 represents the percentage of bulk capsule concentration cleared by a lg fabric swatch after high speed vortexing in a solution loaded with a diluted softener solution containing 0.2 wt% encapsulated oil.
  • Figure 9 represents the olfactive evaluation of microcapsules deposited onto hair from a model surfactant mixture before and after combing (capsule Z -not part of the invention and capsule G - according to the invention).
  • Figure 10 represents scanning electron micrographs showing stability of mineralized microcapsules subjected to various pH conditions and different surfactant systems after a period of 4 weeks.
  • Figure 11 represents scanning electron micrographs showing mineralized
  • microcapsule stability after being subjected to drying by lyophilization.
  • Figure 12 depicts measured total and curvature-corrected surface roughness profiles (y axis) as a function of analyzed segment scan length (x axis) obtained using a Keyence VK laser scanning confocal microscope for Capsule V smooth control.
  • Figure 13 depicts measured total and curvature-corrected surface roughness profiles (y axis) as a function of analyzed segment scan length (x axis) obtained using Keyence VK laser scanning confocal microscope for Capsule F rough mineralized capsule.
  • Figure 14 depicts measured roughness profiles for smooth (V) and rough (F) capsules analyzed using a Dimension ICON Atomic Force Microscope from Bruker along the 1 micron scan lines indicated.
  • Figure 15 depicts measured roughness parameters determined using two instruments (Keyence VK confocal laser scanning microscope profilometer and Dimension ICON atomic force microscope) plotted against capsule deposition performance onto hair from a model surfactant mixture after rinsing for rough (A, F) and smooth control capsules (V, Y). Using both characterization techniques, increased surface roughness strongly correlates with increased deposition of capsules onto hair after rinsing.
  • a "core-shell microcapsule”, or the similar, in the present invention is meant to designate a capsule that has a particle size distribution in the micron range (e.g. a mean diameter (d(v, 0.5)) comprised between about 1 and 3000 ⁇ ) and comprises an external solid oligomer-based shell or a polymeric shell and an internal continuous phase enclosed by the external shell.
  • a mean diameter d(v, 0.5)
  • coacervates are considered as core-shell microcapsules in the present invention.
  • mineralized core-shell microcapsule it should be understood a microcapsule having a mineralized surface induced by growth of inorganic solid crystalline material.
  • charged emulsifier it should be understood a compound having emulsifying properties and that is negatively charged and/or positively charged.
  • the charged emulsifier can be a charged biopolymer.
  • charged biopolymer it should be understood a biopolymer that is negatively charged (anionic biopolymer), and/or positively charged (cationic or protonated biopolymer), and/or zwitterionic.
  • anionic biopolymer a biopolymer that is negatively charged (anionic biopolymer), and/or positively charged (cationic or protonated biopolymer), and/or zwitterionic.
  • biopolymers it is meant biomacromolecules produced by living organisms. Biopolymers are characterized by molecular weight distributions ranging from 1,000 (1 thousand) to 1,000,000,000 (1 billion) Daltons. These macromolecules may be carbohydrates (sugar based) or proteins (amino-acid based) or a combination of both (gums) and can be linear or branched. The biopolymers according to the invention may be further chemically modified.
  • biopolymers are amphiphilic or anionic namely negatively charged in water at a pH greater than 9.
  • a “mineral layer” is composed of a stable inorganic crystalline phase that grows normal to the terminating charged surface of the shell to yield a rough, spinulose, rugose, platy, ridged or otherwise highly textured mineral aspect.
  • mineral precursor it should be understood a mineral precursor required for growth of the desired crystalline phase.
  • the mineral precursor is preferably a mineral water- soluble salt containing the necessary ions for growth of the desired crystalline phase.
  • incubating is used in the context of the present invention to describe the act of submerging the microcapsules in the precursor solution and allowing it time to interact with the microcapsules.
  • polyurea-based wall or shell it is meant that the polymer comprises urea linkages produced by either an amino-functional crosslinker or hydrolysis of isocyanate groups to produce amino groups capable of further reacting with isocyanate groups during interfacial polymerization.
  • polyurethane-based wall or shell it is meant that the polymer comprises urethane linkages produced by reaction of a polyol with the isocyanate groups during interfacial polymerization.
  • 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.
  • hydrophobic active ingredient any active ingredient - single ingredient or a mixture of ingredients - which forms a two-phase dispersion when mixed with water.
  • Hydrophobic active ingredients are preferably chosen from the group consisting of flavor, flavor ingredients, perfume, perfume ingredients, nutraceuticals, cosmetics, insect control agents, biocide actives and mixtures thereof.
  • insect control agents present in the hydrophobic internal 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 the intended use or application.
  • insect control agents are birch, DEET (N,N-diethyl-m-toluamide), essential oil of the lemon eucalyptus (Corymbia citriodora) and its active compound p- menthane-3,8-diol(PMD), icaridin (hydroxyethyl isobutyl piperidine carboxylate) , Nepelactone, Citronella oil, Neem oil, Bog Myrtle (Myrica Gale), Dimethyl carbate, Tricyclodecenyl allyl ether, IR3535 (3-[N-Butyl-N-acetyl]-aminopropionic acid, ethyl ester, Ethylhexanediol, Dimethyl phthalate, Metofluthrin, Indalone, SS220, anthranilate -based insect repellents, and mixtures thereof.
  • the hydrophobic-active ingredient comprises a mixture
  • the hydrophobic active ingredient comprises a perfume.
  • the hydrophobic active ingredient consists of a perfume.
  • perfume oil (or also “perfume”) what is meant here is an ingredient or 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 combination of perfuming ingredients with substances which together improve, enhance or modify the delivery of the perfuming ingredients, such as perfume precursors, emulsions or dispersions, as well as combinations which impart an additional benefit beyond that of modifying or imparting an odor, such as long-lasting, blooming, malodor counteraction, antimicrobial effect, microbial stability, insect control.
  • perfuming ingredients such as perfume precursors, emulsions or dispersions, as well as combinations which impart an additional benefit beyond that of modifying or imparting an odor, such as long-lasting, blooming, malodor counteraction, antimicrobial effect, microbial stability, insect control.
  • perfuming ingredients present in the hydrophobic internal 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 sulphurous heterocyclic compounds and essential oils, and said perfuming co-ingredients can be of natural or synthetic origin. Many of these co-ingredients are in any case listed in reference texts such as the book by S.
  • the perfuming ingredients may be dissolved in a solvent of current use in the perfume industry.
  • the solvent is preferably not an alcohol.
  • solvents are diethyl phthalate, isopropyl myristate, Abalyn ® (rosin resins, available from Eastman), benzyl benzoate, ethyl citrate, limonene or other terpenes, or isoparaffins.
  • the solvent is very hydrophobic and highly sterically hindered, like for example Abalyn ® or benzyl benzoate.
  • the perfume comprises less than 30% of solvent. More preferably the perfume comprises less than 20% and even more preferably less than 10% of solvent, all these percentages being defined by weight relative to the total weight of the perfume. Most preferably, the perfume is essentially free of solvent.
  • a first object of the invention is therefore a mineralized core-shell microcapsule slurry comprising at least one microcapsule having:
  • an oil-based core comprising a hydrophobic active ingredient, preferably a perfume
  • the mineral layer forms a spinulose surface covered by small spikes, ridges or platy protuberances perpendicular to the terminating charged functional surface (typically having a length between 100 and 600 nm and having an aspect ratio greater than 1).
  • the surface of the mineral layer has a rough, spiny, spiky, ridged, rugose, dendritic or textured appearance with rough heterogeneous crystalline features over the surface.
  • the mineral layer has an arithmetical mean roughness value (R a ) greater than 15nm, preferably greater than 50nm and/or a mean roughness depth (R z ) greater than 50nm, preferably greater than lOOnm.
