WO2019121657A1 - Improvements in or relating to organic compounds - Google Patents

Improvements in or relating to organic compounds Download PDF

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Publication number
WO2019121657A1
WO2019121657A1 PCT/EP2018/085457 EP2018085457W WO2019121657A1 WO 2019121657 A1 WO2019121657 A1 WO 2019121657A1 EP 2018085457 W EP2018085457 W EP 2018085457W WO 2019121657 A1 WO2019121657 A1 WO 2019121657A1
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WO
WIPO (PCT)
Prior art keywords
innermost
microcapsules
outermost
microcapsule
active agent
Prior art date
Application number
PCT/EP2018/085457
Other languages
French (fr)
Inventor
Emmanuel Aussant
Original Assignee
Givaudan 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 Givaudan Sa filed Critical Givaudan Sa
Publication of WO2019121657A1 publication Critical patent/WO2019121657A1/en

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Classifications

    • CCHEMISTRY; METALLURGY
    • C11ANIMAL OR VEGETABLE OILS, FATS, FATTY SUBSTANCES OR WAXES; FATTY ACIDS THEREFROM; DETERGENTS; CANDLES
    • C11DDETERGENT COMPOSITIONS; USE OF SINGLE SUBSTANCES AS DETERGENTS; SOAP OR SOAP-MAKING; RESIN SOAPS; RECOVERY OF GLYCEROL
    • C11D3/00Other compounding ingredients of detergent compositions covered in group C11D1/00
    • C11D3/50Perfumes
    • C11D3/502Protected perfumes
    • C11D3/505Protected perfumes encapsulated or adsorbed on a carrier, e.g. zeolite or clay
    • AHUMAN NECESSITIES
    • A61MEDICAL OR VETERINARY SCIENCE; HYGIENE
    • A61KPREPARATIONS FOR MEDICAL, DENTAL OR TOILETRY PURPOSES
    • A61K8/00Cosmetics or similar toiletry preparations
    • A61K8/02Cosmetics or similar toiletry preparations characterised by special physical form
    • A61K8/11Encapsulated compositions
    • AHUMAN NECESSITIES
    • A61MEDICAL OR VETERINARY SCIENCE; HYGIENE
    • A61KPREPARATIONS FOR MEDICAL, DENTAL OR TOILETRY PURPOSES
    • A61K8/00Cosmetics or similar toiletry preparations
    • A61K8/18Cosmetics or similar toiletry preparations characterised by the composition
    • A61K8/72Cosmetics or similar toiletry preparations characterised by the composition containing organic macromolecular compounds
    • A61K8/84Cosmetics or similar toiletry preparations characterised by the composition containing organic macromolecular compounds obtained by reactions otherwise than those involving only carbon-carbon unsaturated bonds
    • A61K8/87Polyurethanes
    • AHUMAN NECESSITIES
    • A61MEDICAL OR VETERINARY SCIENCE; HYGIENE
    • A61KPREPARATIONS FOR MEDICAL, DENTAL OR TOILETRY PURPOSES
    • A61K8/00Cosmetics or similar toiletry preparations
    • A61K8/18Cosmetics or similar toiletry preparations characterised by the composition
    • A61K8/72Cosmetics or similar toiletry preparations characterised by the composition containing organic macromolecular compounds
    • A61K8/84Cosmetics or similar toiletry preparations characterised by the composition containing organic macromolecular compounds obtained by reactions otherwise than those involving only carbon-carbon unsaturated bonds
    • A61K8/88Polyamides
    • AHUMAN NECESSITIES
    • A61MEDICAL OR VETERINARY SCIENCE; HYGIENE
    • A61QSPECIFIC USE OF COSMETICS OR SIMILAR TOILETRY PREPARATIONS
    • A61Q19/00Preparations for care of the skin
    • BPERFORMING OPERATIONS; TRANSPORTING
    • B01PHYSICAL OR CHEMICAL PROCESSES OR APPARATUS IN GENERAL
    • B01JCHEMICAL OR PHYSICAL PROCESSES, e.g. CATALYSIS OR COLLOID CHEMISTRY; THEIR RELEVANT APPARATUS
    • B01J13/00Colloid chemistry, e.g. the production of colloidal materials or their solutions, not otherwise provided for; Making microcapsules or microballoons
    • B01J13/02Making microcapsules or microballoons
    • B01J13/06Making microcapsules or microballoons by phase separation
    • B01J13/14Polymerisation; cross-linking
    • BPERFORMING OPERATIONS; TRANSPORTING
    • B01PHYSICAL OR CHEMICAL PROCESSES OR APPARATUS IN GENERAL
    • B01JCHEMICAL OR PHYSICAL PROCESSES, e.g. CATALYSIS OR COLLOID CHEMISTRY; THEIR RELEVANT APPARATUS
    • B01J13/00Colloid chemistry, e.g. the production of colloidal materials or their solutions, not otherwise provided for; Making microcapsules or microballoons
    • B01J13/02Making microcapsules or microballoons
    • B01J13/20After-treatment of capsule walls, e.g. hardening
    • B01J13/22Coating
    • CCHEMISTRY; METALLURGY
    • C11ANIMAL OR VEGETABLE OILS, FATS, FATTY SUBSTANCES OR WAXES; FATTY ACIDS THEREFROM; DETERGENTS; CANDLES
    • C11DDETERGENT COMPOSITIONS; USE OF SINGLE SUBSTANCES AS DETERGENTS; SOAP OR SOAP-MAKING; RESIN SOAPS; RECOVERY OF GLYCEROL
    • C11D17/00Detergent materials or soaps characterised by their shape or physical properties
    • C11D17/0039Coated compositions or coated components in the compositions, (micro)capsules
    • AHUMAN NECESSITIES
    • A61MEDICAL OR VETERINARY SCIENCE; HYGIENE
    • A61KPREPARATIONS FOR MEDICAL, DENTAL OR TOILETRY PURPOSES
    • A61K2800/00Properties of cosmetic compositions or active ingredients thereof or formulation aids used therein and process related aspects
    • A61K2800/10General cosmetic use
    • AHUMAN NECESSITIES
    • A61MEDICAL OR VETERINARY SCIENCE; HYGIENE
    • A61KPREPARATIONS FOR MEDICAL, DENTAL OR TOILETRY PURPOSES
    • A61K2800/00Properties of cosmetic compositions or active ingredients thereof or formulation aids used therein and process related aspects
    • A61K2800/40Chemical, physico-chemical or functional or structural properties of particular ingredients
    • A61K2800/56Compounds, absorbed onto or entrapped into a solid carrier, e.g. encapsulated perfumes, inclusion compounds, sustained release forms
    • AHUMAN NECESSITIES
    • A61MEDICAL OR VETERINARY SCIENCE; HYGIENE
    • A61QSPECIFIC USE OF COSMETICS OR SIMILAR TOILETRY PREPARATIONS
    • A61Q5/00Preparations for care of the hair
    • A61Q5/02Preparations for cleaning the hair
    • AHUMAN NECESSITIES
    • A61MEDICAL OR VETERINARY SCIENCE; HYGIENE
    • A61QSPECIFIC USE OF COSMETICS OR SIMILAR TOILETRY PREPARATIONS
    • A61Q5/00Preparations for care of the hair
    • A61Q5/12Preparations containing hair conditioners

Definitions

  • the present disclosure relates to suspensions of microcapsules providing programmed release of one or more active agents in an application.
  • the one or more active agents include one or more fragrance or one or more cosmetic agent.
  • the present disclosure relates also to a method to prepare compartmentalized microcapsules providing such benefits.
  • microcapsules can increase the stability and life of the encapsulated perfume ingredients; they can facilitate the manipulation, handling and storage of the encapsulated perfume compositions, and control the emanation of pleasant odours in time and space; and they can also protect perfume ingredients from chemical attack of aggressive external media in which they are suspended. They can also act as a mean of controlling the spatio-temporal release of perfume. More particularly, frangible microcapsules can release a boost of perfume when ruptured mechanically, for example by rubbing the substrate on which these capsules are deposited. Using such microcapsules to provide such perfume benefits is well known to the art.
  • perfumed microcapsules are used in a consumer product, such as a detergent or a fabric conditioner, together with a free, non-encapsulated perfume.
  • the role of the free perfume is to provide a pleasant odour to the neat product, for example when the perfume is assessed when opening the bottle containing the product, and during washing or conditioning the substrate, while the encapsulated perfume is released at later stages, such as wearing a fabric or combing hair.
  • An additional surprising effect may be generated by admixing an encapsulated perfume that has a different odour than that of the free perfume.
  • the release of free perfumes is mainly controlled by the vapour pressure of the perfume ingredients and the possibility to spatio- temporal release of the perfume is limited.
  • WO 2011/094681 discloses the use of two different encapsulated perfume compositions based on the selection of perfume ingredients having different boiling points
  • WO 2014029695 A1 discloses the use of two different encapsulated perfume compositions based on the selection of perfume ingredients having different odour thresholds.
  • using mixtures of microcapsules require each of these microcapsules to be manufactured separately and then mixed together. This adds in process complexity and cost.
  • GB 1,046,409 (1966), example 10 discloses multiwall capsules obtained by the steps of (i) emulsifying a first hydrophobic internal phase (or core phase) comprising a reactive intermediate dispersed in a second hydrophilic continuous phase comprising a second reactive intermediate, (ii) performing first interfacial polymerization of both reactive intermediates to form a condensation polymer at the interface between both internal and external phase and thereby forming primary core-wall capsules, (iii) filtering and/or drying the primary core-wall capsules obtained in step (ii) and transferring these primary microcapsules in a third hydrophobic continuous phase comprising a third reactive intermediate that can be identical to the first reactive intermediate, (iv) dispersing the primary microcapsule-containing second hydrophobic phase obtained in step (iii) into a fourth hydrophilic continuous phase comprising a fourth reactive intermediate that can be identical to the second reactive intermediate and (v) performing second interfacial polymerization of third and fourth reactive intermediates to form a second wall
  • the interfacial polymers disclosed in GB 1,046, 409 encompass polyamides, polyureas obtained from the polycondensation of phosgene and polyamines or polyurethanes obtained from the polycondensation of tetramethylene bischloroformate and polyamines.
  • the multiwall microcapsules obtained by this process have a size ranging from 1 to 10 mm and would therefore be visible and therefore not suitable for the applications contemplated in the present disclosure.
  • the process disclosed involves environmentally problematic reactive intermediates, and is complex and difficult to conduct at industrial scales.
  • US 4,891,172 A discloses a process for producing double capsules comprising one or more primary capsules included in a larger capsule. These double capsules are obtained by the steps of (i) preparing a slurry of primary aminoplast capsules in water, (ii) dispersing said slurry in a hydrophobic (oil) phase having a viscosity such that a capsule-in-oil-in-water double emulsion is formed and (iii) encapsulating the dispersed phase of the double emulsion obtained under (ii) in order to form larger aminoplast capsules including the primary capsules.
  • the capsules obtained may be used for example to combine two reactive adhesive components that react when the capsules are broken, for example under pressure.
  • the phase which is encapsulated in the primary capsules and the hydrophobic phase may be a fragrance.
  • the method requires the use of a separate hydrophobic phase having a viscosity between 40 and 150000 mPas, preferably between 300 and 8000 mPas, in which the slurry of primary capsules has to be transferred. This is a source of complexity and significant on-cost.
  • W02002060573A2 [Henkel] discloses capsule-in-capsule systems obtained by transferring drop wise a dispersion of primary capsules in a first continuous phase containing a polymer into a second continuous phase of same polarity as that of the first continuous phase. Phase separation of the polymer occurs following a change of pH or temperature, or by addition of a salt or a second polymer, providing a second dispersion of larger capsule containing the primary capsules.
  • the process is complex and difficult to execute at industrial scales.
  • the second encapsulated phase is also an aqueous or a polar phase.
  • EP 1097693A2 discloses capsule-in-capsule systems for use in adhesives and as delivery system for active agents including perfumes
  • WO 2012146637A1 discloses double capsule containing anti-icing material, said anti-icing material being released following the osmotically-induced breakage of internal capsules. In no instance, a method is given on how these capsule-in-capsule systems can be obtained and manufactured.
  • Capsules comprising a core with primary capsules dispersed therein and an outer wall are well known to the art.
  • US20050067726A1 [DSM] discloses complex coacervate capsules including primary capsules dispersed therein for application as delivery systems for food complements.
  • EP1736060B1 discloses solid forms consisting of dried agglomerated primary capsules surrounded by an outer wall which is a complex coacervate.
  • coacervate walls usually swell in aqueous media and are known to be ineffective in retaining low molecular and/or volatile ingredients in aqueous consumer products.
  • these processes require also multiple steps, such as re-dispersion and drying.
  • encapsulated compositions that provide programmed release of active agents, such as fragrances and/or cosmetic agents, while being easy to prepare and to handle, and inducing no significant on-cost compared to conventional, single encapsulated forms.
  • active agents such as fragrances and/or cosmetic agents
  • encapsulated fragrance compositions that exhibit perceptibly enhanced odour linearity throughout an application compared to conventional mixtures of free and encapsulated fragrances.
  • encapsulated fragrance compositions that release fragrances having different odour characteristics depending on assessment conditions, for example at different stages of use or application of the perfumed products, from the wet stage, e.g.
  • a composition comprising at least one microcapsule in a suspending medium, wherein microcapsule is compartmentalized and comprises at least one innermost microcapsule, having an innermost capsule wall and an innermost compartment surrounded by said innermost capsule wall, with a first active agent A1 located in the innermost compartment; and at least one outermost microcapsule, having an outermost capsule wall and an outermost compartment surrounded by said outermost capsule wall, with a second active agent A2 in the outermost compartment; wherein at least one innermost microcapsule is accommodated in the outermost microcapsule.
  • the compartmentalized microcapsules may comprise one or more intermediate microcapsules, the intermediate microcapsules having an intermediate capsule wall and an intermediate compartment surrounded by said intermediate capsule wall, wherein the at least one intermediate microcapsule accommodates at least one of the innermost microcapsules, and wherein the at least one intermediate microcapsule is accommodated in the outermost microcapsule.
  • Each intermediate microcapsule may optionally comprise a further active agent Ax in the intermediate compartment.
  • active agent Al A2, ... Ax is meant any substance or ingredient providing a benefit, in particular a fragrance ingredient or a cosmetic ingredient.
  • a method for manufacturing a composition comprising at least one compartmentalized microcapsule in a suspending medium according to the invention in a single batch process, comprising at least the steps of: a) preparing an innermost microcapsule comprising an innermost compartment comprising first active agent Al and an innermost capsule wall, wherein the innermost capsule wall consists of a thermosetting resin, thereby forming a slurry of innermost microcapsules; b) adding second active agent A2 to said slurry of innermost microcapsules formed in step a) under stirring, thereby forming innermost microcapsules coated with the second active agent A2; c) encapsulating said coated innermost microcapsules formed in step b) within an outermost wall of a thermosetting resin, thereby forming compartmentalized microcapsules with first active agent Al located in at least one innermost compartment and second active agent A2 located in the outermost compartment between innermost and outermost capsule walls.
  • Step b) and c) may be repeated, optionally with same or different active agents A3, A4 etc, if it is desirable to provide compartmentalized microcapsules with more than two compartments.
  • compartmentalized microcapsules of the invention may provide a broad range of benefits, such as enhanced fragrance performance, enhanced fragrance linearity, programmed release of differentiated odours or improved efficacy of cosmetic active agent.
  • the active agents Al, A2, ... Ax are identical to each other.
  • the active agents Al, A2, ... Ax are different from each other.
  • Fig. 1 A describes a spherical arrangement of the compartments in a compartmentalized microcapsule according to the present invention with two compartments: an innermost compartment 1, comprising a first active agent Al, and an outermost compartment 2, comprising a second active agent A2 that can be identical to or different from the first active agent, as well as the innermost capsule wall 3 and the outermost capsule wall 4.
  • Fig. 1 B describes a microcapsule according to the present invention with an innermost compartment 1, an intermediate compartment 5 and an outermost compartment 2, and three capsule walls: innermost capsule wall 3, intermediate capsule wall 6 and outermost capsule wall 4.
  • Fig. 2 shows a typical schematic thermo-gravimetric curve of moist two-compartment microcapsules according to the present invention, wherein both active agents A1 and A2 are volatile, for example fragrances FI and F2.
  • the compartmentalized microcapsules are separated from the slurry by filtration and available in the form of a wet cake.
  • a portion of the wet cake is transferred to the micro-balance of the thermogravimetric analyser (TGA), and the weight loss of the sample is measured as a function of the temperature.
  • TGA thermogravimetric analyser
  • the temperature is increased at a rate of 5 °C/min from 4 °C to 800 °C.
  • TGA instruments are available commercially (for example Model TGA Q50, from Anton Paar company).
  • the Figure represents the specific case of a two- compartment microcapsule comprising two active agents A1 and A2, wherein second active agent A2 is located in the outermost compartment of the microcapsule and first active agent A1 is located in the innermost compartment of the microcapsule.
  • the first shoulder 7 in the curve corresponds to a loss of weight associated with the release of water from the microcapsule wet cake
  • the second shoulder 8 corresponds to a loss of weight associated with the release of second active agent A2
  • the third shoulder 9 in the curve corresponds to a loss of weight associated with the release of first active agent Al.
  • the fact that second active agent A2 is released within a lower temperature range than first active agent Al confirms that, in the case depicted in Fig. 2, the outermost capsule wall of the microcapsule is less impervious or more frangible than the innermost capsule wall.
  • the microcapsules contain about 40 wt% (100 wt% minus 60 wt%) of water, 10 wt% (60 wt% minus 50 wt%) of second active agent A2, about 40 wt% (50 wt% minus 10 wt%) of first active agent Al and about 10% of encapsulating material, referred to the theoretical weight of the wet microcapsule cake. Possibly, the encapsulated material may be degraded at higher temperature (not shown in the figure).
  • this figure may change depending on the relative amounts of active agents Al and A2 and on the relative permeability and/or frangibility of the capsule walls.
  • the skilled person will also easily understand that the presence of very low or non-volatile materials (for example materials with a vapour pressure lower than 10 5 mmHg) in one or both or the compartments may also change the magnitude of the corresponding weight loss.
  • the relative amount the second active agent A2 located in the outermost compartment will be lower than the relative amount of the first active agent Al located in the innermost compartment.
  • the relative amounts of the active agents located in different compartments are equal, or the relative amount the second active agent A2 located in the outermost compartment is higher than the relative amount of the first active agent Al located in the innermost compartment.
  • the present invention is concerned with the differentiated programmed release of at least one active agent in an application, wherein said active agent is encapsulated in at least two different compartments within the same microcapsule (which is a compartmentalized microcapsule); and with the use of such compartmentalized microcapsules in consumer products to provide consumer with an enhanced hedonic experience.
  • compartmentalized microcapsules comprising at least one active agent, said active agent being distributed in two or more compartments, in a simple single batch process.
  • the at least one active agent is selected from the group consisting of fragrances, essential oils, pheromones, cosmetic ingredients and the like, and mixture thereof.
  • the compartmentalized microcapsules comprise a first active agent A1 located in an innermost compartment surrounded by an innermost capsule wall and a second active agent A2 located in an outermost compartment surrounded by an outermost capsule wall, wherein the innermost compartment and innermost capsule wall are accommodated in the outermost compartment.
  • the active agent A1 may be a fragrance or and/or a cosmetic active agent and the active agent A2 may be a fragrance and/or a cosmetic active agent.
  • the system according to this embodiment is further characterized in such that: if first active agent A1 is a fragrance FI and second active agent A2 is a fragrance F2, then fragrances FI and F2 may be identical or different; if first active agent A1 is a cosmetic agent Cl and second active agent A2 is a cosmetic agent C2, then the cosmetic agents Cl and C2 may be identical or different; if first active agent A1 is a mixture M l containing fragrance FI and cosmetic agent Cl and second active agent A2 is a mixture M2 containing fragrance F2 and cosmetic agent C2, then the mixtures M l and M2 may be identical or different; if first active agent A1 is a fragrance FI, then second active agent A2 may be a cosmetic agent C2 or a mixture M2 containing fragrance F2 and cosmetic agent C2, for example; the capsule wall separating the innermost compartment from the outermost compartment is substantially impervious to active ingredients A1 and A2; the normalized resin weight in the outermost capsule wall is either identical or lower than the normalized resin weight in the inner
  • substantially impervious is meant that the inter-diffusion of active agents from one to the other compartment is limited, so that the benefit expected from the programmed release remain noticeable, even after a prolonged period of time and when the compartmentalized microcapsules are submitted to real life storage conditions (for example one month at a temperature of 37 °C, in a consumer product base).
  • the remanence of a consumer noticeable benefit after storage, as confirmed by an evaluation panel, is taken as a sufficient hint that inter-diffusion between the compartments was limited during storage.
