WO2002060573A2 - Systeme capsules dans capsule et son procede de production - Google Patents

Systeme capsules dans capsule et son procede de production Download PDF

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Publication number
WO2002060573A2
WO2002060573A2 PCT/EP2002/000816 EP0200816W WO02060573A2 WO 2002060573 A2 WO2002060573 A2 WO 2002060573A2 EP 0200816 W EP0200816 W EP 0200816W WO 02060573 A2 WO02060573 A2 WO 02060573A2
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WO
WIPO (PCT)
Prior art keywords
capsule
capsules
inner capsules
shell
medium
Prior art date
Application number
PCT/EP2002/000816
Other languages
German (de)
English (en)
Other versions
WO2002060573A3 (fr
Inventor
Michael Dreja
Wolfgang Von Rybinski
Ute Krupp
Original Assignee
Henkel Kommanditgesellschaft Auf Aktien
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 Henkel Kommanditgesellschaft Auf Aktien filed Critical Henkel Kommanditgesellschaft Auf Aktien
Priority to AU2002250858A priority Critical patent/AU2002250858A1/en
Publication of WO2002060573A2 publication Critical patent/WO2002060573A2/fr
Publication of WO2002060573A3 publication Critical patent/WO2002060573A3/fr

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Classifications

    • 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
    • A61K8/30—Cosmetics or similar toiletry preparations characterised by the composition containing organic compounds
    • A61K8/67—Vitamins
    • A61K8/676—Ascorbic acid, i.e. vitamin C
    • 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
    • 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
    • B01J13/04—Making microcapsules or microballoons by physical processes, e.g. drying, spraying
    • B01J13/043—Drying and spraying
    • B—PERFORMING OPERATIONS; TRANSPORTING
    • B01—PHYSICAL OR CHEMICAL PROCESSES OR APPARATUS IN GENERAL
    • B01J—CHEMICAL OR PHYSICAL PROCESSES, e.g. CATALYSIS OR COLLOID CHEMISTRY; THEIR RELEVANT APPARATUS
    • B01J13/00—Colloid chemistry, e.g. the production of colloidal materials or their solutions, not otherwise provided for; Making microcapsules or microballoons
    • B01J13/02—Making microcapsules or microballoons
    • B01J13/06—Making microcapsules or microballoons by phase separation
    • B01J13/14—Polymerisation; cross-linking
    • B01J13/16—Interfacial polymerisation
    • B—PERFORMING OPERATIONS; TRANSPORTING
    • B01—PHYSICAL OR CHEMICAL PROCESSES OR APPARATUS IN GENERAL
    • B01J—CHEMICAL OR PHYSICAL PROCESSES, e.g. CATALYSIS OR COLLOID CHEMISTRY; THEIR RELEVANT APPARATUS
    • B01J13/00—Colloid chemistry, e.g. the production of colloidal materials or their solutions, not otherwise provided for; Making microcapsules or microballoons
    • B01J13/02—Making microcapsules or microballoons
    • B01J13/06—Making microcapsules or microballoons by phase separation
    • B01J13/14—Polymerisation; cross-linking
    • B01J13/18—In situ polymerisation with all reactants being present in the same phase
    • B—PERFORMING OPERATIONS; TRANSPORTING
    • B01—PHYSICAL OR CHEMICAL PROCESSES OR APPARATUS IN GENERAL
    • B01J—CHEMICAL OR PHYSICAL PROCESSES, e.g. CATALYSIS OR COLLOID CHEMISTRY; THEIR RELEVANT APPARATUS
    • B01J13/00—Colloid chemistry, e.g. the production of colloidal materials or their solutions, not otherwise provided for; Making microcapsules or microballoons
    • B01J13/02—Making microcapsules or microballoons
    • B01J13/20—After-treatment of capsule walls, e.g. hardening
    • B01J13/22—Coating
    • C—CHEMISTRY; METALLURGY
    • C09—DYES; PAINTS; POLISHES; NATURAL RESINS; ADHESIVES; COMPOSITIONS NOT OTHERWISE PROVIDED FOR; APPLICATIONS OF MATERIALS NOT OTHERWISE PROVIDED FOR
    • C09J—ADHESIVES; NON-MECHANICAL ASPECTS OF ADHESIVE PROCESSES IN GENERAL; ADHESIVE PROCESSES NOT PROVIDED FOR ELSEWHERE; USE OF MATERIALS AS ADHESIVES
    • C09J9/00—Adhesives characterised by their physical nature or the effects produced, e.g. glue sticks
    • 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
    • A—HUMAN NECESSITIES
    • A61—MEDICAL OR VETERINARY SCIENCE; HYGIENE
    • A61K—PREPARATIONS FOR MEDICAL, DENTAL OR TOILETRY PURPOSES
    • A61K2800/00—Properties of cosmetic compositions or active ingredients thereof or formulation aids used therein and process related aspects
    • A61K2800/40—Chemical, physico-chemical or functional or structural properties of particular ingredients
    • A61K2800/41—Particular ingredients further characterized by their size
    • A61K2800/412—Microsized, i.e. having sizes between 0.1 and 100 microns
    • 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

Definitions

  • the present invention relates to an active ingredient-containing capsule-in-capsule system and a method for its production and the use of this capsule-in-capsule system, in particular as a delivery or metering system for active ingredients or active ingredients, preferably for use in washing and Detergents, cosmetic products, adhesives and adhesive compositions and the like.
