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EP3890838A1 - Microcapsules - Google Patents

Microcapsules

Info

Publication number
EP3890838A1
EP3890838A1 EP19809503.6A EP19809503A EP3890838A1 EP 3890838 A1 EP3890838 A1 EP 3890838A1 EP 19809503 A EP19809503 A EP 19809503A EP 3890838 A1 EP3890838 A1 EP 3890838A1
Authority
EP
European Patent Office
Prior art keywords
oil
microcapsules
phenolic resin
methyl
groups
Prior art date
Legal status (The legal status is an assumption and is not a legal conclusion. Google has not performed a legal analysis and makes no representation as to the accuracy of the status listed.)
Pending
Application number
EP19809503.6A
Other languages
German (de)
English (en)
Inventor
Benjamin ROST
Ralf Bertram
Daniela GREGOR
Lara-Joy KLEINE-BENNE
Current Assignee (The listed assignees may be inaccurate. Google has not performed a legal analysis and makes no representation or warranty as to the accuracy of the list.)
Symrise AG
Original Assignee
Symrise AG
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 Symrise AG filed Critical Symrise AG
Publication of EP3890838A1 publication Critical patent/EP3890838A1/fr
Pending legal-status Critical Current

Links

Classifications

    • B—PERFORMING OPERATIONS; TRANSPORTING
    • B01—PHYSICAL OR CHEMICAL PROCESSES OR APPARATUS IN GENERAL
    • B01J—CHEMICAL OR PHYSICAL PROCESSES, e.g. CATALYSIS OR COLLOID CHEMISTRY; THEIR RELEVANT APPARATUS
    • B01J13/00—Colloid chemistry, e.g. the production of colloidal materials or their solutions, not otherwise provided for; Making microcapsules or microballoons
    • B01J13/02—Making microcapsules or microballoons
    • B01J13/20—After-treatment of capsule walls, e.g. hardening
    • B01J13/22—Coating
    • A—HUMAN NECESSITIES
    • A01—AGRICULTURE; FORESTRY; ANIMAL HUSBANDRY; HUNTING; TRAPPING; FISHING
    • A01N—PRESERVATION OF BODIES OF HUMANS OR ANIMALS OR PLANTS OR PARTS THEREOF; BIOCIDES, e.g. AS DISINFECTANTS, AS PESTICIDES OR AS HERBICIDES; PEST REPELLANTS OR ATTRACTANTS; PLANT GROWTH REGULATORS
    • A01N25/00—Biocides, pest repellants or attractants, or plant growth regulators, characterised by their forms, or by their non-active ingredients or by their methods of application, e.g. seed treatment or sequential application; Substances for reducing the noxious effect of the active ingredients to organisms other than pests
    • A01N25/26—Biocides, pest repellants or attractants, or plant growth regulators, characterised by their forms, or by their non-active ingredients or by their methods of application, e.g. seed treatment or sequential application; Substances for reducing the noxious effect of the active ingredients to organisms other than pests in coated particulate form
    • A01N25/28—Microcapsules or nanocapsules
    • A—HUMAN NECESSITIES
    • A61—MEDICAL OR VETERINARY SCIENCE; HYGIENE
    • A61K—PREPARATIONS FOR MEDICAL, DENTAL OR TOILETRY PURPOSES
    • A61K8/00—Cosmetics or similar toiletry preparations
    • A61K8/02—Cosmetics or similar toiletry preparations characterised by special physical form
    • A61K8/11—Encapsulated compositions
    • A—HUMAN NECESSITIES
    • A61—MEDICAL OR VETERINARY SCIENCE; HYGIENE
    • A61K—PREPARATIONS FOR MEDICAL, DENTAL OR TOILETRY PURPOSES
    • A61K8/00—Cosmetics or similar toiletry preparations
    • A61K8/18—Cosmetics or similar toiletry preparations characterised by the composition
    • A61K8/72—Cosmetics or similar toiletry preparations characterised by the composition containing organic macromolecular compounds
    • A61K8/84—Cosmetics or similar toiletry preparations characterised by the composition containing organic macromolecular compounds obtained by reactions otherwise than those involving only carbon-carbon unsaturated bonds
    • A—HUMAN NECESSITIES
    • A61—MEDICAL OR VETERINARY SCIENCE; HYGIENE
    • A61Q—SPECIFIC USE OF COSMETICS OR SIMILAR TOILETRY PREPARATIONS
    • A61Q13/00—Formulations or additives for perfume preparations
    • B—PERFORMING OPERATIONS; TRANSPORTING
    • B01—PHYSICAL OR CHEMICAL PROCESSES OR APPARATUS IN GENERAL
    • B01J—CHEMICAL OR PHYSICAL PROCESSES, e.g. CATALYSIS OR COLLOID CHEMISTRY; THEIR RELEVANT APPARATUS
    • B01J13/00—Colloid chemistry, e.g. the production of colloidal materials or their solutions, not otherwise provided for; Making microcapsules or microballoons
    • B01J13/02—Making microcapsules or microballoons
    • B01J13/06—Making microcapsules or microballoons by phase separation
    • B01J13/14—Polymerisation; cross-linking
    • B—PERFORMING OPERATIONS; TRANSPORTING
    • B01—PHYSICAL OR CHEMICAL PROCESSES OR APPARATUS IN GENERAL
    • B01J—CHEMICAL OR PHYSICAL PROCESSES, e.g. CATALYSIS OR COLLOID CHEMISTRY; THEIR RELEVANT APPARATUS
    • B01J13/00—Colloid chemistry, e.g. the production of colloidal materials or their solutions, not otherwise provided for; Making microcapsules or microballoons
    • B01J13/02—Making microcapsules or microballoons
    • B01J13/20—After-treatment of capsule walls, e.g. hardening
    • B01J13/206—Hardening; drying
    • C—CHEMISTRY; METALLURGY
    • C11—ANIMAL OR VEGETABLE OILS, FATS, FATTY SUBSTANCES OR WAXES; FATTY ACIDS THEREFROM; DETERGENTS; CANDLES
    • C11D—DETERGENT COMPOSITIONS; USE OF SINGLE SUBSTANCES AS DETERGENTS; SOAP OR SOAP-MAKING; RESIN SOAPS; RECOVERY OF GLYCEROL
    • C11D17/00—Detergent materials or soaps characterised by their shape or physical properties
    • C11D17/0039—Coated compositions or coated components in the compositions, (micro)capsules
    • C—CHEMISTRY; METALLURGY
    • C11—ANIMAL OR VEGETABLE OILS, FATS, FATTY SUBSTANCES OR WAXES; FATTY ACIDS THEREFROM; DETERGENTS; CANDLES
    • C11D—DETERGENT COMPOSITIONS; USE OF SINGLE SUBSTANCES AS DETERGENTS; SOAP OR SOAP-MAKING; RESIN SOAPS; RECOVERY OF GLYCEROL
    • C11D3/00—Other compounding ingredients of detergent compositions covered in group C11D1/00
    • C11D3/50—Perfumes
    • C11D3/502—Protected perfumes
    • C11D3/505—Protected perfumes encapsulated or adsorbed on a carrier, e.g. zeolite or clay
    • F—MECHANICAL ENGINEERING; LIGHTING; HEATING; WEAPONS; BLASTING
    • F28—HEAT EXCHANGE IN GENERAL
    • F28D—HEAT-EXCHANGE APPARATUS, NOT PROVIDED FOR IN ANOTHER SUBCLASS, IN WHICH THE HEAT-EXCHANGE MEDIA DO NOT COME INTO DIRECT CONTACT
    • F28D20/00—Heat storage plants or apparatus in general; Regenerative heat-exchange apparatus not covered by groups F28D17/00 or F28D19/00
    • F28D20/02—Heat storage plants or apparatus in general; Regenerative heat-exchange apparatus not covered by groups F28D17/00 or F28D19/00 using latent heat
    • F28D20/023—Heat storage plants or apparatus in general; Regenerative heat-exchange apparatus not covered by groups F28D17/00 or F28D19/00 using latent heat the latent heat storage material being enclosed in granular particles or dispersed in a porous, fibrous or cellular structure
    • A—HUMAN NECESSITIES
    • A61—MEDICAL OR VETERINARY SCIENCE; HYGIENE
    • A61K—PREPARATIONS FOR MEDICAL, DENTAL OR TOILETRY PURPOSES
    • A61K2800/00—Properties of cosmetic compositions or active ingredients thereof or formulation aids used therein and process related aspects
    • A61K2800/40—Chemical, physico-chemical or functional or structural properties of particular ingredients
    • A61K2800/56—Compounds, absorbed onto or entrapped into a solid carrier, e.g. encapsulated perfumes, inclusion compounds, sustained release forms
    • Y—GENERAL TAGGING OF NEW TECHNOLOGICAL DEVELOPMENTS; GENERAL TAGGING OF CROSS-SECTIONAL TECHNOLOGIES SPANNING OVER SEVERAL SECTIONS OF THE IPC; TECHNICAL SUBJECTS COVERED BY FORMER USPC CROSS-REFERENCE ART COLLECTIONS [XRACs] AND DIGESTS
    • Y02—TECHNOLOGIES OR APPLICATIONS FOR MITIGATION OR ADAPTATION AGAINST CLIMATE CHANGE
    • Y02E—REDUCTION OF GREENHOUSE GAS [GHG] EMISSIONS, RELATED TO ENERGY GENERATION, TRANSMISSION OR DISTRIBUTION
    • Y02E60/00—Enabling technologies; Technologies with a potential or indirect contribution to GHG emissions mitigation
    • Y02E60/14—Thermal energy storage