  • R a and R z mean roughness depth
  • the instrument used in the present invention to evaluate surface features and determine surface roughness parameters R a and R z is a Keyence VK-X series confocal laser scanning microscope profilometer with a violet range laser.
  • a Dimension ICON Atomic Force Microscope (AFM) from Bruker was also used to evaluate the surface features.
  • Roughness parameters are well known by the skilled person in the art and can be defined as follows.
  • the arithmetical mean roughness value (R a ) is the average deviation of the surface height from the mean height of the roughness profile.
  • the mean roughness depth (R z ) is the mean localized maximum roughness, or average peak-to-valley height difference per unit length analyzed.
  • microcapsules of the invention due notably to this specific spinulose or rough textured surface that adheres strongly to the targeted substrates. Nature/formation of the shell
  • the polymeric shell is formed by interfacial polymerisation in the presence of a charged emulsifier.
  • the polymeric shell has a terminating charged functional surface covered by a mineral layer.
  • the terminating charged functional surface can be anionic or cationic.
  • the terminating charged functional surface is a terminating anionic functional surface.
  • Emulsifier anionic emulsifier
  • the charged emulsifier is an anionic emulsifier and forms an anionic surface once the interfacial polymerization is completed.
  • the anionic emulsifier can be amphiphilic materials, colloidal stabilizers or biopolymers. According to an embodiment, the anionic emulsifier is selected from the group consisting of polyvinyl alcohol, polyvinyl pyrrolidone, gum acacia, casein, sodium caseinate, soy protein, pea protein, milk protein, whey protein, pectin, sericin, bovine serum albumin, gelatin, and mixtures thereof.
  • gum acacia is preferred.
  • the anionic surface (formed by the anionic emulsifier) is the terminating anionic functional surface that is directly covered by the mineral layer.
  • a polyelectrolyte scaffolding composed of oppositely-charge polyelectrolyte layer can be disposed between the anionic surface and the mineral layer.
  • the microcapsule comprises a polyelectrolyte scaffolding on the anionic surface, said polyelectrolyte scaffolding including at least one cationic polyelectrolyte layer and at least one anionic polyelectrolyte layer, the terminating layer being an anionic polyelectrolyte layer to form the terminating anionic functional surface of the shell.
  • the first layer of the polyelectrolyte scaffolding is a cationic polyelectrolyte layer disposed on the anionic surface (formed by the anionic emulsifier) and the last layer of the polyelectrolyte scaffolding is an anionic polyelectrolyte layer to form the terminating anionic functional surface on which the mineral layer is coated.
  • the number of layers of the polyelectrolyte scaffolding is not particularly limited.
  • the polyelectrolyte scaffolding consists of two pairs of oppositely charged polyelectrolytes layers.
  • the microcapsule according to the invention comprises the following successive layers on the polymeric shell:, a first cationic polyelectrolyte layer 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 terminating anionic functional surface) and a mineral layer.
  • Emulsifier cationic emulsifier
  • the charged emulsifier is a cationic emulsifier that forms a cationic surface
  • the microcapsule comprises at least one anionic polyelectrolyte layer on the cationic surface.
  • the cationic emulsifier is obtained by mixing a weakly anionic emulsifier (such as PVOH) with a strongly charged cationic polymer or polyquaternium (such as Salcare® SC-60 by BASF).
  • a weakly anionic emulsifier such as PVOH
  • a strongly charged cationic polymer or polyquaternium such as Salcare® SC-60 by BASF.
  • cationic emulsifiers one may cite for example cationic functionalized polyvinyl alcohol (as an example, cationic C-506 by Kuraray) or chitosan at an appropriate pH (typically at a weakly acidic pH (approximately pH 6.5).
  • cationic functionalized polyvinyl alcohol as an example, cationic C-506 by Kuraray
  • chitosan at an appropriate pH (typically at a weakly acidic pH (approximately pH 6.5).
  • the anionic surface (formed by the anionic polyelectrolyte layer) is the terminating anionic functional surface that is directly covered by the mineral layer.
  • At least one cationic polyelectrolyte layer and at least a second anionic polyelectrolyte layer are deposited successively on the anionic polyelectrolyte layer.
  • this embodiment is not limited to only one pair of opposite polyelectrolyte layers but includes 2, 3, 4 or even more of pair of opposite polyelectrolyte layers, with the proviso that the last polyelectrolyte layer is an anionic polyelectrolyte layer to form the terminating anionic functional surface.
  • the cationic polyelectrolyte layer is chosen in the group consisting of poly(allylamine hydrochloride), poly-L-lysine and chitosan.
  • the anionic polyelectrolyte layer is chosen in the group consisting of poly(sodium 4 styrene sulfonate) (PSS), polyacrylic acid, polyethylene imine, humic acid, carrageenan, gum acacia, and mixtures thereof.
  • PSS poly(sodium 4 styrene sulfonate)
  • polyacrylic acid polyethylene imine
  • humic acid polyethylene imine
  • carrageenan humic acid
  • gum acacia and mixtures thereof.
  • the anionic polyelectrolyte layer is PSS.
  • the shell can be made of a polymeric material selected from the group consisting of polyurea, polyurethane, polyamide, polyacrylate, polysiloxane, polycarbonate, polysulfonamide, urea formaldehyde, melamine formaldehyde resin, melamine urea resin, melamine glyoxal resin, gelatin/ gum acacia shell wall, coacervates and mixtures thereof.
  • the microcapsule comprises a mineral layer on the terminating charged functional surface.
  • the terminating functional surface is anionic and can be obtained by using an anionic emulsifier with optionally a polyelectrolyte scaffolding as defined above or by using a cationic emulsifier with at least one anionic polyelectrolyte layer.
  • the mineral layer comprises a material chosen in the group consisting of iron oxides, iron oxyhydroxide, titanium oxides, zinc oxides, calcium carbonates, calcium phosphates and mixtures thereof.
  • the mineral layer is an iron oxide, an iron oxyhydroxide, or a calcium phosphate.
  • the mineral layer is iron oxyhydroxide goethite (a-FeO(OH)).
  • the mineral layer is calcium phosphate.
  • the mineral layer does not comprise silicon oxides.
  • Another object of the invention is a core-shell microcapsule powder obtained by drying the core-shell microcapsule slurry as defined above.
  • Another object of the present invention is a process for preparing a mineralized core-shell microcapsule slurry as defined above comprising the steps of:
  • Step(i) Preparing a core-shell microcapsule slurry comprising microcapsules having a terminating charged functional surface
  • the polymeric shell is formed by interfacial polymerisation in the presence of a charged emulsifier.
  • the polymeric shell has a terminating charged functional surface on which a mineral precursor will be adsorbed in step (ii).
  • Different ways can be used to impart such charged surface on the polymeric shell.
  • the terminating charged functional surface is a terminating anionic functional surface.
  • Emulsifier anionic emulsifier
  • the charged emulsifier is an anionic emulsifier and forms an anionic surface once the interfacial polymerization is completed.
  • the anionic emulsifier can be amphiphilic materials, colloidal stabilizers or biopolymers.
  • the anionic emulsifier is selected from the group consisting of polyvinyl alcohol, polyvinyl pyrrolidone, gum acacia, casein, sodium caseinate, soy
  • protein hydrolyzed soy protein, pea protein, milk protein, whey protein, pectin, sugar beet pectin, sericin, bovine serum albumin, gelatin, and mixtures thereof.
  • gum acacia is preferred.
  • the anionic surface (formed by the anionic emulsifier) is the terminating anionic functional surface on which a mineral precursor will be adsorbed in step (ii).
  • step (i) can further comprise an additional step consisting of adding a polyelectrolyte scaffolding composed of oppositely-charge polyelectrolyte layer once the microcapsules are formed.