  • Active substances or active substances such as fragrances, essential oils, perfume oils and care oils, dyes or antibacterial active substances that are used in cosmetic products or in detergents and cleaning agents often lose their activity during storage or directly during use. Some of these substances can also have insufficient stability for use or cause interfering interactions with other product components.
  • Sensitive substances are often enclosed in capsules of various sizes, adsorbed on suitable carrier materials or chemically modified. The release can then be activated with the aid of a suitable mechanism, for example mechanically by shearing, or diffusively directly from the matrix material.
  • European patent application EP 0 967 007 A2 describes a process for the microencapsulation of solid, biologically active substances, in particular pesticides, by polycondensation of a melamine or phenol / formaldehyde resin or a urea / formalin resin in dispersion in the presence of the active substance to be encapsulated in each case and a nonionic polymeric protective colloid for stabilizing the emulsion, microcapsules having average particle diameters of 0.1 to 300 ⁇ m being obtained.
  • This method is only suitable for the encapsulation of solid biological active substances.
  • the emulsion must have a polymeric protective colloid be added. Only conventional capsule systems with a simple shell structure are described.
  • WO 98/02466, DE 196 28 142 A1, DE 196 28 143 A1 and EP 818471 A1 describe the preparation of aqueous polymerization dispersions by free radical polymerization of free-radically polymerizable compounds in the state of the miniemulsion. Encapsulation of active substances is nowhere mentioned.
  • DE 44 36 535 A1 describes a process for the preparation of microcapsule dispersions by means of interfacial polyaddition, which works with a certain minimum solubility in the oil phase using special oil-soluble emulsifiers (fatty acid esters, fatty amides, polyglycol ethers or polypropylene glycol ethers). Only conventional capsule systems with a simple shell structure are described.
  • US Pat. No. 4,626,471 describes a process for the microencapsulation of colorless organic dye precursor molecules by in-situ polymerization of polyfunctional amines with special multifunctional epoxy resins based on methylolated bisphenol-A or 4-glycidyloxy-N, N-diglycidylaniline. Only conventional capsule systems with a simple shell structure are described.
  • German Offenlegungsschrift 18 17 316 describes active ingredient-containing capsules with a multi-layer shell and a process for their production.
  • the capsules contain a liquid inside the capsule, in particular a color developer for pressure-sensitive copying material, fertilizer solutions, fragrances or adhesives.
  • EP 1 020 177 A1 describes a multi-layer soft capsule designed as a capsule-in-capsule system for removing malodorous breath, which contains a first soft capsule and a second soft capsule located therein, both the first and outer capsules the second, inner capsule contain an active ingredient for combating malodorous breath, the second, inner capsule should only dissolve in the stomach.
  • German Offenlegungsschrift 22 15 441 describes aqueous detergents which contain 1 to 50% of a detersive surfactant, at least 1% electrolyte and capsules which contain a water-soluble polymer in gelled form on their surface, the electrolyte, the concentration of the electrolyte and the polymer the capsules are selected such that the stability of the capsules in the detergent and the dissolution of the capsules when diluted with water are ensured.
  • These are also conventional capsule systems with a simple shell.
  • the object of the present invention is to provide a capsule or delivery system (metering system) which avoids the disadvantages of conventional capsule systems described above.
  • Another object of the present invention is to provide in particular an encapsulation technique which leads to systems which can react in particular to two or more environmental parameters in an application.
  • Another object of the present invention is to provide an encapsulation system which offers a good to increased protective action for the encapsulated ingredients.
  • Such a system is said to be particularly suitable for applications in detergents and cleaning agents, cosmetics and personal care products and in adhesive technology.
  • capsules which contain further smaller, preferably active substance-loaded capsules, in particular microcapsules or nanocapsules, or else smaller, active substance-loaded particles ("capsules-in-capsule” Systems "), especially in connection with suitably assembled solid, liquid or gel-like ingredients.
  • the present invention thus relates to a capsule-in-capsule system 1 with an outer capsule (outer capsule) 2 with an outer capsule shell 3 and an inner capsule (inner capsule) 4 located therein, the capsule-in-capsule system 1 according to the invention contains a plurality of inner capsules 4 which are completely surrounded by the capsule shell 3 of the outer capsule 2.
  • the outer capsule 2 also includes a first medium 5, in particular a carrier medium, in which the inner capsules 4 are located.
  • This first medium 5 can, for example, be a solid or liquid medium.
  • the first medium 5 can comprise, for example, an oil phase, an aqueous phase, an oil-in-water emulsion or a water-in-oil emulsion.
  • the oil of the oil phase or the emulsion can for example be a higher hydrocarbon, in particular with a carbon atom number of more than twelve, a paraffin oil, a silicone oil, a perfume or Fragrance oil, an essential oil or a care oil or a mixture of at least two such substances.