Definitions

  • the invention is in the field of microcapsules and their use in cosmetic preparations, pharmaceutical agents, household and cleaning agents and technical compositions, such as e.g. Adhesive and coating compositions, paints, varnishes, binders, materials such as plastics, paper, textiles, lubricants, building materials, dyes, organic and inorganic powders, pigment dispersions, agrochemicals, phase change materials, flame retardants and the manufacture of the capsules.
  • Adhesive and coating compositions paints, varnishes, binders, materials such as plastics, paper, textiles, lubricants, building materials, dyes, organic and inorganic powders, pigment dispersions, agrochemicals, phase change materials, flame retardants and the manufacture of the capsules.
  • ingredients such as fragrances, insecticides, odor-counteracting substances, fungicides and mildewicides and the like can be encapsulated in a microcapsule that includes a solid shell or membrane that protects them from their immediate environment.
  • a popular method for making such encapsulated formulations is to disperse the ingredient in a liquid and create a polymer membrane on the surface of the droplets. Examples of suitable methods include the simple and complex coacervation of gelatin with gum arabic, followed by crosslinking with glutaraldehyde.
  • many polymers or polymer mixtures that are capable of forming insoluble complexes under specific conditions can be used to form such interface membranes by a so-called polymer phase separation process.
  • microcapsules include those of the aminoplast type.
  • the production of these capsules is simplified by first producing an O / W emulsion with strong shear and in the presence of emulsifiers, which contains the water-soluble monomer, a so-called amine-formaldehyde precondensate, and the water-insoluble active ingredient, such as a perfume oil .
  • emulsifiers which contains the water-soluble monomer, a so-called amine-formaldehyde precondensate, and the water-insoluble active ingredient, such as a perfume oil .
  • the polycondensation is initiated by a change in pH, for example by adjusting the pH to about 3.5 by adding acid.
  • the polycondensates deposit on the oil droplets in the emulsion and gradually envelop them. After the polycondensation had ended, a microcapsule dispersion resulted from the emulsion.
  • the capsules still have a soft, elastic shell, which does not yet provide the necessary diffusion stability and texture properties.
  • the third step then follows, in which the temperature is raised to about 60 ° C., which leads to crosslinking of the polymers in the wall and hardening of the capsules.
  • a corresponding method is known for example from EP 2111214 B1 (GIVAUDAN).
  • the capsules described above are so stable that the encapsulated active ingredient, such as perfume oil, is not released in time to obtain a satisfactory result.
  • free, non-encapsulated perfume oil must be used, which causes additional effort and costs, since this perfume oil differs from the encapsulated perfume oil with regard to various properties such as strength and quality.
  • the invention is therefore based on the object to overcome the disadvantages of the prior art.
  • the invention is based on the object of providing microcapsules which are distinguished by a high diffusion density and at the same time have an easily breakable capsule wall, in order thus to ensure the sufficient release of the encapsulated active ingredient.
  • a first subject of the invention relates to microcapsules comprising
  • a capsule wall wherein the capsule wall consists of at least three polymer layers and at least one of the polymer layers consists of a first phenolic resin, the first phenolic resin comprising 3 to 50% by weight of groups derived from at least one aromatic polyol and at least one further the polymer layers consist of a second phenolic resin, the second phenolic resin comprising 3 to 50% by weight of groups derived from at least one triphenol.
  • the microcapsules according to the invention are particularly stable to diffusion but nevertheless have a capsule wall which ensures release of the active ingredient contained in the end product even with very little to no friction, but which are nevertheless stable in storage.
  • the capsule wall having at least three polymer layers, one of the three polymer layers consisting of a first phenolic resin, the first phenolic resin comprising groups derived from at least one aromatic polyol and at least one further of the polymer layers consisting of a second phenolic resin , wherein the second phenolic resin comprises groups derived from at least one triphenol.
  • the inner polymer layer in the sense of the invention is the part of the capsule wall which directly adjoins the core of the microcapsule and thus the active ingredient.
  • the middle polymer layer Adjacent to the inner polymer layer is the middle polymer layer, which also borders on the outer polymer layer.
  • the structure of the microcapsule is shown again in an exemplary manner. It goes without saying that the The capsule wall can also contain further layers, which in turn adjoin the outer layer shown in FIG. 1.
  • the at least three polymer layers are very thin-walled and consequently lead to a generally very thin capsule wall. This naturally also influences the amount of polymer to be used, which is thereby reduced by up to 90% compared to a microcapsule having only one polymer layer, in particular by 50 to 90%. These thin layers are also advantageous because they only require a very small amount of polymer to be used. Of course, this saves additional material costs.
  • the capsules of the present invention allow the active ingredient to be released quickly, but are nevertheless fully mechanically loadable.
  • the adhesion properties of the microcapsules improve.
  • the capsule wall being composed of at least three polymer layers, the at least three polymer layers each being very thin-walled and at least one of the polymer layers consisting of a first phenolic resin, the first phenolic resin comprising groups derived from at least one aromatic polyol and at least one further of the polymer layers consists of a second phenolic resin, the second phenolic resin comprising groupings which are derived from at least one triphenol