  • the polyelectrolyte scaffolding including at least one cationic polyelectrolyte layer and at least one anionic polyelectrolyte layer, the terminating layer being an anionic polyelectrolyte layer to form the terminating anionic functional surface of the shell.
  • the first layer of the polyelectrolyte scaffolding is a cationic polyelectrolyte layer disposed on the anionic surface (formed by the anionic emulsifier) and the last layer of the polyelectrolyte scaffolding is an anionic polyelectrolyte layer to form the terminating anionic functional surface on which on which a mineral precursor will be adsorbed in step (ii).
  • the number of layers of the polyelectrolyte scaffolding is not particularly limited.
  • the polyelectrolyte scaffolding consists of two pairs of oppositely charged polyelectrolytes layers.
  • the microcapsule according to the invention comprises the following successive layers on the polymeric shell:, a first cationic polyelectrolyte layer 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 terminating anionic functional surface).
  • Emulsifier cationic emulsifier
  • the charged emulsifier is a cationic emulsifier that forms a cationic surface when the interfacial polymerization is completed, and wherein step (i) further comprises a step of coating at least one anionic polyelectrolyte layer on the cationic surface to form core-shell microcapsule having a terminating anionic functional surface.
  • the cationic emulsifier is obtained by mixing a weakly anionic emulsifier (such as PVOH) with a strongly charged cationic polymer or polyquaternium (such as Salcare® SC-60 by BASF).
  • cationic emulsifiers one may cite for example cationic functionalized polyvinyl alcohol (as an example, cationic C-506 by Kuraray) or chitosan at an appropriate pH (typically at a weakly acidic pH (approximately pH 6.5).
  • cationic functionalized polyvinyl alcohol as an example, cationic C-506 by Kuraray
  • chitosan at an appropriate pH (typically at a weakly acidic pH (approximately pH 6.5).
  • the anionic surface (formed by the anionic polyelectrolyte layer) is the terminating anionic functional surface on which a mineral precursor will be adsorbed in step (ii).
  • at least one cationic polyelectrolyte layer and at least a second anionic polyelectrolyte layer are deposited successively on the anionic polyelectrolyte layer.
  • this embodiment is not limited to only one pair of opposite polyelectrolyte layers but includes 2, 3, 4 or even more of pair of opposite polyelectrolyte layers, with the proviso that the last polyelectrolyte layer is an anionic polyelectrolyte layer to form the terminating anionic functional surface.
  • the cationic polyelectrolyte layer is chosen in the group consisting of poly(allylamine hydrochloride), poly-L-lysine and chitosan.
  • the anionic polyelectrolyte layer is chosen in the group consisting of poly(sodium 4 styrene sulfonate) (PSS), polyacrylic acid, polyethylene imine, humic acid, carrageenan, gum acacia, and mixtures thereof.
  • PSS poly(sodium 4 styrene sulfonate)
  • polyacrylic acid polyethylene imine
  • humic acid polyethylene imine
  • carrageenan humic acid
  • gum acacia and mixtures thereof.
  • the anionic polyelectrolyte layer is PSS.
  • said microcapsule wall material may comprise any suitable resin and especially including melamine, glyoxal, polyurea, polyurethane, polyamide, polyester, etc.
  • suitable resins include the reaction product of an aldehyde and an amine
  • suitable aldehydes include, formaldehyde and glyoxal.
  • suitable amines include melamine, urea, benzoguanamine, glycoluril, and mixtures thereof.
  • Suitable melamines include, methylol melamine, methylated methylol melamine, imino melamine and mixtures thereof.
  • Suitable ureas include, dimethylol urea, methylated dimethylol urea, urea-resorcinol, and mixtures thereof.
  • Suitable materials for making may be obtained from one or more of the following companies Solutia Inc. (St Louis, Missouri U.S.A.), Cytec Industries (West Paterson, New Jersey U.S.A.), Sigma-Aldrich (St. Louis, Missouri U.S.A.).
  • capsules according to the present invention are polyurea-based capsules.
  • interfacial polymerization is induced by addition of a polyamine reactant.
  • the reactant is selected from the group consisting of water soluble guanidine salts and guanazole to form a polyurea wall with the polyisocyanate.
  • polyurea-based capsules are formed in absence of added polyamine reactant, and result only from the autopolymerization of the at least one polyisocyanate.
  • capsules according to the present invention are polyurethane -based capsules.
  • interfacial polymerization is induced by addition of a polyol reactant.
  • the reactant is selected from the group consisting of monomeric and polymeric polyols with multiple hydroxyl groups available for reaction and mixtures thereof.
  • capsules according to the present invention are polyurea/polyurethane based.
  • interfacial polymerization is induced by addition of a mixture of the reactant mentioned under precedent first and second embodiments.
  • crosslinkers with both amino groups and hydroxyl groups can be used to generate polyurea/polyurethane materials.
  • polyisocyanates with both urea and urethane functionalities can be used to generate polyurea/polyurethane materials.
  • the shell is polyurea-based made from, for example but not limited to isocyanate-based monomers and amine-containing crosslinkers such as guanidine carbonate and/or guanazole.
  • Preferred polyurea-based 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
  • a colloidal stabilizer or emulsifier for example a colloidal stabilizer or emulsifier
  • an encapsulated perfume for example a water soluble guanidine salt and guanidine
  • the use of an amine can be omitted.
  • the shell is polyurethane -based made from, for example but not limited to polyisocyanate and polyols, polyamide, polyester, etc.
  • the colloidal stabilizer includes an aqueous solution of between 0.1% and 0.4% of polyvinyl alcohol, between 0.6% and 1% of a cationic copolymer of vinylpyrrolidone and of a quaternized vinylimidazole (all percentages being defined by weight relative to the total weight of the colloidal stabilizer).
  • the emulsifier is an anionic or amphiphilic biopolymer preferably chosen from the group consisting of polyacrylate (and copolymers especially with acrylamide), gum acacia, soy protein, pectin, gelatin, sodium caseinate and mixtures thereof.
  • the polyisocyanate is an aromatic polyisocyanate, preferably comprising a phenyl, a toluyl, a xylyl, a naphthyl or a diphenyl moiety.
  • Preferred aromatic polyisocyanates are biurets and polyisocyanurates, more preferably a polyisocyanurate of toluene diisocyanate (commercially available from Bayer under the tradename Desmodur ® RC), a trimethylol propane-adduct of toluene diisocyanate (commercially available from Bayer under the tradename Desmodur ® L75), a trimethylol propane-adduct of xylylene diisocyanate (commercially available from Mitsui Chemicals under the tradename Takenate ® D-l ION).
  • a polyisocyanurate of toluene diisocyanate commercially available from Bayer under the tradename Desmodur ® RC
  • Desmodur ® L75 a trimethylol propane-adduct of xylylene diisocyanate
  • Takenate ® D-l ION a trimethylol propane-adduct of xylylene diisocyanate
  • the polyisocyanate is a trimethylol propane- adduct of xylylene diisocyanate (commercially available from Mitsui Chemicals under the tradename Takenate ® D-l ION).
  • the shell of the microcapsule is based on melamine formaldehyde resin or melamine formaldehyde resin cross-linked with at least one polyisocyanate or aromatic polyols.
  • the shell comprises an aminoplast copolymer, such as melamine-formaldehyde or urea-formaldehyde or cross-linked melamine formaldehyde or melamine glyoxal.
  • the core-shell microcapsules are cross-linked melamine formaldehyde microcapsules obtainable by a process comprising the steps of:
  • the core-shell microcapsule is a formaldehyde-free capsule.