  • the first medium 5 can be designed, for example, as a powder or granulate.
  • the inner capsules 4 comprise a second medium 6.
  • the second medium 6 can in particular comprise at least one active substance or active substance, either in pure substance or in solution or suspension.
  • the active substance or active substance can be, for example, a substance that is active in washing and / or cleaning.
  • washing and / or cleaning active inorganic and organic acids in particular carboxylic acids, soil repellent and soil release active substances, bleaching agents such as in particular hypochlorites, bleach activators, washing and cleaning active enzymatic systems and Enzymes such as, in particular, amylases, cellulases, lipases and proteases, fragrances, in particular perfume oils, antimicrobial active substances, in particular antibacterial, antiviral and / or fungicidal active substances, builders and cobuildem, antiredeposition additives, oxidants, graying and discoloration inhibitors, active substances and color additives Laundry care, optical brighteners, foam inhibitors, all types of surfactants such as, in particular, surfactants with fabric softener properties as well as pH adjusting agents and pH buffer substances.
  • bleaching agents such as in particular hypochlorites, bleach activators, washing and cleaning active enzymatic systems and Enzymes
  • Enzymes such as, in particular, amylases, cellulases, lipases and protea
  • the active ingredient or active ingredient can also be an ingredient for cosmetics or personal care products.
  • the active ingredient can also be an adhesive or an adhesive component.
  • the inner capsules contain 4 identical active ingredients.
  • the inner capsules 4 can also contain different active substances.
  • part of the inner capsules 4 can contain a detergent enzyme, while the other part of the inner capsules 4 can contain a surfactant with fabric softener properties, the inner capsules 4 filled with different ingredients - after the outer capsule shell 3 has dissolved - the ingredients ( release enzyme or surfactant) specifically at different times of the washing process, for example due to different dissolution behavior of the inner capsules 4 z. B. depending on the ambient temperature.
  • the second medium 6 of the inner capsules 4 can be designed as a matrix, in particular a solid or gel-like matrix, in which the at least one active substance or active substance is embedded.
  • the inner capsules 4 can preferably also have a capsule shell 7 which completely encloses the second medium 6.
  • the first medium 5 can also comprise at least one active substance or active substance, either in pure substance or in solution or suspension.
  • This can be an identical active substance or active substance as in the inner capsules 4, or else a different active substance or active substance.
  • the first medium 5 and the second medium 6 can be identical or different. However, the first medium 5 and the second medium 6 are preferably different from one another.
  • the average diameter of the inner capsules 4 is at least one order of magnitude smaller than the average diameter of the outer capsule 2.
  • the ratio of the average diameter of the inner capsules 4 to the average diameter of the outer capsule 2 is generally approximately 1:10 to about 1: 100,000, in particular about 1: 100 to about 1: 30,000, preferably about 1: 1,000 to about 1: 20,000.
  • the average diameter of the inner capsules 4 is approximately
  • the mean diameter of the outer capsule 2 is approximately 1 ⁇ m to approximately 10 mm, in particular approximately 10 ⁇ m to approximately 5 mm, preferably approximately
  • the capsule shells (3, 7) are generally formed from a polymer or from polymers.
  • the capsule shell material of the capsule shells 7 of the inner capsules 4 can be identical or different with respect to the capsule shell material of the capsule shells 3 of the outer capsules 2.
  • the capsule shells 7 of the inner capsules 4 and the capsule shells 3 of the outer capsule 2 are made of different materials, i. H. the capsule shell material of the capsule shells 7 of the inner capsules 4 is preferably different from the capsule shell material of the capsule shell 3 of the outer capsule 2.
  • the capsule shells 7 of the inner capsule 4 formed from polymers can consist, for example, of polyelectrolytes or polyelectrolyte complexes, polystyrenes, epoxy resins, polyurethanes, polyureas, polycyanoacrylates, poly (meth) acrylates, melamine resins, formaldehyde resins, phenolic resins, polyisocyanates, waxes, solid paraffins or polysaccharides.
  • the capsule shell 3 of the outer capsule 2 formed from polymers can also consist, for example, of polyelectrolytes or polyelectrolyte complexes, polystyrenes, epoxy resins, polyurethanes, polyureas, polycyanoacrylates, poly (meth) acrylates, melamine resins, formaldehyde resins, phenolic resins, polyisocyanates, waxes, solid paraffins or polysaccharides.
  • the capsule-in-capsule system 1 generally has an active substance content of 0.001% by weight to 80% by weight, in particular 0.005 to 50% by weight, preferably 0.01 to 30% by weight, on, based on the entire capsule-in-capsule system 1.
  • the weight of the inner capsules 4 generally makes up 0.1 to 50% by weight, in particular 0.1 to 30% by weight, preferably 1 to 10% by weight, of the total weight of the capsule-in-capsule system 1 ,
  • the weight of the polymer from which the outer shell 3 is made generally represents 0.1 to 10% by weight, in particular 0.1 to 5% by weight, of the total weight of the capsule-in-capsule system 1.