  • the microcapsules are therefore distinguished by the fact that they have a high diffusion density but at the same time have a slightly fragile capsule wall, in order thus to ensure the sufficient release of the encapsulated active ingredient.
  • This is achieved by adding at least one aromatic polyol in at least one polymer layer and adding at least one triphenol in another polymer layer.
  • the addition of the polyol and the triphenol on the one hand results in a high stability of the microcapsules and on the other hand reduces the capsule wall itself, which, as mentioned above, saves costs with regard to the amount of polymer to be used and ensures a release of the active ingredient.
  • the inner layer of the capsule wall preferably consists of a first phenolic resin, the first phenolic resin comprising 3-50% by weight, preferably 5 to 45% by weight, more preferably 10 to 40% by weight, of groups which differ from an aromatic Derive polyol.
  • the first phenolic resin can also comprise 30 to 80%, preferably 40 to 75% by weight, preferably 45 to 65% by weight of groups derived from an aromatic polyol.
  • the middle layer of the capsule wall preferably consists of an aminoplast resin, in particular a melamine-formaldehyde resin, the aminoplast resin comprising 3 to 90% by weight, preferably 10 to 85%, preferably 20 to 80% by weight of groups which differ from one another Derive polyamine, especially melamine.
  • the outer layer of the capsule wall preferably consists of a second phenolic resin, the second phenolic resin comprising 3 to 50% by weight, preferably 5 to 45% by weight, further preferably 10 to 40% by weight, of groups derived from a triphenol.
  • the second phenolic resin can also comprise 30 to 80%, preferably 40 to 75% by weight, preferably 45 to 65% by weight of groups which are derived from a triphenol.
  • the at least three polymer layers of the capsule wall each consist of resins which comprise groups which are derived from different substances.
  • the at least three polymer layers have an alternating structure, a polymer layer which is composed of a phenolic resin being separated by a polymer layer which is composed of an aminoplast resin, preferably melamine-formaldehyde resin.
  • the at least three polymer layers have an alternating structure, a polymer layer which comprises groupings which are derived from the condensation of phenols or polyols with an aldehyde being in each case separated by a polymer layer which comprises groupings which differ from one another derive from the condensation of polyamines with an aldehyde, in particular formaldehyde.
  • the present invention also relates to microcapsules comprising
  • capsule wall (b) a capsule wall, wherein the capsule wall consists of at least three polymer layers and comprises at least one of the polymer layers groupings which are derived from the condensation of at least one aromatic polyol and at least one aldehyde and at least one further of the polymer layers comprises groupings which result from the condensation of at least one triphenol and derive at least one aldehyde.
  • a particularly preferred embodiment of the invention can consist of a first polymer layer composed of groups derived from the condensation of resorcinol and aldehyde, a second polymer layer composed of groups derived from the condensation of melamine and aldehyde and a third Polymer layer consisting of groups derived from the condensation of phloroglucin and aldehyde. Or a first from triethanolamine-formaldehyde groups, a second from resorcinol-aldehyde groups and a third from phloroglucin-aldehyde groups.
  • a first of melamine-formaldehyde groups a second of resorcinol-aldehyde groups and a third of phloroglucin-aldehyde groups.
  • precondensates such as Luracoll ® SD can also be used instead of an amine-formaldehyde component.
  • a further particularly preferred embodiment of the invention consists of a first polymer layer consisting of a first phenolic resin, the first phenolic resin comprising groups derived from resorcinol, a second polymer layer consisting of aminoplast resin, the aminoplast resin comprising groups consisting of Derive melamine and a third polymer layer consisting of a second phenolic resin, wherein the second phenolic resin comprises groups derived from phloroglucin. Or a first from triethanolamine-formaldehyde groups, a second from resorcinol groups and a third from phloroglucin groups.
  • a first from melamine-formaldehyde groups a second from resorcinol groups and a third from phloroglucin groups.
  • precondensates such as Luracoll ® SD can also be used instead of an amine-formaldehyde component.
  • grouping or “groupings” is meant a chemical entity that is part of a polymer and is derived from a particular molecule.
  • the polymer layers described above can be any polymer layers that comprise the groupings described above of the many suitable methods known in the art.
  • the The polymer layers described above consist of different resins, such as, for example, phenol resins or aminoplast resins, in particular melamine-formaldehyde resins, which comprise the groups described above.
  • the aromatic polyol groups are derived from resorcinol.
  • resorcinol or “resorcinol” are synonymous terms and are also used synonymously in the light of the invention.
  • a triphenol in the sense of the invention is a trihydric phenol, ie a phenol with three hydroxyl groups.
  • Suitable triphenols are, for example, phloroglucin (1,3,5-trihydroxybenzene), pyrogallol (1,2,3-trihydroxybenzene) or hydroxyhydro smell (1,2,4-trihydroxybenzene).
  • Preferred triphenols are 1, 3, 5-triaminoalkylbenzene and phloroglucin.
  • the outer polymer layer of the capsule wall consists of a second phenolic resin, the second phenolic resin comprising a group which is derived from at least one triphenol.
  • the particularly preferred triphenol is phloroglucin.
  • the capsule wall consists of three polymer layers.
  • the three polymer layers of the capsule wall each consist of different resins, the resins comprising groups which are derived from different substances.
  • the outer polymer layer consists of a second phenolic resin, the second phenolic resin comprising groups which are derived from phloroglucinol.