  • a typical process for the preparation of aminoplast formaldehyde-free microcapsules slurry comprises the steps of:
  • an aldehyde component in the form of a mixture of glyoxal, a C 4 -6 2,2-dialkoxy- ethanal and optionally a glyoxalate, said mixture having a molar ratio glyoxal/C 4 - 6
  • 2,2-dialkoxy-ethanal comprised between 1/1 and 10/1;
  • n stands for 2 or 3 and 1 represents a C 2 -C 6 group optionally comprising from 2 to 6 nitrogen and/or oxygen atoms;
  • microcapsules are rinsed to remove the excess of emulsifier.
  • Microcapsules can be rinsed for example by centrifugation and resuspended in water after withdrawing the supernatant.
  • Step (ii) and step (iii) Mineralization and crystal growth
  • the charged terminating surface is providing functional anchoring sites and a high local density of charge groups and nucleation sites onto the surface of the microcapsules resulting in improved adsorption of mineral precursor species followed by initiation of the crystal growth process through in-situ addition of a precipitating species.
  • Mineral precursors are adsorbed to the surface of microcapsules by incubating the charged capsules in at least one solution containing oppositely charged mineral precursor, providing sufficient agitation and time to allow for complete coverage of capsule surfaces. Removal of excess precursor from solution to prevent generation of free crystalline material in solution can be done and is followed by initiation of the crystal growth process through in- situ addition of a precipitating species.
  • suitable conditions for the crystal growth process for example, precursor selection, reaction conditions, the solution concentrations, incubation times, agitation speeds, temperatures and pH conditions).
  • the nature of the precipitation species depends on the nature of the precursor.
  • the mineral precursor solution is chosen in the group consisting of an iron (II) sulfate solution (comprising iron ions as precursor), an iron (III) chloride solution (comprising iron ions as precursor), calcium-based salt solution (comprising calcium ions as precursor), phosphate -based salt solution (comprising phosphate ions as precursor), carbonate-based salt solution (comprising carbonate ions as precursor), titanium-based precursor solution, zinc-based precursor solution, and mixtures thereof.
  • an iron (II) sulfate solution comprising iron ions as precursor
  • an iron (III) chloride solution comprising iron ions as precursor
  • calcium-based salt solution comprising calcium ions as precursor
  • phosphate -based salt solution comprising phosphate ions as precursor
  • carbonate-based salt solution comprising carbonate ions as precursor
  • titanium-based precursor solution comprising titanium-based precursor solution, zinc-based precursor solution, and mixtures thereof.
  • titanium alkoxides as titanium-based precursor or zinc alkoxides, zinc acetate, zinc chloride as zinc-based precursor solution.
  • the mineral precursor solution is chosen in the group consisting of an iron (II) sulfate solution (comprising iron ions as precursor), an iron (III) chloride solution (comprising iron ions as precursor), calcium-based salt solution (comprising calcium ions as precursor), phosphate-based salt solution (comprising phosphate ions as precursor) and mixtures thereof.
  • the water-soluble calcium-based salt can be chosen in the group consisting of calcium chloride (CaCl 2 ), calcium nitrate (Ca(N03) 2 ), calcium bromide (CaBr 2 ), calcium iodide (Cal 2 ), calcium chromate (CaCr0 4) , calcium acetate (CaCH3C0 2 ) and mixtures thereof. Most preferred are calcium chloride and calcium nitrate.
  • the water-soluble phosphate-based salt can be chosen in the group consisting of sodium phosphate (monobasic) (NaH 2 P0 4 ), sodium phosphate (dibasic) (Na 2 HP0 4 ), sodium phosphate (tribasic): Na 3 P0 4 , Potassium phosphate (monobasic): KH 2 P0 4 , Potassium phosphate (dibasic) (K 2 HP0 4 ), potassium phosphate (tribasic) (K 3 P0 4 ), ammonium phosphate (monobasic) ((NH 4 )H 2 P04), ammonium phosphate(dibasic) ((NH 4 ) 2 HP0 4 ), ammonium phosphate(tribasic) ((NH 4 )3P0 4) and mixtures thereof.
  • the water-soluble carbonate-based salt can be chosen in the group consisting of sodium, potassium and ammonium based carbonates.
  • step (ii) of the process is driven by the charge of the terminating surface of the microcapsules.
  • the mineral precursor solution is chosen in the group consisting of an iron (II) sulfate solution, or an iron (III) chloride solution.
  • the initiation of the crystal growth process can be done through in-situ addition of a precipitating species.
  • the mineral precursor is an iron solution
  • irons ions are adsorbed on the anionic surface and precipitating species used is a base for hydrolysis to form an iron oxide layer (for example by addition of a sodium hydroxide solution).
  • the mineral precursor solution is a calcium-based salt (comprising calcium ions as precursor).
  • calcium ions are adsorbed on the anionic surface.
  • Precipating species in that case is the addition of another salt, preferably a phosphate-based salt (for one hour for example).
  • microcapsules are introduced sequentially in at least two solutions comprising respectively at least one precursor.
  • the first solution comprises water-soluble calcium-based salt including a calcium precursor and the second solution comprises water-soluble phosphate -based salt including a phosphate precursor.
  • Addition order could change according to the selection and charge of the underlying terminating layer.
  • the first solution comprises calcium nitrate (Ca(N0 3 ) 2 ) and the second solution comprises sodium phosphate (dibasic) (Na 2 HP0 4 ).
  • Embodiment 3 when the terminating surface of the microcapsules are cationic, the microcapsules are firstly incubating in carbonate-based salt solution or in a phosphate-based salt solution to adsorb carbonate ions CO 3 2" or phosphate ions P0 4 3" respectively on the cationic surface followed by an incubation in a calcium-based mineral solution.
  • the process for the preparation of the microcapsule slurry comprises the following steps:
  • the shell has an anionic surface when the emulsifier used in step b) is an anionic emulsifier;
  • the shell has a cationic surface when the emulsifier used in step b) is a cationic emulsifier;
  • the process comprises the preparation of an oil phase by dissolving a polyisocyanate having at least two isocyanate groups in an oil comprising a hydrophobic active ingredient as defined above.
  • a polyisocyanate having at least two isocyanate groups in an oil comprising a hydrophobic active ingredient as defined above.
  • Suitable polyisocyanates used according to the invention include aromatic polyisocyanate, aliphatic polyisocyanate and mixtures thereof. Said polyisocyanate comprises at least 2, preferably at least 3 but may comprise up to 6, or even only 4, isocyanate functional groups. According to a particular embodiment, a triisocyanate (3 isocyanate functional group) is used.
  • said polyisocyanate is an aromatic polyisocyanate.
  • aromatic polyisocyanate is meant here as encompassing any polyisocyanate comprising an aromatic moiety. Preferably, it comprises a phenyl, a toluyl, a xylyl, a naphthyl or a diphenyl moiety, more preferably a toluyl or a xylyl moiety.
  • Preferred aromatic polyisocyanates are biurets, polyisocyanurates and trimethylol propane adducts of diisocyanates, more preferably comprising one of the above-cited specific aromatic moieties.
  • the aromatic polyisocyanate is a polyisocyanurate of toluene diisocyanate (commercially available from Bayer under the tradename Desmodur ® RC), a trimethylol propane-adduct of toluene diisocyanate (commercially available from Bayer under the tradename Desmodur ® L75), a trimethylol propane-adduct of xylylene diisocyanate (commercially available from Mitsui Chemicals under the tradename Takenate ® D-l 10N).
  • the aromatic polyisocyanate is a trimethylol propane-adduct of xylylene diisocyanate.
  • said polyisocyanate is an aliphatic polyisocyanate.
  • aliphatic polyisocyanate is defined as a polyisocyanate which does not comprise any aromatic moiety.