  • the capsule-in-capsule system 1 generally has a content of the first medium 5 of 0.1 to 70% by weight, in particular 0.1 to 50% by weight, preferably 1 to 20% by weight.
  • the capsule shells 7 of the inner capsules 4 are hydrophobic and the capsule shell 3 of the outer capsule 2 is hydrophilic or vice versa.
  • the capsule shells 7 of the inner capsules 4 can be semipermeable and preferably in particular permeable to water molecules, but impermeable or essentially impermeable to the optionally encapsulated active substance or active ingredient.
  • Essentially impermeable in the sense of the present invention means that the capsule shells 7 are designed in particular in such a way that the active substance or active ingredient diffuses through the semipermeable capsule shell (membrane) considerably more slowly, preferably by at least one order of magnitude, than water molecules.
  • the production of capsules with a semipermeable capsule shell is known per se to the person skilled in the art and is described, for example, in German patent application 101 00 689, the content of which is hereby incorporated by reference.
  • the capsule shell 3 of the outer capsule 2 can be semipermeable and in particular permeable to water molecules.
  • the capsule shells 7 of the inner capsules 4 and the capsule shell 3 of the outer capsule 2 can dissolve at different temperatures and / or be soluble and / or melt in a given external medium.
  • This effect can be used, for example, in detergents (e.g. for the delayed release of wash-active enzymes or to protect fragrances that should only be released when the laundry is ironed), but also in personal care products, cosmetics and adhesives.
  • the capsule shells 7 of the inner capsules 4 and the capsule shell 3 of the outer capsule 2 can go into solution at different pH values and / or be soluble and / or melt in a given external medium.
  • This effect can be used, for example, in detergents (e.g. for the delayed release of wash-active enzymes or to protect fragrances that should only be released when the laundry is ironed), but also in personal care products, cosmetics and adhesives.
  • the capsule shells 7 of the inner capsules 4 and the capsule shell 3 of the outer capsule 2 can dissolve at different ion concentrations and / or be soluble and / or melt in a given external medium.
  • This effect can be used, for example, in detergents (e.g. for the delayed release of wash-active enzymes or to protect fragrances that should only be released when the laundry is ironed), but also in personal care products, cosmetics and adhesives.
  • the capsule shells 7 of the inner capsules 4 and the capsule shell 3 of the outer capsule 2 can have different degradation times in a given external medium.
  • This effect can be used, for example, in detergents (e.g. to delay the release of wash-active enzymes or to protect fragrances, which should only be released when the laundry is ironed), but also in personal care products, cosmetics and adhesives.
  • the capsule shells 7 of the inner capsules 4 and the capsule shell 3 of the outer capsule 2 can have different strengths. This effect can be used for example in the case of adhesives by z. B. the inner capsules 4 are firmer than the outer shell 3 and contain a catalyst for adhesive curing, which is only released by the action of high shear forces (z. B. by pressing) with destruction of the inner capsules 4.
  • the capsule shells 7 of the inner capsules 4 and the capsule shell 3 of the outer capsule 2 can have different affinities or chemical-physical properties with respect to an external medium.
  • the inner capsules may contain a fragrance and have a high affinity for textiles, while the outer capsule 2 e.g. B. can be temperature sensitive and z. B. dissolves during the washing process, so that the inner capsules 4 are released during the washing process and can attach to the fibers.
  • the capsule shells 7 of the inner capsules 4 and the capsule shell 3 of the outer capsule 2 can have different thicknesses.
  • the capsule shells 7 of the inner capsules 4 and / or the capsule shell 3 of the outer capsule 2 can consist of single- or multi-layer shells.
  • the inner capsules 4 can have a high affinity for textiles and in particular can adhere to the fibers of the textiles.
  • the capsule shells 7 of the inner capsules 4 and the capsule shell 3 of the outer capsule 2 can also have several of the aforementioned different properties.
  • the inner capsules 4 can be temperature-stable, in particular up to at least 30 ° C., preferably up to 95 ° C. and / or of a given external medium, in particular a detergent or cleaning agent solution, can be non-dissolvable and have a high affinity for textile fibers, while the outer capsule 2 cannot be temperature-stable and / or dissolved by a given external medium, in particular a detergent or cleaning agent solution can be.
  • the capsule shells 7 of the inner capsules 4 and / or the capsule shell 3 of the outer capsule 2 are designed to be environmentally friendly, in particular biodegradable.
  • the present invention also relates to a method for producing the capsule-in-capsule system 1 according to the invention, which comprises the following method steps:
  • step (b) Encapsulation of the dispersion prepared in step (a) and containing the inner capsules 4 by polymerization using methods known per se, in particular by gelation, coacervation, solution dropletization, melt dropletization, emulsion evaporation, spray drying or interfacial polymerization, so that a capsule-in -Capsule system 1, in which several inner capsules 4 are completely surrounded by an outer capsule shell 3, and finally
  • step (c) separation of the capsule-in-capsule system 1 obtained in step (b) using methods known per se.