  • the middle polymer layer consists of an aminoplast resin, the aminoplast resin comprising groups which are derived from a mixture of melamine and formaldehyde.
  • the inner polymer layer consists of a first phenolic resin, the first phenolic resin comprising groups which are derived from resorcinol.
  • groups which are derived from resorcinol and phloroglucin in different polymer layers is also particularly advantageous since this enables the formation of a three-layer capsule wall, which also meets all requirements such as stability, efficient perfume release, etc. As already mentioned above, they are particularly thin Capsule walls enabled.
  • the outer polymer layer consists of a second phenolic resin, the second phenolic resin comprising groups derived from phloroglucin and the middle polymer layer consisting of an aminoplast resin, the amino resin comprising groups derived from mixtures of melamine and formaldehyde and the inner polymer layer made of a first phenolic resin, the first phenolic resin comprising groups derived from resorcinol.
  • the inner polymer layer of the microcapsule according to the invention is a first phenolic resin, the first phenolic resin comprising groups which are derived from at least one aromatic polyol.
  • the groupings comprising the first phenolic resin are derived from resorcinol.
  • the middle polymer layer of the microcapsule according to the invention is an aminoplast resin, in particular a melamine
  • Formaldehyde resin the aminoplast resin comprising groups derived from at least one polyamine.
  • the groupings comprising the aminoplast resin are derived from melamine.
  • the outer polymer layer of the microcapsule according to the invention is a second phenolic resin, the second phenolic resin comprising groups which are derived from at least one triphenol.
  • the groupings comprising the second phenolic resin are derived from phloroglucin.
  • Phenolic resins in the sense of the invention are synthetic resins (condensation resins) which are produced by polycondensation from phenols and aldehydes. Important starting materials for the production of the resins are, for example, phenol and formaldehyde.
  • Aminoplast resins in the sense of the invention are curable synthetic resins which are produced by polycondensation of aldehydes and compounds with NH or NH2 groups, such as, for example, urea, melamine or dicyandiamide.
  • formaldehyde is used as the Aldeyhd.
  • the capsule wall content based on the slurry is 0.3 to 3% by weight. In a further preferred embodiment of the invention the portion of the capsule wall based on the slurry is 0.3 to 2% by weight. In a further preferred embodiment of the invention, the capsule wall content, based on the slurry, is 0.3 to 0.9% by weight.
  • Microcapsules of the type described above are provided in the form of a slurry with a solids content of typically 20 to 50%, preferably 30 to 45%, the term "solids content” referring to the total weight of the microcapsules.
  • the average size of the microcapsules can range from 1 micron to 100 microns or more. The selection of the most suitable microcapsule size range and size distribution depends on the intended application.
  • a “slurry” in the sense of the invention is nothing more than a suspension in water.
  • a synonymous term would also be “slurry”, for example.
  • the capsule wall proportion, based on the active ingredient, in particular on the perfume oil, is 0.5 to 7% by weight.
  • Preferred polyamines for the purposes of the invention are so-called polyamine precondensates, in particular amine-formaldehyde precondensates or precondensates (AFP).
  • these form the material which finally forms the shell or wall of the capsule by polycondensation and encloses the active ingredient.
  • precondensates or precondensates can be used synonymously.
  • the amine component of the AFP is usually fluorine or in particular melamine.
  • the polycondensation is thermally controlled, it is Control is sometimes difficult.
  • aminoplasts are made by polycondensing formaldehyde with compounds containing two or more amino groups (e.g. urea, thiourea, melamine, cyanamide, diaminohexane, benzoguanamine).
  • this reaction proceeds via the addition of urea to form N-hydroxymethyl groups and then chain growth via polycondensation with elimination of water.
  • This reaction is usually carried out in basic solution, since OH ions are required as a catalyst and uncrosslinked precondensates are formed.
  • the precondensates are stable for several months at room temperature.
  • the preferred AFPs are therefore alkylation products of melamine with short-chain alcohols and in particular the so-called highly or partially alkoxylated and optionally also alkylated melamines, such as those offered by BASF in aqueous methanolic formaldehyde solution under the name Luracoll ® , in particular Luracoll ® SD.
  • Preferred polyamines are: optionally alkylated mono- and polymethylol-urea and mono- and polymethylol-melamine precondensates, such as those marketed under the name URAC (Cytec Corp.) or partially methylated mono- and Polymethylol-l, 3,5-triamino-2,4,6-triazine precondensates, the are commercially available under the name CYMEL (Cytec Corp.).
  • mono- and polyalkylolbenzoguanamine or mono- and polyalkylolglycuril precondensates are also suitable. If these precondensates have alkyl groups, they are less reactive and can be stored longer.
  • the preferred precondensates include the polymethylolmelamines and the polymethylol-l- (3,5-dihydroxy-methylbenzyl) -3,5-triamino-2,4,6-triazine.
  • Poly [N- (2,2-dimethoxy-l-hydroxy)] - polyamines such as, for example, di- [N- (2,2-dimethoxy-l-hydroxy)] urea, tri- [N - (2,2-dimethoxy-l-hydroxy)] melamine, tetra- [N- (2,2-dimethoxy-l-hydroxy)] glycouryl and di- [N- (2,2-dimethoxy-l- hydroxy)] benzoguanidine and mixtures thereof.
  • the polyamines are melamine-formaldehyde directly and / or Luracoll ® SD as the pre-condensate.
  • the selection of the raw materials to be encapsulated is not critical per se and is determined exclusively by the desired application.
  • the only limitation is that these are either in the form of an oil or must be sufficiently oil-soluble, that is, lipophilic, in order to be soluble in an oil phase, preferably together with the aromatic polyol.