  • Preferred aliphatic polyisocyanates are a trimer of hexamethylene diisocyanate, a trimer of isophorone diisocyanate, a trimethylol propane-adduct of hexamethylene diisocyanate (available from Mitsui Chemicals) or a biuret of hexamethylene diisocyanate (commercially available from Bayer under the tradename Desmodur ® N 100), among which a biuret of hexamethylene diisocyanate is even more preferred.
  • the at least one polyisocyanate is in the form of a mixture of at least one aliphatic polyisocyanate and of at least one aromatic polyisocyanate, both comprising at least two or three isocyanate functional groups, such as a mixture of a biuret of hexamethylene diisocyanate with a trimethylol propane-adduct of xylylene diisocyanate, a mixture of a biuret of hexamethylene diisocyanate with a polyisocyanurate of toluene diisocyanate and a mixture of a biuret of hexamethylene diisocyanate with a trimethylol propane-adduct of toluene diisocyanate.
  • the molar ratio between the aliphatic polyisocyanate and the aromatic polyisocyanate is ranging from 80:20 to 10:90.
  • the at least one polyisocyanate used in the process according to the invention is present in amounts representing from 1 to 15%, preferably from 2 to 8% and more preferably from 2 to 6% by weight of the microcapsule slurry.
  • the at least one polyisocyanate is dissolved in an oil, which in a particular embodiment contains a perfume or flavour.
  • the oil can contain a further oil-soluble benefit agent to be co-encapsulated with the perfume and flavour with the purpose of delivering additional benefit on top of perfuming or taste-related.
  • ingredients such as cosmetic, skin caring, malodor counteracting, bactericide, fungicide, pharmaceutical or agrochemical ingredient, a diagnostic agent and/or an insect repellent or attractant and mixtures thereof can be used.
  • the process of the present invention includes the use of an anionic or amphiphilic biopolymer in the preparation of the aqueous phase.
  • materials defined above include in particular proteins and polysaccharides.
  • the biopolymer is preferably comprised in an amount ranging from 0.1 to 5.0% by weight of the microcapsule slurry, preferably between 0.5 and 2 wt% of the microcapsule slurry.
  • the charged emulsifier used in step b) is an anionic emulsifier and forms an anionic surface when step d) is completed.
  • the anionic emulsifier is selected from the group consisting of polyvinyl alcohol, polyvinyl pyrilidone, gum acacia, casein, sodium caseinate, soy protein, pea protein, milk protein, whey protein, pectin, sericin, bovine serum albumin, gelatin, and mixtures thereof.
  • the anionic emulsifier is gum acacia.
  • a cationic emulsifier is used in step b) and forms a cationic surface when step d) is completed.
  • cationic emulsifiers one may cite for example cationically modified polyvinyl alcohol (as an example, cationic C-506 by Kuraray) or chitosan.
  • the process further comprises a step consisting in coating an anionic polyelectrolyte layer to impart a negatively charged surface necessary to induce the crystal growth of the mineral.
  • said surface can be modified through the adsorption of a polyelectrolyte multilayered scaffolding.
  • the process comprises a further step after step d) or after step e), consisting in coating at least one cationic polyelectrolyte layer and at least one anionic polyelectrolyte layer, the terminating layer being an anionic polyelectrolyte layer to form the terminating anionic functional surface.
  • the cationic polyelectrolyte layer is disposed on the anionic surface and the anionic polyelectrolyte layer is the last layer to form the terminating anionic functional surface on which the mineral precursor is adsorbed.
  • Oppositely-charge polyelectrolytes may be sequentially coated onto microcapsules using layer-by-layer polyelectrolyte deposition in order to provide a multi-layered polyelectrolyte scaffold for adsorption of mineral precursors.
  • the number of layers of the polyelectrolyte scaffolding is not particularly limited.
  • the polyelectrolyte scaffolding consists of two pairs of oppositely charged polyelectrolytes layers. It means that according to this embodiment, after step d) or step e), the process comprises:
  • the cationic polyelectrolyte layer is chosen in the group consisting of poly(allylamine hydrochloride), poly-L-lysine and chitosan.
  • the anionic polyelectrolyte layer is chosen in the group consisting of poly(sodium 4 styrene sulfonate) (PSS), polyacrylic acid, polyethylene imine, humic acid, carrageenan, gum acacia, and mixtures thereof.
  • PSS poly(sodium 4 styrene sulfonate)
  • polyacrylic acid polyethylene imine
  • humic acid polyethylene imine
  • carrageenan humic acid
  • gum acacia and mixtures thereof.
  • the anionic polyelectrolyte layer is PSS.
  • the process comprises after step h) a further step consisting of hydrolysis of the mineral layer. This can be done for example by addition of sodium hydroxide.
  • the microcapsule slurry can be submitted to a drying, like lyophilisation or spray-drying, to provide the microcapsules as such, i.e. in a powder form.
  • a drying like lyophilisation or spray-drying
  • the slurry may be spray- dried preferably in the presence of a polymeric carrier material such as polyvinyl acetate, polyvinyl alcohol, dextrins, maltodextrin, natural or modified starch, sugars, vegetable gums such as gum acacia, pectins, xanthans, alginates, carrageenans or cellulose derivatives to provide microcapsules in a powder form.
  • the carrier is a gum Acacia.
  • the carrier material contains free perfume oil which can be same or different from the perfume from the core of the microcapsules.
  • a microcapsule slurry obtainable by the process as defined above is also a subject of the present invention.
  • Another object of the invention is a microcapsule powder obtained by drying the microcapsule slurry defined above.
  • Another object of the invention is a perfuming composition
  • a perfuming composition comprising
  • microcapsules as defined above, wherein the oil-based core comprises a perfume
  • liquid perfumery carrier one may cite, as non-limiting examples, an emulsifying system, i.e. a solvent and a surfactant system, or a solvent commonly used in perfumery.
  • a solvent and a surfactant system i.e. a solvent and a surfactant system
  • a detailed description of the nature and type of solvents commonly used in perfumery cannot be exhaustive.
  • solvents such as dipropyleneglycol, diethyl phthalate, isopropyl myristate, benzyl benzoate, 2-(2- ethoxyethoxy)-l -ethanol or ethyl citrate, which are the most commonly used.
  • compositions which comprise both a perfumery carrier and a perfumery co-ingredient can be also ethanol, water/ethanol mixtures, limonene or other terpenes, isoparaffins such as those known under the trademark Isopar ® (origin: Exxon Chemical) or glycol ethers and glycol ether esters such as those known under the trademark Dowanol ® (origin: Dow Chemical Company).
  • perfumery co- ingredient it is meant here a compound, which is used in a perfuming preparation or a composition to impart a hedonic effect and which is not a microcapsule as defined above.
  • such 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.
  • the nature and type of the perfuming co-ingredients present in the perfuming composition do not warrant a more detailed description here, which in any case would not be exhaustive, the skilled person being able to select them on the basis of his general knowledge and according to the intended use or application and the desired organoleptic effect.
  • these perfuming co-ingredients belong to chemical classes as varied as alcohols, lactones, aldehydes, ketones, esters, ethers, acetates, nitriles, terpenoids, nitrogenous or sulphurous heterocyclic compounds and essential oils, and said perfuming co- ingredients can be of natural or synthetic origin.
  • 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. It is also understood that said co-ingredients may also be compounds known to release in a controlled manner various types of perfuming compounds.
  • perfumery adjuvant we mean here an ingredient capable of imparting additional added benefit such as a color, a particular light resistance, chemical stability, etc.
  • additional added benefit such as a color, a particular light resistance, chemical stability, etc.
  • the perfuming composition according to the invention comprises between 0.05 to 30%, preferably between 0.1 and 30 % by weight of microcapsules as defined above.
  • microcapsules can advantageously be used in many application fields and used in consumer products.
  • Microcapsules can be used in liquid form applicable to liquid consumer products as well as in powder form, applicable to powdered consumer products.