  • the very small, in particular active substance-loaded, inner capsules 4 in step (a) can be carried out in particular as follows: Drug-loaded micro- and nanocapsules, microparticles or sponge particles can be produced in a manner known per se, e.g. B. by miniemulsion polymerization, interfacial polymerization of reactive surfactants (see e.g. German patent applications 100 37 656 and 100 31 132), by interfacial polymerization of cyanoacrylates (see e.g. BG Puglisi et al., Int. J. Pharm. 1995, 125 , Pages 283-287), by melamine-formaldehyde resin reactions (see, for example, BK Hong, S. Park, Mater. Chem.
  • the particles obtained are usually in the form of an aqueous or oil-containing dispersion after their preparation.
  • the shell or matrix material of the inner capsules 4 is selected in particular so that it can produce the desired second switching mechanism when released in later use. Capsules with a delayed release of active ingredient and capsules with a substantial surface quality are particularly interesting.
  • a method for producing the inner capsules 4 according to step (a) of the method according to the invention is e.g. B. described in German patent application 100 44 635, which relates to a process for the preparation of polymer capsules with encapsulated active ingredients or active ingredients by sol-gel polycondensation of monomeric, trifunctional, surface-active organosilicon compounds polymerizable by polycondensation in emulsion, the organosilicon compound being selected in particular from the group of trifunctional alkylhalosilanes and the corresponding alkylsilanols and trifunctional alkylsiloxanes, each with a long-chain alkyl chain, for.
  • German patent application 100 37 656 describes the production of polymer capsules containing active substance or active substance by non-radical emulsion polymerization of suitable monomers in the presence of the active substance or active substance to be encapsulated under mini-emulsion polymerization conditions.
  • the polyaddition of di- or polyfunctional amines, alcohols, carboxylic acid anhydrides and mercaptans to di- and / or polyfunctional epoxides is used.
  • the polyaddition of di- and polyfunctional amines and alcohols onto di- and / or polyfunctional isocyanates is also suitable.
  • active ingredient-containing polymer capsules based on epoxy resins, polyurethanes or polyureas are formed as the capsule material.
  • step (a) of the method according to the invention are described in WO 00/29465, in EP 0 967 007 A2, in WO 98/02466, in DE 196 28 142 A1, in DE 196 28 143 A1, in EP 818 471 A1, in DE 44 36 535 A1 and in US-A-4 626 471.
  • Further methods according to the invention for carrying out step (a) of the method according to the invention are described by Landfester et al. "Polyaddition in miniemulsions: A new mute to polymer dispersions" in Macromol. Chem. Phys.
  • a further method according to the invention for producing the inner capsules 4 is described in the German patent application 100 31 132.
  • the heat, plasma or radiation-induced radical interfacial polymerization in dispersion for the in-situ encapsulation of active substances in polymer capsules produced by interfacial polymerization is described
  • Another method which is suitable according to the invention is described in German patent application 100 00 689, which describes a method for producing microcapsules with a semipermeable capsule shell with encapsulated detergent and / or cleaning substances by in-situ complexation of suitable polyelectrolytes or polyelectrolyte mixtures.
  • step (a) in step (b) of the method according to the invention is carried out in particular as follows:
  • step (b) The encapsulation carried out in step (b) can be carried out, for example, by dripping the dispersion prepared in step (a) after adding suitable monomers or polymers into a suitable template, in particular an acidic, basic or neutral salt or ion solution.
  • the capsule or particle dispersion or granulate produced according to step (a) is z. B. via a known method, such as. B. gelation, coacervation, solution drop or melt drop (e.g. with waxes or wax-like substances), emulsion evaporation, spray drying or interfacial polymerization (see e.g. German patent application 100 44 635), as is known from the prior art for "simple" Encapsulation is known, encapsulated again.
  • the outer shell or matrix material becomes the outer one Capsules 2 in particular chosen so that it can generate the desired first switching mechanism in the release in the later application.
  • z. B. water-soluble polymers such as. B. in German Offenlegungsschrift 22 15 441 (z.
  • polyvinyl alcohol, cellulose derivatives, polysaccharides, polyacrylates, etc. are used, which can either melt or which form insoluble complexes with suitable, especially polyvalent ions ("gelling ") or can be salted out or crosslinked (e.g. alginates by dropletization in alkaline earth metal ion solutions or e.g. polyvinyl alcohols by dropletization in solutions which contain alkaline earth metal ions, borates, aluminum ions, etc.).
  • the resulting capsules which have a switching mechanism for the pH value (for example via polyacrylate casings, e.g.
  • LCST polymers such as poly-N-isopropylacrylamide derivatives
  • ionic strength for example polyvinyl alcohol, for example from Erkol
  • the present invention also relates to the use of the capsule-in-capsule system 1 according to the invention for the field of cosmetics and personal care, for the production and processing of adhesives and / or for the field of detergents and cleaning agents.
  • the capsule-in-capsule system 1 can be used as a delivery system or dosing system, preferably for the controlled release of active substances or active substances.