  • the compartmentalized microcapsules comprise more than two compartments, numbered 1 to N, each of these compartments being surrounded by a capsule wall, wherein each compartment may comprise an active agent, provided at least two compartments comprise an active agent.
  • the more than two compartments may be arranged in such a way that the compartmented microcapsule comprises an innermost compartment, an outermost compartment and intermediated compartments located between the innermost compartment and the outermost compartment, each compartment being separated from the neighbouring compartment by a capsule wall, hereby forming innermost, intermediate and outermost microcapsules.
  • an outermost compartment may accommodate more than one innermost or intermediate compartment.
  • an intermediate compartment may accommodate more than one innermost compartment.
  • the more than one compartment may have the same or different active agent in their core, respectively.
  • the capsule walls consist of one or more thermosetting resins selected from the group comprising aminoplast (like for example melamine-formaldehyde or urea-formaldehyde) resins, polyurea, polyacrylic resins and the like, and mixtures thereof.
  • aminoplast like for example melamine-formaldehyde or urea-formaldehyde
  • thermosetting resins are used to form capsule walls of different chemical nature.
  • thermosetting resin used to form the outermost capsule wall of the microcapsule is different from that or those used to form the innermost capsule wall or the intermediate capsule walls.
  • the innermost and intermediate capsule walls may comprise an aminoplast resin and the outermost capsule wall a polyurea resin, or vice-versa.
  • the aminoplast resin comprises a terpolymer comprising moieties derived from a triamine, moieties derived from a diamine and moieties derived from the group consisting of alkylene and alkylenoxy moieties, as disclosed in WO 2017001672 Al; or a terpolymer comprising moieties derived from a triamine, moieties derived from an aromatic polyol and moieties derived from the group consisting of alkylene and alkylenoxy moieties, as disclosed in EP 2111214 Bl.
  • the outermost capsule wall comprises a positively charged aminoplast thermosetting resin as disclosed in WO 2016207180 Al.
  • the outermost capsule wall is a coacervate or a hydrogel.
  • the weight of thermosetting resin comprised in the capsule wall of one microcapsule is defined as the weight of thermosetting resin forming material added to the reaction medium in which the microcapsules are formed (so-called "slurry") during the stage where said wall is formed, divided by the number of microcapsules in the slurry.
  • slurry the weight of thermosetting resin forming material added to the reaction medium in which the microcapsules are formed
  • the volume-averaged surface of a capsule wall is calculated by using the volume-average radius of the microcapsules measured by laser light diffraction after said wall has been formed.
  • the applicant used a Mastersizer 2000 supplied by Malvern. The technique is based on the principle that the light from a coherent source, in this case the laser beam, will scatter as particles pass through the beam, with the angle of the scattered light being directly related to the size of the particles. A decrease in particle size results in a logarithmic increase in the observed scattering angle. The observed scattering intensity is also dependent on particle size and diminishes relative to the particle's cross-sectional area. Large particles therefore scatter light at narrow angles with high intensity, whereas small particles scatter at wider angles but with low intensity.
  • Detectors are used to measure the scattered light pattern produced over a wide range of angles and, hence, determine the particle size distribution of the sample using an appropriate optical model.
  • the angular distribution of the scattering intensity is measured and analysed by Malvern proprietary software to provide the average size and size-distribution of the droplets present in the sample.
  • the median of the distribution is taken as a measure of the mean diameter of the microcapsules.
  • the sample was placed in the Malvern Hydro2000 SM module, supplied with the Mastersizer 2000, for the measurement of wet dispersions.
  • the supplied software was used to transform the measured scattered light pattern into the microcapsule size distribution.
  • the optical model parameters used were 1.47 and 0 for the refractive index and absorption index, respectively. Sample measurement was taken over a period of five seconds using 5000 measurement snaps.
  • the number of microcapsules in the slurry N c is calculated by assuming that (i) the total weight ( w t ) of active agents and encapsulating materials (i.e. polymers and resins) added to the slurry are present in the microcapsules, (ii) the population of microcapsules is nearly monodisperse, i.e. all microcapsules have approximately the average diameter d 50 , and (iii) the density of both the active agents and the encapsulating materials (i.e.
  • N c (6 w t / p c ) / ⁇ ? r(c 50 ) 3 ) .
  • the weight of thermosetting resin comprised in the capsule wall of one microcapsule w cr is the weight of wall material added to the slurry to form the capsule wall of all microcapsules w r divided by the number of microcapsules N c .
  • the above calculation is used to calculate the normalized resin weight of the innermost wall.
  • the number of microcapsules is kept constant and the increase of capsule size following the addition of active agent A2 and the addition of the thermosetting resin of the outermost wall is used to calculate the surface area of the outermost wall.
  • two or more fragrances are encapsulated as active agents in compartmentalized microcapsules comprising an innermost compartment and outermost compartment, and optionally intermediate compartments.
  • the two or more encapsulated fragrances are identical, or have similar odours, and are released sequentially throughout the application, providing a linear perfume perception throughout the entire application, e.g. from its point of purchase and its application onto a wet substrate, through to the dry stage.
  • the fragrance located in the outermost compartment of the capsule is first released by diffusion through and/or soft mechanical action on the outermost capsule wall, for example by handling, touching, wearing etc. the substrate.
  • the fragrances located in the one or more sub-compartment(s) meaning the innermost compartment and, optionally the intermediate compartments, is(are) released under the actions of further mechanical actions, such as squeezing or rubbing.
  • the two or more encapsulated fragrances have differentiated odours.
  • the compartmentalized microcapsule of the present invention can provide odours that are perceptibly different, depending on whether the odour is assessed initially under wet conditions or under dry conditions. These different perceptions maintain an overall odour perception for the consumer during the usage of the perfumed product.
  • the term "perceptibly different" as it relates to the odour characteristics of fragrances assessed under different conditions means that trained panellists are capable of differentiating unambiguously the odour of a given fragrance under a first condition, for example on a wet substrate, for example on a substrate out of the wash machine, from that of the same perfumed product, under a second condition, for example after substrate has dried or is being manipulated or worn. Under such conditions, the difference is deemed to be consumer noticeable, that is, a majority of consumers will perceive the change of odour from said first condition to said second condition.
  • an odour may be defined by using pre-defined semantic attributes, such as "CITRUS/ALDEFIYDIC", as in the case of a lemon odour, a lime odour, an orange odour or a grapefruit odour and the like; "FRUITY”, as in the case of an apple odour, a peach odour, a berry odour, and the like; "GREEN”, as in the case of a freshly cut grass odour, a leaf odour, and the like; "AROMATIC/HERBAL”, as in the case of a resinous odour, a turpentine odour, a straw odour, and the like; "FLORAL”, as in the case of a rose odour, a lily of the valley odour, and the like; "WOODY”, as in the case of
  • semantic attributes may be defined if needed, depending on the desired accuracy of the odour definition.
  • An odour may also be defined as a combination of semantic attributes. Numerous examples of alternative semantic attributes suitable for odour definitions may be found, for example, in S. Arctander, "Perfume and Flavor Chemicals", Allured Publisher Corp. Wheaton, 1969 and on web sites, such as www.thegoodscentscompany.com.
  • Admixing perfumery ingredients having similar odour to form a fragrance usually confers to said fragrance an odour that is strongly pronounced of the odour of the admixed perfumery ingredients.
  • admixing perfumery ingredients having a CITRUS odour usually provide a fragrance having a CITRUS odour.
  • Fragrances may be more complex and may comprise ingredients having diverse odour characteristics. Flowever, even in this case, it is still usually possible to assign an overall odour characteristic to such complex fragrances by using secondary attributes or nuances.
  • a complex fragrance compositions may be described as having a CITRUS odour (primary semantic attributes) with GREEN and WOODY nuances (secondary attributes), while another complex fragrance composition may be described as having a GREEN odour (primary semantic attributes) with FLORAL and M USKY nuances (secondary attributes).
  • Two fragrances that are perceptibly different are preferably composed by using ingredients having a first odour 01 in first fragrance and preferably ingredients having a second odour 02 in second fragrance, wherein both first and second odours are different.
  • Both the primary and secondary semantic attributes of the odours 01 and 02 may be different, or only the primary or only the secondary semantic attributes may be different.
  • a fragrance having a GREEN primary attribute and FLORAL and WOODY secondary attributes may be perceived as different from a fragrance having a GREEN primary attribute and FRUITY and SWEET secondary attributes.
  • fragrances that differ only in their primary attributes such as for example two fragrances having of one of them a GREEN primary attribute and for the other of them an AROMATIC/FIERBAL primary attribute, but both fragrance having the same FLORAL and WOODY secondary attributes, may be perceived as having differentiated odours.
  • fragrances may be maximized by using certain types of fragrances, which are referred to as "mutually opposing fragrances".
  • Two fragrances are mutually opposing if their primary attributes are selected from the following pairs: CITRUS versus FLORAL (rose, tuberose); CITRUS versus WOODY; CITRUS versus MUSK; CITRUS versus SWEET; CITRUS versus FRUITTY (peach, prune); CITRUS vs.
  • HERBAL / AROMATIC versus FLORAL rose, tuberose
  • HERBAL / AROMATIC versus SWEET HERBAL / AROMATIC versus FRUITTY (peach, prune); and HERBAL / AROMATIC vs. ANIMALIC.
  • a complex fragrance may also be decomposed into top notes, middle (or heart) notes and bottom notes, wherein the top notes correspond often to ingredients having high vapour pressures, the middle notes to those having intermediate vapour pressures, and the bottom notes to those having low vapour pressures.
  • the top notes evaporate faster, followed by the middle notes and, finally, by the bottom notes.
  • the perception of the perfume may change during the course of the evaporation, especially when the odours of the top, middle and bottom notes are different, as it is frequently the case in perfumery.
  • the top note odours are typically characterized by attributes such as ALDEHYDIC, CITRUS, AROMATIC/HERBAL, GREEN and FRUITTY attributes.
  • the middle note odours are typically characterized by attributes such as FRUITTY, WATERY/OZONIC, GREEN and FLORAL attributes.
  • the bottom note odours are typically characterized by attributes such as AMBERY/WOODY, SWEET and MUSKY attributes.
  • fragrances to be encapsulated accordingly to the present invention by selecting perfumery ingredients having various odours.
  • Perfumery ingredients having an ALDEHYDIC odour may be selected from the group consisting of decanal; dodecanal; 4-isopropylbenzonitrile; 4-isopropylbenzaldehyde; (E)-dodec-2-enal; decanal; 2-methyldecanal; undecanal; 2-methylundecanal; octanal; nonanal; (E)-dodec-2-enal; (E)-dec-4-enal; dihydrocitronellyl nitrile; undec-10-enal; (E)-undec-9-enal; dodecanenitrile; 2-methylundecanoic acid, and mixtures thereof.
  • Perfumery ingredients having an AM BER/WOODY odour may be selected from the group consisting of (3aR,5aS,9aS,9bR)-3a,6,6,9a-tetramethyl-2,4,5,5a,7,8,9,9b-octahydro-lH-benzo[e][l]benzofuran; (lR,2S,4R)-2'- isopropyl-l,7,7-trimethylspiro[bicyclo[2.2.1]heptane-2,4'-[l,3]dioxane]; 2,4a,5,8a-tetramethyl-l,2,3,4,4a,7,8,8a- octahydronaphthalen-l-yl formate; l-((2E,5Z,9Z)-2,7,8-trimethylcyclododeca-2,5,9-trien-l-yl)ethanone; N-ethyl-N- (m-
  • Perfumery ingredients having an ANIMALIC odour may be selected from the group consisting of 2-(2- methylpropyl)quinoline; Castoreum oil; lH-indole; 6-butan-2-yl-quinoline; 4,4a,5,9b-tetrahydroindeno[l,2- d][l,3]dioxine; 8,8-di(lH-indol-3-yl)-2,6-dimethyloctan-2-ol; 6-isopropylquinoline; 6-(sec-butyl)quinoline; 5- isopropyl-2-methylphenol; 4-methyl-2-propan-2-yl-l,3-thiazole; and mixtures thereof.
  • Perfumery ingredients having an AROMATIC/HERBAL odour may be selected from the group consisting of (E)-l-methoxy-4-(prop-l-en-l-yl)benzene; Anise oil; (lS,2S,4S)-l,7,7-trimethylbicyclo[2.2.1]heptan-2-ol; (2S,4S)- l,7,7-trimethylbicyclo[2.2.1]heptan-2-yl acetate; (lS,4S)-l,7,7-trimethylbicyclo[2.2.1]heptan-2-one; Clary sage oil;
  • Perfumery ingredients having a CITRUS odour may be selected from the group consisting of 3,7- dimethyloct-6-enitrile; Tamarine oil; 4,7-dimethyloct-6-en-3-one; l-methyl-4-(prop-l-en-2-yl)cyclohex-l-ene; Lime terpenes; 6,6-dimethoxy-2,5,5-trimethylhex-2-ene; Bergamot oil; (E)-3,7-dimethylocta-2,6-dienal; (E)-3,7- dimethylocta-2,6-dienal; (Z)-l,l-diethoxy-3,7-dimethylocta-2, 6-diene; Citronella oil; 3,7-dimethyloct-6-enal; Citrus terpenes; Lemon oil; Lemon terpenes; (2E,6Z)-3,7-dimethylnona-2,6-dienenitrile
  • Perfumery ingredients having a FLORAL odour may be selected from the group consisting of 8,8-dimethyl- l,2,3,4,5,6,7,8-octahydronaphthalene-2-carbaldehyde; (E)-4-((3aS,7aS)-hexahydro-lH-4,7-methanoinden-5(6H)- ylidene)butanal; 4-(4-methylpent-3-en-l-yl)cyclohex-3-enecarbaldehyde; 3,7-dimethyloctan-l-ol; dec-9-en-l-ol; 1- methoxy-4-methylbenzene; 2-methylpropyl 2-hydroxybenzoate; 2-methoxynaphthalene; 2,6-dimethyloct-7-en-2- ol; 2,6-dimethylheptan-2-ol; 2-(2-hydroxypropan-2-yl)-5-methylcyclohexanol
  • Perfumery ingredients having a FRUITTY odour may be selected from the group consisting of 2- methyldecanenitrile; l-(3,3-dimethylcyclohexyl)ethyl formate; (3aS,4S,7R,7aS)-ethyl octahydro-lH-4,7- methanoindene-3a-carboxylate; (E)-3,7-dimethylocta-2, 6-diene- 1-thiol; 2,2,5-trimethyl-5-pentylcyclopentanone; methyl 3-phenyl prop-2-enoate; (4S)-4,7,7-trimethyl-6-thiabicyclo[3.2.1]octane; 2-methyl-4-propyl-l,3-oxathiane;
  • Perfumery ingredients having a GREEN odour may be selected from the group consisting of hexan-l-ol; Armoise oil; (3R,5R)-3-ethoxy-l,l,5-trimethylcyclohexane; 2,4,6-trimethylcyclohex-3-enecarbaldehyde; 7-methyl-
  • Perfumery ingredients having a MARINE/WATERY odour may be selected from the group consisting of 2,6,10-trimethylundec-9-enal; (z)-3,7,ll-trimethyldodeca-6,10-dienal; 3-(2,3-dihydro-l,l-dimethyl-lH-inden-6- yl)propanal; l-methyl-4-(4-methylpent-3-en-l-yl)cyclohex-3-enecarbaldehyde; (Z)-non-6-en-l-ol; 7-isopentyl-2H- benzo[b][l,4]dioxepin-3(4H)-one; 8-methyl-l,5-benzodioxepin-3-one; 2,6-dimethylhept-5-enal; Ozonal oil; tricyclo[5.2.1.02,6]decane-3-carbaldehyde; and mixtures thereof.
  • Perfumery ingredients having a MUSK odour may be selected from the group consisting of tricyclo[5.2.1.02,6]decane-3-carbaldehyde; (Z)-oxacycloheptadec-10-en-2-one; (Z)-3-methylcyclotetradec-5-enone; l,4-dioxacycloheptadecane-5,17-dione; l-(3,5,5,6,8,8-hexamethyl-5,6,7,8-tetrahydronaphthalen-2-yl)ethanone;
  • Perfumery ingredients having a SPICY odour may be selected from the group consisting of (4- methylphenyl) 2-methylpropanoate; (E)-3-phenylprop-2-enenitrile; (E)-2-methoxy-4-(prop-l-en-l-yl)phenol; (E(- l,2-dimethoxy-4-(prop-l-en-l-yl (benzene; (E)-3-phenylprop-2-en-l-ol; (2E)-3-phenylprop-2-enal; #N/A#N/A4-allyl- 2-methoxyphenol; Nutmeg oil; Pepper black oil; 2-ethoxy-4-(methoxymethyl)phenol; (Z)-4,ll,ll-trimethyl-8- methylenebicyclo[7.2.0]undec-4-ene; 4-allyl-2-methoxyphenyl acetate; and mixtures thereof.
  • Perfumery ingredients having a SWEET odour may be selected from the group consisting of 1-butoxy-l- oxopropan-2-yl butanoate; 2-methoxy-4-methylphenol; (4-methylphenyl) 2-phenylacetate; 2,4-dimethyl-4,4a,5,9b- tetrahydroindeno[l,2-d][l,3]dioxine; 1-phenylethanone ; benzyl benzoate; benzo[d][l,3]dioxole-5-carbaldehyde; Neroli oil; octahydro-2H-chromen-2-one; (E)-5-methylhept-2-en-4-one; methyl 2-hydroxybenzoate; 2-methoxy-3- (4-methylpentyl)pyrazine; 3-hydroxybutan-2-one; l-(2-pyrazinyl)ethanone; 4-methoxybenzaldehyde; benzaldehyde; 2
  • the innermost compartment of the compartmentalized microcapsule comprises a full, hedonically balanced fragrance FI comprising top note ingredients, middle note ingredients and bottom note ingredients, whereas the outermost compartment comprises an overwhelming amount of characteristic powerful ingredients.
  • the compartmentalized microcapsule according to this embodiment provides an intense odour during the early stage of an application and a pleasant odour afterward.
  • Characteristic powerful ingredients particularly useful for encapsulation in outermost compartment may be selected from the group consisting of (2-(l-propoxyethoxy)ethyl)benzene; l-(pyrazin-2-yl)ethanone; 2,6,10- trimethylundec-9-enal; 2-methyldecanal; undec-10-enal; Hexan-l-ol; heptanal; 3,5,5-trimethylhexanal; (E)-undec- 9-enal; 3,8,8,lla-tetramethyldodecahydro-lH-3,5a-epoxynaphtho[2,l-c]oxepine; 1,3,4,5,6,7-hexahydro-
  • the skilled perfumer may easily select ingredients having similar odour and, and distribute these ingredients in the different compartments of the compartmentalized microcapsules according to the present invention, so that an enhanced perfume linearity is perceived throughout the entire application of the encapsulated fragrance composition.
  • the term "odour linearity" as it relates to the odour characteristics of fragrances assessed under different conditions, means that trained panellists are capable of perceiving the odour of a given fragrance under a first condition, for example on a wet substrate, for example on a substrate out of the wash machine, and that of the same perfumed product, under a second condition, for example after substrate has dried or is being manipulated or worn, whereas both odour are same or similar. This may be particularly challenging because it is known that a prolonged exposure to a given, unchanged odour usually leads to a lack of perception of this odour by the panellist, owing to habituation or fatigue of the olfactive sense.
  • any of the used fragrances may comprise a low odour adjuvant, such as a solvent, an oil, a wax, a surfactant, a polymer, and the like, and a mixture thereof.
  • a low odour adjuvant such as a solvent, an oil, a wax, a surfactant, a polymer, and the like, and a mixture thereof.
  • the cosmetic active agents for use in the compartmentalized microcapsules are preferably hydrophobic.
  • the cosmetic active agents have a calculated octanol/water partition coefficient (ClogP) of 1.5 or more, more preferably 3 or more.
  • the ClogP of the cosmetic active agent is from about 2 to about 7.
  • Particularly useful cosmetic active agents may be selected from the group consisting of emollients, smoothening active agents, hydrating active agents, soothing and relaxing active agents, decorative active agents, deodorants, anti-aging active agents, draining active agents, remodelling active agents, skin levelling active agents, preservatives, anti-oxidants, antibacterial or bacteriostatic active agents, cleansing active agents, lubricating active agents, structuring active agents, hair conditioning active agents, whitening active agents, texturing active agents, softening active agents, anti-dandruff active agents, and exfoliating active agents.