  • a consumer product preferably in the form of a laundry care product, a home care product, a body care product, a skin care product, a hair care product, an air care product, or a hygiene product, comprising microcapsules as defined above, or a perfuming composition as defined above is also an object of the present invention.
  • Another object of the present invention is a liquid consumer product comprising: a) from 2 to 65% by weight, relative to the total weight of the consumer product, of at least one surfactant;
  • a powdered consumer product comprising
  • the 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 home-care products including laundry care and air care.
  • another object of the present invention consists of a perfumed consumer product comprising as a perfuming ingredient, the microcapsules defined above or a perfuming composition as defined above.
  • the perfume element of said consumer product can be a combination of perfume microcapsules as defined above and free or non-encapsulated perfume, as well as other types of perfume microcapsule than those here-disclosed.
  • liquid consumer product comprising:
  • powdered consumer product comprising:
  • a perfuming composition as defined above is part of the invention.
  • the invention's microcapsules can therefore be added as such or as part of an invention's perfuming composition in a perfumed consumer product.
  • 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 perfumery consumer product can be a perfume, such as a fine perfume, a cologne or an after-shave lotion; a fabric care product, such as a liquid or solid detergent, tablets and pods, a fabric softener, a dryer sheet, a fabric refresher, an ironing water, or a bleach; a body-care product, such as a hair care product (e.g. a shampoo, hair conditioner, a colouring 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 hair care product e.g. a shampoo, hair conditioner, a colouring 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.
  • the consumer product is selected from the group consisting of a shampoo, a shower gel, a rinse-off conditioner, a soap bar, a powder or a liquid detergent, a fabric softener and a floor cleaner.
  • the consumer product is a shampoo or a rinse- off conditioner.
  • the product is a perfumed soap.
  • the product is a body wash.
  • the product is a fabric care product.
  • the consumer product comprises from 0.05 wt%, preferably from 0.1 to 15wt%, more preferably between 0.2 and 5wt% 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 olfactive effect desired in each product.
  • the mineral layer on microcapsule shell is surprisingly significantly boosting the deposition efficiency and retention of microcapsules on targeted surfaces such as hair and fabric.
  • the percentage of deposition is much higher than that of known delivery systems.
  • Another object of the invention is a method for depositing microcapsules on a surface, which comprises treating said surface with a perfuming composition as defined above or a consumer product as defined above.
  • the capsules of the invention have proven to be particularly useful in rinse-off application as their deposition is much superior to delivery systems known heretofore.
  • Polyurea microcapsules were synthesized according to the formulation described in Table 1 , and loaded with a model perfume mixture outlined in Table 2. These microcapsules were then surface-modified with alternating polyelectrolyte multilayers prior to adsorption and hydrolysis of mineral precursors as described in this example.
  • Table 1 Composition of capsules A according to the invention prior to mineralization
  • At least one polyisocyanate e.g. Trimethylol propane adduct of xylylene diisocyanate Takenate ® D-110N
  • a perfume oil with Uvinul A Plus tracer
  • the oil phase was then added to an aqueous emulsifier solution (e.g. 2% polyvinyl alcohol aqueous solution) and homogenized for 4 min using an Ultra-Turrax T25 disperser at 20000 rpm to form an O/W emulsion.
  • the emulsion was pH adjusted to 10 using NaOH solution (counted as the aqueous phase).
  • This emulsion was then stirred at 500 rpm using a mechanical overhead stirrer and optionally a reactant (e.g. a guanidine carbonate solution) was slowly added over 1 hour. Once the addition was complete, the reaction temperature was gradually elevated to 70 °C over 1 h and was maintained at 70 °C for 2 h before being allowed to cool to room temperature.
  • a reactant e.g. a guanidine carbonate solution
  • a core-shell microcapsule slurry is obtained.
  • Capsules which do not terminate in an anionic polyelectrolyte can be coated using alternating, sequential layer-by-layer deposition of oppositely charged polyelectrolytes.
  • anionic PVOH-stabilized capsules can be coated with cationic polyelectrolyte, polyallylamine hydrochloride (PAH) resulting in a cationic surface.
  • modified capsules can be again rinsed, and coated with oppositely-charged anionic polystyrene sulfonate (PSS) polyelectrolyte resulting in an anionic surface.
  • PSS polystyrene sulfonate
  • the surface layer process, punctuated by rinsing steps can be repeated as many times as required to achieve the desired surface modification.
  • Mineralization of the microcapsule surfaces requires seeding mineral precursor species at the surface of the microcapsules and initiating an in-situ crystal formation reaction. Mineral precursors are adsorbed to the surface of microcapsules by incubating the anionically charged capsules in solutions containing mineral precursor cations, providing sufficient agitation and time to allow for complete coverage of capsule surfaces. Removal of excess precursor from solution to prevent generation of free crystalline material in solution is followed by initiation of the crystal growth process through in-situ addition of a precipitating species.
  • Iron (II) sulfate crystals were dissolved in deionized water. 10 millilitres of the slurry of anionically charged microcapsules was added to 100 millilitres of the iron (II) sulfate solution and was incubated for 24 hours in a flask while being vigorously stirred by stir bar at 800 rpm. The incubation procedure was punctuated by repeatedly rinsing the capsules. Using centrifugation at 5000 rpm for five minutes to induce phase separation, the remaining iron-laden supernatant was removed and replaced with deionized water.
  • This rinsing procedure was performed three times before inducing hydrolysis of the iron layer on the capsules by dropwise addition of sodium hydroxide until the suspension reached a pH of 9.0, at which point the suspension was incubated on a rotating plate for one hour. After hydrolysis, the suspension was subjected to the rinsing procedure in triplicate by centrifugation at 5000 rpm for five minutes, complete removal of the supernatant, and resuspension in deionized water.
  • Example 1 A similar protocol as described in Example 1 was followed to prepare microcapsules with a composition as reported in Table 1. Instead of 4 polyelectrolyte layers, only 2 polyelectrolyte layers (PAH/PSS) were adsorbed to the anionic PVOH capsules, terminating in a negatively charged PSS layer. Mineral precursor incubation and hydrolysis were performed according to protocol described in Example 1.
  • Example 2 A similar protocol as described in Example 1 was applied to prepare microcapsules with a composition as reported in Table 6 below.
  • a cationic PVOH emulsifier (Kuraray C506) was used to emulsify the capsules. Only one polyelecrolyte layer of PSS was adsorbed to provide a terminating negative surface charge. Mineral precursor adsorption and hydrolysis were performed according to the protocol described in Example 1.
  • Example 1 A similar protocol as described in Example 1 was applied to prepare microcapsules with a composition as reported in Table 1. Polyelectrolyte and mineral precursor adsorption, as well as hydrolysis procedures were the same as described in Example 1. A terminating layer of negatively charged polyelectrolyte (PSS) was adsorbed to the positively charged mineral layer by the same polyelectrolyte adsorption procedure described in Example 1.
  • PSS negatively charged polyelectrolyte
  • Example 7 A similar protocol as described in Example 1 using a biopolymer emulsifier without additional polyelectrolyte layers was applied to prepare microcapsules with a composition as reported in Table 7 below. A negatively charged biopolymer, gum acacia, was used as the emulsifier to stabilize the microcapsules. No polyelectrolyte addition or rinsing procedures were performed on the microcapsules prior to mineralization of the surface. Mineral precursor adsorption and hydrolysis were performed according to the procedure described in Example 1.
  • Example 7 Similar protocol as described in Example 5 was applied to prepare microcapsules with a composition as reported in Table 7. Microcapsules were rinsed three times by centrifugation at 5000 rpm and resuspended in deionized water after withdrawing the supernatant to remove residual gum acacia emulsifier before applying the mineral layer by the procedure described in Example 1.