  • the present invention further also relates to cosmetics or personal care products, adhesives or adhesive components or else in particular detergents and cleaning agents which contain the capsule-in-capsule system 1 according to the invention - in one or more phases of the product.
  • the present invention offers a number of advantages:
  • the present invention provides an encapsulation system 1 or an encapsulation technology that can react to two or more environmental parameters in an application.
  • the system 1 according to the invention provides a good to increased protective effect for the encapsulated ingredients.
  • the main focus of the applications for the system 1 according to the invention are washing and cleaning agents, cosmetics and personal care products and adhesives.
  • the present invention readily enables "capsule-in-capsule system 1 to be” tailored "for the respective application.
  • the capsule-in-capsule system 1 according to the invention can, for. B. can be tailored for the respective application by selecting the suitable material for the release on both "size levels" of the capsules in a suitable manner.
  • the release profile of the active ingredients can also be tailored via the "size levels" of the capsules by utilizing surface effects. Small capsules with a thin wall and a large surface area, for example, lead to a faster release than large capsules of the same material.
  • Z. B. also optical or acoustic effects during the release, such as. B. a color change of an indicator by pH change or the formation of a gas in the reaction of the capsule ingredient with the outer phase.
  • a suitable ingredient of the smaller capsules is selected accordingly.
  • Particularly preferred polymers for the outer capsule shell 3 are therefore in particular those which protect the enclosed smaller capsules 4 from the surrounding medium, so that a reaction and / or release of the encapsulated ingredient does not occur during storage.
  • an oil phase as the carrier phase 6 for the smaller capsules 4 (similar to a w / o / w emulsion), if as the outer phase 5 an aqueous phase and an active ingredient in the inner capsules 4 a water-soluble active ingredient, since the (diffusive) exchange of the phases is thus minimized.
  • the oil phase is then in the form of a gel by adding a suitable gelator (low molecular weight or polymer).
  • aqueous phase which, in addition to the monomers to be polymerized (alkyl cyanoacrylate) and optionally conventional additives such as emulsifiers, contains 10% by weight of an active ingredient (fragrance oil or orange oil), known methods (see Puglisi et al.) a 10% aqueous dispersion of 2 to 20 ⁇ m large poly (alkyl cyanoacrylate) capsules (e.g. poly (methyl cyanoacrylate) capsules or poly (ethyl cyanoacrylate) capsules), which contain the fragrance oil in encapsulated form ,
  • an active ingredient fragment oil or orange oil
  • the dispersion of poly (alkyl cyanoacrylate) microcapsules produced in this way is added dropwise to a 20% sodium sulfate solution after the addition of 5% by weight of polyvinyl alcohol. Due to the ion concentration-dependent solubility of polyvinyl alcohol in water, capsules of 100 to 2,000 ⁇ m in size form spontaneously with an outer shell made of polyvinyl alcohol, which encapsulate the dispersion with the smaller, active substance-loaded poly (alkyl cyanoacrylate) and can then be filtered off if necessary.
  • capsule-in-capsule delivery system with an oil-like active ingredient (fragrance oil), which is used, for example, in liquid detergents when diluted, ie. H. in use when washing, e.g. B. in washing machines, the active ingredient-filled inner capsules, which have a substantivity to the tissue, only releases with delay.
  • the inner capsules remain on the fabric treated in this way even after the laundry has dried. This results in an improved fragrance when ironing the laundry.
  • the dispersion of active substance-loaded nanocapsules produced in this way is added to a solution containing 2% calcium chloride and 0.2% poly-L-lysine after the addition of 1.8% by weight sodium alginate. Due to the complexation of the alginate, 30 to 300 ⁇ m capsules with an outer shell made of an alginate complex are formed, which surround the dispersion with the smaller, active substance-loaded nanocapsules and can then be filtered off if necessary.
  • capsule-in-capsule delivery system with an oil-like active ingredient (fragrance oil) which, for example, as in Example 1, in liquid detergents when diluted, ie. H. in use when washing, e.g. B. in washing machines, the active ingredient-filled inner capsules, which have a substantivity to the tissue, only releases with delay.
  • the inner capsules remain on the fabric treated in this way even after the laundry has dried. This results in an improved fragrance when ironing the laundry.
  • the oil-containing dispersion (Cetiol OE) of nanocapsules loaded with active ingredient produced in this way is added after adding 12% by weight of Eudragit®, a Methacrylate polymer from Röhm or Rohm & Haas, dripped into a solution with 5% HCl and 2% sucrose. Due to the solubility of the Eudragit® polymer, which is dependent on the pH of the medium, capsules of 500 to 2,000 ⁇ m in size are created with an outer shell made of Eudragit®, which surround the dispersion with the smaller, active ingredient-loaded nanocapsules and can then be filtered off if necessary.
  • Eudragit® a Methacrylate polymer from Röhm or Rohm & Haas
  • the result is a capsule-in-capsule delivery system according to the invention with a hydrophilic active ingredient which, for example when used in a hair colorant, releases the active ingredient-filled capsules with a delay when applied to the hair and thereby achieves an antioxidative effect on the scalp.