  • Particularly useful cosmetic active agents include, but are not limited to hydrophobic polymers, such as alkyldimethylsiloxanes, polymethylsilsesquioxanes, polyethylene, polyisobutylene, styrene-ethylene-styrene and styrene-butylene-styrene block copolymers, and the like; mineral oils, such as hydrogenated isoparaffins, silicone oils and the like; vegetable oils, such as argan oil, jojoba oil, aloe vera oil, and the like; fatty acids and fatty alcohols and their esters; glycolipides; phospholipides; sphingolipides, such as ceramides; sterols and steroids; terpenes, sesquiterpenes, triterpenes and their derivatives; essential oils, such as Arnica oil, Artemisia oil, Bark tree oil, Birch leaf oil, Calendula oil, Cinnamon oil, Echinacea oil, Eucalyp
  • the cosmetic active may be selected from the group consisting oSandal wood oil, such as Fusanus Spicatus kernel oil; Panthenyl triacetate (CAS-No: 94089-18-6); Tocopheryl acetate; Tocopherol; Naringinin; Ethyl linoleate; Farnesyl acetate; Farnesol; Citronellyl methyl crotonate (CAS-No: 20770-40-5); Ceramide-2 (l-Stearoiyl-C18-Sphingosine, CAS-No: 100403-19-8); and mixtures thereof.
  • oSandal wood oil such as Fusanus Spicatus kernel oil
  • Panthenyl triacetate CAS-No: 94089-18-6
  • Tocopheryl acetate Tocopherol
  • Naringinin Ethyl linoleate
  • Farnesyl acetate Farnesol
  • Citronellyl methyl crotonate CAS-No: 20
  • any of the used cosmetic agents may comprise an adjuvant, such as a solvent, an oil, a wax, a surfactant, a polymer, and the like, and a mixture thereof.
  • an adjuvant such as a solvent, an oil, a wax, a surfactant, a polymer, and the like, and a mixture thereof.
  • the compartmentalized microcapsules according to the present invention provide a programmed release of the encapsulated active agents, characterized in such that the active agent located in the outermost compartment of the microcapsules is released first and the active agent located in the innermost compartment of the microcapsule, is the last one to be released.
  • This programmed release is conveniently assessed by monitoring the weight loss of microcapsules in a thermo-gravimetric measurement. In such a measurement, a sample of microcapsules is placed on a micro-balance and is heated continuously, according to a pre-determined heating program. Weight loss occurs when a material comprised in the microcapsule is released by evaporation or when degradation of the material with emission of a gaseous degradation product occurs. This method is particularly suitable for volatile active agents.
  • a typical thermogravimetric weight loss curve is shown in Fig. 2, as discussed hereinabove.
  • the compartmentalized microcapsules comprise two fragrances FI and F2, wherein fragrance FI is present at a level of about 5 to 90 wt%, more particularly from 10 to 60 wt%, still more particularly from 20 wt% to 50 wt% in the innermost compartment; and fragrance F2 is present at a level of about 5 to 90 wt%, more particularly from 10 to 60 wt%, still more particularly from 20 wt% to 50 wt%; in the outermost compartment; and the total level of fragrance FI and F2 is from 70 to 98 wt% , more particularly from 80 to 96 wt% or higher, more particularly from 85 to 94 wt% referred to the total weight of the compartmentalized microcapsules.
  • the total weight of the compartmentalized microcapsules is defined as being identical to the theoretical solid content of the slurry, which in turn is equal to the sum of the weight of active agents, resin, and stabilizing colloids involved in the slurry, expressed in wt% based on the total weight of the slurry.
  • the weight ratio of the outermost to innermost fragrances is from 0.05 to 5, more particularly from 0.1 to 2, still more particularly from 0.15 to 1.
  • the weight ratio of the outermost to innermost fragrances is from 0.05 to 1, more particularly from 0.08 to 0.5, still more particularly from 0.1 to 0.3.
  • Microcapsules having such outermost to innermost fragrances weight ratios are particularly suitable for providing the right balance of early stage fragrance release (for example on wet fabrics) and later stage, prolonged release (for example on dry fabric).
  • the encapsulated fragrance composition comprise a fragrance and a cosmetic active, wherein the fragrance is located in the innermost compartment and the cosmetic active agent is located in the outermost compartment of a two-compartment microcapsule, or vice-versa.
  • the normalized resin weight W r of the innermost capsule wall(s) is from about 0.01 g/m 2 to about 1 g/m 2 , more particularly from about 0.05 g/m 2 to about 0.8 g/m 2 and still more particularly from about 0.1 g/m 2 to 0.6 g/m 2 .
  • the normalized resin weight of the outermost wall is smaller hat the normalized weight of the innermost wall.
  • the ratio of the normalized resin weight of the outermost wall by the normalized weight of the innermost wall is 0.01 to 1, more particularly from 0.05 to 0.5 and more particularly from
  • composition comprising at least one microcapsule in a suspending medium, wherein the microcapsule is compartmentalized as described hereinabove.
  • Microcapsules with two compartments according to the invention may be obtained by performing the steps of: a) emulsifying an active agent Al, optionally admixed with an adjuvant Dl, in an aqueous phase comprising an emulsifier El and a thermosetting resin precursor PI using a propeller, a turbine, a cross-beam stirrer with pitched bean, such as Mig stirrer, and the like, wherein said thermosetting resin precursor is added before emulsification, during emulsification or after emulsification has been completed; b) adjusting the pH of the emulsion obtained in step a) to a value pHl and heating the system to a temperature Tl; c) maintaining the temperature Tl over a period of time tl under stirring, to form thermosetting resin R1 innermost capsule walls around the droplets of active agent Al and optional adjuvant Dl, thereby forming a slurry of innermost microcapsules including active agent Al and optional adjuvant Dl;
  • the stirring speed is preferably reduced at this stage in order to prevent emulsification of the active agent A2 in the water phase and promote its adsorption onto the innermost microcapsules; e) adjusting the pH to a value pH2 and bringing the slurry to a temperature T2; f) adding thermosetting resin precursor P2 to the slurry obtained in step e), optionally with an emulsifier E2, and maintaining the temperature T2 over a period of time t2, to form a thermosetting resin R2 outermost capsule wall around the adsorbed active agent A2 layer obtained in step d), thereby forming outermost capsule, in which at least one innermost microcapsule is accommodated; g) cooling down the slurry to a temperature T3; h) optionally adjusting the pH to a value pH3; i) optionally adding excipients to the slurry, such as a scavenger, a protective colloid, a preservative and the like; j) if necessary cooling down the s
  • thermosetting resin The above generic process may be executed in various ways, depending on the desired thermosetting resin.
  • the thermosetting resin Rl, R2 etc. is an aminoplast resin formed by the polycondensation of amino-aldehyde pre-condensates.
  • the amino-aldehyde pre-condensate may be a reaction product, such as a polymer or co-polymer of at least one amine, such as urea, thiourea, alkyl urea, 6-substituted- 2, 4-diamino- 1, 3, 5-triazines such as benzoguanamine or glycol uril, and melamine; and at least one aldehyde, such us formaldehyde, acetaldehyde, glyoxal or glutaraldehyde.
  • Suitable amino-aldehyde pre-condensates include but are not limited to partially methylated mono- and poly-methylol-l,3,5-triamino-2,4,6-triazine pre-condensates, such as those commercially available under the Trade Mark CYMEL (ex Cytec Technology Corp.) or LURACOLL (ex BASF), and/or mono- and polyalkylol-benzoguanamine pre-condensates, and/or mono- and polyalkylol-glycouril pre-condensates.
  • These alkylolated polyamines may be provided in partially alkylated forms, obtained by addition of short chain alcohols having typically 1 to 6 methylene units.
  • a cross-linker is added to the reaction medium in order to improve the encapsulating properties of the resin.
  • the cross-linker may be an aromatic polyol or a diamine.
  • Diamine cross-linkers useful in the present invention include, but are not limited to urea, melamine, glycouryl, chitosan, guanidine and benzoguanidin. A particularly suitable diamine is urea.
  • Useful aromatic polyols include, but are not limited to phenol, 3,5-dihydroxy toluene, Bisphenol A, resorcinol, hydroquinone, xylenols, polyhydroxy naphthalene, and polyphenols produced by the degradation of cellulose and humic acids.
  • thermosetting resin Rl, R2 etc. is an aminoplast
  • the emulsifier E is a preferably polymeric stabilizer selected from the group consisting of acrylic copolymers bearing sulfonate groups, such as those available commercially under the trade mark LUPASOL (ex BASF), such as LUPASOL PA 140 or LUPASOL VFR; copolymers of acrylamide and acrylic acid, copolymers of alkyl acrylates and N-vinylpyrrolidone, such as those available under the trade mark Luviskol (e.g.
  • LUVISKOL K 15, K 30 or K 90 ex BASF sodium polycarboxylates (ex Polyscience Inc.) or sodium polystyrene sulfonate) (ex Polyscience Inc.); vinyl and methyl vinyl ether-maleic anhydride copolymers (e.g. AGRIMER VEMATM AN, ex ISP), and ethylene, isobutylene or styrene-maleic anhydride copolymers (e.g.
  • ampholytic co-polymer formed from a cationic monomer containing quaternary ammonium groups; and a monomer that can form anions, more particularly a monomer that is based on acrylic acid, methacrylic acid or a derivative thereof, such as a copolymer of acrylic acid or methacrylic acid, and acrylamidopropyl-trimethylammonium chloride (APTAC) or methacrylamidopropyl-trimethylammonium chloride (MAPTAC), a terpolymer formed from acrylic acid monomer, MAPTAC monomer and acrylamide monomer).
  • ATAC acrylamidopropyl-trimethylammonium chloride
  • MATAC methacrylamidopropyl-trimethylammonium chloride
  • MAPTAC methacrylamidopropyl-trimethylammonium chloride
  • the pH range is 3.9 ⁇ 1
  • time range t is from about 1 to about 4 hours, more particularly 2 to 3 hours.
  • the emulsifiers El, E2... may be the identical or different.
  • the pH3 is preferably between 5 and 7 and the temperature T3 is preferably below 40 °C.
  • the thermosetting resin Rl, R2 etc. is a polyurea resin formed by the polyaddition of a polyisocyanate on a polyamine.
  • the polyisocyanates may be selected from the group consisting of 1,6- diisocyanatohexane (CAS No. 822-06-0), l,5-diisocyanato-2-methylpentane (CAS No. 34813-62-2), 1,4- diisocyanato-2,3-dimethylbutane, 2-ethyl-l,4-diisocyanatobutane, 1,5-diisocyanatopentane (CAS No. 4538-42-5), 1,4- diisocyanatobutane (CAS No.
  • 1,3-diisocyanatopropane (CAS NO. 3753-93-3 ), 1,10- diisocyanatodecane (CAS No. 538-39-0), 1,2- diisocyanatocyclobutane, bis(4-isocyanatocyclohexyl)methane (CAS No. 5124-30-1), 3,3,5-trimethyl-5- isocyanatomethyl-l-isocyanatocyclohexane (CAS No. 4098-71-9), 2-
  • Imidodicarbonic diamide (CAS No. 4035-89-6), biuret (CAS No. 108-19-0), polyisocyanurate of toluene diisocyanate (CAS No. CAS NO.141-78-6, commercially available from Bayer under the Trade Name DESMODUR ® RC), trimethylol propane pre-condensate of polyisocyanurate of 1,6-diisocyanatohexane (CAS No. 53200-31-0, commercially available from Bayer under the Trade Name DESMODUR ® N100), trimethylol propane pre condensate of toluene diisocyanate (CAS No.
  • Polyamines may be selected from the group comprising 1,2- ethylenediamine; 1,3-diaminopropane; 1 ,4-diaminobutane; 1,6-diaminohexane; hydrazine; 1,4- diaminocyciohexane; 1, 3-diamino- 1-methylpropane; diethylenetriamine; triethylenetetramine; bis(2- methylaminoethyl)ether (CAS No. 3033-62-3), guanidine (CAS No. 113-00-8); guanidine carbonate salt (CAS No 593-85-1); 3, 5-Diamino-l, 2, 4-triazole (CAS No.
  • polymeric polyamines such as poly(vinylamine), such as those available commercially under the trade name LUPAMINE (ex BASF); poly(ethyleneimine) (CAS No. 9002-98-6)), such as those available commercially under the trade name LUPASOL (ex BASF); poly(etheramine), such as those available commercially under the trade name JEFFAMINE (ex Huntsman); and mixtures thereof.
  • the emulsifier E is a preferably polymeric stabilizer selected from the group consisting of maleic - vinyl copolymers, sodium lignosulfonates, maleic anhydride/styrene copolymers, ethylene/maleic anhydride copolymers, and copolymers of propylene oxide, ethylenediamine and ethylene oxide, polyvinylpyrrolidone, polyvinyl alcohols, fatty acid esters of polyoxyethylenated sorbitol and sodium dodecylsulfate.
  • Polyvinylpyrrolidone and polyvinyl alcohols are the G- polymer type, having a degree of hydrolysis in the range of 85 to 99.9 %, available under the trade name GOSHENOL from Nichigo.
  • the temperature range is at least 50°C, preferably 60°C, more preferably in a range of from 75°C to 90°C and in particular 85°C to 90°C
  • the pH range is from 3 to 12, in particular between 5 to 10, and more particular in the range from 7 to 10
  • time range t is from 1 to 8 hours, more particularly from 3 to 6 hours.
  • the pH3 is preferably between 5 and 7 and the temperature T3 is preferably below 40 °C.
  • steps d) to f) may be repeated in order to provide additional compartments, with all thermosetting resins R,, emulsifiers E, and conditions T r , pH,, t, being identical, similar or different.
  • suitable hydrocolloids include starch and starch derivatives, such as modified starch, dextrin, maltodextrin; gums, such as gum Arabic or gum acacia, xanthan gum, gum tragacanth, gum karaya, guar gum; cellulose and cellulose derivatives, such as carboxy methyl cellulose, hydroxyethyl cellulose, hydroxyethyl cellulose/lauryl-dimethylammoniumepoxy condensat, hydroxypopyl cellulose, cationic cellulose (for example Polyquaternium-4), cellulose gum; carrageenan; agar-agar; pectines and pectic acid; gelatine; protein hydrolysates; polymer and copolymers of vinyl and allyl monomers, such as polyvinylpyrrolidone; poly(vinyl pyrrolidone)
  • poly(alkyleneoxide); polyurethanes and polyureas such as anionic, cationic non-ionic and amphoteric polyurethanes and polyureas; mixed copolymers thereof; and mixture thereof.
  • suitable preservatives for the purpose includes but are not limited to quaternary compounds, biguanide compounds (CAS#: 32289-58-0 / 27083-27-8 / 28757-47-3 / 133029-32-0), poylaminopropyl biguanidine, Hexetidine, para-chloro- meta-cresol, methenamine, 3-Bis(hydroxymethyl)-5,5-dimethylimidazolidine-2,4-dione, Quaternium-15, benzoic acid, salicylic acid, undec-10-enoic acid, formic acid, biphenyl-2-ol and their salts, 4-hydroxybenzoic acid and its esters and salts; sorbic acid and its salts, Isothiazolinones, Bronopol (2-Bromo-2-nitro- 1,3-propanediol), 5-bromo-5- nitro-l,3-dioxane,
  • the slurry may also contain other commonly employed adjuvants.
  • adjuvants refers to ingredients that may affect the performance of a slurry, other than its hedonic performance.
  • an adjuvant may be an ingredient that acts as an aid to processing a perfume composition or consumer product containing said composition, or it may improve handling or storage of a perfume composition or consumer product. It might also be an ingredient that provides additional benefits such as imparting colour or texture. It might also be an ingredient that imparts light resistance or chemical stability to one or more ingredients contained in a perfume composition or consumer product.
  • a detailed description of the nature and type of adjuvants commonly used in perfume compositions or consumer products cannot be exhaustive, but such ingredients are well known to a person skilled in the art.
  • adjuvants include solvents, waxes, oils, pigments, dyestuffs and colouring matters; extenders, fillers and reinforcing agents; stabilizers against the detrimental effects of heat and light, bulking agents, acidulants, buffering agents and antioxidants.
  • a slurry may be spray dried in a further step.
  • a flow aid such as silica or the like to the slurry to ensure the realization of fine, free- flowing powdered microcapsules with low surface perfume oil.
  • the resulting slurry of microcapsules may be spray-dried in a conventional spray drying tower, using a two-fluid nozzle, or spin-dried in a conventional spin dryer.
  • at least one hydrocolloid may be added to the microcapsule slurry, as such or in the form of an aqueous solution.
  • Typical hydrocolloids include starch, modified starch such as dextrin-modified with octenyl succinate anhydride, and gum Arabic.
  • maltodextrins and sugar alcohols, such as sorbitol, mannitol or maltitol may also be added.
  • the hydrocolloid may itself contain a functional ingredient. This functional ingredient may be the same as, or different form, that in the capsule.
  • a process is described in WO 2007137441 Al, Example 5, which is taken herein as reference.
  • the suspending medium comprising the core-shell microcapsules according to the present invention is a hydrophilic matrix comprising one or more hydrocolloids, optionally one or more maltodextrins and optionally one or more functional ingredients that may be identical, similar or different from the functional ingredient encapsulated in the core-shell microcapsules.
  • compositions of the present invention may be used to perfume all manners of consumer products, including laundry care detergents, laundry care conditioners, fabric refreshers, personal care cleansing compositions, such as shampoos, bath and shower gels, liquid soaps, soap bars and the like, personal care conditioning composition, such as hair care conditioners, bath and shower lotions, deodorant compositions, antiperspirant compositions, home care compositions, such as hard surface cleaners, heavy duty detergents and the like.
  • personal care cleansing compositions such as shampoos, bath and shower gels, liquid soaps, soap bars and the like
  • personal care conditioning composition such as hair care conditioners, bath and shower lotions, deodorant compositions, antiperspirant compositions
  • home care compositions such as hard surface cleaners, heavy duty detergents and the like.
  • Typical consumer products concerned by the present invention include personal care cleaning and cleansing compositions, such as shampoos, bath and shower gels, liquid soaps, soap bars and the like, laundry care products, such as detergents, and home care products, such as hard surface cleaners.
  • personal care cleaning and cleansing compositions such as shampoos, bath and shower gels, liquid soaps, soap bars and the like
  • laundry care products such as detergents
  • home care products such as hard surface cleaners.
  • the consumer products according to the present invention may be used for treating substrates, such as fabrics, skin, hair, animate and inanimate surfaces, hard surfaces and the like, wherein the action of treating a substrate includes washing, cleansing, softening, caring, finishing, scenting and/or deodorizing this substrate.
  • substrates such as fabrics, skin, hair, animate and inanimate surfaces, hard surfaces and the like
  • the action of treating a substrate includes washing, cleansing, softening, caring, finishing, scenting and/or deodorizing this substrate.
  • a consumer product contains the compositions according to the present invention preferably at a level of about 0.02 to 5 wt%, more particularly from about 0.1 to 2 wt% and still more particularly from about 0.2 to 1 wt% of the consumer product.
  • the consumer products concerned by the present invention contain surfactants, such as anionic, cationic, amphoteric or non-ionic surfactants.
  • the consumer product containing the microcapsules of the present invention is a fabric care product, such as a laundry powder detergent, a heavy duty liquid detergent, or a liquid fabric care conditioner.
  • a fabric care product such as a laundry powder detergent, a heavy duty liquid detergent, or a liquid fabric care conditioner.
  • Typical formulation ingredients for use in laundry care products may be found in WO2016207179A1 page 74 line 1 to page 78 line 18.
  • the consumer product containing the microcapsules of the present invention is a shampoo, containing anionic surfactants, witterionic and/or amphoteric surfactants, non-ionic surfactants, as well as, optionally, water-soluble solvents, preservatives, and benefit agents, such as moisturizers, emollients, thickeners, anti-dandruff agents, hair growth promoting agents, vitamins, nutrients, dyes, hair colorants, and the like.
  • benefit agents such as moisturizers, emollients, thickeners, anti-dandruff agents, hair growth promoting agents, vitamins, nutrients, dyes, hair colorants, and the like.
  • Typical formulation ingredients for use in shampoo with our without microcapsules may be found, for example, in EP 0191564 A2 or WO 1997023194 Al.
  • the consumer product comprising core-shell microcapsules of the present invention is a liquid soap comprising one or more anionic surfactants, and other surfactants that may be selected from the group consisting of mixtures of fatty acids and neutralized fatty acids, aminoxide surfactants, non-ionic surfactants, zwitterionic surfactants, and mixture thereof; electrolytes; one or more preservatives; and optionally benefit agents that may be selected from the group consisting of pH-control agents, skin care agents, moisturizers, emollients, thickeners, vitamins, nutrients, dyes, and the like.
  • Typical formulation ingredients for use in liquid soaps may be found, for example, in CA 2812137 Al and US 20030050200.
  • the consumer product comprising core-shell microcapsules and chitosan of the present invention is a shower gel comprising one or more anionic surfactants, and other surfactants that may be selected from the group consisting of mixtures of fatty acids and neutralized fatty acids, aminoxide surfactants, non-ionic surfactants, zwitterionic surfactants, and mixture thereof; electrolytes, such one or more preservatives; and optionally benefit agents that may be selected from the group consisting of thickeners, pH-control agents; skin care agents, moisturizers, emollients, thickeners, vitamins, nutrients, dyes, and the like.
  • Typical formulation ingredients for use in shower gels may be found, for example, in US 5607678 A and US 20120263668 Al.