  • the active substances in particular include perfume oils and oil-soluble fragrances, as listed below by way of example:
  • Extracts from natural raw materials such as essential oils, concretes, absolutes, resins, resinoids, balms, tinctures such as. B. ambratincture; Amyris oil; Angelica seed oil; Angelica root oil; Anise oil; Valerian oil; Basil oil; Tree moss absolute; Bay oil; Mugwort oil; Benzoresin; Bergamot oil; Beeswax absolute; Birch tar oil; Bitter almond oil; Savory oil; Bucco leaf oil; Cabreuva oil; Cade oil; Calmus oil; Camphor oil; Cananga oil; Cardamom oil; Cascarilla oil; Cassia oil; Cassie absolute; Castoreum absolute; Cedar leaf oil; Cedarwood oil; Cistus oil; Citronell oil; Lemon oil; Copaiva balm; Copaiva balsam oil; Coriander oil; Costus root oil; Cumin oil; Cypress oil; Davana oil; Dill herb oil; Dill seed oil; Eau de brouts-absolute; Oakmoss absolute; Elemi oil
  • Hydrocarbons such as. B. 3-carene; a-pinene; beta -pinene; alpha terpinene; gamma terpinene; p-cymene; Bisabolene; Camphene; Caryophyllene; Cedren; Farnese; Lime; Longifolene; Myrcene; Ocimen; Valencene; (E, Z) -l, 3,5-undecatriene;
  • Aliphatic alcohols such as. B. hexanol; Octanol; 3-octanol; 2,6-dimethylheptanol; 2-methylheptanol, 2-methyloctanol; (E) -2-hexenol; (£ " ) - and (Z) -3-hexenol; l-octen-3-ol; mixture of 3,4,5,6,6-pentamethyl-3/4-hepten-2-ol and 3,5, 6,6-tetramethyl-4-methyleneheptan-2-ol; (£, Z) -2,6-nonadienol; 3,7-dimethyl-7-methoxyoctan-2-ol; 9-decenol; 10-undecenol; 4- Methyl-3-decen-5-ol;
  • Aliphatic aldehydes and their acetals such as.
  • Aliphatic sulfur-containing compounds such as. B. 3-methylthiohexanol; 3-methylthiohexyl acetate; 3-mercaptohexanol; 3-mercaptohexyl acetate; 3-mercaptohexyl butyrate; 3-acetylthiohexyl acetate; l-menthen-8-thiol;
  • Aliphatic nitriles such as. B. 2-Nonenonitrile; 2-tridecenonitrile; 2,12-tridecenonitrile; 3,7-dimethyl-2,6-octadienonitrile; 3,7-dimethyl-6-octenonitrile;
  • Aliphatic carboxylic acids and their esters such as. B. (£) - and (Z) -3-hexenyl formate; Ethyl acetoacetate; Isoamyl acetate; Hexyl acetate; 3,5,5-trimethylhexyl acetate; 3-methyl-2-butenyl acetate; (£) -2-hexenyl acetate; (£) - and (Z) -3-hexenyl acetate; Octyl acetate; 3-octyl acetate; l-octen-3-ylacetate; Ethyl butyrate; Butyl butyrate; Isoamyl butyrate; Hexyl butyrate; (E) - and (Z) -3- hexenyl isobutyrate; Hexyl crotonate; Ethyl isovalerate; Ethyl 2-methylpentanoate; Ethyl hexanoate;
  • Acyclic terpene alcohols such as. B. Citronellol; Geraniol; Nerol; Linalool; Lavadulol; Nerolidol; Farnesol; Tetrahydrolinalool; Tetrahydrogeraniol; 2,6-dimethyl-7-octen-2-ol; 2,6-dimethyloctan-2-ol; 2-methyl-6-methylene-7-octen-2-ol; 2,6-dimethyl-5,7-octadien-2-ol; 2,6-dimethyl-3,5-octadien-2-ol; 3,7-dimethyl-4,6-octadien-3-ol; 3,7-dimethyl-1,5,7-octatrien-3-ol; 2,6-dimethyl-2,5,7-octatrien-l-ol; as well as their formates, acetates, propionates, isobutyrates, butyrates, isovalerianates,
  • Acyclic terpene aldehydes and ketones such as. B. Geranial; Neral; Citronellal; 7-hydroxy-3,7-dimethyloctanal; 7-methoxy-3,7-dimethyloctanal; 2,6,10-trimethyl-9-undecenal; Geranylacetone; as well as the dimethyl and diethyl acetals of geranial, neral, 7-hydroxy-3,7-dimethyloctanal;
  • Cyclic terpene alcohols such as. B. menthol; Isopulegol; a-terpineol; Terpinenol-4; Menthan-8-ol; Menthan-l-ol; Menthan-7-ol; Borneol; Isoborneol; Linalool oxide; Nopol; Cedrol; Ambrinol; Vetiverol; Guajol; as well as their formates, acetates, propionates, isobutyrates, butyrates, isovalerianates, pentanoates, hexanoates, crotonates, tiglinates, 3-methyl-2-butenoates; Cyclic terpene aldehydes and ketones, such as. B.
  • Cyclic alcohols such as. B. 4-te / t-butylcyclohexanol; 3,3,5-trimethylcyclohexanol;
  • cycloaliphatic alcohols such as. B. a, 3,3-trimethylcyclohexylmethanol; 2-methyl-4- (2,2,3-trimethyl-3-cyclopent-l-yl) butanol; 2-methyl-4- (2,2,3-trimethyl-3-cyclopent-l-yl) -2-buten-l-ol; 2-ethyl-4- (2,2,3-trimethyl-3-cyclopent-l-yl) -2-buten-l-ol; 3-methyl-5- (2,2,3-trimethyl-3-cyclopent-l-yl) pentan-2-ol; 3-methyl-5- (2,2,3-trimethyl-3-cyclopent-l-yl) -4-penten-2-ol; 3,3-dimethyl-5- (2,2,3-trimethyl-3-cyclopent-l-yl) -
  • Cyclic and cycloaliphatic ethers such as. B. Cineol; Cedryl methyl ether; Cyclododecyl methyl ether; (Ethoxymethoxy) cyclododecane; a-cedrenepoxide; 3a, 6, 6, 9a-tetramethyldodecahydronaphtho [2, l-b] furan; 3a-ethyl-6,6,9a-trimethyl-dodecahydronaphtho [2, l-b] furan; 1,5,9-trimethyl-13-oxabicyclo [10.1.0] trideca-4,8-diene; Rose oxide; 2- (2,4-dimethyl-3-cyclohexen-l-yl) -5-methyl-5- (l-methylpropyl) -l, 3-dioxane;
  • Cyclic ketones such as. B. 4-tert-butylcyclohexanone; 2,2,5-trimethyl-5-pentylcyclopentanone; 2-heptylcyclopentanone; 2-pentylcyclopentanone; 2-hydroxy-3-methyl-2-cyclopenten-l-one; 3-methyl-cis-2-penten-l-yl-2-cyclopenten-l-one; 3-methyl-2-pentyl-2-cyclopenten-l-one; 3-methyl-4-cyclopentadecenone; 3-methyl-5-cyclopentadecenone; 3-methylcyclopentadecanone; 4- (l-ethoxyvinyl) -3,3,5,5-tetramethylcyclohexanone; 4-tert-pentylcyclohexanone; 5-cyclohexadecen-1-one; 6,7-dihydro-l, l, 2,3,3-pentamethyl-4 (5H) - indanon; 9-cycloheptadec
  • Cycloaliphatic aldehydes such as. B. 2,4-dimethyl-3-cyclohexenecarbaldehyde; 2-methyl-4- (2,2,6-trimethyl-cyclohexen-1-yl) -2-butenal; 4- (4-hydroxy-4-ethylpentyl) -3-cyclohexenecarbaldehyde; 4- (4-methyl-3-penten-l-yl) -3-cyclohexenecarbaldehyde; Cycloaliphatic ketones, such as. B.
  • Esters of cyclic alcohols such as. B. 2-tert-butylcyclohexyl acetate; 4-tert-butylcyclohexyl acetate; 2-th / t-pentylcyclohexyl acetate; 4-th / t-pentylcyclohexyl acetate; Decahydro-2-naphthyl acetate; 3-pentyltetrahydro-2H-pyran-4-ylacetate; Decahydro-2,5,5,8a-tetramethyl-2-naphthyl acetate; 4,7-methano-3a, 4,5,6,7,7a-hexahydro-5- or -6-indenyl acetate; 4,7-methano-3a, 4,5,6,7,7a-hexahydro-5- or -6-indenylpropionate; 4,7-methano-3a, 4,5,6,7,7a-hexahydro-5-
  • Esters of cycloaliphatic carboxylic acids such as. B. allyl-3-cyclohexylpropionate; Allylcyclohexyloxyacetate; Methyl dihydrojasmonate; Methyl jasmonate; Methyl 2-hexyl-3-oxocyclopentane carboxylate; Ethyl 2-ethyl-6,6-dimethyl-2-cyclohexenecarboxylate; Ethyl 2, 3,6,6-tetramethyl-2-cyclohexenecarboxylate; Ethyl 2-methyl-1,3-dioxolane-2-acetate;
  • Aromatic hydrocarbons such as. B. styrene and diphenylmethane
  • Araliphatic alcohols such as. B. benzyl alcohol; 1-phenylethyl alcohol; 2-phenylethyl alcohol; 3-phenylpropanol; 2-phenylpropanol; 2-phenoxyethanol; 2,2-dimethyl