Abstract

L'invention concerne des systèmes capsules dans capsule (1) qui sont constitués d'une capsule extérieure (2) pourvue d'une enveloppe de capsule extérieure (3), dans laquelle se trouvent des capsules intérieures (4). L'invention concerne également un procédé permettant de produire de tels systèmes. Les systèmes capsules dans capsule (1) peuvent, en particulier, être utilisés dans le domaine de la cosmétique et des soins corporels, dans la production et le traitement d'adhésifs et/ou dans le domaine des produits de lavage et de nettoyage.
PCT/EP2002/000816 2001-02-01 2002-01-26 Systeme capsules dans capsule et son procede de production WO2002060573A2 (fr)

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AU2002250858A AU2002250858A1 (en) 2001-02-01 2002-01-26 Capsule-in-capsule system and method for the production thereof

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DE2001104841 DE10104841A1 (de) 2001-02-01 2001-02-01 Kapseln-in-Kapsel-System und Verfahren zu seiner Herstellung
DE10104841.6 2001-02-01

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WO2007072052A3 (fr) * 2005-12-23 2008-11-27 Syngenta Ltd Formulation
WO2010070602A2 (fr) 2008-12-18 2010-06-24 Firmenich Sa Microcapsules et leurs applications
WO2013164542A1 (fr) * 2012-05-03 2013-11-07 Universite Claude Bernard Lyon I Particules constituees d'une matrice hydrophobe emprisonnant des gouttelettes d'une dispersion aqueuse d'un compose adhesif, procede d'obtention et utilisation
WO2013182855A2 (fr) * 2012-06-08 2013-12-12 Imerys Minerals Limited Microcapsules
CN107349112A (zh) * 2017-05-27 2017-11-17 清远初曲智能科技有限公司 一种减少唇纹长效深层保湿滋润的变色唇膏及其制备方法
GB2552130A (en) * 2016-03-14 2018-01-17 Justyna Sniegocka Luiza Hand soap capsule
WO2018169421A1 (fr) * 2017-03-14 2018-09-20 Octagon International Trade Zbigniew Bąbelek Détergent complexe capsule-dans-capsule
DE102017111445A1 (de) 2017-05-24 2018-11-29 Henkel Ag & Co. Kgaa Mikrokapselsystem für polysensorische Dufteffekte
DE102017111444A1 (de) 2017-05-24 2018-11-29 Henkel Ag & Co. Kgaa Mikrokapselsystem für polysensorische Dufteffekte
WO2019121657A1 (fr) * 2017-12-20 2019-06-27 Givaudan Sa Perfectionnements apportés ou se rapportant aux composés organiques
WO2020193536A1 (fr) 2019-03-25 2020-10-01 Sphera Technology Gmbh Système à plusieurs composants et procédé de fabrication d'un système à plusieurs composants
CN112028050A (zh) * 2020-08-31 2020-12-04 山西大学 内部结构可控的高强度多孔毫米碳球及其制备方法和应用
CN112410130A (zh) * 2020-11-30 2021-02-26 广州市白云区大荣精细化工有限公司 一种织物用清洁留香固形物及其制备方法
EP3765036A4 (fr) * 2018-03-14 2021-11-24 Premier Dental Products Company Compositions microencapsulées tamponnées et méthodes associées
WO2022140407A1 (fr) * 2020-12-23 2022-06-30 Baik Steven S Adhésif encapsulé
WO2022064014A3 (fr) * 2020-09-24 2022-08-11 Sphera Technology Gmbh Système multiconstituant
EP4101529A1 (fr) * 2021-06-11 2022-12-14 Henkel AG & Co. KGaA Milieu contenant des microcapsules dégradables de couleur neutre avec composition de parfum
EP4101528A1 (fr) * 2021-06-11 2022-12-14 Henkel AG & Co. KGaA Milieu contenant des microcapsules dégradables de couleur neutre
WO2022258808A1 (fr) * 2021-06-11 2022-12-15 Henkel Ag & Co. Kgaa Compositions contenant des microcapsules dégradables neutres en couleur
US11850294B2 (en) 2009-04-27 2023-12-26 Premier Dental Products Company Buffered microencapsulated compositions and methods

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DE102004062328A1 (de) * 2004-12-20 2006-06-29 Henkel Kgaa Dosiereinheit für Wasch- oder Reinigungsmittel
DE102011018717A1 (de) * 2011-04-26 2012-10-31 Fraunhofer-Gesellschaft zur Förderung der angewandten Forschung e.V. Mikrokapsel und Stoffgemisch
CN112973589B (zh) * 2021-02-05 2022-04-29 中国工程物理研究院激光聚变研究中心 一种磺化rf气凝胶微球的制备方法

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US8808720B2 (en) 2005-12-23 2014-08-19 Syngenta Limited Formulation