  • the core-shell microcapsules are able to release their core material by diffusion through the microcapsule shell or following the mechanical rupture of the microcapsule shell.
  • Mechanical rupture may follow a mechanical action, such as rubbing, squeezing, combing, washing and the like or heating, for example using a hair dryer.
  • Diffusion-mediated release is particularly desired if the core material is a perfume composition, because, in this case, a nice smell may be perceived over a long time, for example several hours, after application of the microcapsules on the substrate. On the other hand a mechanical rupture may provoke a surprising and pleasant boost of odour.
  • Example 1 Two-compartment microcapsules with cationic aminoplast resin
  • This example discloses the preparation of cationic compartmentalized microcapsules with two compartments with both innermost and outermost capsule walls comprising a cationic aminoplast thermosetting resin.
  • step d) The process of example 1 is repeated without performing step d) in order to form conventional core-wall capsules comprising fragrance FI and a cationic aminoplast capsule wall.
  • This example discloses the preparation of anionic compartmentalized microcapsules with two compartments with both innermost and outermost capsule walls comprising anionic aminoplast thermosetting resins.
  • Said microcapsules were prepared by performing the steps of: a) emulsifying 355 g of Fragrance FI in an aqueous phase containing 252 g polymeric stabilizer ZEMAC solution at 2.85% in water (i.e. 7.2 g), 15.3 g of formaldehyde precondensate (Luracoll SD, solution at 70% active content, i.e.
  • Example 4 comparative example to example 3
  • step c) The process of example 3 is repeated without performing step c) in order to form conventional core-wall capsules comprising fragrance FI and an anionic aminoplast capsule wall.
  • Example 5 two-compartment microcapsules with polvurea resin
  • This example discloses the preparation of compartmentalized microcapsules with two compartments with both innermost and outermost capsule walls comprising polyurea thermosetting resins.
  • microcapsules were prepared by performing the steps of:
  • Example 6 comparative example to example 5
  • step d) The process of example 5 is repeated without performing step d) in order to form conventional core-wall capsules comprising fragrance FI and a polyurea capsule wall.
  • Table 1 summarizes the trials performed with various compartmentalized microcapsules and comparative examples.
  • the first number in the reference codes refer to examples 1 through 6.
  • microcapsules depicted as 1.1 through 2.2 (cationic aminoplast) in Table 1 were evaluated in a proprietary unperfumed liquid fabric care conditioner base.
  • the microcapsules depicted as 3.1 through 4.2 (anionic aminoplast) in Table 1 were evaluated in a proprietary unperfumed powder laundry detergent base.
  • the microcapsules depicted as 5.1 through 6.2 (poylurea) in Table 1 were evaluated in proprietary unperfumed shampoo base. 0.5 wt% of microcapsule slurry was dispersed in each base.
  • liquid fabric care conditioner 21 g of the base was used in a side-loaded wash machine (20 L capacity, loaded with 1 kg terry towelling, preferably washed beforehand with an unperfumed laundry detergent); a rinse cycle was performed at a temperature of 20 °C, followed by spin drying.
  • the pre-rub olfactive evaluation was performed on wet laundry directly out of the machine and after 4 hours.
  • the post-rub olfactive evaluation was performed after line drying the terry towelling for 24 hours at room temperature. This evaluation was performed by gently rubbing one part of the terry towelling on another part of same terry towelling.
  • the compartmentalized microcapsules provide noticeable olfactive benefit compared to microcapsules known in the art.
  • the benefit may encompass both enhanced perfume linearity and differentiate perfume perception over time.
  • Example 9 Storage stability The system having reference number 1.2 in Table 1 was stored one month at 37°C in proprietary unperfumed liquid detergent base 1. The evaluation was performed as described in example 5. The results are reported in Table 3.

Abstract

A composition comprising at least one microcapsule in a suspending medium, wherein the microcapsule is compartmentalized and comprises at least one innermost microcapsule, having an innermost capsule wall and an innermost compartment surrounded by said innermost capsule wall, with a first active agent Al located in the innermost compartment; and at least one outermost microcapsule, having an outermost capsule wall and an outermost compartment surrounded by said outermost capsule wall, with a second active agent A2 in the outermost compartment; wherein at least one innermost microcapsule is accommodated in the outermost microcapsule. Furthermore, a method for manufacturing said composition is disclosed.

Description

IMPROVEMENTS IN OR RELATING TO ORGANIC COMPOUNDS
FIELD OF THE INVENTION
The present disclosure relates to suspensions of microcapsules providing programmed release of one or more active agents in an application. In a particular aspect, the one or more active agents include one or more fragrance or one or more cosmetic agent. The present disclosure relates also to a method to prepare compartmentalized microcapsules providing such benefits.
BACKGROUND OF THE INVENTION
One sought after benefit of perfumed products is the generation of surprising olfactive effects during use. A well-known method to achieve this task is to provide the perfume in an encapsulated form. The advantages of encapsulating perfumes in this way are well known in the art. In particular, microcapsules can increase the stability and life of the encapsulated perfume ingredients; they can facilitate the manipulation, handling and storage of the encapsulated perfume compositions, and control the emanation of pleasant odours in time and space; and they can also protect perfume ingredients from chemical attack of aggressive external media in which they are suspended. They can also act as a mean of controlling the spatio-temporal release of perfume. More particularly, frangible microcapsules can release a boost of perfume when ruptured mechanically, for example by rubbing the substrate on which these capsules are deposited. Using such microcapsules to provide such perfume benefits is well known to the art.
Usually, perfumed microcapsules are used in a consumer product, such as a detergent or a fabric conditioner, together with a free, non-encapsulated perfume. The role of the free perfume is to provide a pleasant odour to the neat product, for example when the perfume is assessed when opening the bottle containing the product, and during washing or conditioning the substrate, while the encapsulated perfume is released at later stages, such as wearing a fabric or combing hair. An additional surprising effect may be generated by admixing an encapsulated perfume that has a different odour than that of the free perfume. However, the release of free perfumes is mainly controlled by the vapour pressure of the perfume ingredients and the possibility to spatio- temporal release of the perfume is limited.
Two different populations of microcapsules having different characteristics, such sizes, wall thicknesses and/or containing different perfumes may be combined in a product, in order to generate differentiated consumer benefits. For example, WO 2011/094681 discloses the use of two different encapsulated perfume compositions based on the selection of perfume ingredients having different boiling points, while WO 2014029695 A1 discloses the use of two different encapsulated perfume compositions based on the selection of perfume ingredients having different odour thresholds. However, using mixtures of microcapsules require each of these microcapsules to be manufactured separately and then mixed together. This adds in process complexity and cost. GB 1,046,409 (1966), example 10, discloses multiwall capsules obtained by the steps of (i) emulsifying a first hydrophobic internal phase (or core phase) comprising a reactive intermediate dispersed in a second hydrophilic continuous phase comprising a second reactive intermediate, (ii) performing first interfacial polymerization of both reactive intermediates to form a condensation polymer at the interface between both internal and external phase and thereby forming primary core-wall capsules, (iii) filtering and/or drying the primary core-wall capsules obtained in step (ii) and transferring these primary microcapsules in a third hydrophobic continuous phase comprising a third reactive intermediate that can be identical to the first reactive intermediate, (iv) dispersing the primary microcapsule-containing second hydrophobic phase obtained in step (iii) into a fourth hydrophilic continuous phase comprising a fourth reactive intermediate that can be identical to the second reactive intermediate and (v) performing second interfacial polymerization of third and fourth reactive intermediates to form a second wall around the primary microcapsules, said second wall being separated from the wall of the primary microcapsule by a layer of third hydrophobic phase. The interfacial polymers disclosed in GB 1,046, 409 encompass polyamides, polyureas obtained from the polycondensation of phosgene and polyamines or polyurethanes obtained from the polycondensation of tetramethylene bischloroformate and polyamines. The multiwall microcapsules obtained by this process have a size ranging from 1 to 10 mm and would therefore be visible and therefore not suitable for the applications contemplated in the present disclosure. Furthermore, the process disclosed involves environmentally problematic reactive intermediates, and is complex and difficult to conduct at industrial scales.
US 4,891,172 A discloses a process for producing double capsules comprising one or more primary capsules included in a larger capsule. These double capsules are obtained by the steps of (i) preparing a slurry of primary aminoplast capsules in water, (ii) dispersing said slurry in a hydrophobic (oil) phase having a viscosity such that a capsule-in-oil-in-water double emulsion is formed and (iii) encapsulating the dispersed phase of the double emulsion obtained under (ii) in order to form larger aminoplast capsules including the primary capsules. The capsules obtained may be used for example to combine two reactive adhesive components that react when the capsules are broken, for example under pressure. The phase which is encapsulated in the primary capsules and the hydrophobic phase may be a fragrance. However, the method requires the use of a separate hydrophobic phase having a viscosity between 40 and 150000 mPas, preferably between 300 and 8000 mPas, in which the slurry of primary capsules has to be transferred. This is a source of complexity and significant on-cost.
W02002060573A2 [Henkel] discloses capsule-in-capsule systems obtained by transferring drop wise a dispersion of primary capsules in a first continuous phase containing a polymer into a second continuous phase of same polarity as that of the first continuous phase. Phase separation of the polymer occurs following a change of pH or temperature, or by addition of a salt or a second polymer, providing a second dispersion of larger capsule containing the primary capsules. Here again, the process is complex and difficult to execute at industrial scales. Furthermore, in the case an aqueous dispersion of capsule-in-capsule entities is targeted, the second encapsulated phase is also an aqueous or a polar phase. These phase arrangements are unlikely to be stable in consumer products containing surfactants and therefore unlikely to deliver the desired programmed release of one or more fragrance and optionally of one or more cosmetic agent in an application. EP 1097693A2 discloses capsule-in-capsule systems for use in adhesives and as delivery system for active agents including perfumes, and WO 2012146637A1 discloses double capsule containing anti-icing material, said anti-icing material being released following the osmotically-induced breakage of internal capsules. In no instance, a method is given on how these capsule-in-capsule systems can be obtained and manufactured.
Capsules comprising a core with primary capsules dispersed therein and an outer wall are well known to the art. For example US20050067726A1 [DSM] discloses complex coacervate capsules including primary capsules dispersed therein for application as delivery systems for food complements. Similarly, EP1736060B1 discloses solid forms consisting of dried agglomerated primary capsules surrounded by an outer wall which is a complex coacervate. However, coacervate walls usually swell in aqueous media and are known to be ineffective in retaining low molecular and/or volatile ingredients in aqueous consumer products. Furthermore, these processes require also multiple steps, such as re-dispersion and drying.
There is therefore a need for encapsulated compositions that provide programmed release of active agents, such as fragrances and/or cosmetic agents, while being easy to prepare and to handle, and inducing no significant on-cost compared to conventional, single encapsulated forms. In particular there is a need for encapsulated fragrance compositions that exhibit perceptibly enhanced odour linearity throughout an application compared to conventional mixtures of free and encapsulated fragrances. Alternatively, there is also a need for encapsulated fragrance compositions that release fragrances having different odour characteristics depending on assessment conditions, for example at different stages of use or application of the perfumed products, from the wet stage, e.g. from its point of purchase and its application onto a substrate to be treated, through to the dry stage, when it has been deposited and dried down on the substrate. Finally, there is a need to provide such olfactive effects together with the controlled release of one or more cosmetic active agent.
SUMMARY OF THE INVENTION
In addressing the deficiencies in the prior art the applicant surprisingly found that it is possible to provide the desired benefits by using compartmentalized microcapsules obtained by a single batch process.
In a first aspect of the invention is provided a composition comprising at least one microcapsule in a suspending medium, wherein microcapsule is compartmentalized and comprises at least one innermost microcapsule, having an innermost capsule wall and an innermost compartment surrounded by said innermost capsule wall, with a first active agent A1 located in the innermost compartment; and at least one outermost microcapsule, having an outermost capsule wall and an outermost compartment surrounded by said outermost capsule wall, with a second active agent A2 in the outermost compartment; wherein at least one innermost microcapsule is accommodated in the outermost microcapsule.
Optionally, the compartmentalized microcapsules may comprise one or more intermediate microcapsules, the intermediate microcapsules having an intermediate capsule wall and an intermediate compartment surrounded by said intermediate capsule wall, wherein the at least one intermediate microcapsule accommodates at least one of the innermost microcapsules, and wherein the at least one intermediate microcapsule is accommodated in the outermost microcapsule. Each intermediate microcapsule may optionally comprise a further active agent Ax in the intermediate compartment.
By active agent Al, A2, ... Ax is meant any substance or ingredient providing a benefit, in particular a fragrance ingredient or a cosmetic ingredient.
In a second aspect of the invention are provided composition rules for assigning a given active agent Al, A2, ... Ax to a given capsule compartment, wherein at least one of the active agents is a fragrance
In a third aspect of the invention is provided a method for manufacturing a composition comprising at least one compartmentalized microcapsule in a suspending medium according to the invention in a single batch process, comprising at least the steps of: a) preparing an innermost microcapsule comprising an innermost compartment comprising first active agent Al and an innermost capsule wall, wherein the innermost capsule wall consists of a thermosetting resin, thereby forming a slurry of innermost microcapsules; b) adding second active agent A2 to said slurry of innermost microcapsules formed in step a) under stirring, thereby forming innermost microcapsules coated with the second active agent A2; c) encapsulating said coated innermost microcapsules formed in step b) within an outermost wall of a thermosetting resin, thereby forming compartmentalized microcapsules with first active agent Al located in at least one innermost compartment and second active agent A2 located in the outermost compartment between innermost and outermost capsule walls.
Step b) and c) may be repeated, optionally with same or different active agents A3, A4 etc, if it is desirable to provide compartmentalized microcapsules with more than two compartments.
The compartmentalized microcapsules of the invention may provide a broad range of benefits, such as enhanced fragrance performance, enhanced fragrance linearity, programmed release of differentiated odours or improved efficacy of cosmetic active agent.
In one embodiment, the active agents Al, A2, ... Ax are identical to each other.
In one embodiment, the active agents Al, A2, ... Ax are different from each other.
BRIEF DESCRIPTION OF THE DRAWINGS
Fig. 1 A describes a spherical arrangement of the compartments in a compartmentalized microcapsule according to the present invention with two compartments: an innermost compartment 1, comprising a first active agent Al, and an outermost compartment 2, comprising a second active agent A2 that can be identical to or different from the first active agent, as well as the innermost capsule wall 3 and the outermost capsule wall 4. Fig. 1 B describes a microcapsule according to the present invention with an innermost compartment 1, an intermediate compartment 5 and an outermost compartment 2, and three capsule walls: innermost capsule wall 3, intermediate capsule wall 6 and outermost capsule wall 4.
Fig. 2 shows a typical schematic thermo-gravimetric curve of moist two-compartment microcapsules according to the present invention, wherein both active agents A1 and A2 are volatile, for example fragrances FI and F2. The compartmentalized microcapsules are separated from the slurry by filtration and available in the form of a wet cake. A portion of the wet cake is transferred to the micro-balance of the thermogravimetric analyser (TGA), and the weight loss of the sample is measured as a function of the temperature. Typically, the temperature is increased at a rate of 5 °C/min from 4 °C to 800 °C. Such TGA instruments are available commercially (for example Model TGA Q50, from Anton Paar company). The Figure represents the specific case of a two- compartment microcapsule comprising two active agents A1 and A2, wherein second active agent A2 is located in the outermost compartment of the microcapsule and first active agent A1 is located in the innermost compartment of the microcapsule. The first shoulder 7 in the curve corresponds to a loss of weight associated with the release of water from the microcapsule wet cake, the second shoulder 8 corresponds to a loss of weight associated with the release of second active agent A2 and the third shoulder 9 in the curve corresponds to a loss of weight associated with the release of first active agent Al. The fact that second active agent A2 is released within a lower temperature range than first active agent Al confirms that, in the case depicted in Fig. 2, the outermost capsule wall of the microcapsule is less impervious or more frangible than the innermost capsule wall.
In the example depicted in Fig. 2, the microcapsules contain about 40 wt% (100 wt% minus 60 wt%) of water, 10 wt% (60 wt% minus 50 wt%) of second active agent A2, about 40 wt% (50 wt% minus 10 wt%) of first active agent Al and about 10% of encapsulating material, referred to the theoretical weight of the wet microcapsule cake. Possibly, the encapsulated material may be degraded at higher temperature (not shown in the figure). However, the skilled person will understand that this figure may change depending on the relative amounts of active agents Al and A2 and on the relative permeability and/or frangibility of the capsule walls. The skilled person will also easily understand that the presence of very low or non-volatile materials (for example materials with a vapour pressure lower than 105 mmHg) in one or both or the compartments may also change the magnitude of the corresponding weight loss.
In an embodiment of the invention, the relative amount the second active agent A2 located in the outermost compartment will be lower than the relative amount of the first active agent Al located in the innermost compartment. Alternatively, the relative amounts of the active agents located in different compartments are equal, or the relative amount the second active agent A2 located in the outermost compartment is higher than the relative amount of the first active agent Al located in the innermost compartment. DETAILED DESCRIPTION OF THE INVENTION
The present invention is concerned with the differentiated programmed release of at least one active agent in an application, wherein said active agent is encapsulated in at least two different compartments within the same microcapsule (which is a compartmentalized microcapsule); and with the use of such compartmentalized microcapsules in consumer products to provide consumer with an enhanced hedonic experience.
In particular, the applicant has made possible the manufacturing of compartmentalized microcapsules comprising at least one active agent, said active agent being distributed in two or more compartments, in a simple single batch process.
The at least one active agent is selected from the group consisting of fragrances, essential oils, pheromones, cosmetic ingredients and the like, and mixture thereof.
In a particular embodiment, the compartmentalized microcapsules comprise a first active agent A1 located in an innermost compartment surrounded by an innermost capsule wall and a second active agent A2 located in an outermost compartment surrounded by an outermost capsule wall, wherein the innermost compartment and innermost capsule wall are accommodated in the outermost compartment. The active agent A1 may be a fragrance or and/or a cosmetic active agent and the active agent A2 may be a fragrance and/or a cosmetic active agent. The system according to this embodiment is further characterized in such that: if first active agent A1 is a fragrance FI and second active agent A2 is a fragrance F2, then fragrances FI and F2 may be identical or different; if first active agent A1 is a cosmetic agent Cl and second active agent A2 is a cosmetic agent C2, then the cosmetic agents Cl and C2 may be identical or different; if first active agent A1 is a mixture M l containing fragrance FI and cosmetic agent Cl and second active agent A2 is a mixture M2 containing fragrance F2 and cosmetic agent C2, then the mixtures M l and M2 may be identical or different; if first active agent A1 is a fragrance FI, then second active agent A2 may be a cosmetic agent C2 or a mixture M2 containing fragrance F2 and cosmetic agent C2, for example; the capsule wall separating the innermost compartment from the outermost compartment is substantially impervious to active ingredients A1 and A2; the normalized resin weight in the outermost capsule wall is either identical or lower than the normalized resin weight in the innermost capsule wall; wherein the normalized resin weight of a capsule wall is defined as the weight of encapsulating thermosetting resin comprised in said wall, without counting any emulsifier, stabilizer and protective colloids, divided by the volume-average surface of said wall. These terms are defined in more details hereinafter. In a further embodiment, the normalized resin weight in the outermost capsule wall is higher than the normalized resin weight in the innermost capsule wall.
By "substantially impervious" is meant that the inter-diffusion of active agents from one to the other compartment is limited, so that the benefit expected from the programmed release remain noticeable, even after a prolonged period of time and when the compartmentalized microcapsules are submitted to real life storage conditions (for example one month at a temperature of 37 °C, in a consumer product base). In the context of the present invention, the remanence of a consumer noticeable benefit after storage, as confirmed by an evaluation panel, is taken as a sufficient hint that inter-diffusion between the compartments was limited during storage.
In another embodiment, the compartmentalized microcapsules comprise more than two compartments, numbered 1 to N, each of these compartments being surrounded by a capsule wall, wherein each compartment may comprise an active agent, provided at least two compartments comprise an active agent.
In another embodiment, the more than two compartments may be arranged in such a way that the compartmented microcapsule comprises an innermost compartment, an outermost compartment and intermediated compartments located between the innermost compartment and the outermost compartment, each compartment being separated from the neighbouring compartment by a capsule wall, hereby forming innermost, intermediate and outermost microcapsules.
In another embodiment, an outermost compartment may accommodate more than one innermost or intermediate compartment. Also an intermediate compartment may accommodate more than one innermost compartment. The more than one compartment may have the same or different active agent in their core, respectively.
In an embodiment, the capsule walls consist of one or more thermosetting resins selected from the group comprising aminoplast (like for example melamine-formaldehyde or urea-formaldehyde) resins, polyurea, polyacrylic resins and the like, and mixtures thereof.
In an embodiment, different thermosetting resins are used to form capsule walls of different chemical nature.