  • Esters of araliphatic alcohols and aliphatic carboxylic acids such as. B.
  • Araliphatic ether such as. B. 2-phenylethyl methyl ether; 2-phenylethyl isoamyl ether; 2-phenylethyl-1-ethoxyethyl ether; Phenylacetaldehyde dimethyl acetal;
  • Aromatic and araliphatic ketones such as. B. acetophenone; 4-methyl acetophenone; 4-methoxyacetophenone; 4-te / t-butyl-2,6-dimethylacetophenone; 4-phenyl-2-butanone; 4- (4-hydroxyphenyl) -2-butanone; 1- (2-naphthalenyl) ethanone; Benzophenone; l, l, 2,3,3,6-hexamethyl-5-indanyl methyl ketone; 6-te / t-butyl-l, l-dimethyl-4-indanylmethyl ketone; l- [2,3-dihydro-1,2,2 ; 6-tetramethyl-3- (1-methylethyl) -IH-5-indenyl] ethanone;
  • Aromatic and araliphatic carboxylic acids and their esters such as. B.
  • Nitrogen-containing aromatic compounds such as. B. 2 / 4,6-trinitro-l / 3-dimethyl-5-tert-butylbenzene; 3,5-dinitro-2,6-dimethyl-4-tert-butylacetophenone; Cinnamic acid nitrile; 5-phenyl-3-methyl-2-pentenenenitrile; 5-phenyl-3-methylpentanoic acid nitrile;
  • Methyl anthranilate Methyl-N-methylanthranilate; Schiff bases of methylanthranilate with 7-hydroxy-3,7-dimethyloctanal, 2-methyl-3- (4-tert-butylphenyl) propanal or 2,4-dimethyl-3-cyclohexenecarbaldehyde; 6-isopropylquinoline; 6-isobutylquinoline; 6-sec-butylquinoline; Indole; Skatole; 2-methoxy-3-isopropylpyrazine; 2-isobutyl-3-methoxypyrazine; 4- (4,8-dimethyl-3,7-nonadienylj-pyridine;
  • Phenols, phenyl ethers and phenyl esters such as. B. Estragol; Anethole; Eugenol; Eugenyl methyl ether; Isougenol; Isougenyl methyl ether; Thymol; Carvacrol; Diphenyl ether; beta -naphthyl methyl ether; beta -naphthyl ethyl ether; beta -naphthyl isobutyl ether; 1.4- Dimethoxybenzene; Eugenyl acetate; 2-methoxy-4-methylphenol; 2-ethoxy-5- (l-propenyl) phenol; p-cresylphenylacetate;
  • Lactones such as. B. 1,4-octanolide; 3-methyl-1,4-octanolide; 1,4-nonanolide; 1,4-decanolide; 8-decene-1,4-olide; 1,4-undecanolide; 1,4-dodecanolide; 1,5-decanolide; 1,5-dodecanolide; 1,15-pentadecanolide; cis- and trans-ll-pentadecene-1,15-olide; cis- and trans-12-pentadecene-1,15-olide; 1,16-hexadecanolide; 9-hexadecen-l, 16-olide; 10-oxa-l, 16-hexadecanolide; ll-oxa-l, 16-hexadecanolide; 12-oxa-1,16-hexadecanolide; Ethylene 1,12-dodecanedioate; Ethylene-l
  • the emulsions additionally contain stabilizers or protective colloids.
  • stabilizers or protective colloids include, in particular acrylic copolymers that have sulfonate groups, such as LUPASOL ® PA140 or LUPASOL VFR ® (BASF).
  • copolymers of acrylamides and acrylic acid copolymers of alkyl acrylates and N-vinylpyrrolidone such as LUVISKOL ® K15, K30 or K90 (BASF); Sodium polycarboxylates, sodium polystyrene sulfonates, vinyl and methyl vinyl ether-maleic anhydride copolymers as well as ethylene, isobutylene or styrene-maleic anhydride copolymers.
  • the preferred stabilizers are the representatives of the LUPASOL ® series mentioned above, in particular in combination with AFP of the LURACOLLL ® type.
  • the amount of stabilizers used can be in the range from approximately 1 to approximately 10% by weight and in particular approximately 2 to approximately 5% by weight, based on the emulsion.
  • Another object of the present invention is a method for producing the microcapsules described above, comprising the following steps:
  • At least one emulsifier and / or stabilizer to form an emulsion at least one emulsifier and / or stabilizer to form an emulsion
  • the aromatic polyol from step (b) is added to the oil phase. This has the advantage that higher storage stability can be achieved despite the thinner capsule wall overall.
  • the mixture in step (f) rests at 50 to 65 ° C for 50 to 70 minutes. In a very preferred embodiment, the mixture in step (f) is at about 60 ° C. for about 60 minutes. In a preferred embodiment of the invention, the mixture in step (i) rests at 50 to 65 ° C for 50 to 70 minutes. In a very preferred embodiment, the mixture in step (f) is at about 60 ° C. for about 60 minutes.
  • reaction with CO 2 is additionally superimposed after step (c).
  • This overlay with C02 has the advantage that discoloration, which is caused by aromatic polyols in the core, is reduced.
  • polyamines precondensates are used which are selected from the group consisting of is formed from optionally alkylated mono- and polymethylol-urea or mono- and polymethylol-melamine precondensates, partially methylated mono- and polymethylol-1, 3,5-triamino-2,4,6-triazine precondensates, mono- and Polyalkylolbenzoguanamine and mono- and polyalkylolglycuril precondensates, poly [N- (2,2-dimethoxy-l-hydroxy)] polyamines, melamine-formaldehyde, Luracoll SD and mixtures thereof.
  • step (e) formaldehyde is used in step (a) as the aldehyde.
  • Luracoll SD is used as the polyamine / precondensate in step (e).
  • a perfume oil is used as the active ingredient to be encapsulated.
  • the mixture is heated to 80 ° C. to 90 ° C. directly after step (i). This step serves to form the outer polymer layer of the capsule wall.
  • the triphenol is phloroglucinol.
  • the pH is reduced to a value from 3 to 5 by adding formic acid or a mixture of formic acid, citric acid and ascorbic acid.
  • This lowering of the pH value in turn serves to prevent unwanted color reactions of the aromatic polyol. Color reactions are of course not, especially with regard to the use of the microcapsules, for example in fabric softener desired and must be avoided as much as possible. This is possible by the described lowering of the pH at the start of the polymerization of the first polymer layer.
  • the addition of at least one aromatic polyol in step (b) and the addition of at least one triphenol in step (g) enables the formation of at least three polymer layers and also the formation of an overall very thin capsule wall.
  • the capsule wall in the sense of the invention consists of at least three polymer layers.
  • thinner capsule walls are formed, which saves material costs but at the same time ensures better stability.
  • the aromatic polyol is resorcinol and the triphenol is phloroglucinol.