AU2006327942B2 (en) * 2005-12-23 2013-09-12 Syngenta Limited Formulation
WO2007072052A3 (fr) * 2005-12-23 2008-11-27 Syngenta Ltd Formulation
CN101466263B (zh) * 2005-12-23 2013-01-02 先正达有限公司 制剂
AU2006327936B2 (en) * 2005-12-23 2013-05-02 Syngenta Limited. Formulation
CN102256588B (zh) * 2008-12-18 2013-07-03 弗门尼舍有限公司 微胶囊及其用途
WO2010070602A2 (fr) 2008-12-18 2010-06-24 Firmenich Sa Microcapsules et leurs applications
WO2010070602A3 (fr) * 2008-12-18 2010-09-16 Firmenich Sa Microcapsules et leurs applications
US8778867B2 (en) 2008-12-18 2014-07-15 Firmenich Sa Microcapsules and uses thereof
US9498411B2 (en) 2008-12-18 2016-11-22 Firmenich Sa Microcapsules and uses thereof
US11850294B2 (en) 2009-04-27 2023-12-26 Premier Dental Products Company Buffered microencapsulated compositions and methods
WO2013164542A1 (fr) * 2012-05-03 2013-11-07 Universite Claude Bernard Lyon I Particules constituees d'une matrice hydrophobe emprisonnant des gouttelettes d'une dispersion aqueuse d'un compose adhesif, procede d'obtention et utilisation
FR2990141A1 (fr) * 2012-05-03 2013-11-08 Univ Claude Bernard Lyon Particules constituees d'une matrice hydrophobe emprisonnant des gouttelettes d'une dispersion aqueuse d'un compose adhesif, procede d'obtention et utilisation
WO2013182855A3 (fr) * 2012-06-08 2014-06-05 Imerys Minerals Limited Microcapsules
WO2013182855A2 (fr) * 2012-06-08 2013-12-12 Imerys Minerals Limited Microcapsules
US9943820B2 (en) 2012-06-08 2018-04-17 Imerys Minerals Limited Microcapsules
GB2552130A (en) * 2016-03-14 2018-01-17 Justyna Sniegocka Luiza Hand soap capsule
WO2018169421A1 (fr) * 2017-03-14 2018-09-20 Octagon International Trade Zbigniew Bąbelek Détergent complexe capsule-dans-capsule
US11401485B2 (en) 2017-05-24 2022-08-02 Henkel Ag & Co. Kgaa Microcapsule system for polysensory olfactory effects I
DE102017111445A1 (de) 2017-05-24 2018-11-29 Henkel Ag & Co. Kgaa Mikrokapselsystem für polysensorische Dufteffekte
WO2018215354A1 (fr) 2017-05-24 2018-11-29 Henkel Ag & Co. Kgaa Système de microcapsules pour effets olfactifs polysensoriels ii
DE102017111444A1 (de) 2017-05-24 2018-11-29 Henkel Ag & Co. Kgaa Mikrokapselsystem für polysensorische Dufteffekte
WO2018215351A1 (fr) 2017-05-24 2018-11-29 Henkel Ag & Co. Kgaa Système de micro-capsules pour effets parfumés polysensoriels
CN107349112B (zh) * 2017-05-27 2018-09-18 清远初曲智能科技有限公司 一种减少唇纹长效深层保湿滋润的变色唇膏及其制备方法
CN107349112A (zh) * 2017-05-27 2017-11-17 清远初曲智能科技有限公司 一种减少唇纹长效深层保湿滋润的变色唇膏及其制备方法
WO2019121657A1 (fr) * 2017-12-20 2019-06-27 Givaudan Sa Perfectionnements apportés ou se rapportant aux composés organiques
EP3765036A4 (fr) * 2018-03-14 2021-11-24 Premier Dental Products Company Compositions microencapsulées tamponnées et méthodes associées
WO2020193536A1 (fr) 2019-03-25 2020-10-01 Sphera Technology Gmbh Système à plusieurs composants et procédé de fabrication d'un système à plusieurs composants
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CN114127217A (zh) * 2019-03-25 2022-03-01 斯皮拉技术有限公司 多组分体系和多组分体系的制造方法
CN112028050B (zh) * 2020-08-31 2021-12-31 山西大学 内部结构可控的高强度多孔毫米碳球及其制备方法和应用
CN112028050A (zh) * 2020-08-31 2020-12-04 山西大学 内部结构可控的高强度多孔毫米碳球及其制备方法和应用
WO2022064014A3 (fr) * 2020-09-24 2022-08-11 Sphera Technology Gmbh Système multiconstituant
CN112410130B (zh) * 2020-11-30 2021-12-28 广州市白云区大荣精细化工有限公司 一种织物用清洁留香固形物及其制备方法
CN112410130A (zh) * 2020-11-30 2021-02-26 广州市白云区大荣精细化工有限公司 一种织物用清洁留香固形物及其制备方法
WO2022140407A1 (fr) * 2020-12-23 2022-06-30 Baik Steven S Adhésif encapsulé
EP4101528A1 (fr) * 2021-06-11 2022-12-14 Henkel AG & Co. KGaA Milieu contenant des microcapsules dégradables de couleur neutre
WO2022258808A1 (fr) * 2021-06-11 2022-12-15 Henkel Ag & Co. Kgaa Compositions contenant des microcapsules dégradables neutres en couleur
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