In an embodiment the thermosetting resin used to form the outermost capsule wall of the microcapsule is different from that or those used to form the innermost capsule wall or the intermediate capsule walls. For example, the innermost and intermediate capsule walls may comprise an aminoplast resin and the outermost capsule wall a polyurea resin, or vice-versa.
Preferably, the aminoplast resin comprises a terpolymer comprising moieties derived from a triamine, moieties derived from a diamine and moieties derived from the group consisting of alkylene and alkylenoxy moieties, as disclosed in WO 2017001672 Al; or a terpolymer comprising moieties derived from a triamine, moieties derived from an aromatic polyol and moieties derived from the group consisting of alkylene and alkylenoxy moieties, as disclosed in EP 2111214 Bl. In another preferred embodiment, the outermost capsule wall comprises a positively charged aminoplast thermosetting resin as disclosed in WO 2016207180 Al.
In an embodiment, the outermost capsule wall is a coacervate or a hydrogel.
Calculation of the normalized weight of a capsule wall
The weight of thermosetting resin comprised in the capsule wall of one microcapsule is defined as the weight of thermosetting resin forming material added to the reaction medium in which the microcapsules are formed (so-called "slurry") during the stage where said wall is formed, divided by the number of microcapsules in the slurry. In applying this definition, the weight loss associated to the release of water associated for example with the polycondensation of aminoplast precursors, such as methylolated melamine and methylolated urea is neglected. However, this approximation is acceptable in the context of the present invention. Other approximations are mentioned herein after.
The volume-averaged surface of a capsule wall is calculated by using the volume-average radius of the microcapsules measured by laser light diffraction after said wall has been formed. The applicant used a Mastersizer 2000 supplied by Malvern. The technique is based on the principle that the light from a coherent source, in this case the laser beam, will scatter as particles pass through the beam, with the angle of the scattered light being directly related to the size of the particles. A decrease in particle size results in a logarithmic increase in the observed scattering angle. The observed scattering intensity is also dependent on particle size and diminishes relative to the particle's cross-sectional area. Large particles therefore scatter light at narrow angles with high intensity, whereas small particles scatter at wider angles but with low intensity. Detectors are used to measure the scattered light pattern produced over a wide range of angles and, hence, determine the particle size distribution of the sample using an appropriate optical model. The angular distribution of the scattering intensity is measured and analysed by Malvern proprietary software to provide the average size and size-distribution of the droplets present in the sample. In the case of a unimodal (monodisperse) droplet distribution, the median of the distribution ( d50 ) is taken as a measure of the mean diameter of the microcapsules.
For the measurement of the microcapsule size, the sample was placed in the Malvern Hydro2000 SM module, supplied with the Mastersizer 2000, for the measurement of wet dispersions. The supplied software was used to transform the measured scattered light pattern into the microcapsule size distribution. The optical model parameters used were 1.47 and 0 for the refractive index and absorption index, respectively. Sample measurement was taken over a period of five seconds using 5000 measurement snaps.
The d50 value is used as volume-average diameter of the microcapsules and the volume-average of the surface of one microcapsule is given by the classical formula for the surface area of a sphere ^ = p(ά50)2. The number of microcapsules in the slurry Nc is calculated by assuming that (i) the total weight ( wt ) of active agents and encapsulating materials (i.e. polymers and resins) added to the slurry are present in the microcapsules, (ii) the population of microcapsules is nearly monodisperse, i.e. all microcapsules have approximately the average diameter d50 , and (iii) the density of both the active agents and the encapsulating materials (i.e. polymers, resins, etc) is equal to pc = 1000 kg/m3. These approximations are acceptable in the context of the present invention. Nc is then given by N c = (6 wt / pc ) /{? r(c 50 )3 ) . The weight of thermosetting resin comprised in the capsule wall of one microcapsule wcr is the weight of wall material added to the slurry to form the capsule wall of all microcapsules wr divided by the number of microcapsules Nc . Finally, the normalized resin weight of the wall (Wr) is given by the ratio Wr = wcr / Sc .
In the context of the present invention, the above calculation is used to calculate the normalized resin weight of the innermost wall. In order to calculate the normalized resin weight of the outermost walls, the number of microcapsules is kept constant and the increase of capsule size following the addition of active agent A2 and the addition of the thermosetting resin of the outermost wall is used to calculate the surface area of the outermost wall.
Fragrances
In an embodiment, two or more fragrances are encapsulated as active agents in compartmentalized microcapsules comprising an innermost compartment and outermost compartment, and optionally intermediate compartments.
In an embodiment, the two or more encapsulated fragrances are identical, or have similar odours, and are released sequentially throughout the application, providing a linear perfume perception throughout the entire application, e.g. from its point of purchase and its application onto a wet substrate, through to the dry stage. In this sequential release process, the fragrance located in the outermost compartment of the capsule is first released by diffusion through and/or soft mechanical action on the outermost capsule wall, for example by handling, touching, wearing etc. the substrate. Then the fragrances located in the one or more sub-compartment(s), meaning the innermost compartment and, optionally the intermediate compartments, is(are) released under the actions of further mechanical actions, such as squeezing or rubbing.
In an embodiment, the two or more encapsulated fragrances have differentiated odours. In particular, the compartmentalized microcapsule of the present invention can provide odours that are perceptibly different, depending on whether the odour is assessed initially under wet conditions or under dry conditions. These different perceptions maintain an overall odour perception for the consumer during the usage of the perfumed product.
In the context of the present disclosure, the term "perceptibly different" as it relates to the odour characteristics of fragrances assessed under different conditions, means that trained panellists are capable of differentiating unambiguously the odour of a given fragrance under a first condition, for example on a wet substrate, for example on a substrate out of the wash machine, from that of the same perfumed product, under a second condition, for example after substrate has dried or is being manipulated or worn. Under such conditions, the difference is deemed to be consumer noticeable, that is, a majority of consumers will perceive the change of odour from said first condition to said second condition.
Methods to define odours exist and can be used in the context of the present invention. For example, an odour may be defined by using pre-defined semantic attributes, such as "CITRUS/ALDEFIYDIC", as in the case of a lemon odour, a lime odour, an orange odour or a grapefruit odour and the like; "FRUITY", as in the case of an apple odour, a peach odour, a berry odour, and the like; "GREEN", as in the case of a freshly cut grass odour, a leaf odour, and the like; "AROMATIC/HERBAL", as in the case of a resinous odour, a turpentine odour, a straw odour, and the like; "FLORAL", as in the case of a rose odour, a lily of the valley odour, and the like; "WOODY", as in the case of a sandal wood odour, a cedar odour, a patchouli odour, and the like; "M USKY", as in the case of a musk odour; or "SWEET", as in the case of a caramel odour, a vanilla odour, a cinnamon odour, and the like. Other semantic attributes may be defined if needed, depending on the desired accuracy of the odour definition. An odour may also be defined as a combination of semantic attributes. Numerous examples of alternative semantic attributes suitable for odour definitions may be found, for example, in S. Arctander, "Perfume and Flavor Chemicals", Allured Publisher Corp. Wheaton, 1969 and on web sites, such as www.thegoodscentscompany.com.
Admixing perfumery ingredients having similar odour to form a fragrance usually confers to said fragrance an odour that is strongly reminiscent of the odour of the admixed perfumery ingredients. For example, admixing perfumery ingredients having a CITRUS odour usually provide a fragrance having a CITRUS odour.
Fragrances may be more complex and may comprise ingredients having diverse odour characteristics. Flowever, even in this case, it is still usually possible to assign an overall odour characteristic to such complex fragrances by using secondary attributes or nuances. Flence, for example, a complex fragrance compositions may be described as having a CITRUS odour (primary semantic attributes) with GREEN and WOODY nuances (secondary attributes), while another complex fragrance composition may be described as having a GREEN odour (primary semantic attributes) with FLORAL and M USKY nuances (secondary attributes).
Two fragrances that are perceptibly different are preferably composed by using ingredients having a first odour 01 in first fragrance and preferably ingredients having a second odour 02 in second fragrance, wherein both first and second odours are different. Both the primary and secondary semantic attributes of the odours 01 and 02 may be different, or only the primary or only the secondary semantic attributes may be different. For example, a fragrance having a GREEN primary attribute and FLORAL and WOODY secondary attributes may be perceived as different from a fragrance having a GREEN primary attribute and FRUITY and SWEET secondary attributes. Similarly, two fragrances that differ only in their primary attributes such as for example two fragrances having of one of them a GREEN primary attribute and for the other of them an AROMATIC/FIERBAL primary attribute, but both fragrance having the same FLORAL and WOODY secondary attributes, may be perceived as having differentiated odours.
The differentiation between two fragrances may be maximized by using certain types of fragrances, which are referred to as "mutually opposing fragrances". Two fragrances are mutually opposing if their primary attributes are selected from the following pairs: CITRUS versus FLORAL (rose, tuberose); CITRUS versus WOODY; CITRUS versus MUSK; CITRUS versus SWEET; CITRUS versus FRUITTY (peach, prune); CITRUS vs. ANIMALIC; FRUITTY (green apple, melon) versus FLORAL (rose, tuberose); FRUITTY (green apple, melon) versus WOODY; FRUITTY (green apple, melon) versus M USK; FRUITTY (green apple, melon) versus SWEET; FRUITTY (green apple, melon) versus FRUITTY (peach, prune); FRUITTY (green apple, melon) vs. ANIMALIC; GREEN versus FLORAL (rose, tuberose); GREEN versus WOODY; GREEN versus M USK; GREEN versus SWEET; GREEN versus FRUITTY (peach, prune); GREEN vs. ANIMALIC; HERBAL / AROMATIC versus FLORAL (rose, tuberose); HERBAL / AROMATIC versus WOODY; HERBAL / AROMATIC versus M USK; HERBAL / AROMATIC versus SWEET; HERBAL / AROMATIC versus FRUITTY (peach, prune); and HERBAL / AROMATIC vs. ANIMALIC.
A complex fragrance may also be decomposed into top notes, middle (or heart) notes and bottom notes, wherein the top notes correspond often to ingredients having high vapour pressures, the middle notes to those having intermediate vapour pressures, and the bottom notes to those having low vapour pressures. When a perfume evaporates, the top notes evaporate faster, followed by the middle notes and, finally, by the bottom notes. As a consequence, the perception of the perfume may change during the course of the evaporation, especially when the odours of the top, middle and bottom notes are different, as it is frequently the case in perfumery. The top note odours are typically characterized by attributes such as ALDEHYDIC, CITRUS, AROMATIC/HERBAL, GREEN and FRUITTY attributes. The middle note odours are typically characterized by attributes such as FRUITTY, WATERY/OZONIC, GREEN and FLORAL attributes. The bottom note odours are typically characterized by attributes such as AMBERY/WOODY, SWEET and MUSKY attributes. Two fragrances having different top notes, but similar middle and bottom notes, may be perceived as having differentiated odours in the early stage of an application and become more and more similar as time elapses. Conversely, perfumes having different middle or bottom notes may be perceived as developing differentiated odours as time elapses.
Hence, by combining differentiated perfumes in a compartmentalized microcapsule, a broad diversity of sensory effects may be obtained, which are not achievable by conventional means.
The skilled in the art perfumer will easily compose fragrances to be encapsulated accordingly to the present invention by selecting perfumery ingredients having various odours.
Perfumery ingredients having an ALDEHYDIC odour may be selected from the group consisting of decanal; dodecanal; 4-isopropylbenzonitrile; 4-isopropylbenzaldehyde; (E)-dodec-2-enal; decanal; 2-methyldecanal; undecanal; 2-methylundecanal; octanal; nonanal; (E)-dodec-2-enal; (E)-dec-4-enal; dihydrocitronellyl nitrile; undec-10-enal; (E)-undec-9-enal; dodecanenitrile; 2-methylundecanoic acid, and mixtures thereof.
Perfumery ingredients having an AM BER/WOODY odour may be selected from the group consisting of (3aR,5aS,9aS,9bR)-3a,6,6,9a-tetramethyl-2,4,5,5a,7,8,9,9b-octahydro-lH-benzo[e][l]benzofuran; (lR,2S,4R)-2'- isopropyl-l,7,7-trimethylspiro[bicyclo[2.2.1]heptane-2,4'-[l,3]dioxane]; 2,4a,5,8a-tetramethyl-l,2,3,4,4a,7,8,8a- octahydronaphthalen-l-yl formate; l-((2E,5Z,9Z)-2,7,8-trimethylcyclododeca-2,5,9-trien-l-yl)ethanone; N-ethyl-N- (m-tolyl)propionamide; Patchouli oil; 4-(tert-pentyl)cyclohexanone; 4-(tert-butyl)cyclohexyl acetate; 3,5,5- trimethyl hexyl acetate; l-((2-(tert-butyl)cyclohexyl)oxy)butan-2-ol; decahydro-2,2,6,6,7,8,8-heptamethyl indenofuran; l,3,4,5,6,7-hexahydro-.beta.,l,l,5,5-pentamethyl-2H-2,4a-Methanonaphthalene-8-ethanol; 2,5,5- trimethyl-l,2,3,4,4a,5,6,7-octahydronaphthalen-2-ol; (4aR,5R,7aS,9R)-Octahydro-2,2,5,8,8,9a-hexamethyl-4H- 4a,9-methanoazuleno[5,6-d]-l,3-dioxole; (ethoxymethoxy)cyclododecane; 5-(sec-butyl)-2-(2,4-dimethylcyclohex-3- en-l-yl)-5-methyl-l,3-dioxane; l-(2,2,6-trimethylcyclohexyl)hexan-3-ol; (3-pentyloxan-4-yl) acetate; (lS,2R,5R)-2- ethoxy-2,6,6-trimethyl-9-methylenebicyclo[3.3.1]nonane; Cedarwood oil; (E)-3-methyl-5-(2,2,3- trimethylcyclopent-3-en-l-yl)pent-4-en-2-ol; methyl 2, 4-di hydroxy-3, 6-dim ethyl benzoate; l-(l,2,8,8-tetramethyl- l,2,3,4,5,6,7,8-octahydronaphthalen-2-yl)ethanone; 2-(3,8-dimethyl-l,2,3,4,5,6,7,8-octahydroazulen-5-yl)propan- 2-yl acetate; methyl ester of hydrogenated rosin; l-(2,3,8,8-tetramethyl-l,2,3,4,5,6,7,8-octahydronaphthalen-2- yl)ethanone; ( l-methyl-2-(( 1, 2, 2-trim ethyl bicyclo[3.1.0]hexan-3-yl)methyl (cyclopropyl (methanol; l-((lS,8aS)- l,4,4,6-tetramethyl-2,3,3a,4,5,8-hexahydro-lH-5,8a-methanoazulen-7-yl)ethanone; (E)-2-ethyl-4-(2,2,3- trimethylcyclopent-3-en-l-yl)but-2-en-l-ol; (E)-2-ethyl-4-(2,2,3-trimethylcyclopent-3-en-l-yl)but-2-en-l-ol; 3- methyl-5-(2,2,3-trimethylcyclopent-3-en-l-yl)pentan-2-ol; 3-((lR,2S,4R,6R)-5,5,6-trimethylbicyclo[2.2.1]heptan-2- yl)cyclohexanol; 3-((lR,2S,4R,6R)-5,5,6-trimethylbicyclo[2.2.1]heptan-2-yl)cyclohexanol; l-((lS,8aS)-l,4,4,6- tetramethyl-2,3,3a,4,5,8-hexahydro-lH-5,8a-methanoazulen-7-yl)ethanone; Wormwood oil; and mixtures thereof.
Perfumery ingredients having an ANIMALIC odour may be selected from the group consisting of 2-(2- methylpropyl)quinoline; Castoreum oil; lH-indole; 6-butan-2-yl-quinoline; 4,4a,5,9b-tetrahydroindeno[l,2- d][l,3]dioxine; 8,8-di(lH-indol-3-yl)-2,6-dimethyloctan-2-ol; 6-isopropylquinoline; 6-(sec-butyl)quinoline; 5- isopropyl-2-methylphenol; 4-methyl-2-propan-2-yl-l,3-thiazole; and mixtures thereof.
Perfumery ingredients having an AROMATIC/HERBAL odour may be selected from the group consisting of (E)-l-methoxy-4-(prop-l-en-l-yl)benzene; Anise oil; (lS,2S,4S)-l,7,7-trimethylbicyclo[2.2.1]heptan-2-ol; (2S,4S)- l,7,7-trimethylbicyclo[2.2.1]heptan-2-yl acetate; (lS,4S)-l,7,7-trimethylbicyclo[2.2.1]heptan-2-one; Clary sage oil;
1-methoxy-4-propylbenzene; l-allyl-4-methoxybenzene; octan-3-one; (Z)-3,7-dimethylnona-l,6-dien-3-yl acetate; (ls,4s)-l,3,3-trimethyl-2-oxabicyclo[2.2.2]octane; Eucalyptus oil; (lS,2R,4R)-l,3,3-trimethylbicyclo[2.2.1]heptan-2- ol; 2-(sec-butyl)cyclohexanone; diethyl cyclohexane-1, 4-dicarboxylate; 2-isopropyl-5-methylcyclohexanone; 3,7- dimethylocta-l,6-dien-3-yl acetate; 2-(4-methylcyclohex-3-en-l-yl)propan-2-ol; 2-isopropyl-5-methylcyclohexanol;
2-isopropyl-5-methylcyclohexanol; 2-isopropyl-5-methylcyclohexanone; Peppermint oil; Petitgrain oil; 2,6,6- trimethylbicyclo[3.1.1]hept-2-ene; 6,6-dimethyl-2-methylenebicyclo[3.1.1]heptane; Rosmary oil; Lavender oil; 2- isopropyl-5-methylphenol; l-(cyclopropylmethyl)-4-methoxybenzene; Thyme oil; l-methyl-4-propan-2-ylbenzene; l-methyl-4-propan-2-ylcyclohexa-l,4-diene; l-methyl-4-(propan-2-ylidene)cyclohex-l-ene; 3-methyl-5- propylcyclohex-2-enone; 2-cyclohexylethyl acetate; cyclohexyl 2-hydroxybenzoate; Lavandin oil; 2-methyl-6- methyleneoct-7-en-2-yl acetate; 2-pentylcyclopentanone; 2-(4-methylcyclohex-3-en-l-yl)propan-2-ol; 2-(4- methylcyclohex-3-en-l-yl)propan-2-yl acetate; 2-(tert-butyl)cyclohexyl acetate; (Z)-l-(cyclooct-3-en-l-yl)ethanone; (5R)-2-methyl-5-prop-l-en-2-ylcyclohex-2-en-l-one; (2S)-l,3,3-trimethylbicyclo[2.2.1]heptan-2-yl acetate; (E)-3- phenylprop-2-en-l-yl acetate; and mixtures thereof.