  • Example 5 Similar protocol as described in Example 5 (without addition of sodium hydroxide or guanidine carbonate) was applied to prepare microcapsules with a composition as reported in Table 8. Microcapsules were rinsed three times by centrifugation at 5000 rpm and resuspended in deionized water after withdrawing the supernatant to remove residual gum acacia emulsifier before applying the mineral layer by the procedure described in Example 1.
  • the microcapsule slurry was placed into a dilute buffer solution and subjected to sequential additions of the ionic precursor solutions, starting with the calcium-containing solution, in order to induce precipitation of the calcium based mineral on the surface of the microcapsules.
  • 45 mL of buffer solution were added to 5 mL of capsule slurry under agitation.
  • Precursor 1 was added over one hour, diluted 1 : 10 with water, followed by an hour long addition of Precursor 2 solution. This sequence was repeated one to four times at 0.3M concentrations to get a range of surface coverage.
  • the samples were imaged after ageing for 24 hours under agitation.
  • Example 2 A similar protocol as described in Example 1 was applied to prepare control microcapsules with a composition as reported in Table 1 (for Capsules V and W), Table 6 (for Capsule X), Table 7 (for Capsule Y), and Table 8 for Capsule Z. Guanidine carbonate was used as reactant for all control capsules with the exception of Capsule Z.
  • the control capsules are unmodified or have polyelectrolyte layers without mineralization.
  • Capsule V had a negative surface charge from the negative polyvinyl alcohol emulsifier and was prepared without the polyelectrolyte addition, rinsing, or mineralization procedures (Capsule V is the control template for Capsule B).
  • Capsule W was prepared by rinsing and adding four polyelectrolyte layers terminating in a negatively charged PSS layer, according to the procedure described in Example 1, but without the mineralization procedure (Capsule W is the control template for Capsule A and Capsule D).
  • Capsule X was prepared by addition of a single negatively charged PSS polyelectrolyte layer to the cationic capsules, but with no subsequent mineralization (Capsule X is the control template for Capsule C).
  • Capsule Y was prepared without rinsing, polyelectrolyte addition, or mineralization of the gum acacia stabilized capsules (Capsule Y is the control template for Capsule E and Capsule F).
  • Capsule Z was prepared without rinsing, polyelectrolyte addition or mineralization of the gum acacia stabilized capsules (Capsule Z is the control template for Capsule G).
  • the samples were filtered through a 0.45 ⁇ PTFE filter and analysed with a HPLC using a UV detector. To determine the percentage of deposition of microcapsules from a model surfactant mixture, the amount of Uvinul extracted from the hair samples was compared to the amount of Uvinul extracted from the control samples.
  • Microcapsule Slurry (Equivalent Oil) 0.5
  • Salcare ® SC 60; origin BASF Deposition onto hair swatches was measured from this simplified model surfactant mixture which is meant to be representative of personal cleansing formulations such as shampoo or shower gel.
  • the quantitative deposition values are given in Table 12 and the results are shown in Figure 4.
  • the data illustrated in Figure 4 demonstrate that the addition of a mineral layer to an anionic PVOH-stabilized capsule increases the deposition onto hair swatches significantly from 1.6% for the control capsules W to 4.8%> for the mineralized capsules A.
  • the capsules according to the invention are boosting deposition up to 3 times better than prior art capsules.
  • Capsule E Comparing Capsule E to the relevant, unmineralized gum acacia-stabilized microcapsule control, Capsule Z, the deposition percentage is increased from 2.16 %> deposition of oil onto hair to 30.71% deposition onto hair. Over one order of magnitude improvement (14x more oil) is achieved through the mineralization of the smooth biopolymer-stabilized capsule surface, and this improvement is tremendous.
  • the specific affinity and improved deposition of the mineralized microcapsules for the targeted biological substrate after rinsing is shown in the micrographs of Figure 5.
  • the deposition protocol was used to test the deposition of Capsule H (capsules with a rough calcium phosphate mineral coating) compared to the deposition performance of the smooth control Capsule Y onto hair swatches from the model surfactant system.
  • the mineralized Capsule Y prototype ( Figure 3) was determined to deposit 3.74 times more oil onto hair swatches after rinsing compared to the unmineralized smooth control Capsule Y.
  • Capsule deposition on fabric from a commercially available, unscented detergent base (“Tide, free & gentle” Procter & Gamble: Water; sodium alcoholethoxy sulfate; propylene glycol; borax; ethanol; linear alkylbenzene sulfonate sodium salt; polyethyleneimine ethoxylate; diethylene glycol; trans sulfated & ethoxylated hexamethylene diamine; alcohol ethoxylate; linear alkylbenzene sulfonate, MEA salt; sodium formate; sodium alkyl sulfate; DTPA; amine oxide; calcium formate; disodium diaminostilbene disulfonate; amylase, protease; dimethicone; benzisothiazolinone) was performed by subjecting fabric swatches to a miniaturized laundry simulator.
  • the detergent base was loaded with capsule slurry at 0.5 wt% equivalent free oil, which was subsequently loaded into tap water at 1% by volume.
  • a 1 gram fabric swatch was submerged into 30 millilitres of the solution in a 50 mL centrifuge tube. The solution containing the fabric swatch was subjected to high speed vortexing for 10 seconds. The fabric swatch was removed and placed into a clean tube, which was filled with fresh tap water and vortexed for another 10 seconds to simulate the rinse cycle. The water was removed from the tube and the process of refilling the tube with fresh tap water and vortexing was repeated an additional two times before removing the fabric swatch and hanging it to air dry on a laundry rack. Once dry, the swatches were subjected to the same extraction and tracer analysis protocol as described for hair deposition in Example 9.
  • Capsules according to the invention deposit very well onto fabric swatches after rinsing off complex formulations such as detergent, and tend to deposit twice the amount of oil compared to the smooth template control capsules.
  • Capsule D deposits twice the mass of oil onto the fabric swatches compared to the relevant control Capsule W.
  • Capsule C deposits twice the oil payload deposited by control Capsule X.
  • Methylchloroisothiazolinone Cationic polymer; Diethylenetriamine pentaacetate, sodium salt
  • Capsules W and Capsules X controls.
  • the capsules were suspended in the model, commercially available fabric softener base 24 hours prior to deposition testing performed as described in Example 9. Capsules were loaded into the fabric softener base at 0.2 wt% equivalent free oil.
  • Table 14 Quantitative deposition results on 1 gram towel fabric swatches after rinsing for Capsules A, B, C, and D and Control Capsules W, X from a commercial, fabric softener formulation using the fabric softener deposition protocol.
  • Example 11 and Example 12 The depletion of capsules from a bulk washing solution by a lg cotton fabric swatch during the miniature laundry cycle described in Example 11 and Example 12 was quantitatively assessed using the same extraction and tracer analysis protocol described in Example 9.
  • the bulk solution comprised 30mL of tap water and 1% by volume fabric softener solution containing capsule slurry (loaded at 0.2 wt% equivalent free oil) of either Capsule A or Capsule W.
  • the initial solution bulk capsule concentration was determined prior to the immersion of a 1 g towel fabric swatch.
  • a lg fabric swatch was added to this bulk solution in a 50mL centrifuge tube and subjected to 10 seconds of vortexing on a high speed vortexer.
  • the fabric swatch remained in the centrifuge, and the bulk capsule concentration was determined by pulling an aliquot of solution. The fabric swatch attracts and removes bound capsules from solution, depleting the bulk concentration. The remaining bulk solution was analyzed for tracer content once again to determine the depletion efficiency of the fabric swatches as a function of capsule type in bulk solution. The percentage of the original capsule content cleared by a fabric swatch for both Capsule A and a control Capsule W are shown in Figure 8. Using this depletion test method, the fabric swatch clears more than 85% of mineralized Capsules A from the starting bulk concentration (100%). In contrast, the same mass and dimension of fabric only removes 40% of control Capsules W from the bulk concentration.