  • crosslinkers in the sense of the invention are valeraldehyde, capronaldehyde, caprylaldehyde, decanal, succindialdehyde, cyclohexanecarbaldehyde, cyclopentanecarbaldehyde, 2-methyl-l-propanal, 2-methylpropionaldehyde, acetaldehyde, acrolein, aldosterone, antimycin A, 8-apoteno- ⁇ -apoteno -8- al, Benzaldehyde, Gutanal, Chloral, Citral, Citronellal, Crotonaldehyde, Dimethylaminobenzaldehyde, Folinic acid, Fosmidomycin, Furfural, Glutaraldehyde, Glyceraldehyde, Glycolaldehyde, Glyoxal, Glyoxylic acid, Heptan
  • An aromatic alcohol also comes from the phenols with two or more hydroxyl groups, preferably from pyrocatechol, resorcinol, hydroquinone and 1,4-naphthohydroquinone, phloroglucinol, pyrogallol, hydroxyhydroquinone.
  • Cresols & phenols methoxyphenoly, napthols, thymol, ethyl or propylphenols, 1, 3, 5-triaminobenzene, 1, 3, 5-triaminoalkylbenzene, 1, 3, 5-trialkoxyaminobenzene, 1, 3, 5-triamidobenzene.
  • heterocyclic compounds having at least one nitrogen atom as hetero atom which is adjacent to either an amino-substituted carbon atom or a carbonyl group, such as, for example, pyridazine, pyrimidine, pyrazine, pyrrolidone and aminopyridine and compounds derived therefrom, aminopyridines, for example melamine, can be used as crosslinkers.
  • 2,6-diaminopyridine substituted and dimeric aminopyridines and mixtures prepared from these compounds, polyamides and dicyandiamide, urea and its derivatives and pyrrolidone and compounds derived therefrom, for example imidazolidinone, hydantoin and its derivatives, allantoin and its derivatives, triamino-1,3. 5-triazine (melamine) into consideration.
  • Another object of the present invention relates to cosmetic preparations, pharmaceutical agents, household and cleaning agents and technical compositions, such as e.g. Adhesive and coating compositions, paints, varnishes, binders, materials such as plastics, paper, textiles, lubricants, building materials, dyes, organic and inorganic powders, pigment dispersions, agrochemicals, phase change materials, flame retardants containing the microcapsules according to the invention.
  • Adhesive and coating compositions such as plastics, paper, textiles, lubricants, building materials, dyes, organic and inorganic powders, pigment dispersions, agrochemicals, phase change materials, flame retardants containing the microcapsules according to the invention.
  • the microcapsules are used in detergents and cleaning agents, cosmetic preparations or perfume compositions.
  • Formation of the third polymer layer 9. Addition of at least one triphenol, preferably phloroglucin
  • compositions of the microcapsules according to the invention are shown in Table 1 below:
  • the capsules according to the invention were compared with capsules of the prior art (1 polymer layer and 2 polymer layers) with regard to their stability and the adhesive properties.
  • the comparison was made as follows: The samples were diluted 1:10 with demineralized water and then placed in a measuring cell. The measurement method was set depending on the respective capsule sizes (Smoluchowski: capsules / particles> 100 nm; Hückel: particles ⁇ 100 nm). The temperature was then set to 25 ° C. and 3 measuring cycles of 10 measurements were carried out. In the end, the mean was formed from the values.
  • Zeta potential generally means the electrostatic potential that is generated by electrically charged objects in solution.
  • Zeta Potential in Colloid Sciences Robot J. Hunter; Academic Press, London 1981, 1988. Its value is a suitable measure of the object's ability to produce electrostatic interactions with other objects in the solution, such as surfactants, polyelectrolytes and surfaces.
  • Table 2 thus clearly shows that a 3-layer structure of the capsule wall thus reduces the surface charge of the capsule, which results in significantly better adhesion, for example to cotton fabric.
  • Table 3 illustrates the relationship between the thickness of the capsule wall and the number of different polymer layers and the diffusion stability. It is very clearly shown here that the microcapsules according to the invention are significantly more stable with respect to diffusion over time. On the one hand, as already mentioned above, this is due to the at least three-layer capsule wall according to the invention.
  • the capsules consisting of 1 layer and 2 layers are capsules of the prior art.
  • the capsules consisting of 3 layers are capsules according to the invention. All capsules in Table 3 are composed according to Table 2. Over a period of 12 weeks, each measured how much residual perfume oil (as a percentage) remained in the capsule. The more stable the capsule, the more perfume oil must be in the capsule.
  • the capsules were stored in fabric softener at 45 ° C.
  • the capsules of the prior art and the capsules according to the invention were increasingly reduced in terms of their shell (proportion of wall [%]). It can thus be clearly seen that the capsules according to the invention, which contain both resorcinol and phloroglucin, have significantly improved stability over a long period of time despite the thinner shell or capsule wall.
  • Table 3 Stability [%] at 45 ° C in fabric softener
  • Table 4 shows a comparison of the fragrance intensity on cotton fabric after treatment with a fabric softener.
  • the results reflect the function of the various capsules of the prior art and the capsules according to the invention, before and after friction.
  • the different cotton rags were tested by 40 trained panelists. A scale of 1-9 was used, 1 corresponding to no fragrance and 9 corresponding to a very strong fragrance.
  • Table 5 also illustrates this comparison, but after the capsules have been stored for 4 weeks at 40 ° C. Here too it can clearly be seen that the microcapsules according to the invention have the highest fragrance intensity, both before and after rubbing.
  • the microcapsules according to the invention have a high diffusion density, but at the same time have a slightly fragile capsule wall, in order to ensure sufficient release of the encapsulated active ingredient.
  • Table 5 Sensor system after 4 weeks at 40 ° C.
  • Table 6 and FIG. 2 clearly show an improvement over the prior art with regard to the sensory properties of the microcapsules. These results suggest that the capsules are very stable in storage due to the at least three polymer layers, but allow the encapsulated active ingredient, in particular a perfume oil, to be released due to low mechanical stress, such as rubbing.