Perfumery ingredients having a CITRUS odour may be selected from the group consisting of 3,7- dimethyloct-6-enenitrile; Tamarine oil; 4,7-dimethyloct-6-en-3-one; l-methyl-4-(prop-l-en-2-yl)cyclohex-l-ene; Lime terpenes; 6,6-dimethoxy-2,5,5-trimethylhex-2-ene; Bergamot oil; (E)-3,7-dimethylocta-2,6-dienal; (E)-3,7- dimethylocta-2,6-dienal; (Z)-l,l-diethoxy-3,7-dimethylocta-2, 6-diene; Citronella oil; 3,7-dimethyloct-6-enal; Citrus terpenes; Lemon oil; Lemon terpenes; (2E,6Z)-3,7-dimethylnona-2,6-dienenitrile; Lime oil; Lime oxide; Mandarin oil; Orange terpenes; (4aS,6R,7S,8aR)-3,3,6,7-tetramethyl-2,4,4a,5,6,7,8,8a-octahydrochromene; 2,4,6-trimethyl-4- phenyl-l,3-dioxane; Grapefruit oil; 2,4-dimethyl-4-phenyltetrahydrofuran; (E)-tridec-2-enenitrile; Litsea cubeba oil; Orange oil; 2,2-dimethyl-4-phenylpentanenitrile; and mixtures thereof. Perfumery ingredients having a FLORAL odour may be selected from the group consisting of 8,8-dimethyl- l,2,3,4,5,6,7,8-octahydronaphthalene-2-carbaldehyde; (E)-4-((3aS,7aS)-hexahydro-lH-4,7-methanoinden-5(6H)- ylidene)butanal; 4-(4-methylpent-3-en-l-yl)cyclohex-3-enecarbaldehyde; 3,7-dimethyloctan-l-ol; dec-9-en-l-ol; 1- methoxy-4-methylbenzene; 2-methylpropyl 2-hydroxybenzoate; 2-methoxynaphthalene; 2,6-dimethyloct-7-en-2- ol; 2,6-dimethylheptan-2-ol; 2-(2-hydroxypropan-2-yl)-5-methylcyclohexanol; Jasmin oil; (Z)-3-methyl-2-(pent-2- en-l-yl)cyclopent-2-enone; (Z)-3,4,5,6,6-pentamethylhept-3-en-2-one; 2-(5-methyl-5-vinyltetrahydrofuran-2- yl)propan-2-ol; 2,6-dimethyloctan-2-ol; 2-phenylethanol; 2-phenylethyl 2-phenylacetate; 3-phenylpropan-l-ol; 3- (2-methylpropyl)-l-methylcyclohexanol; pentyl 2-hydroxybenzoate; (E)-methyl 2-((7-hydroxy-3,7- dimethyloctylidene)amino)benzoate; benzyl 2-hydroxybenzoate; 3-(4-(tert-butyl)phenyl)propanal; 3,7- dimethyloct-6-en-l-ol; 4-cyclohexyl-2-methylbutan-2-ol; 3-(4-isopropyl phenyl )-2-methylpropanal; 4-(4-hydroxy-4- methylpentyl)cyclohex-3-enecarbaldehyde; methyl 2-(methylamino)benzoate; 2-methyl-l-phenylpropan-2-ol; (E)-
3.7-dim ethyl nona-l,6-dien-3-ol; 3-(4-ethyl phenyl)-2, 2-dimethyl propanal; tetrahydro-4-methyl-2-(2-methylpropyl)- 2H-pyran-4-ol; (E)-3,7-dimethylocta-2,6-dien-l-ol; (E)-3,7-dimethylocta-2,6-dien-l-ol; Geranium oil; methyl 3-oxo- 2-pentylcyclopentaneacetate; (E)-2-benzylideneoctanal; hexyl 2-hydroxybenzoate; 7-hydroxy-3,7-dimethyloctanal; (E)-4-(2,6,6-trimethylcyclohex-2-en-l-yl)but-3-en-2-one; (E)-4-(2,6,6-trimethylcyclohex-2-en-l-yl)but-3-en-2-one; 2-hexylcyclopent-2-enone; (E)-l-(2,6,6-trimethylcyclohex-2-en-l-yl)pent-l-en-3-one; (E)-3-methyl-4-(2,6,6- trimethylcyclohex-2-en-l-yl)but-3-en-2-one; (E)-3-methyl-4-(2,6,6-trimethylcyclohex-2-en-l-yl)but-3-en-2-one; 3- pentyltetrahydro-2H-pyran-4-yl acetate; 3-(4-(tert-butyl)phenyl)-2-methylpropanal; 3,7-dimethylocta-l,6-dien-3- ol; 3-methyl-5-phenylpentan-l-ol; methyl 2-aminobenzoate; methyl benzoate; 2-ethoxynaphthalene; l-(2- naphtalenyl)-ethanone; 2-cyclohexylidene-2-phenylacetonitrile; 2-phenyl-ethanal; 2,2-dimethyl-2-pheylethyl propionate; 2,2,2-trichloro-l-phenylethyl acetate; 2-methyl-3-[4-(2-methylpropyl)phenyl]propanal; (E)-6-ethyl-3- methyloct-6-en-l-ol; 3,7-dimethyloctan-3-ol; benzyl acetate; benzyl propionate; 3,7-dimethyloct-6-en-l-yl acetate;
3.7-dimethyloct-6-en-l-yl formate; 3,7-dimethyloct-6-en-l-yl propionate; 2-methyl-l-phenylpropan-2-yl acetate; ethyl benzoate; (3aR,6S,7aS)-3a,4,5,6,7,7a-hexahydro-lH-4,7-methanoinden-6-yl propionate; (3aR,6S,7aS)- 3a,4,5,6,7,7a-hexahydro-lH-4,7-methanoinden-6-yl 2-methyl propanoate; (E)-3,7-dimethylocta-2,6-dien-l-yl acetate; (E)-3,7-dimethylocta-2,6-dien-l-yl 2-methyl propanoate; (3aR,6S,7aS)-3a,4,5,6,7,7a-hexahydro-lH-4,7- methanoinden-6-yl acetate; 2-hexylcyclopentanone; 3-butyl-5-methyltetrahydro-2H-pyran-4-yl acetate; (Z)-3,7- dimethylocta-2,6-dien-l-yl acetate; 2-cyclohexylidene-2-(o-tolyl)acetonitrile; 2-(phenoxy)ethyl 2- methylpropionate; 2-phenylethyl acetate; oxydibenzene; (Z)-hex-3-en-l-yl benzoate; (Z)-hex-3-en-l-yl 2- hydroxybenzoate; [(Z)-hex-3-enyl] cyclopropanecarboxylate; (E)-3,7,ll-trimethyldodeca-l,6,10-trien-3-ol; (Z)- 3,7,ll-trimethyldodeca-l,6,10-trien-3-yl acetate; 6,8-dimethylnonan-2-ol; 2-methyl-4-methylene-6- phenyltetrahydro-2H-pyran; 2-phenylethyl formate; 4-methyl-2-phenyl-3,6-dihydro-2H-pyran; 3-(3- isopropyl phenyl (butanal; 3-(benzo[d][l,3]dioxol-5-yl)-2-methyl propanal; l-(3,3-dimethylcyclohexyl)ethyl acetate; diphenylmethanone; (E)-methyl 2-((3-(4-(tert-butyl)phenyl)-2-methylprop-l-en-l-yl)amino)benzoate; Ylang oil; 4- (2-methoxypropan-2-yl)-l-methylcyclohexene; 4-(2,6,6-trimethylcyclohex-l-en-l-yl)butan-2-one; (E)-4-(2, 6,6- trim ethyl cyclohex- l-en-l-yl)but-3-en-2-one; (E)-4-(2,5,6,6-tetramethylcyclohex-2-en-l-yl)but-3-en-2-one; and mixtures thereof. Perfumery ingredients having a FRUITTY odour may be selected from the group consisting of 2- methyldecanenitrile; l-(3,3-dimethylcyclohexyl)ethyl formate; (3aS,4S,7R,7aS)-ethyl octahydro-lH-4,7- methanoindene-3a-carboxylate; (E)-3,7-dimethylocta-2, 6-diene- 1-thiol; 2,2,5-trimethyl-5-pentylcyclopentanone; methyl 3-phenyl prop-2-enoate; (4S)-4,7,7-trimethyl-6-thiabicyclo[3.2.1]octane; 2-methyl-4-propyl-l,3-oxathiane;
2-ethyl-N-methyl-N-(m-tolyl)butanamide; (E)-l-(2,6,6-trimethylcyclohexa-l,3-dien-l-yl)but-2-en-l-one; (E)-l- (2,6,6-trimethylcyclohex-2-en-l-yl)but-2-en-l-one; l-(2,6,6-trimethyl-l-cyclohex-3-enyl)but-2-en-l-one; 2-methyl- l-phenylpropan-2-yl butanoate; ethyl 2,6,6-trimethylcyclohexa-l,3-diene-l-carboxylate; ethyl 2-ethyl-6,6- dimethylcyclohex-2-enecarboxylate; undecan-2-one; 2-phenylethyl 2-methylpropanoate; (2E,5E)-5,6,7- trimethylocta-2,5-dien-4-one; hexyl acetate; prop-2-enyl hexanoate; prop-2-enyl 3-cyclohexylpropionate; prop-2- enyl heptanoate; 3a,4,5,6,7,7a-hexahydro-lH-4,7-methanoinden-l-yl butyrate; 5-hexyloxolan-2-one; Dewfruit oil; (Methylsulfanyl)methane; 5-octyloxolan-2-one; ethyl acetate; ethyl butanoate; ethyl hexanoate; ethyl octanoate; ethyl heptanoate; (2S)-ethyl 3-isopropylbicyclo[2.2.1]hept-5-ene-2-carboxylate; 3-methylbutyl acetate; 2-(4- methylcyclohex-3-en-l-yl)propane-2-thiol; 6-methylhept-5-en-2-one; octan-2-one; 2-(2-(4-methylcyclohex-3-en-l- yl)propyl)cyclopentanone; 5-butyloxolan-2-one; 5-heptyldihydrofuran-2(3H)-one; 3-methylbut-2-en-l-yl acetate; 5-pentyldihydrofuran-2(3H)-one; 4-(4-hydroxyphenyl)butan-2-one; pentyl butanoate; 5-tert-butyl-2-methyl-5- propyl-2H-furan; 2-(2-mercaptopropan-2-yl)-5-methylcyclohexanone; ethyl 3-oxobutanoate; ethyl 2- methylbutanoate; ethyl 2-(2-methyl-l,3-dioxolan-2-yl)acetate; (Z)-hex-3-en-l-yl acetate; isopropyl 2- methylbutanoate; (3E,6E)-2,4,4,7-tetramethylnona-6,8-dien-3-one oxime; (Z)-hex-3-en-l-yl methyl carbonate; ethyl 2-methylpentanoate; 10-isopropyl-2,7-dimethyl-l-oxaspiro[4.5]deca-3, 6-diene; ethyl 2-methylpropionate; 2- methyl-4-oxo-4H-pyran-3-yl 2-methylpropanoate; 4-(4-methoxyphenyl)butan-2-one; 8-methyl-l- oxaspiro[4.5]decan-2-one; ethyl methyl phenyl glycidate; and mixtures thereof.
Perfumery ingredients having a GREEN odour may be selected from the group consisting of hexan-l-ol; Armoise oil; (3R,5R)-3-ethoxy-l,l,5-trimethylcyclohexane; 2,4,6-trimethylcyclohex-3-enecarbaldehyde; 7-methyl-
3-methyleneocta-l, 6-diene; Galbanum oil; (E)-undec-9-enenitrile; 2-butyl-4,6-dimethyl-3,6-dihydro-2H-pyran; 3- methyl-5-phenylpentanal; (2Z,6E)-2,6-nonadien-l-ol; (2-methoxyethyl)benzene; 2-phenoxyacetaldehyde; 3- phenylbutanal; (2,2-dimethoxyethyl)benzene; prop-2-enyl 2-(3-methylbutoxy)acetate; allyl 2- (cyclohexyloxy)acetate; l-(5,5-dimethylcyclohex-l-en-l-yl)pent-4-en-l-one; l-(5,5-dimethylcyclohex-l-en-l- yl)pent-4-en-l-one; (E)-hex-2-enal; (E)-hex-2-enal; (Z)-hex-3-en-l-yl butanoate; (Z)-hex-3-en-l-yl formate; (Z)-hex- 3-en-l-yl 2-methylpropanoate; hexyl 2-methylpropanoate; (E)-methyl non-2-enoate; 2-cyclohexylhepta-l,6-dien-3- one; 4-vinylcyclohex-l-enecarbaldehyde; l-(spiro[4.5]dec-6-en-7-yl)pent-4-en-l-one; (3E,5Z)-undeca-l,3,5-triene; undec-10-enenitrile; (2-(l-propoxyethoxy)ethyl)benzene; (2-(isopentyloxy)ethyl)benzene; 8-(sec-butyl)-5, 6,7,8- tetrahydroquinoline; 2,4-dimethylcyclohex-3-ene-l-carbaldehyde; methyl oct-2-ynoate; 1-phenylethyl acetate; (Z)- hex-3-en-l-ol; 2-methylpropyl-3-methoxypyrazine; methyl non-2-ynoate; (2E,6Z)-nona-2,6-dienal; 2-propan-2- yloxyethyl benzene; 4-methyl-2-(2-methylprop-l-en-l-yl)tetrahydro-2H-pyran; 4-methyl-2-(2-methylprop-l-en-l- yl)tetrahydro-2H-pyran; (E)-5-methylheptan-3-one oxime; 2,4-dimethylcyclohex-3-enecarbaldehyde; (E)-4- methyldec-3-en-5-ol; (2E,6Z)-nona-2,6-dienenitrile; (Z)-non-6-enal; Liatrix oil; bicyclo[2.2.2]oct-5-ene-2- carboxaldehyde; hexyl butanoate; (E)-methyl 2-(((2,4-dimethylcyclohex-3-en-l-yl)methylene)amino)benzoate; and mixtures thereof. Perfumery ingredients having a MARINE/WATERY odour may be selected from the group consisting of 2,6,10-trimethylundec-9-enal; (z)-3,7,ll-trimethyldodeca-6,10-dienal; 3-(2,3-dihydro-l,l-dimethyl-lH-inden-6- yl)propanal; l-methyl-4-(4-methylpent-3-en-l-yl)cyclohex-3-enecarbaldehyde; (Z)-non-6-en-l-ol; 7-isopentyl-2H- benzo[b][l,4]dioxepin-3(4H)-one; 8-methyl-l,5-benzodioxepin-3-one; 2,6-dimethylhept-5-enal; Ozonal oil; tricyclo[5.2.1.02,6]decane-3-carbaldehyde; and mixtures thereof.
Perfumery ingredients having a MUSK odour may be selected from the group consisting of tricyclo[5.2.1.02,6]decane-3-carbaldehyde; (Z)-oxacycloheptadec-10-en-2-one; (Z)-3-methylcyclotetradec-5-enone; l,4-dioxacycloheptadecane-5,17-dione; l-(3,5,5,6,8,8-hexamethyl-5,6,7,8-tetrahydronaphthalen-2-yl)ethanone;
4,6,6,7,8,8-hexamethyl-l,3,4,6,7,8-hexahydrocyclopenta[g]isochromene; (E)-oxacyclohexadec-12-en-2-one; (Z)-3- methylcyclopentadec-5-enone; 2-(l-(3,3-dimethylcyclohexyl)ethoxy)-2-methyl propyl cyclopropanecarboxylate; cyclopentadecanone, hexadecanolide; cyclopentadecanone, hexadecanolide; (E)-2-((3,5-dimethylhex-3-en-2- yl)oxy)-2-methylpropyl cyclopropanecarboxylate; oxacyclohexadecan-2-one; and mixtures thereof.
Perfumery ingredients having a SPICY odour may be selected from the group consisting of (4- methylphenyl) 2-methylpropanoate; (E)-3-phenylprop-2-enenitrile; (E)-2-methoxy-4-(prop-l-en-l-yl)phenol; (E(- l,2-dimethoxy-4-(prop-l-en-l-yl (benzene; (E)-3-phenylprop-2-en-l-ol; (2E)-3-phenylprop-2-enal; #N/A#N/A4-allyl- 2-methoxyphenol; Nutmeg oil; Pepper black oil; 2-ethoxy-4-(methoxymethyl)phenol; (Z)-4,ll,ll-trimethyl-8- methylenebicyclo[7.2.0]undec-4-ene; 4-allyl-2-methoxyphenyl acetate; and mixtures thereof.
Perfumery ingredients having a SWEET odour may be selected from the group consisting of 1-butoxy-l- oxopropan-2-yl butanoate; 2-methoxy-4-methylphenol; (4-methylphenyl) 2-phenylacetate; 2,4-dimethyl-4,4a,5,9b- tetrahydroindeno[l,2-d][l,3]dioxine; 1-phenylethanone ; benzyl benzoate; benzo[d][l,3]dioxole-5-carbaldehyde; Neroli oil; octahydro-2H-chromen-2-one; (E)-5-methylhept-2-en-4-one; methyl 2-hydroxybenzoate; 2-methoxy-3- (4-methylpentyl)pyrazine; 3-hydroxybutan-2-one; l-(2-pyrazinyl)ethanone; 4-methoxybenzaldehyde; benzaldehyde; 2H-chromen-2-one; 2-ethyl-3-hydroxy-4H-pyran-4-one; 2-ethyl-3-hydroxy-4H-pyran-4-one; 3- ethoxy-4-hydroxybenzaldehyde; 2-ethyl-4-hydroxy-5-methylfuran-3(2H)-one; 4-formyl-2-methoxyphenyl 2- methylpropanoate; 3,6-dimethyl-3a,4,5,6,7,7a-hexahydro-3H-benzofuran-2-one; 3-hydroxy-2-methyl-4H-pyran-4- one; 2-methyl pyrazine; 2-phenylacetic acid; 4-hydroxy-3-methoxybenzaldehyde; and mixtures thereof.
In one embodiment, the innermost compartment of the compartmentalized microcapsule comprises a full, hedonically balanced fragrance FI comprising top note ingredients, middle note ingredients and bottom note ingredients, whereas the outermost compartment comprises an overwhelming amount of characteristic powerful ingredients. The compartmentalized microcapsule according to this embodiment provides an intense odour during the early stage of an application and a pleasant odour afterward.
Characteristic powerful ingredients particularly useful for encapsulation in outermost compartment may be selected from the group consisting of (2-(l-propoxyethoxy)ethyl)benzene; l-(pyrazin-2-yl)ethanone; 2,6,10- trimethylundec-9-enal; 2-methyldecanal; undec-10-enal; Hexan-l-ol; heptanal; 3,5,5-trimethylhexanal; (E)-undec- 9-enal; 3,8,8,lla-tetramethyldodecahydro-lH-3,5a-epoxynaphtho[2,l-c]oxepine; 1,3,4,5,6,7-hexahydro-
.beta.,l,l,5,5-pentamethyl-2H-2,4a-Methanonaphthalene-8-ethanol; 2,5,5-trimethyl-l,2,3,4,4a,5,6,7- octahydronaphthalen-2-ol; (4aR,5R,7aS,9R)-Octahydro-2,2,5,8,8,9a-hexamethyl-4H-4a,9-methanoazuleno[5,6-d]-
1.3-dioxole; oct-l-en-3-ol; 7-isopentyl-2H-benzo[b][l,4]dioxepin-3(4H)-one; 8-(sec-butyl)-5, 6,7,8- tetrahydroquinoline; (lR,5S,E)-l,5-dimethylbicyclo[3.2.1]octan-8-one oxime; 6-(sec-butyl)quinoline; 7-methyl-2H- benzo[b][l,4]dioxepin-3(4H)-one; 3-hydroxy-4,5-dimethylfuran-2(5H)-one; 5-isopropyl-2-methyl phenol; 5-tert- butyl-2-methyl-5-propyl-2H-furan; (E)-l-(2,6,6-trimethylcyclohex-2-en-l-yl)hepta-l,6-dien-3-one; 2-((3,7- dimethyloct-6-en-l-yl)oxy)acetaldehyde; 2-(2-mercaptopropan-2-yl)-5-methylcyclohexanone; (4S)-4,7,7-trimethyl- 6-thiabicyclo[3.2.1]octane; 2-(3-phenylpropyl)pyridine; 2-hydroxy-3-methylcyclopent-2-enone; p-tolyl octanoate; l-methoxy-4-methylbenzene; 4-isopropyl benzonitrile; 4-isopropyl benzaldehyde; (E)-l-(2,6,6-trimethylcyclohexa-
1.3-dien-l-yl)but-2-en-l-one; (E)-l-(2,6,6-trimethylcyclohex-3-en-l-yl)but-2-en-l-one; decanenitrile; (E)-dec-2- enal; (E)-dec-4-enal; 9-decenal; 2-(2-(3,3,5-trimethylcyclohexyl)acetyl)cyclopentanone; (E)-dodec-2-enal; (E)-4- ((3aS,7aS)-hexahydro-lH-4,7-methanoinden-5(6H)-ylidene)butanal; Ethyl-3 dimethyl-2(5 or 6) pyrazine; 8-ethyl-l- oxaspiro[4.5]decan-2-one; methyl 2,4-dihydroxy-3,6-dimethylbenzoate; (E)-undec-9-enenitrile; methyl oct-2- ynoate; l-(3,3-dimethylcyclohex-l-en-l-yl)pent-4-en-l-one; 2-methoxyphenol; E-hex-2-enal; 2-ethyl-4-hydroxy-5- methylfuran-3(2H)-one; 2-phenylpropanal; 2-isobutyl-3-methoxypyrazine; 2-isobutylquinoline; (E)-2-methoxy-4- (prop-l-en-l-yl (phenol; 6-isopropylquinoline; (l-methyl-2-(( 1,2, 2-trim ethyl bicyclo[3.1.0]hexan-3- yl (methyl (cyclopropyl (methanol; 5-(sec-butyl)-2-(2,4-dimethylcyclohex-3-en-l-yl)-5-methyl-l,3-dioxane; (3E,6E(- 2,4,4,7-tetramethylnona-6,8-dien-3-one oxime; bicyclo[2.2.2]oct-5-ene-2-carboxaldehyde; 2-methoxy-3- methyl pyrazine; 2-hydroxy-3,4-dimethyl-2-cyclopenten-l-one; 4,4,8a-trimethyldecahydronaphthalen-4a-ol; 2- ethyl-4-methyl-l,3-thiazole; 8-methyl-l-oxaspiro[4.5]decan-2-one; methyl non-2-ynoate; 10-isopropyl-2,7- dimethyl-l-oxaspiro[4.5]deca-3, 6-diene; (E)-methyl non-2-enoate; l-(3-methylbenzofuran-2-yl)ethanone; (2E,6Z(- nona-2,6-dienal; (Z)-non-6-enal; 2-methyl-4-propyl-l,3-oxathiane; 2-(4-methylcyclohex-3-en-l-yl)propane-2-thiol; 5-methyl-2(2-methylethyl (-cyclohexanone; 2-methyl-4-methylene-6-phenyltetrahydro-2H-pyran; 2- cyclohexylhepta-l,6-dien-3-one; 2-phenyl-ethanal; (2E,5E)-5,6,7-trimethylocta-2,5-dien-4-one; 6-(sec- butyl)quinoline; dec-9-en-l-ol; 4-methyl-2-(2-methylprop-l-en-l-yl)tetrahydro-2H-pyran; 4-methylene-2- phenyltetrahydro-2H-pyran; 2,3,3-trimethyl-2,3-dihydro-lH-inden-l-one; 2,6,6-trimethylcyclohexa-l,3- dienecarbaldehyde; 4-vinylcyclohex-l-enecarbaldehyde; l-spiro[4.5]dec-7-en-7-yl-4-penten-l-one; 2-(p- tolyl)acetaldehyde; (E)-3,7-dimethylocta-2, 6-diene- 1-thiol; 4-methylbenzaldehyde; l-(cyclopropylmethyl)-4- methoxybenzene; E-hex-2-enal; (E)-tridec-2-enenitrile; 3-phenylbutanal; 2-ethoxy-4-methylphenol; (3E,5Z(- undeca-l,3,5-triene; (E)-undec-2-enal; (E)-4-isopropyl-l-methyl-2-(prop-l-en-l-yl (benzene; 2,4-diethoxy-5- methylpyrimidine; (2E,6Z)-nona-2,6-dienenitrile; 2-(2,4-dimethylcyclohexyl)pyridine; and mixtures thereof.