  • Capsules G and Capsules Z were each separately placed into model surfactant mixture (Table 11) at 0.5wt%> equivalent oil and applied to hair swatches by the same procedure described in Example 10, rinsed, and allowed to dry on a rack for 24 hours. Hair swatches were then evaluated for olfactive intensity, combed, then reevaluated. Olfactive intensities were rated on a scale from 1-7, 1 indicating no fragrance intensity and 7 indicating extremely strong fragrance intensity. The results for olfactive intensity are shown in Table 15, and in Figure 9. Mineralized Capsule G provided much stronger olfactive intensity after combing than did smooth control Capsule Z.
  • Capsule A microcapsules were incubated in different solution with varying pH values (pH adjusted deionized water at pH 3, pH 6 and pH 9), as well as in different application formulations (laundry detergent and fabric softener). As shown in the micrographs of Figure 10, the surface features were maintained following incubation in the various harsh solution conditions after 4 weeks. This is an indication of the robustness of the surface architecture of the mineral layer, which does not dissolve or undergo appreciable structural changes.
  • Capsules E from Example 5 were synthesized and dried to produce varied powder formulations using a Labconco Freezone 6 lyophilization unit.
  • the capsule slurries containing 5-40 % oil were dried by freezing the slurries to the internal walls of round- bottom flasks by rotating the slurry-filled flasks in dry ice and then affixing the flask to a lyophilization tower and increasing the vacuum to remove the frozen water phase by sublimation. Images of the freeze-dried powders are given in Figure 11.
  • Characterization of microcapsule surfaces was conducted using a Keyence VK laser scanning confocal microscope profilometer to quantify the surface roughness of different microcapsules.
  • the profile of each capsule was surveyed using a violet range confocal laser and the resulting surface profiles were analyzed by Keyence software to calculate the key roughness parameters of each profile, including average roughness (Ra), mean roughness depth (R z ) and additionally, root mean square roughness (R q ).
  • Curvature of surveyed capsules was accounted for using a filter to flatten the characterized area for measurement purposes. Measurements of vertical profiles were determined along scan lines.
  • An Atomic Force Microscope (Dimension Icon AFM with a ScanAsyst-Air cantilever by Bruker) was also used in PeakForce tapping topographical mode to evaluate surface features and roughness parameters (processed using Bruker NanoScope Analysis software) to correlate different surface roughness parameters such as maximum roughness (R t ) with deposition.

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  • Chemical & Material Sciences (AREA)
  • Organic Chemistry (AREA)
  • Dispersion Chemistry (AREA)
  • Chemical Kinetics & Catalysis (AREA)
  • Life Sciences & Earth Sciences (AREA)
  • Engineering & Computer Science (AREA)
  • Oil, Petroleum & Natural Gas (AREA)
  • Wood Science & Technology (AREA)
  • Manufacturing Of Micro-Capsules (AREA)

Abstract

La présente invention concerne une suspension de microcapsules à noyau-enveloppe minéralisé comprenant au moins une microcapsule ayant : a) un noyau à base d'huile comprenant un ingrédient actif hydrophobe, de préférence un parfum;b) une enveloppe polymère ayant une surface fonctionnelle chargée de terminaison; et c) une couche minérale sur la surface fonctionnelle chargée de terminaison. L'invention concerne également le processus de préparation desdites microcapsules. L'invention concerne en outre des compositions parfumantes et des produits de consommation comprenant lesdites microcapsules, en particulier des produits de consommation parfumés qui se présentent sous la forme de produits de soins d'entretien pour la maison ou de soins personnels.
PCT/EP2017/084178 2016-12-22 2017-12-21 Microcapsules à couche minérale Ceased WO2018115330A1 (fr)

Priority Applications (5)

Application Number Priority Date Filing Date Title
US16/471,804 US11135561B2 (en) 2016-12-22 2017-12-21 Microcapsules having a mineral layer
MX2019006632A MX2019006632A (es) 2016-12-22 2017-12-21 Microcapsulas que tienen una capa de mineral.
CN201780079605.6A CN110099743B (zh) 2016-12-22 2017-12-21 具有矿物层的微胶囊
EP17818582.3A EP3558509B1 (fr) 2016-12-22 2017-12-21 Microcapsules présentant une couche minérale
JP2019534264A JP7078629B2 (ja) 2016-12-22 2017-12-21 無機質層を有するマイクロカプセル

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US201662438155P 2016-12-22 2016-12-22
US62/438,155 2016-12-22
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EP17151928 2017-01-18

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WO2020089651A1 (fr) * 2018-11-01 2020-05-07 The University Of Sheffield Matériaux intégrés
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CN113845888A (zh) * 2021-11-09 2021-12-28 北京斯迪莱铂油气技术有限公司 一种相变微胶囊及含有其的热交换流体
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EP3932536A1 (fr) * 2020-07-02 2022-01-05 Follmann GmbH & Co. KG Microcapsules améliorées et leur procédé de production et d'utilisation
WO2022207525A1 (fr) * 2021-03-31 2022-10-06 Firmenich Sa Microcapsules coeur-écorce enrobées
EP4130219A1 (fr) * 2021-08-02 2023-02-08 Henkel AG & Co. KGaA Capsules de parfum à force adhésive pour surfaces

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WO2019243427A1 (fr) * 2018-06-21 2019-12-26 Firmenich Sa Processus pour la préparation de microcapsules méniralisées
WO2019243426A1 (fr) * 2018-06-21 2019-12-26 Firmenich Sa Procédé de préparation de microcapsules
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WO2020016086A1 (fr) * 2018-07-17 2020-01-23 Unilever Plc Particules de distribution d'agent bénéfique
CN112469807A (zh) * 2018-07-17 2021-03-09 联合利华知识产权控股有限公司 有益剂递送颗粒
JP7387638B2 (ja) 2018-09-19 2023-11-28 フイルメニツヒ ソシエテ アノニム ポリスクシンイミド誘導体ベースのマイクロカプセルを製造するための方法
JP2022500227A (ja) * 2018-09-19 2022-01-04 フイルメニツヒ ソシエテ アノニムFirmenich Sa ポリスクシンイミド誘導体ベースのマイクロカプセルを製造するための方法
WO2020089651A1 (fr) * 2018-11-01 2020-05-07 The University Of Sheffield Matériaux intégrés
EP3673984A1 (fr) * 2018-12-31 2020-07-01 Clariant International Ltd Microencapsulation de parfum
WO2020141080A1 (fr) * 2018-12-31 2020-07-09 Clariant International Ltd Microencapsulation de parfum
WO2020227762A1 (fr) * 2019-05-10 2020-11-19 Commonwealth Scientific And Industrial Research Organisation Microcapsule
WO2022002764A1 (fr) * 2020-07-02 2022-01-06 Follmann Gmbh & Co. Kg Microcapsules améliorées et procédés pour leur production et leur utilisation
EP3932536A1 (fr) * 2020-07-02 2022-01-05 Follmann GmbH & Co. KG Microcapsules améliorées et leur procédé de production et d'utilisation
WO2022207525A1 (fr) * 2021-03-31 2022-10-06 Firmenich Sa Microcapsules coeur-écorce enrobées
EP4130219A1 (fr) * 2021-08-02 2023-02-08 Henkel AG & Co. KGaA Capsules de parfum à force adhésive pour surfaces
CN113845888A (zh) * 2021-11-09 2021-12-28 北京斯迪莱铂油气技术有限公司 一种相变微胶囊及含有其的热交换流体
CN113845888B (zh) * 2021-11-09 2024-05-07 北京斯迪莱铂油气技术有限公司 一种相变微胶囊及含有其的热交换流体

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