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Abstract

L'invention concerne des microcapsules, comprenant (a) un noyau, contenant au moins un principe actif, et (b) une paroi de capsule, cette dernière étant constituée d'au moins trois couches polymères, au moins une de ces couches polymères étant constituée d'une première résine phénolique comprenant 3 à 50 % en poids de groupements dérivés d'au moins un polyol aromatique et au moins une autre de ces couches polymères étant constituée d'une deuxième résine phénolique comprenant 3 à 50 % en poids de groupements dérivés d'au moins un triphénol.
EP19809503.6A 2018-12-03 2019-12-02 Microcapsules Pending EP3890838A1 (fr)

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WO2024094318A1 (fr) 2022-11-03 2024-05-10 Symrise Ag Microcapsules, processus pour la préparation de microcapsules et utilisation de microcapsules pour parfumer un produit de consommation

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DE1817316A1 (de) * 1967-12-28 1969-12-18 Pilot Pen Co Ltd Kapsel mit mehrschichtiger Huelle und Verfahren zu ihrer Herstellung

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JPS5955342A (ja) * 1982-09-24 1984-03-30 Idemitsu Kosan Co Ltd マイクロカプセルの製造方法
CN101605526B (zh) 2007-02-13 2015-03-25 奇华顿股份有限公司 微胶囊
GB0802489D0 (en) * 2008-02-11 2008-03-19 Givaudan Sa Product
DE102009012455A1 (de) * 2009-03-12 2010-09-23 Follmann & Co. Gesellschaft Für Chemie-Werkstoffe Und -Verfahrenstechnik Mbh & Co. Kg Verbesserte Mikrokapseln und ihre Herstellung
DE102010040564A1 (de) * 2010-09-10 2012-03-15 Henkel Ag & Co. Kgaa Mikrokapselhaltiges Wasch- oder Reinigungsmittel
DE102011082496A1 (de) * 2011-09-12 2013-03-14 Henkel Ag & Co. Kgaa Mikrokapselhaltiges Mittel
ES2737975T3 (es) * 2012-07-26 2020-01-17 Koehler Se August Papierfabrik Encapsulación de aceite aromático
WO2015031418A1 (fr) * 2013-08-28 2015-03-05 The Procter & Gamble Company Microcapsule contenant un détergent ou un agent de nettoyage
BR112016002180B1 (pt) * 2013-11-11 2022-08-02 Unilever Ip Holdings B.V. Composição amaciante de tecido, método para tratamento de tecido e uso de uma composição
JP6532010B2 (ja) * 2015-03-25 2019-06-19 トッパン・フォームズ株式会社 マイクロカプセル、シート、樹脂組成物及び液状組成物
GB201511605D0 (en) * 2015-07-02 2015-08-19 Givaudan Sa Microcapsules
DE102017111445A1 (de) * 2017-05-24 2018-11-29 Henkel Ag & Co. Kgaa Mikrokapselsystem für polysensorische Dufteffekte

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JP7381583B2 (ja) 2023-11-15
CN113242750A (zh) 2021-08-10
WO2020114571A1 (fr) 2020-06-11

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