Alternatively, the skilled perfumer may easily select ingredients having similar odour and, and distribute these ingredients in the different compartments of the compartmentalized microcapsules according to the present invention, so that an enhanced perfume linearity is perceived throughout the entire application of the encapsulated fragrance composition.
In the context of the present disclosure, the term "odour linearity", as it relates to the odour characteristics of fragrances assessed under different conditions, means that trained panellists are capable of perceiving the odour of a given fragrance under a first condition, for example on a wet substrate, for example on a substrate out of the wash machine, and that of the same perfumed product, under a second condition, for example after substrate has dried or is being manipulated or worn, whereas both odour are same or similar. This may be particularly challenging because it is known that a prolonged exposure to a given, unchanged odour usually leads to a lack of perception of this odour by the panellist, owing to habituation or fatigue of the olfactive sense.
Optionally, any of the used fragrances may comprise a low odour adjuvant, such as a solvent, an oil, a wax, a surfactant, a polymer, and the like, and a mixture thereof.
Cosmetic active agents
The cosmetic active agents for use in the compartmentalized microcapsules are preferably hydrophobic. Preferably, the cosmetic active agents have a calculated octanol/water partition coefficient (ClogP) of 1.5 or more, more preferably 3 or more. Preferably, the ClogP of the cosmetic active agent is from about 2 to about 7.
Particularly useful cosmetic active agents may be selected from the group consisting of emollients, smoothening active agents, hydrating active agents, soothing and relaxing active agents, decorative active agents, deodorants, anti-aging active agents, draining active agents, remodelling active agents, skin levelling active agents, preservatives, anti-oxidants, antibacterial or bacteriostatic active agents, cleansing active agents, lubricating active agents, structuring active agents, hair conditioning active agents, whitening active agents, texturing active agents, softening active agents, anti-dandruff active agents, and exfoliating active agents.
Particularly useful cosmetic active agents include, but are not limited to hydrophobic polymers, such as alkyldimethylsiloxanes, polymethylsilsesquioxanes, polyethylene, polyisobutylene, styrene-ethylene-styrene and styrene-butylene-styrene block copolymers, and the like; mineral oils, such as hydrogenated isoparaffins, silicone oils and the like; vegetable oils, such as argan oil, jojoba oil, aloe vera oil, and the like; fatty acids and fatty alcohols and their esters; glycolipides; phospholipides; sphingolipides, such as ceramides; sterols and steroids; terpenes, sesquiterpenes, triterpenes and their derivatives; essential oils, such as Arnica oil, Artemisia oil, Bark tree oil, Birch leaf oil, Calendula oil, Cinnamon oil, Echinacea oil, Eucalyptus oil, Ginseng oil, Jujube oil, Helianthus oil, Jasmine oil, Lavender oil, Lotus seed oil, Perilla oil, Rosmary oil, Sandal wood oil, Tea tree oil, Thyme oil, Valerian oil, Wormwood oil, Ylang Ylang oil, Yucca oil and the like.
In an embodiment, the cosmetic active may be selected from the group consisting oSandal wood oil, such as Fusanus Spicatus kernel oil; Panthenyl triacetate (CAS-No: 94089-18-6); Tocopheryl acetate; Tocopherol; Naringinin; Ethyl linoleate; Farnesyl acetate; Farnesol; Citronellyl methyl crotonate (CAS-No: 20770-40-5); Ceramide-2 (l-Stearoiyl-C18-Sphingosine, CAS-No: 100403-19-8); and mixtures thereof.
Optionally, any of the used cosmetic agents may comprise an adjuvant, such as a solvent, an oil, a wax, a surfactant, a polymer, and the like, and a mixture thereof.
Programmed release
The compartmentalized microcapsules according to the present invention provide a programmed release of the encapsulated active agents, characterized in such that the active agent located in the outermost compartment of the microcapsules is released first and the active agent located in the innermost compartment of the microcapsule, is the last one to be released. This programmed release is conveniently assessed by monitoring the weight loss of microcapsules in a thermo-gravimetric measurement. In such a measurement, a sample of microcapsules is placed on a micro-balance and is heated continuously, according to a pre-determined heating program. Weight loss occurs when a material comprised in the microcapsule is released by evaporation or when degradation of the material with emission of a gaseous degradation product occurs. This method is particularly suitable for volatile active agents. A typical thermogravimetric weight loss curve is shown in Fig. 2, as discussed hereinabove.
In an embodiment, the compartmentalized microcapsules comprise two fragrances FI and F2, wherein fragrance FI is present at a level of about 5 to 90 wt%, more particularly from 10 to 60 wt%, still more particularly from 20 wt% to 50 wt% in the innermost compartment; and fragrance F2 is present at a level of about 5 to 90 wt%, more particularly from 10 to 60 wt%, still more particularly from 20 wt% to 50 wt%; in the outermost compartment; and the total level of fragrance FI and F2 is from 70 to 98 wt% , more particularly from 80 to 96 wt% or higher, more particularly from 85 to 94 wt% referred to the total weight of the compartmentalized microcapsules. In the context of the present invention, the total weight of the compartmentalized microcapsules is defined as being identical to the theoretical solid content of the slurry, which in turn is equal to the sum of the weight of active agents, resin, and stabilizing colloids involved in the slurry, expressed in wt% based on the total weight of the slurry.
In a particular embodiment, the weight ratio of the outermost to innermost fragrances (F2:F1) is from 0.05 to 5, more particularly from 0.1 to 2, still more particularly from 0.15 to 1.
In a particular embodiment, the weight ratio of the outermost to innermost fragrances (F2:F1) is from 0.05 to 1, more particularly from 0.08 to 0.5, still more particularly from 0.1 to 0.3. Microcapsules having such outermost to innermost fragrances weight ratios are particularly suitable for providing the right balance of early stage fragrance release (for example on wet fabrics) and later stage, prolonged release (for example on dry fabric).
In an embodiment, the encapsulated fragrance composition comprise a fragrance and a cosmetic active, wherein the fragrance is located in the innermost compartment and the cosmetic active agent is located in the outermost compartment of a two-compartment microcapsule, or vice-versa.
In an embodiment, the normalized resin weight Wr of the innermost capsule wall(s) is from about 0.01 g/m2 to about 1 g/m2, more particularly from about 0.05 g/m2 to about 0.8 g/m2 and still more particularly from about 0.1 g/m2 to 0.6 g/m2.
In an embodiment, the normalized resin weight of the outermost wall is smaller hat the normalized weight of the innermost wall.
In a particular embodiment the ratio of the normalized resin weight of the outermost wall by the normalized weight of the innermost wall is 0.01 to 1, more particularly from 0.05 to 0.5 and more particularly from
0.08 to 0.25. The benefits of the programmed release of active agents are illustrated in the examples hereunder.
Method for manufacturing the compartmentalized microcapsules of the invention
In another aspect of the invention is provided a method for manufacturing the composition comprising at least one microcapsule in a suspending medium, wherein the microcapsule is compartmentalized as described hereinabove.
Microcapsules with two compartments according to the invention may be obtained by performing the steps of: a) emulsifying an active agent Al, optionally admixed with an adjuvant Dl, in an aqueous phase comprising an emulsifier El and a thermosetting resin precursor PI using a propeller, a turbine, a cross-beam stirrer with pitched bean, such as Mig stirrer, and the like, wherein said thermosetting resin precursor is added before emulsification, during emulsification or after emulsification has been completed; b) adjusting the pH of the emulsion obtained in step a) to a value pHl and heating the system to a temperature Tl; c) maintaining the temperature Tl over a period of time tl under stirring, to form thermosetting resin R1 innermost capsule walls around the droplets of active agent Al and optional adjuvant Dl, thereby forming a slurry of innermost microcapsules including active agent Al and optional adjuvant Dl; d) adding the active agent A2 and optional adjuvant D2 to the slurry of innermost microcapsules obtained in step c) while maintaining the slurry at temperature Tl and under stirring, thereby adsorbing the active agent A2 and optional adjuvant D2 in the form of a layer on the innermost capsule wall of the innermost microcapsules. The stirring speed is preferably reduced at this stage in order to prevent emulsification of the active agent A2 in the water phase and promote its adsorption onto the innermost microcapsules; e) adjusting the pH to a value pH2 and bringing the slurry to a temperature T2; f) adding thermosetting resin precursor P2 to the slurry obtained in step e), optionally with an emulsifier E2, and maintaining the temperature T2 over a period of time t2, to form a thermosetting resin R2 outermost capsule wall around the adsorbed active agent A2 layer obtained in step d), thereby forming outermost capsule, in which at least one innermost microcapsule is accommodated; g) cooling down the slurry to a temperature T3; h) optionally adjusting the pH to a value pH3; i) optionally adding excipients to the slurry, such as a scavenger, a protective colloid, a preservative and the like; j) if necessary cooling down the slurry to room temperature RT.
The above generic process may be executed in various ways, depending on the desired thermosetting resin.
In an embodiment, the thermosetting resin Rl, R2 etc. is an aminoplast resin formed by the polycondensation of amino-aldehyde pre-condensates. The amino-aldehyde pre-condensate may be a reaction product, such as a polymer or co-polymer of at least one amine, such as urea, thiourea, alkyl urea, 6-substituted- 2, 4-diamino- 1, 3, 5-triazines such as benzoguanamine or glycol uril, and melamine; and at least one aldehyde, such us formaldehyde, acetaldehyde, glyoxal or glutaraldehyde. Suitable amino-aldehyde pre-condensates include but are not limited to partially methylated mono- and poly-methylol-l,3,5-triamino-2,4,6-triazine pre-condensates, such as those commercially available under the Trade Mark CYMEL (ex Cytec Technology Corp.) or LURACOLL (ex BASF), and/or mono- and polyalkylol-benzoguanamine pre-condensates, and/or mono- and polyalkylol-glycouril pre-condensates. These alkylolated polyamines may be provided in partially alkylated forms, obtained by addition of short chain alcohols having typically 1 to 6 methylene units. Advantageously, a cross-linker is added to the reaction medium in order to improve the encapsulating properties of the resin. The cross-linker may be an aromatic polyol or a diamine. Diamine cross-linkers useful in the present invention include, but are not limited to urea, melamine, glycouryl, chitosan, guanidine and benzoguanidin. A particularly suitable diamine is urea. Useful aromatic polyols include, but are not limited to phenol, 3,5-dihydroxy toluene, Bisphenol A, resorcinol, hydroquinone, xylenols, polyhydroxy naphthalene, and polyphenols produced by the degradation of cellulose and humic acids.
In the case the thermosetting resin Rl, R2 etc. is an aminoplast, then the emulsifier E is a preferably polymeric stabilizer selected from the group consisting of acrylic copolymers bearing sulfonate groups, such as those available commercially under the trade mark LUPASOL (ex BASF), such as LUPASOL PA 140 or LUPASOL VFR; copolymers of acrylamide and acrylic acid, copolymers of alkyl acrylates and N-vinylpyrrolidone, such as those available under the trade mark Luviskol (e.g. LUVISKOL K 15, K 30 or K 90 ex BASF); sodium polycarboxylates (ex Polyscience Inc.) or sodium polystyrene sulfonate) (ex Polyscience Inc.); vinyl and methyl vinyl ether-maleic anhydride copolymers (e.g. AGRIMER VEMA™ AN, ex ISP), and ethylene, isobutylene or styrene-maleic anhydride copolymers (e.g. ZEMAC™); ampholytic co-polymer formed from a cationic monomer containing quaternary ammonium groups; and a monomer that can form anions, more particularly a monomer that is based on acrylic acid, methacrylic acid or a derivative thereof, such as a copolymer of acrylic acid or methacrylic acid, and acrylamidopropyl-trimethylammonium chloride (APTAC) or methacrylamidopropyl-trimethylammonium chloride (MAPTAC), a terpolymer formed from acrylic acid monomer, MAPTAC monomer and acrylamide monomer). The temperature range is T=85 °C ± 10 °C, the pH range is 3.9 ± 1 and time range t is from about 1 to about 4 hours, more particularly 2 to 3 hours. These temperature, pH and time ranges apply to the formation of all of the capsule walls based on aminoplast thermosetting resin, i.e. T=T1=T2=..., pH=pH l=pH2=..., and t=tl=t2... However, the emulsifiers El, E2... may be the identical or different. The pH3 is preferably between 5 and 7 and the temperature T3 is preferably below 40 °C.
In an embodiment, the thermosetting resin Rl, R2 etc. is a polyurea resin formed by the polyaddition of a polyisocyanate on a polyamine. The polyisocyanates may be selected from the group consisting of 1,6- diisocyanatohexane (CAS No. 822-06-0), l,5-diisocyanato-2-methylpentane (CAS No. 34813-62-2), 1,4- diisocyanato-2,3-dimethylbutane, 2-ethyl-l,4-diisocyanatobutane, 1,5-diisocyanatopentane (CAS No. 4538-42-5), 1,4- diisocyanatobutane (CAS No. 4538-37-8), 1,3-diisocyanatopropane (CAS NO. 3753-93-3 ), 1,10- diisocyanatodecane (CAS No. 538-39-0), 1,2- diisocyanatocyclobutane, bis(4-isocyanatocyclohexyl)methane (CAS No. 5124-30-1), 3,3,5-trimethyl-5- isocyanatomethyl-l-isocyanatocyclohexane (CAS No. 4098-71-9), 2-
Imidodicarbonic diamide (CAS No. 4035-89-6), biuret (CAS No. 108-19-0), polyisocyanurate of toluene diisocyanate (CAS No. CAS NO.141-78-6, commercially available from Bayer under the Trade Name DESMODUR® RC), trimethylol propane pre-condensate of polyisocyanurate of 1,6-diisocyanatohexane (CAS No. 53200-31-0, commercially available from Bayer under the Trade Name DESMODUR® N100), trimethylol propane pre condensate of toluene diisocyanate (CAS No. 9081-90-7, commercially available from Bayer under the Trade Name DESMODUR® L75), trimethylol propane pre-condensate of xylylene diisocyanate (CAS No. 865621-91-6 (commercially available from Mitsui Chemicals under the Trade Name TAKENATE® D-110N). Also included are modified isocyanates, such as aliphatic polyisocyanate based on hexamethylene diisocyanate and alkylene oxide, especially ethylene oxide, (sold under the name BAYHYDUR), for example Bayhydur® XP 2547 (commercially available from Bayer); and mixtures thereof. Polyamines may be selected from the group comprising 1,2- ethylenediamine; 1,3-diaminopropane; 1 ,4-diaminobutane; 1,6-diaminohexane; hydrazine; 1,4- diaminocyciohexane; 1, 3-diamino- 1-methylpropane; diethylenetriamine; triethylenetetramine; bis(2- methylaminoethyl)ether (CAS No. 3033-62-3), guanidine (CAS No. 113-00-8); guanidine carbonate salt (CAS No 593-85-1); 3, 5-Diamino-l, 2, 4-triazole (CAS No. 1455-77-2); melamine; urea; polymeric polyamines such as poly(vinylamine), such as those available commercially under the trade name LUPAMINE (ex BASF); poly(ethyleneimine) (CAS No. 9002-98-6)), such as those available commercially under the trade name LUPASOL (ex BASF); poly(etheramine), such as those available commercially under the trade name JEFFAMINE (ex Huntsman); and mixtures thereof.
In the case the thermosetting resin Rl, R2 etc. is polyurea, then the emulsifier E is a preferably polymeric stabilizer selected from the group consisting of maleic - vinyl copolymers, sodium lignosulfonates, maleic anhydride/styrene copolymers, ethylene/maleic anhydride copolymers, and copolymers of propylene oxide, ethylenediamine and ethylene oxide, polyvinylpyrrolidone, polyvinyl alcohols, fatty acid esters of polyoxyethylenated sorbitol and sodium dodecylsulfate. Polyvinylpyrrolidone and polyvinyl alcohols are the G- polymer type, having a degree of hydrolysis in the range of 85 to 99.9 %, available under the trade name GOSHENOL from Nichigo. The temperature range is at least 50°C, preferably 60°C, more preferably in a range of from 75°C to 90°C and in particular 85°C to 90°C, the pH range is from 3 to 12, in particular between 5 to 10, and more particular in the range from 7 to 10, and time range t is from 1 to 8 hours, more particularly from 3 to 6 hours. These temperature, pH and time ranges apply to the formation of all of the capsule walls based on polyurea thermosetting resin, i.e. T=T1=T2=..., pH=pHl=pH2=..., and t=tl=t2... However, the emulsifiers El, E2... may be the identical or different. The pH3 is preferably between 5 and 7 and the temperature T3 is preferably below 40 °C.
In an embodiment the steps d) to f) may be repeated in order to provide additional compartments, with all thermosetting resins R,, emulsifiers E, and conditions Tr, pH,, t, being identical, similar or different.
Additives
Should a suspending agent be employed to stably suspend the microcapsules in a slurry, suitable hydrocolloids may be employed. Suitable hydrocolloids include starch and starch derivatives, such as modified starch, dextrin, maltodextrin; gums, such as gum Arabic or gum acacia, xanthan gum, gum tragacanth, gum karaya, guar gum; cellulose and cellulose derivatives, such as carboxy methyl cellulose, hydroxyethyl cellulose, hydroxyethyl cellulose/lauryl-dimethylammoniumepoxy condensat, hydroxypopyl cellulose, cationic cellulose (for example Polyquaternium-4), cellulose gum; carrageenan; agar-agar; pectines and pectic acid; gelatine; protein hydrolysates; polymer and copolymers of vinyl and allyl monomers, such as polyvinylpyrrolidone; poly(vinyl pyrrolidone-co-vinylacetate);poly(vinyl alcohol-co-vinyl acetate), more particularly hydrolyzed polyvinylacetates having a degree of hydrolysis between 85 and 92%; vinyl ester homopolymers and copolymers, such as vinyl acetate, vinyl pivalate, vinyl versatate; poly(vinyl methyl ether), poly(vinyl alkyl amines), such as poylvinylmethylamine; quaternized polyvinyl alkyl amines, vinyl pyridine and quaternized vinyl pyridine, vinyl imidazoline, vinyl imidazole, vinyl imidazolinium, dimethyldiallyl ammonium chloride; and vinyl sulphonate homopolymers and copolymers; polyamines and polyimines;ethoxylated polyamines; polymers, copolymers and cross-polymers derived from (meth)acryloyl monomers, such as methyl methacrylate, ethyl methacrylate, 2-ethyl- hexyl acrylate, lauryl methacrylate, C10-C30 alkyl acrylate, and the like, hydroxyalkyl (meth)acrylate, such as 2- hydroxypropyl acrylate and 2-hydroxypropyl methacrylate, and the like; acrylamidodimethyl taurate; aryl (meth)acrylates, such as phenyl acrylate and benzyl acrylate, (meth)acrylic acids and their salts, such as sodium and potassium (meth)acrylates, sodium acryloyldimethyltaurate; (meth)acrylamides; N-alkyl (meth)acrylamides, such as N,N-dimethylaminoalkyl methacrylate; quaternized N-alkyl (meth)acrylamides, such as methacrylamidopropyl-trimethylammonium chloride; acrylamidoe-thyltrimonium chloride; acrylamidolauryltrimethylammonium chloride; and (meth)acrylamido alkyl sulphonates poly(maleic anhydride) and poly(maleic anhydride-co-vinyl ether), and their hydrolysates;poly(acrylic acid-co-maleic acid)copolymer;
poly(alkyleneoxide); polyurethanes and polyureas , such as anionic, cationic non-ionic and amphoteric polyurethanes and polyureas; mixed copolymers thereof; and mixture thereof.
Should it be desired to employ preservatives to guard against microbial contamination, suitable preservatives for the purpose includes but are not limited to quaternary compounds, biguanide compounds (CAS#: 32289-58-0 / 27083-27-8 / 28757-47-3 / 133029-32-0), poylaminopropyl biguanidine, Hexetidine, para-chloro- meta-cresol, methenamine, 3-Bis(hydroxymethyl)-5,5-dimethylimidazolidine-2,4-dione, Quaternium-15, benzoic acid, salicylic acid, undec-10-enoic acid, formic acid, biphenyl-2-ol and their salts, 4-hydroxybenzoic acid and its esters and salts; sorbic acid and its salts, Isothiazolinones, Bronopol (2-Bromo-2-nitro- 1,3-propanediol), 5-bromo-5- nitro-l,3-dioxane, Thiabendazone, Benzimidazole carbamate, Triclocarban; 3-lodo-2-propynylbutylcarbamate, Thiomersal; Triclosan, dichlorobenzyl alcohol, chloroxylenol, imidazolidinyl urea, phenoxyethanol, benzyl alcohol; and mixture thereof.
The slurry may also contain other commonly employed adjuvants. The term "adjuvants" refers to ingredients that may affect the performance of a slurry, other than its hedonic performance. For example, an adjuvant may be an ingredient that acts as an aid to processing a perfume composition or consumer product containing said composition, or it may improve handling or storage of a perfume composition or consumer product. It might also be an ingredient that provides additional benefits such as imparting colour or texture. It might also be an ingredient that imparts light resistance or chemical stability to one or more ingredients contained in a perfume composition or consumer product. A detailed description of the nature and type of adjuvants commonly used in perfume compositions or consumer products cannot be exhaustive, but such ingredients are well known to a person skilled in the art. Examples of adjuvants include solvents, waxes, oils, pigments, dyestuffs and colouring matters; extenders, fillers and reinforcing agents; stabilizers against the detrimental effects of heat and light, bulking agents, acidulants, buffering agents and antioxidants.
Dry forms
If it is desired to isolate the microcapsules in the form of a dry powder, a slurry may be spray dried in a further step. Prior to the spray drying step, it may be desirable to add a flow aid, such as silica or the like to the slurry to ensure the realization of fine, free- flowing powdered microcapsules with low surface perfume oil.
The resulting slurry of microcapsules may be spray-dried in a conventional spray drying tower, using a two-fluid nozzle, or spin-dried in a conventional spin dryer. If desired, at least one hydrocolloid may be added to the microcapsule slurry, as such or in the form of an aqueous solution. Typical hydrocolloids include starch, modified starch such as dextrin-modified with octenyl succinate anhydride, and gum Arabic. Optionally, maltodextrins and sugar alcohols, such as sorbitol, mannitol or maltitol may also be added. The hydrocolloid may itself contain a functional ingredient. This functional ingredient may be the same as, or different form, that in the capsule. This is achieved by performing the step of (1) emulsifying a second functional ingredient in aqueous hydrocolloid solution, optionally comprising maltodextrins and sugars or sugar alcohols to form a second slurry (2) mixing the second slurry with a slurry of microcapsules comprising a first functional ingredient and (3) drying this mixture. Such a process is described in WO 2007137441 Al, Example 5, which is taken herein as reference.
In a particular embodiment, the suspending medium comprising the core-shell microcapsules according to the present invention is a hydrophilic matrix comprising one or more hydrocolloids, optionally one or more maltodextrins and optionally one or more functional ingredients that may be identical, similar or different from the functional ingredient encapsulated in the core-shell microcapsules.
Consumer products
The compositions of the present invention may be used to perfume all manners of consumer products, including laundry care detergents, laundry care conditioners, fabric refreshers, personal care cleansing compositions, such as shampoos, bath and shower gels, liquid soaps, soap bars and the like, personal care conditioning composition, such as hair care conditioners, bath and shower lotions, deodorant compositions, antiperspirant compositions, home care compositions, such as hard surface cleaners, heavy duty detergents and the like.
Typical consumer products concerned by the present invention include personal care cleaning and cleansing compositions, such as shampoos, bath and shower gels, liquid soaps, soap bars and the like, laundry care products, such as detergents, and home care products, such as hard surface cleaners.
The consumer products according to the present invention may be used for treating substrates, such as fabrics, skin, hair, animate and inanimate surfaces, hard surfaces and the like, wherein the action of treating a substrate includes washing, cleansing, softening, caring, finishing, scenting and/or deodorizing this substrate.
In one aspect of the invention, a consumer product contains the compositions according to the present invention preferably at a level of about 0.02 to 5 wt%, more particularly from about 0.1 to 2 wt% and still more particularly from about 0.2 to 1 wt% of the consumer product.
In many cases, the consumer products concerned by the present invention contain surfactants, such as anionic, cationic, amphoteric or non-ionic surfactants.
In an embodiment of the present invention, the consumer product containing the microcapsules of the present invention is a fabric care product, such as a laundry powder detergent, a heavy duty liquid detergent, or a liquid fabric care conditioner. Typical formulation ingredients for use in laundry care products may be found in WO2016207179A1 page 74 line 1 to page 78 line 18.
In another embodiment of the present invention, the consumer product containing the microcapsules of the present invention is a shampoo, containing anionic surfactants, witterionic and/or amphoteric surfactants, non-ionic surfactants, as well as, optionally, water-soluble solvents, preservatives, and benefit agents, such as moisturizers, emollients, thickeners, anti-dandruff agents, hair growth promoting agents, vitamins, nutrients, dyes, hair colorants, and the like. Typical formulation ingredients for use in shampoo with our without microcapsules may be found, for example, in EP 0191564 A2 or WO 1997023194 Al.
In another embodiment of the present invention, the consumer product comprising core-shell microcapsules of the present invention is a liquid soap comprising one or more anionic surfactants, and other surfactants that may be selected from the group consisting of mixtures of fatty acids and neutralized fatty acids, aminoxide surfactants, non-ionic surfactants, zwitterionic surfactants, and mixture thereof; electrolytes; one or more preservatives; and optionally benefit agents that may be selected from the group consisting of pH-control agents, skin care agents, moisturizers, emollients, thickeners, vitamins, nutrients, dyes, and the like. Typical formulation ingredients for use in liquid soaps may be found, for example, in CA 2812137 Al and US 20030050200.
In another embodiment of the present invention, the consumer product comprising core-shell microcapsules and chitosan of the present invention is a shower gel comprising one or more anionic surfactants, and other surfactants that may be selected from the group consisting of mixtures of fatty acids and neutralized fatty acids, aminoxide surfactants, non-ionic surfactants, zwitterionic surfactants, and mixture thereof; electrolytes, such one or more preservatives; and optionally benefit agents that may be selected from the group consisting of thickeners, pH-control agents; skin care agents, moisturizers, emollients, thickeners, vitamins, nutrients, dyes, and the like. Typical formulation ingredients for use in shower gels may be found, for example, in US 5607678 A and US 20120263668 Al.
Once deposited on the substrate, the core-shell microcapsules are able to release their core material by diffusion through the microcapsule shell or following the mechanical rupture of the microcapsule shell. Mechanical rupture may follow a mechanical action, such as rubbing, squeezing, combing, washing and the like or heating, for example using a hair dryer.
Diffusion-mediated release is particularly desired if the core material is a perfume composition, because, in this case, a nice smell may be perceived over a long time, for example several hours, after application of the microcapsules on the substrate. On the other hand a mechanical rupture may provoke a surprising and pleasant boost of odour.
In order to further illustrate the present invention and the advantages thereof, the following specific examples and comparative example are given, it being understood that same are intended only as illustrative and non-limiting.
EXAMPLES
Example 1: Two-compartment microcapsules with cationic aminoplast resin
This example discloses the preparation of cationic compartmentalized microcapsules with two compartments with both innermost and outermost capsule walls comprising a cationic aminoplast thermosetting resin.
Said microcapsules were prepared by performing the steps of: a) emulsifying 357 g of Fragrance FI in an aqueous phase containing 95 g polymeric stabilizer Floset DP/CAP 371L, 7 g of resorcinol as cross-linker 19 g of formaldehyde precondensate (Luracoll SD) and 375 g of deionized water, at a stirring speed of 800 rpm and at a temperature of 20 °C; b) adjusting the pH of the emulsion obtained in a) to a value of 4.5 ± 0.5 by adding 22 g of 10 % formic acid and heating the emulsion to 90 °C; c) maintaining the temperature at 90 °C over a period of one 1 hour under agitation, to form thermosetting aminoplast resin R1 capsule wall around the droplets, thereby forming a slurry of innermost microcapsules having an average diameter D50 = 10 micrometres (pm); d) adding 50 g of Fragrance F2, 2.7 g of formaldehyde precondensate (Luracoll SD, while maintaining the stirring at 800 rpm, the pH at 4.5 ± 0.5 by adding 8 g of 10 % formic acid solution in water, and maintaining the temperature at 90 °C for an additional hour, forming thereby a slurry of outermost microcapsules, wherein the outermost microcapsules accommodate the innermost microcapsules. These outermost microcapsules have an average diameter D50 = 11 pm; e) adding 64.3 g of deionized water, cooling the slurry to room temperature, and keeping this slurry under agitation for an additional 1 hour. le 2: comparative example to example 1
The process of example 1 is repeated without performing step d) in order to form conventional core-wall capsules comprising fragrance FI and a cationic aminoplast capsule wall.
Example 3: Two-compartment microcapsules with anionic aminoplast resin
This example discloses the preparation of anionic compartmentalized microcapsules with two compartments with both innermost and outermost capsule walls comprising anionic aminoplast thermosetting resins.
Said microcapsules were prepared by performing the steps of: a) emulsifying 355 g of Fragrance FI in an aqueous phase containing 252 g polymeric stabilizer ZEMAC solution at 2.85% in water (i.e. 7.2 g), 15.3 g of formaldehyde precondensate (Luracoll SD, solution at 70% active content, i.e. 10.7 g precondensate), 9.7 g or urea, and 472.1 g of deionized water, at a steering speed of 400 rpm and at a temperature of 20 °C; adjusting the pH of the emulsion obtained in a) to a value of 4.6 ± 0.2 by adding 10 % (=6.85 g) formic acid and heating the emulsion to 85 °C over 1 hour; b) maintaining the temperature at 85 °C over a period of one 1 hour under agitation to form thermosetting aminoplast resin R1 capsule wall around the droplets, thereby forming a slurry of innermost microcapsules having an average diameter D50 = 9 pm; c) adding 60 g of Fragrance F2, 8.8 g of formaldehyde precondensate (Luracoll SD solution at 70% active content, i.e. 6.2 g precondensate), while maintaining the steering at 400 rpm, the pH at 4.5 ± 0.5 and temperature at 90 °C for an additional hour, and forming thereby a slurry of outermost microcapsules, wherein the outermost microcapsules accommodate the innermost microcapsules. These outermost microcapsules have an average diameter D50 = 9.5 pm; d) cooling the slurry to room temperature, stirring it for an additional 1 hour, adding 4 g of caprylyl glycol and 4 g of phenoxy ethanol and finally adjusting the pH of the slurry to a pH range of 5.7 to 6.7 by adding ammonia. Example 4: comparative example to example 3
The process of example 3 is repeated without performing step c) in order to form conventional core-wall capsules comprising fragrance FI and an anionic aminoplast capsule wall.
Example 5: two-compartment microcapsules with polvurea resin
This example discloses the preparation of compartmentalized microcapsules with two compartments with both innermost and outermost capsule walls comprising polyurea thermosetting resins.
Said microcapsules were prepared by performing the steps of:
a) emulsifying 302 g Fragrance FI, 39 g Desmodur® W and 11 g Bayhydur® XP 2547 A in an aqueous phase containing 25 g polyvinyl pyrolidone K60 and 482.5g deionized water and having a pH adjusted to a value of 10.0 using sodium hydroxide solution, at a stirring speed of 1000 rpm; b) adjusting the pH of the emulsion to a value of 8 using aqueous sodium hydroxide solution and adding 12.7 g of polyethyleneimine (Lupasol® G 100 solution at 35% active content, i.e. 4.44 g active) in one step; c) heating the emulsion to 80 °C and maintaining this temperature for 5 hours under stirring, thereby forming a slurry of innermost microcapsules having an average diameter D50 = 20 pm; d) adding 50 g of Fragrance F2 containing 2g Bayhydur® XP 2547, and then 3 g of polyethyleneimine (Lupasol® G 100 solution at 35% active content, i.e. 1.05 g active), and 20g of water, while maintaining the stirring at 1000 rpm, the pH at 8 and the temperature at 80 °C for lh additional hour, and forming thereby a slurry of outermost microcapsules, wherein the outermost microcapsules accommodate the innermost microcapsules. These outermost microcapsules have an average diameter D50 = 20.5 pm; e) cooling the slurry to room temperature, stirring it for an additional 1 hour, adding 4 g of caprylyl glycol and 4 g of phenoxy ethanol and finally adjusting the pH of the slurry to a pH range of 6.6 ± 0.2 by adding citric acid.
Example 6: comparative example to example 5
The process of example 5 is repeated without performing step d) in order to form conventional core-wall capsules comprising fragrance FI and a polyurea capsule wall.
Example 7: Overview of trials
Table 1 summarizes the trials performed with various compartmentalized microcapsules and comparative examples. The first number in the reference codes refer to examples 1 through 6.
Figure imgf000028_0001
Figure imgf000029_0001
Figure imgf000030_0001
Example 8: Evaluation in application
The microcapsules depicted as 1.1 through 2.2 (cationic aminoplast) in Table 1 were evaluated in a proprietary unperfumed liquid fabric care conditioner base. The microcapsules depicted as 3.1 through 4.2 (anionic aminoplast) in Table 1 were evaluated in a proprietary unperfumed powder laundry detergent base. The microcapsules depicted as 5.1 through 6.2 (poylurea) in Table 1 were evaluated in proprietary unperfumed shampoo base. 0.5 wt% of microcapsule slurry was dispersed in each base.
In case the liquid fabric care conditioner was used, 21 g of the base was used in a side-loaded wash machine (20 L capacity, loaded with 1 kg terry towelling, preferably washed beforehand with an unperfumed laundry detergent); a rinse cycle was performed at a temperature of 20 °C, followed by spin drying.
In case the powder detergent base was used, 75 g of this base was used in a side-loaded wash machine (20 L capacity, loaded with 1 kg terry towelling); a wash cycle was performed at a temperature of 40 °C, followed by spin-drying.
In both laundry rinse and wash cases, the pre-rub olfactive evaluation was performed on wet laundry directly out of the machine and after 4 hours. For this evaluation, the terry towelling was handled carefully in order minimize the risk of breaking the microcapsules mechanically. The post-rub olfactive evaluation was performed after line drying the terry towelling for 24 hours at room temperature. This evaluation was performed by gently rubbing one part of the terry towelling on another part of same terry towelling. The olfactive performance (intensity) has been assessed by a panel of 4 experts rated on a scale of 1-5 (1 = barely noticeable, 2 = weak, 3 = medium, 4 = strong and 5 = very strong). When relevant, qualitative comments on the perceived odour direction were recorded.
In case the shampoo base was used, 4.8 g of base was applied on 48 g hair swatches by rubbing over 20 seconds. The swatches were then let to rest for 1 minute and then rinsed 30 seconds under running tap water at 37 °C at a flow rate of 3.2 l/min, without touching the swatch by hand. Olfactive evaluation was performed after 5 minutes on wet swatches, and after 24 hour before and after combing. Table 2 Quantitative and qualitative evaluation results on freshly prepared consumer products.
Figure imgf000031_0001
The results demonstrate that in all cases, the compartmentalized microcapsules provide noticeable olfactive benefit compared to microcapsules known in the art. The benefit may encompass both enhanced perfume linearity and differentiate perfume perception over time.
Example 9: Storage stability The system having reference number 1.2 in Table 1 was stored one month at 37°C in proprietary unperfumed liquid detergent base 1. The evaluation was performed as described in example 5. The results are reported in Table 3.
Table 3 Quantitative and qualitative evaluation results after storage
Figure imgf000032_0001
The results demonstrate that the olfactive benefits perceived with fresh samples remain after the microcapsules have been stored in a product for a prolonged period of time and at elevated temperature.

Claims

Claims:
1. A composition comprising at least one microcapsule in a suspending medium, wherein the microcapsule is compartmentalized and comprises: a) at least one innermost microcapsule, having an innermost capsule wall and an innermost compartment surrounded by said innermost capsule wall, with a first active agent A1 located in the innermost compartment; and b) at least one outermost microcapsule, having an outermost capsule wall and an outermost compartment surrounded by said outermost capsule wall, with a second active agent A2 in the outermost compartment; wherein at least one innermost microcapsule is accommodated in the outermost microcapsule.
2. The composition according to claim 1, wherein the compartmentalized microcapsules additionally comprise one or more intermediate microcapsules, the intermediate microcapsules having an intermediate capsule wall and an intermediate compartment surrounded by said intermediate capsule wall, wherein the at least one intermediate microcapsule accommodates at least one of the innermost microcapsules, and wherein the at least one intermediate microcapsule is accommodated in the outermost microcapsule, optionally with a further active agent Ax in the intermediate compartment.
3. The composition according to any of the preceding claim, wherein the innermost capsule wall, the outermost capsule wall and, optionally, the intermediate capsule walls comprise a thermosetting resin independently selected from the group consisting of aminoplast resins, polyurea resins, polyurethane resins, polyacrylate resins, and mixtures thereof.
4. The composition according to any of the preceding claim, wherein the innermost and outermost walls comprise different thermosetting resins.
5. The composition according to any of the preceding claim, wherein the ratio of the normalized resin weight of the outermost wall or intermediate wall to the normalized weight of the innermost wall is from 0.01 to 1, more particularly from 0.05 to 0.75 and more particularly from 0.08 to 0.5.
6. The composition according to any of the preceding claim, wherein the first active agent Al, the second active agent A2, and optionally the further active agent Ax is selected from the group consisting of fragrances, essential oils, pheromones, cosmetic ingredients and the like, and mixtures thereof.
7. A method for manufacturing the composition according to any of the preceding claim in a single batch process by performing the step of: a. preparing an innermost microcapsule comprising an innermost compartment comprising first active agent Al and an innermost capsule wall, wherein the innermost capsule wall consists of a thermosetting resin, thereby forming a slurry of innermost microcapsules; b. adding second active agent A2 to said slurry of innermost microcapsules formed in step a) under stirring, thereby forming innermost microcapsules coated with the second active agent A2; c. encapsulating said coated innermost microcapsules formed in step b) within an outermost wall of a thermosetting resin, thereby forming compartmentalized microcapsules with first active agent A1 located in at least one innermost compartment and second active agent A2 located in the outermost compartment between innermost and outermost capsule walls.
8. The method according to claim 7, wherein steps b) and c) are repeated in order to provide intermediate microcapsules, the intermediate microcapsules having an intermediate capsule wall and an intermediate compartment surrounded by said intermediate capsule wall, wherein the at least one intermediate microcapsule accommodates at least one of the innermost microcapsules, and wherein the at least one intermediate microcapsule is accommodated in the outermost microcapsule, optionally with a further active agent Ax in the intermediate compartment.
9. The method according to claim 7 and 8, wherein the thermosetting resin is selected from the group consisting of aminoplast thermosetting resins, polyurea thermosetting resins and polyacrylate thermosetting resin.
10. The method according to claim 7 to 9, wherein the thermosetting resin is obtained by polycondensation of amino-aldehyde pre-condensates and optionally a cross-linking agent, in the presence of an emulsifier.
11. The method according to claim 7 to 9, and wherein the thermosetting resin is obtained by polycondensation of polyisocyanates and polyamines, in the presence of an emulsifier.
12. Use of the composition according to any of the claims 1 to 6, to provide a programmed release of one or more active agents in the application of a consumer product, wherein the one or more than one active agents include one or more fragrances, and/or one or more cosmetic active agents.
13. The use of the composition according to claim 12 to enhance the linearity of a fragrance perceived by a consumer at various stages of the application of a consumer product, including perception on wet substrate, on dry substrate, and on handling and wearing the substrate, wherein the substrate is a fabrics, a keratinous substrate or a hard surface.
14. The use of the composition according to any of the claims 20 to 21 to release different fragrances at various stages of the application of a consumer product, wherein the different fragrances are characterized by different odours.
15. A consumer product comprising the composition according to any of the claims 1 to 6, wherein the consumer product is selected from the group comprising laundry detergents, laundry care conditioners, soap bars, liquid soaps, shower gels, shampoo, hair care conditioners, deodorants and antiperspirants, hard surface cleaner, and dish washing compositions.
PCT/EP2018/085457 2017-12-20 2018-12-18 Improvements in or relating to organic compounds WO2019121657A1 (en)

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WO2022023110A1 (en) * 2020-07-29 2022-02-03 Givaudan Sa Improvements in or relating to organic compounds

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